CN104628202A - Natural freezing-Fenton oxidation-coagulation combined method for treating TNT red water - Google Patents
Natural freezing-Fenton oxidation-coagulation combined method for treating TNT red water Download PDFInfo
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- CN104628202A CN104628202A CN201510092557.7A CN201510092557A CN104628202A CN 104628202 A CN104628202 A CN 104628202A CN 201510092557 A CN201510092557 A CN 201510092557A CN 104628202 A CN104628202 A CN 104628202A
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Abstract
The invention relates to a treatment method of TNT produced wastewater (abbreviated as TNT red water), belongs to the technical field of environment protection wastewater treatment, and particularly relates to a natural freezing-Fenton oxidation-coagulation combined method for treating TNT red water. The method comprises the following steps: firstly naturally freezing the TNT red water with freezing temperature of -25 to -5 degrees centigrade and freezing time of 1-7 days, fishing out the ice, naturally drying the residual components, and then destroying; melting the fished ice as water (the water is hereinafter referred to as melting ice water, pH value is 7-9, and the COD removal rate is 70%-99%), adding acid to regulate pH value to about 3, adding moderate ferrous sulfate particles accounting for 0.1%-1% of the melting ice water amount, stirring to dissolve, adding moderate hydrogen peroxide with concentration of 30% accounting for 0.4%-4% of the melting ice water amount, stirring for 10 min, and standing for 10-30 hours till the pH is mot more than 2; finally adding a neutralizer to adjust the pH to between 6-9, aerating to produce ferric hydroxide floc, and separating the floc. The experiment result expresses that the TNT production wastewater treated by using the combined technology can be directly discharged to reach standard.
Description
Technical field
The present invention relates to TNT production wastewater treatment method, belong to environment protection technical field of waste water processing, i.e. the red water method of naturally frozen-Fenton oxidation-coagulation coupling technique Treatment of TNT.
Background technology
The red water of TNT raw TNT is carried out to a kind of waste water of producing in treating process with Arbiso process, and its composition is very complicated, and toxicity is very large, and in scarlet, organic concentration that is opaque, alkaline, dissolving is high.Often produce 1 ton of TNT product about produce 80 ~ 90 kilograms of waste water, its colourity is 6000 ~ 10000 times, COD be 60000 ~ 100000mg/L, pH between 10 ~ 12, entering environment and can cause great harm, is the difficult point in this type of wastewater treatment.Its typical composition is water 76.5%; Organism 17.6%, the organic components complex in red water, the known fluorescence probe wherein contained reaches more than 70 kinds, and its main component is α-TNT and dinitrotoluene (DNT) sulfonate, and the chemical structure of red tar thing wherein is not yet understood fully so far; Inorganics 5.9%, main component is NaNO
3(1.7%), NaNO
2(3.5%), Na
2sO
4(0.6%), Na
2sO
3(2.3%); Its solid content about 15%.TNT toxicity is very large, and have mutagenic toxicity, the suction lethal quantity of human body is 2g, and route of intoxication is sucked by respiratory tract to try to make a good showing or dust, and absorbed by skin.When in water, TNT content reaches 1mg/L, fish will be dead.Soil is comparatively strong to TNT adsorption, can immerse soil and permeate the ground, polluted underground water, causing serious harm to environment.
At present, the treatment process of the red water of TNT is a lot, but these treatment processs all Shortcomings parts: and technical process is complicated, and processing costs is high, and causes secondary pollution.Patent CN 201010176578.4 provides one and processes 2 by immobilized microorganism-anaerobic biofilter (I-AF) and immobilized microorganism-BAF (I-BAF), the method of 4,6-trotyl (being called for short TNT) waste water.Patent CN 201210024488.2 provides one stearic acid solution combustion method and prepares ultra-fine perovskite type catalyzer, and it is used for the method for photocatalysis treatment TNT simulated wastewater.Patent CN 201210108961.5 provides a kind of method adopting the red water of supercritical oxidation process Treatment of TNT.This method can reduce the processing load of subsequent technique.CN 200710039935.0 provides the treatment process containing dynamite component waste water under anaerobic agent catalytic condition in a kind of super (closely) critical, treatment process of the present invention has good degradation effect, and the clearance of TNT, RDX, HMX in waste water can reach more than 90%.CN 200610045842.4 provides the treatment process of waste acid containing nitro compound in a kind of TNT production, the method treatment process is simple, obvious processing effect, the clearance > 98% of the nitro-compounds such as its TNT, DNT, nitro-compound content in waste water is down to 0.24mg/l, far below primary standard in national tritonal (TNT) industrial water pollution thing emission standard (GB4274-84).Equipment used is few, cost is low, and investment, running cost is low, is applicable to industrialization promotion and implements.
Method based on cold method process waste water does not all relate to TNT factory effluent.Patent CN 101544436 A provides and a kind ofly utilizes freezing and crystallizing to remove and the method for vitriol in recover acrylonitrile waste water.Patent CN 102249353 A has invented freeze-thaw inverted-stage integrated wastewater recycling treatment equipment, for the process of waste water.Patent CN 101428921 A provides a kind for the treatment of process of wastewater discharged from p-toluene sulfonyl chloride production.Patent CN 102205994 A provides a kind of waste water reclamation circulation process method based on naturally frozen process.Patent CN101891269 A provides a kind of method of waste water desalination.Patent CN 101885569 A provides a kind for the treatment of process of organic high-salinity wastewater.Patent CN 103787543 A provides a kind of with the method for cold method Pretreatment for AN Wastewater.Patent CN 101066819 A provides a kind of non-biodegradable organic industrial effluent with high salt content combined treatment process.
The method of naturally frozen-Fenton-coagulation coupling technique process ordnance factory's explosive waste water and the red water of TNT is adopted to have no report.
Summary of the invention
goal of the invention:the invention provides the red water method of a kind of naturally frozen-Fenton process oxidation-coagulation coupling Treatment of TNT, solve technical process complexity, avoid while processing costs high problem and cause secondary pollution.
technical scheme:
The red water method of naturally frozen-Fenton process oxidation-coagulation coupling Treatment of TNT, is characterized in that: said method comprising the steps of:
Step one: naturally frozen is carried out to the red water of TNT, freezing temp is-5 ~-25 DEG C, and freezing time is 1 ~ 7 day, is pulled out by ice, and remaining ingredient is throw out, and natural air drying, then destroys;
Step 2: by the ice-melt water of ice-out gained pulled out, adjust ph to 3, then ferrous sulfate particle is added, add-on is 0.1% ~ 1% of the ice-melt water yield by percentage to the quality, after stirring and dissolving, then adds the hydrogen peroxide that concentration is 30%, add-on is 0.4% ~ 4% of the ice-melt water yield by percentage to the quality, stir after 10 minutes, leave standstill 10 ~ 30 hours, now pH≤2;
Step 3: finally adding neutralizing agent to pH is between 6 ~ 9, and passes into pressurized air aeration 30 ~ 60 minutes, produces ironic hydroxide flco, isolates flco; TNT factory effluent after process, can direct qualified discharge.
In described step 2, the pH value range of ice-melt water is that 7 ~ 9, COD clearance is 70% ~ 99%.
In described step 2, ferrous sulfate particle is ferrous sulfate hydrate crystal.
In described step 2, pH value regulates acid used to be any one in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
Neutralizing agent is any one in Wingdale, rhombspar, slaked lime, caustic soda, and its medium-slaking lime is preferred neutralizing agent.
advantageous effect:
Treatment process of the present invention adopts cold method to carry out pre-treatment, winter cold energy be easy to get, belong to natural energy source.Coupling technique technique is simple, and technical requirements is low, good effect of separating solid from liquid, and treatment effect is good, and running cost is low.
Accompanying drawing explanation
Fig. 1: be TNT wastewater treatment process figure.
embodiment:
Embodiment 1
1) get 500 milliliters of red water of TNT, be placed on open air and carry out naturally frozen, freezing temp is-5 ~-10 DEG C, and freezing time is 2 days, is pulled out by ice, and remaining ingredient natural air drying, then destroys;
2) be water (hereinafter referred to as ice-melt water) by the ice-out pulled out, volume is 310mL.Add sulfuric acid and pH value is adjusted to 3, then appropriate ferrous sulfate particle is added, add-on is 0.2% of the ice-melt water yield by percentage to the quality, after stirring and dissolving, add the hydrogen peroxide that appropriate concentration is 30% again, add-on is 0.5% of the ice-melt water yield by percentage to the quality, stirs after 10 minutes, leave standstill 12 hours, now pH=1.5;
3) finally add neutralizing agent slaked lime, solution being neutralized to pH is 7, and passes into pressurized air aeration 30 minutes, produces ironic hydroxide flco, isolates flco, and now comparatively other neutralizing agent effects are more rapid for neutralization, and reaction is more abundant.Water after process can direct qualified discharge.
Embodiment 2
1) get 1 liter of red water of TNT, be placed on open air and carry out naturally frozen, freezing temp is-7 ~-15 DEG C, and freezing time is 5 days, is pulled out by ice, and remaining ingredient natural air drying, then destroys;
2) by the ice-out pulled out be water (hereinafter referred to as ice-melt water), volume is 680 milliliters, add hydrochloric acid and pH value is adjusted to 3, then add appropriate ferrous sulfate particle, add-on is 0.5% of the ice-melt water yield by percentage to the quality, after stirring and dissolving, add the hydrogen peroxide that appropriate concentration is 30% again, add-on is 2% of the ice-melt water yield, stirs after 10 minutes, leave standstill 20 hours, now pH=1.2;
3) finally add neutralizing agent Wingdale, solution being neutralized to pH is 8, and passes into pressurized air aeration 40 minutes, produces ironic hydroxide flco, isolates flco.Water after process can direct qualified discharge.
Embodiment 3
1) get 5 liters of red water of TNT, be placed on open air and carry out naturally frozen, freezing temp is-8 ~-21 DEG C, and freezing time is 6 days, is pulled out by ice, and remaining ingredient natural air drying, then destroys;
2) by the ice-out pulled out be water (hereinafter referred to as ice-melt water), volume is 3.5 liters, add nitric acid and pH value is adjusted to 3, then add appropriate ferrous sulfate particle, add-on is 0.8% of the ice-melt water yield by percentage to the quality, after stirring and dissolving, add the hydrogen peroxide that appropriate concentration is 30% again, add-on is 3.5% of the ice-melt water yield by percentage to the quality, stirs after 10 minutes, leave standstill 28 hours, now pH=0.95;
3) finally add neutralizing agent rhombspar, solution being neutralized to pH is between 6 ~ 9, and passes into pressurized air aeration 45 minutes, produces ironic hydroxide flco, isolates flco.Water after process can direct qualified discharge.
Embodiment 4
1) get 10 liters of red water of TNT, be placed on open air and carry out naturally frozen, freezing temp is-5 ~-23 DEG C, and freezing time is 2 days, is pulled out by ice, and remaining ingredient natural air drying, then destroys;
2) by the ice-out pulled out be water (hereinafter referred to as ice-melt water), volume is 6.5 liters, add phosphoric acid and pH value is adjusted to 3, then add appropriate ferrous sulfate particle, add-on is 0.7% of the ice-melt water yield by percentage to the quality, after stirring and dissolving, add the hydrogen peroxide that appropriate concentration is 30% again, add-on is 0.9% of the ice-melt water yield by percentage to the quality, stirs after 10 minutes, leave standstill 25 hours, now pH=1.3;
3) finally add neutralizing agent caustic soda, solution being neutralized to pH is between 6 ~ 9, and passes into pressurized air aeration 55 minutes, produces ironic hydroxide flco, isolates flco.Water after process can direct qualified discharge.
In described step 2, the pH value range of ice-melt water is that 7 ~ 9, COD clearance is 70% ~ 99%.
In described step 2, ferrous sulfate particle is ferrous sulfate hydrate crystal.
In described step 2, pH value regulates acid used to be any one in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
Neutralizing agent is any one in Wingdale, rhombspar, slaked lime, caustic soda, and its medium-slaking lime is preferred neutralizing agent.
Claims (6)
1. the red water method of naturally frozen-Fenton process oxidation-coagulation coupling Treatment of TNT, is characterized in that: said method comprising the steps of:
Step one: naturally frozen is carried out to the red water of TNT, freezing temp is-5 ~-25 DEG C, and freezing time is 1 ~ 7 day, is pulled out by ice, and remaining ingredient is throw out, and natural air drying, then destroys;
Step 2: by the ice-melt water of ice-out gained pulled out, adjust ph to 3, then ferrous sulfate particle is added, add-on is 0.1% ~ 1% of the ice-melt water yield by percentage to the quality, after stirring and dissolving, then adds the hydrogen peroxide that concentration is 30%, add-on is 0.4% ~ 4% of the ice-melt water yield by percentage to the quality, stir after 10 minutes, leave standstill 10 ~ 30 hours, now pH≤2;
Step 3: finally adding neutralizing agent to pH is between 6 ~ 9, and passes into pressurized air aeration 30 ~ 60 minutes, produces ironic hydroxide flco, isolates flco; TNT factory effluent after process, can direct qualified discharge.
2. the red water method of naturally frozen according to claim 1-Fenton process oxidation-coagulation coupling Treatment of TNT, is characterized in that: in described step 2, the pH value range of ice-melt water is that 7 ~ 9, COD clearance is 70% ~ 99%.
3. the red water method of naturally frozen according to claim 1-Fenton process oxidation-coagulation coupling Treatment of TNT, is characterized in that: in described step 2, ferrous sulfate particle is ferrous sulfate hydrate crystal.
4. the red water method of naturally frozen according to claim 1-Fenton process oxidation-coagulation coupling Treatment of TNT, is characterized in that: in described step 2, pH value regulates acid used to be any one in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid.
5. the red water method of naturally frozen according to claim 1-Fenton process oxidation-coagulation coupling Treatment of TNT, is characterized in that: neutralizing agent is any one in Wingdale, rhombspar, slaked lime, caustic soda, and its medium-slaking lime is preferred neutralizing agent.
6. the red water method of naturally frozen according to claim 1-Fenton process oxidation-coagulation coupling Treatment of TNT, is characterized in that: adopt pressurized air aeration, and the time is 30 ~ 60 minutes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814466A (en) * | 2017-12-07 | 2018-03-20 | 西安近代化学研究所 | A kind of DPT production wastewater treatments technique |
| CN117326752A (en) * | 2023-11-13 | 2024-01-02 | 江苏天从环保科技有限公司 | High-efficient combination processing system of reuse of reclaimed water in high salt waste water |
| CN117509977A (en) * | 2023-12-13 | 2024-02-06 | 广州中环万代环境工程有限公司 | Wastewater pretreatment equipment and treatment method thereof |
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| JPS5732800A (en) * | 1980-08-07 | 1982-02-22 | Mitsubishi Electric Corp | Freeze-thaw treatment of sludge |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5732800A (en) * | 1980-08-07 | 1982-02-22 | Mitsubishi Electric Corp | Freeze-thaw treatment of sludge |
| KR20060105106A (en) * | 2005-04-01 | 2006-10-11 | 주식회사 새 한 | Method of and apparatus for the treatment of wastewater |
| CN101066819A (en) * | 2007-06-13 | 2007-11-07 | 天津城市建设学院 | Combined treatment process for non-biodegradable organic industrial effluent with high salt content |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814466A (en) * | 2017-12-07 | 2018-03-20 | 西安近代化学研究所 | A kind of DPT production wastewater treatments technique |
| CN107814466B (en) * | 2017-12-07 | 2020-12-15 | 西安近代化学研究所 | DPT production wastewater treatment process |
| CN117326752A (en) * | 2023-11-13 | 2024-01-02 | 江苏天从环保科技有限公司 | High-efficient combination processing system of reuse of reclaimed water in high salt waste water |
| CN117509977A (en) * | 2023-12-13 | 2024-02-06 | 广州中环万代环境工程有限公司 | Wastewater pretreatment equipment and treatment method thereof |
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