CN110372150A - A kind of processing method of chlopyrifos waste water - Google Patents
A kind of processing method of chlopyrifos waste water Download PDFInfo
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- CN110372150A CN110372150A CN201910614262.XA CN201910614262A CN110372150A CN 110372150 A CN110372150 A CN 110372150A CN 201910614262 A CN201910614262 A CN 201910614262A CN 110372150 A CN110372150 A CN 110372150A
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- waste water
- chlopyrifos
- processing method
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- chlopyrifos waste
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5254—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using magnesium compounds and phosphoric acid for removing ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/306—Pesticides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of processing methods of chlopyrifos waste water, by to the waste water after acidification recycling trichloro pyridyl sodium alcoholate is aoxidized, magnesium salts precipitates, the processing such as biochemistry, to realize the qualified discharge of waste water, this method is without taking out salt, the phosphorus in waste water can also be become guanite to be recycled, while processing cost has biggish decline.By the Process, treated that chlopyrifos waste water total phosphorus reaches 97% or more, COD concentration and trichloro pyridyl sodium alcoholate concentration sharp fall, and a large amount of larger molecular organics are changed into alcohols after oxidation, improve the biodegradability of waste water.And can be comprehensively utilized by the phosphate that the precipitation method remove, there is significant environmental benefit and economic benefit.
Description
Technical field
The invention belongs to technical field of waste water processing more particularly to a kind of processing methods of chlopyrifos waste water.
Background technique
Chlopyrifos is that Dow Chemical researches and develops a kind of successfully efficient, safety and wide spectrum nitrogen-containing heterocycle class desinsection first
Acaricide pesticide is widely used on the crops such as rice, wheat, soybean, peanut, corn, cotton, fruit tree, tea tree, vegetables, tool
There is good insecticidal effect, high-efficiency low-toxicity is a kind of important pesticide of pest control, and worldwide production and sales volume occupy kill always
Worm agent first, it is flourishing long time.
The problem of development of chlopyrifos is swift and violent, and waste water that is adjoint and generating is extremely difficult to processing.In chlopyrifos production process
The waste water of discharge is the organism P wastewater for belonging to high saliferous, bio-refractory, it is domestic at present it is general be by being concentrated by evaporation, then
The processing that sodium chloride salt slag is burned, not only energy consumption is high, and in sodium chloride salt slag harmful substance in not melting
It is difficult to handle the solid waste for thoroughly becoming newborn.Therefore it needs to seek a kind of new chlopyrifos wastewater treatment approach.
Summary of the invention
The object of the invention is to remedy the disadvantages of known techniques, provides a kind of processing method of chlopyrifos waste water, leads to
The waste water crossed after recycling trichloro pyridyl sodium alcoholate to acidification is aoxidized, magnesium salts precipitates, the processing such as biochemistry, to realize the up to standard of waste water
Discharge.
In order to achieve the above purpose, the present invention the following technical schemes are provided:
A kind of processing method of chlopyrifos waste water, comprising the following steps:
(1) chlopyrifos waste water is adjusted with acid trichloropyridine alcohol of the pH value for acidity, after recycling precipitating；
(2) it adds waste water into high-pressure reactor, while hydrogen peroxide and catalyst is added, close valve and determine reactor
Stirring is started to warm up after being fully sealed and keeps the temperature 5 hours；
(3) keep the temperature after close heating, ventilation when being down to 20 DEG C, with sodium hypochlorite to tail gas carry out oxidation processes with
Absorb tail gas；
(4) magnesium salts and ammonium hydroxide are added into remaining waste water, and adjusts pH value to alkalinity, is separated by solid-liquid separation after reaction.
Preferably, acid used in the step 1 is sulfuric acid.
Preferably, pH value is adjusted to 2.0 in the step 1.
Preferably, catalyst is ferrous sulfate in the step 2.
It is warming up to 150 DEG C in the step 2, keeps pressure in 0.5Mpa hereinafter, temperature is not less than 145 DEG C during heat preservation.
Further, sediment isolated in the step 4 is mainly ammonium magnesium phosphate, can be applied to the system of slow-release fertilizer
It is standby.
Further, supernatant isolated in the step 4 can be 3-4 times of mixed diluting with Low-salinity waste water, and use is resistance to
Salt bacterium carries out biochemical treatment, to reduce the COD and trichloro pyridyl sodium alcoholate concentration in water.
The invention has the advantages that
(1) the method for the present invention is without taking out salt, moreover it is possible to the phosphorus in waste water be become guanite and be recycled, together
When processing cost have biggish decline.
(2) treated by the method for the invention, and chlopyrifos waste water total phosphorus reaches 97% or more, COD concentration and trichloropyridine
Alcohol na concn sharp fall, a large amount of larger molecular organics are changed into alcohols after oxidation, improve the biodegradability of waste water, and lead to
The phosphate for crossing precipitation method removal can comprehensively utilize, and have significant environmental benefit and economic benefit.
Detailed description of the invention
Fig. 1 show oxydrolysis stage COD removal effect in embodiment 1.
Fig. 2 show oxydrolysis stage total phosphorus removal effect in embodiment 1.
Fig. 3 show oxydrolysis stage trichloro pyridyl sodium alcoholate removal effect in embodiment 1.
Fig. 4 show 2 mesophytization stage of embodiment COD removal effect.
Fig. 5 show 2 mesophytization stage of embodiment trichloro pyridyl sodium alcoholate removal effect.
Specific embodiment
Below in conjunction with specific example, technical scheme is described further:
The waste water that embodiment is selected is derived from red sun group chlopyrifos waste water.The waste water mainly contain trichloro pyridyl sodium alcoholate,
The organic phosphorus compound and heterocycle type organic of the difficult for biological degradation such as diethylaluminum monochloride.For the waste water quality that enables that treated
Reach the primary standard in " integrated wastewater discharge standard " (GB 8978-1996), the past uses the processing of the waste water more
Group technology process biochemical after sanitary sewage dilutes is matched in effect evaporation-, and the waste residue after multiple-effect evaporation, which takes into incinerator, to be burned
The method filled again, this method treatment effeciency is high, but operating cost is also high, is especially concentrated by evaporation salt igloss after burning of production
Rate is lower, fill it is costly, need to find it is a kind of efficiently, economy, the simple processing method of operational administrative substitute above-mentioned technique.
Analysis method measures with the following method in embodiment:
(1) it COD: is measured using standard circumfluence method.
(2) TP: molybdenum-antimony anti-spectrophotometric method is used.
(3) it pH value: is measured using pHSJ-4A type acidometer.
(4) it coloration: is measured using extension rate method.
(5) phenolate trichloropyridine: liquid chromatography.
Embodiment 1
It is degraded under conditions of not carrying out desalination the agricultural chemicals waste water using oxydrolysis method, investigates the treatment effect of the method.
A certain amount of sulfuric acid is added in the 700mL waste water measured, pH value is adjusted to 2, while a certain amount of sulphur is added
Sour ferrous and hydrogen peroxide is used as reactant, and addition is started to warm up after check valve, opens stirring, add to autoclave after stirring
Heat keeps pressure in 0.5Mpa hereinafter, temperature is not less than 145 DEG C, closes heating after reaction 5 hours to timing is kept the temperature after 150 DEG C,
Ventilation when being down to 20 DEG C absorbs tail gas with sodium hypochlorite, magnesium salts and ammonium hydroxide is added into remaining waste water, and adjust pH value to
Alkalinity is separated by solid-liquid separation after reaction.It is discharged each index of water sample dephosphorization post analysis.
Wherein waste water quality situation is as shown in table 1:
Table 1 tests waste water quality situation
Since the Phos that is changed into organic phosphorus under normal temperature and pressure is slower, accelerated by high temperature, high pressure organic phosphorus etc. big
The decomposition of molecule, water quality situation is as shown in table 2 after processing, and COD removal rate reacts more stable (Fig. 1) up to 60% or more, and
Long-chain macromolecule organic matter becomes the substance of the easily biochemical degradation such as alcohols of short chain after Degradation and Transformation, therefore waste water is given birth to
The property changed increases substantially；Organic phosphorus to be precipitated by magnesium salts also by the phosphate radical of machine, removal rate is more than 97%, outlet effect
Sufficiently stable (Fig. 2), if improving the factors such as temperature, pressure still has bigger removal potentiality；Trichloro pyridyl sodium alcoholate is also due to oxidation
It is degraded, degradation rate is more than 95%, and effect is also relatively stable (Fig. 3).
The acidification of table 2, oxidation pre-treatment reaction result
Embodiment 2
Biochemical treatment stage wastewater treatment
Since remaining waste water is after being separated by solid-liquid separation, salinity is higher, thus need to by the waste water and Low-salinity waste water mixed processing,
Again since the toxicity of trichloro pyridyl sodium alcoholate can not be handled with conventional activated sludge process, especially a collection of efficient drop has been cultivated in domestication
The special strain for solving trichloro pyridyl sodium alcoholate, for the biochemical treatment after waste water hydrolysis.Since the hydrolysis acidification stage before is big
Amplitude improves the biodegradability of waste water, therefore obviously than direct biochemical treatment, the waste water is good for biochemical effects, and COD removal rate reaches
88% or more (Fig. 4), the COD and total phosphorus of water outlet directly reach adapter tube standard, and water quality situation is as shown in table 3；The special bacteria of domestication
There is extraordinary removal effect to trichloro pyridyl sodium alcoholate, not only aqueous concentration is low, and color will not become after sunshine
Change.When improve waste water in trichloro pyridyl sodium alcoholate concentration after, be discharged still sufficiently stable (Fig. 5), will not because of concentration increase and
Degradation efficiency is reduced, therefore when facing emergency situations as can be also answered when trichloro pyridyl sodium alcoholate concentration increases suddenly in water inlet
To freely.
3 biochemical stage reaction effect of table
| Influent concentration mg/L | Aqueous concentration mg/L | Removal rate | |
| COD | 873.3 | 99.7 | 88.6% |
| Trichloro pyridyl sodium alcoholate | 5-60 | 0.5 | 99% |
As can be seen from the above embodiments, oxydrolysis method of the present invention can effectively handle chlopyrifos organism P wastewater,
COD and total phosphorus can be reduced to adapter tube standard, and trichloro pyridyl sodium alcoholate can remove substantially, be discharged non-discolouring after sunshine.
By estimation, the cost that the method for the present invention handles chlopyrifos condensation waste water is 150-200 yuan/ton, more present mainstream
450 yuan/ton of evaporation can save 50% or more cost, it is economical.
Claims (7)
1. a kind of processing method of chlopyrifos waste water, which comprises the following steps:
(1) chlopyrifos waste water is adjusted with acid trichloropyridine alcohol of the pH value for acidity, after recycling precipitating；
(2) it adds waste water into high-pressure reactor, while hydrogen peroxide and catalyst is added, close valve and determine that reactor is complete
Stirring is started to warm up after sealing and keeps the temperature 5 hours；
(3) heating is closed after keeping the temperature, ventilation when being down to 20 DEG C carries out oxidation processes to tail gas with sodium hypochlorite to absorb
Tail gas；
(4) magnesium salts and ammonium hydroxide are added into remaining waste water, and adjusts pH value to alkalinity, is separated by solid-liquid separation after reaction.
2. the processing method of chlopyrifos waste water according to claim 1, which is characterized in that acid used in the step 1
For sulfuric acid.
3. the processing method of chlopyrifos waste water according to claim 1, which is characterized in that pH value is adjusted in the step 1
It is 2.0.
4. the processing method of chlopyrifos waste water according to claim 1, which is characterized in that catalyst is in the step 2
Ferrous sulfate.
5. the processing method of chlopyrifos waste water according to claim 1, which is characterized in that be warming up to 150 in the step 2
DEG C, keep pressure in 0.5Mpa hereinafter, temperature is not less than 145 DEG C during heat preservation.
6. the processing method of chlopyrifos waste water according to claim 1, which is characterized in that isolated in the step 4
Sediment be mainly ammonium magnesium phosphate, can be applied to the preparation of slow-release fertilizer.
7. the processing method of chlopyrifos waste water according to claim 1, which is characterized in that isolated in the step 4
Supernatant can be 3-4 times of mixed diluting with Low-salinity waste water, biochemical treatment is carried out with Facultative Halophiles, to reduce the COD and three in water
Chloropyridine alcohol na concn.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115321707A (en) * | 2022-08-04 | 2022-11-11 | 内蒙古犇星化学有限公司 | Method for treating alkaline hydrolysis wastewater of mother liquor of sodium trichloropyridinol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103771657A (en) * | 2013-12-20 | 2014-05-07 | 安徽国星生物化学有限公司 | Treatment method for chlorpyrifos wastewater |
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- 2019-07-09 CN CN201910614262.XA patent/CN110372150A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103771657A (en) * | 2013-12-20 | 2014-05-07 | 安徽国星生物化学有限公司 | Treatment method for chlorpyrifos wastewater |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115321707A (en) * | 2022-08-04 | 2022-11-11 | 内蒙古犇星化学有限公司 | Method for treating alkaline hydrolysis wastewater of mother liquor of sodium trichloropyridinol |
| CN115321707B (en) * | 2022-08-04 | 2023-11-21 | 内蒙古犇星化学有限公司 | Mother liquor alkaline hydrolysis wastewater treatment method of sodium trichloropyridine alkoxide |
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Application publication date: 20191025 |