CN105712576A - Rifampicin wastewater biochemical pretreatment method - Google Patents
Rifampicin wastewater biochemical pretreatment method Download PDFInfo
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- CN105712576A CN105712576A CN201610073018.3A CN201610073018A CN105712576A CN 105712576 A CN105712576 A CN 105712576A CN 201610073018 A CN201610073018 A CN 201610073018A CN 105712576 A CN105712576 A CN 105712576A
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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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
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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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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Abstract
The embodiment of the invention discloses a rifampicin wastewater biochemical pretreatment method.CODCr of rifampicin wastewater is 10000-300000 mg/L, and chroma is 2048 times or above.The method includes the following steps that firstly, the pH value of rifampicin wastewater is adjusted to 1-5, microelectrolysis catalytic reduction oxidation filler is added, continuous aeration is conducted, and filtering is conducted after treatment is carried out for 0.5-3 h; the pH value of an obtained filtered solution is adjusted to 2-5, a synergistic oxidant is added for continuous aeration, and treatment is conducted for 0.5-6 h; secondly, the pH value of the liquid obtained through treatment in the first step is adjusted to 9-12, and filtering is conducted; thirdly, the pH value of the filtered solution obtained in the second step is adjusted to 6-8, hydrolysis acidification bacteria are added, treatment is conducted for 12-48 h, outflow water is collected, and the outflow water is pretreatment outflow water.The method solves the problem that biodegradability of high-concentration rifampicin wastewater is difficult to improve.
Description
Technical field
The present invention relates to technical field of waste water processing, particularly to the biochemical pre-treating method of a kind of rifamycin wastewater.
Background technology
Rifamycin wastewater refers to and produces the waste water that rifampicin produces.This waste water mainly contains the organic pollutions such as dimethylformamide, acetic acid, methyl piperazine, butanol.Due to rifamycin wastewater complicated component, organic contamination substrate concentration is high, and containing biological inhibition material, biodegradability (BiochemicalOxygenDemand/ChemicalOxygenDemand, B/C) is poor, difficult treatment.Generally before carrying out biochemical treatment, it is necessary to first carry out pre-treatment, to improve the biodegradability of rifamycin wastewater.
The biochemical pre-treating method of rifamycin wastewater disclosed in present stage mainly has micro-electrolysis method, a hydrolysis acidification method, but at present these methods disclosed can only improve in low concentration (CODCr(adopt potassium dichromate (K2Cr2O7) COD (ChemicalOxygenDemand) that determines as oxidant)≤36000mg/L) the biodegradability of rifamycin wastewater, for improving the biodegradability of high concentration rifamycin wastewater, effect is still not good enough.
Summary of the invention
The embodiment of the invention discloses the biochemical pre-treating method of a kind of rifamycin wastewater, for solving the problem that high concentration rifamycin wastewater biodegradability improves difficulty.Technical scheme is as follows:
A kind of biochemical pre-treating method of rifamycin wastewater, the COD of described rifamycin wastewaterCrBeing 10000～300000mg/L, colourity is more than 2048 times, comprises the following steps:
1), the pH value of rifamycin wastewater is adjusted to 1～5, adds light electrolysis catalysis reduction-oxidation filler, carry out continuous aeration, filter after processing 0.5～3h, collect filtrate；The pH value of the filtrate of acquisition being adjusted to 2～5, adds Cooperative oxidant, carry out continuous aeration, synergistic oxidation processes 0.5～6h；
Or
The pH value of rifamycin wastewater being adjusted to 1～5, adds light electrolysis catalysis reduction-oxidation filler, be simultaneously introduced Cooperative oxidant, carry out continuous aeration, synergistic oxidation processes 0.5～6h；
The mass volume ratio of described light electrolysis catalysis reduction-oxidation filler and described rifamycin wastewater is 0.5:1～3:1g/ml；
Described Cooperative oxidant includes: one or more in hydrogen peroxide, chlorine dioxide, calper calcium peroxide, ozone, sodium hypochlorite, sodium peroxydisulfate；
The addition of described Cooperative oxidant is COD in described rifamycin wastewaterCrThe 5%～50% of quality；
2), by step 1) process the pH value of liquid obtained and be adjusted to 9～12, filter, collect filtrate；
3), by step 2) pH value of filtrate that obtains is adjusted to 6～8, adds hydrolysis acidification antibacterial, collects water outlet after processing 12～48h, and water outlet is pre-treatment water outlet.
In the preferred embodiment of the present invention, step 1) in the pH value of rifamycin wastewater is adjusted to 2～5.
One in the present invention is more highly preferred in embodiment, and described light electrolysis catalysis reduction-oxidation filler is Fe-C micro electrolysis filler.
One in the present invention is more highly preferred in embodiment, and the air water volume ratio of the gas of described continuous aeration and described rifamycin wastewater is 3:1～10:1.
One in the present invention is more highly preferred in embodiment, step 1) in synergistic oxidation process the time be 1～3h.
One in the present invention is more highly preferred in embodiment, and the addition of described Cooperative oxidant is COD in described rifamycin wastewaterCrThe 10%～25% of quality.
One in the present invention is more highly preferred in embodiment, step 2) in by step 1) process the pH value of liquid obtained and be adjusted to 10.
One in the present invention is more highly preferred in embodiment, step 3) in by step 2) pH value of filtrate that obtains is adjusted to 6.5～7.5.
The biochemical pre-treating method of a kind of rifamycin wastewater provided by the invention, first passes through light electrolysis catalysis reduction-oxidation and the bio-toxicity of two kinds of chemical methodes reduction waste water of oxidant synergistic oxidation, destroys difficult degradation macromole simultaneously, improve the biodegradability of waste water；Improve the biodegradability of waste water further again through the biological method of hydrolysis acidification, pre-treatment water outlet can be directly entered biochemical treatment system, solves the problem that high concentration rifamycin wastewater biodegradability improves difficulty.
Detailed description of the invention
The invention provides the biochemical pre-treating method of a kind of rifamycin wastewater, the COD of described rifamycin wastewaterCrBeing 10000～300000mg/L, colourity is more than 2048 times, comprises the following steps:
1), the pH value of rifamycin wastewater is adjusted to 1～5, adds light electrolysis catalysis reduction-oxidation filler, carry out continuous aeration, filter after processing 0.5～3h, collect filtrate；The pH value of the filtrate of acquisition being adjusted to 2～5, adds Cooperative oxidant, carry out continuous aeration, synergistic oxidation processes 0.5～6h；
Or
The pH value of rifamycin wastewater being adjusted to 1～5, adds light electrolysis catalysis reduction-oxidation filler, be simultaneously introduced Cooperative oxidant, carry out continuous aeration, synergistic oxidation processes 0.5～6h；
The mass volume ratio of described light electrolysis catalysis reduction-oxidation filler and described rifamycin wastewater is 0.5:1～3:1g/ml；
Described Cooperative oxidant includes: one or more in hydrogen peroxide, chlorine dioxide, calper calcium peroxide, ozone, sodium hypochlorite, sodium peroxydisulfate；
The addition of described Cooperative oxidant is COD in described rifamycin wastewaterCrThe 5%～50% of quality；
2), by step 1) process the pH value of liquid obtained and be adjusted to 9～12, filter, collect filtrate；
3), by step 2) pH value of filtrate that obtains is adjusted to 6～8, adds hydrolysis acidification antibacterial, collects water outlet after processing 12～48h, and water outlet is pre-treatment water outlet.
The step 1 of the present invention program) in the pH value of rifamycin wastewater is adjusted to 1～5, it is preferred that the pH value of rifamycin wastewater is adjusted to 2～5；It is subsequently adding light electrolysis catalysis reduction-oxidation filler, carries out continuous aeration process.Described light electrolysis catalysis reduction-oxidation filler is to be merged catalyst by the metal alloy with high potential difference and adopted high temperature micropore activating technology to produce, concrete, can be Fe-C micro electrolysis filler, namely by means such as high temperature sinterings, ferrum and metallic catalyst and charcoal are included in the framework formula ferrum carbon structure collectively formed.The gas of described continuous aeration is air or oxygen, it is preferred to air.
In the present invention program, step 1) in light electrolysis catalysis reduction-oxidation process and synergistic oxidation process can be separately performed, it is also possible to be synchronously performed.When light electrolysis catalysis reduction-oxidation process and synergistic oxidation process separately performed, filter after light electrolysis catalysis reduction-oxidation processes, and regulate the pH value of filtrate, then add Cooperative oxidant.Light electrolysis catalysis reduction-oxidation process and synergistic oxidation process when being synchronously performed, and what add light electrolysis catalysis reduction-oxidation filler is simultaneously introduced Cooperative oxidant, reacts, so can shorten the process time, improve treatment effeciency.Preferably, step 1) in synergistic oxidation process the time be 1～3h.
In the present invention program, the addition of described Cooperative oxidant is COD in described rifamycin wastewaterCrThe 5%～50% of quality；Wherein, COD in rifamycin wastewaterCrQuality is equal to the volume of rifamycin wastewater and COD in rifamycin wastewaterCrThe product of value；Such as: the volume of rifamycin wastewater is 2L, COD in rifamycin wastewaterCrFor 40000mg/L, then COD in rifamycin wastewaterCrQuality is 80000mg.Preferably, the addition of described Cooperative oxidant is COD in described rifamycin wastewaterCrThe 10%～25% of quality.
In the present invention program, the volume of the gas of continuous aeration can be determined according to the air water volume ratio of the gas of the volume of rifamycin wastewater and continuous aeration Yu rifamycin wastewater.In concrete operating process, control the volume of gas generally by the flow of gas and process time that control continuous aeration.In experimentation, inventor have found that, the air water volume ratio of the gas of described continuous aeration and described rifamycin wastewater is within the scope of 3:1～10:1, and the treatment effect that light electrolysis catalysis reduction-oxidation process and synergistic oxidation process is preferably.
The step 2 of the present invention program) in by step 1) processing the pH value of liquid obtained, to be adjusted to 9～12 be to terminate step 1) and oxidation processes, decompose the Cooperative oxidant having neither part nor lot in reaction, in order to carry out subsequent treatment.Inventor have found that, if the pH value regulated is less than 9, oxidation processes only has portion ends, if the pH value regulated is more than 12, regulates the amount of reagent used by pH value too much, but it is similar to the pH value situation less than 12 to terminate degree, so pH is 9～12 is appropriate scope.Preferably, by step 1) process the pH value of liquid obtained and be adjusted to 10.
In the present invention, adding before hydrolysis acidification antibacterial and need step 2) pH value of filtrate that obtains is adjusted to 6～8, is beneficial to hydrolysis acidification bacteria for hydrolysis acidifying；Preferably, by step 2) pH value of filtrate that obtains is adjusted to 6.5～7.5.Described hydrolysis acidification antibacterial is hydrolytic bacteria and the mixed vaccine of acidifying fermentation antibacterial, those skilled in the art can pass through commercially to obtain, then according to hydrolysis acidification antibacterial is activated by description before use subsidiary when buying, the step 2 of modulated good pH value it is then added to after activation) in the filtrate that obtains, be hydrolyzed acidification to filtrate；Can also cultivate from mud etc. and obtain hydrolysis acidification antibacterial, then mud is joined the step 2 of modulated good pH value) in the filtrate that obtains, be hydrolyzed acidification to filtrate, specifically how to obtain the hydrolysis acidification antibacterial present invention and does not specifically limit at this.Have been reported that owing to hydrolysis acidification technology more, the related process of hydrolysis acidification technology is known to the skilled person, therefore, those skilled in the art can carry out the addition of controlled hydrolysis acidification bacteria according to the concrete condition of the rifamycin wastewater of required process, and the present invention does not specifically limit at this.
Generally including sucking filtration, husky filter, filter press etc. it should be noted that filter, the present invention is not especially limited at this.
Below in conjunction with specific embodiment, technical scheme being described, described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
The hydrolysis acidification antibacterial used in embodiment commercially obtains, and activates in accordance with the following methods:
Preparation nutritional solution: weigh 4g glucose, 1g peptone in conical flask, add 100ml water, seals conical flask with gauze, is placed in high temperature sterilize pot by the conical flask after sealing, steams 30min at 135 DEG C, takes out and stand cooling after completing.
Activation: take 45.4g hydrolysis acidification antibacterial, join in 1L water, adds 50ml nutritional solution, places 24h, the hydrolysis acidification antibacterial after being activated.
Reagent used in embodiment is all commercially.
Embodiment 1
The Raw performance of rifamycin wastewater: CODCrFor 80360mg/L, colourity 4096 times, B/C is 0.08.
Taking 1L rifamycin wastewater, regulate pH value to 2, add 500g Fe-C micro electrolysis filler, pass into air and carry out continuous aeration, aeration rate is 1.5L/h, processes 2h；Process is filtered after terminating, and regulates the pH value of filtrate to 3, adds 5gH2O2, passing into air and carry out continuous aeration, aeration rate is 1.5L/h, regulates pH to 10 by NaOH solution after reaction 4h, terminates reaction and produces precipitation simultaneously, regulates the pH to 6 of filtrate after filtration, adds the 50ml hydrolysis acidification antibacterial activated, and collects water outlet after processing 24h.
Effluent index: CODCrFor 62198mg/L, colourity 256 times, B/C is 0.37, and water outlet can be directly entered biochemical system and process.
Embodiment 2
The Raw performance of rifamycin wastewater: CODCrFor 111360mg/L, colourity 8192 times, B/C is 0.08.
Taking 500ml rifamycin wastewater, regulate pH value to 3, add 500g Fe-C micro electrolysis filler, pass into oxygen and carry out continuous aeration, aeration rate is 1.2L/h, processes 1.5h；Process is filtered after terminating, and regulate the pH value of filtrate to 4, add 4g sodium hypochlorite, passing into oxygen and carry out continuous aeration, aeration rate is 1.2L/h, regulates pH to 9 by NaOH solution after reaction 3h, terminate reaction and produce precipitation simultaneously, regulate the pH to 7 of filtrate after filtration, add the 2.5ml hydrolysis acidification antibacterial activated, after processing 36h, collect water outlet.
Effluent index: CODCrFor 58497mg/L, colourity 256 times, B/C is 0.41, and water outlet can be directly entered biochemical system and process.
Embodiment 3
The Raw performance of rifamycin wastewater: CODCrFor 181012mg/L, colourity 8192 times, B/C is 0.08.
Taking 500ml rifamycin wastewater, regulate pH value to 4, add 500g Fe-C micro electrolysis filler, pass into air and carry out continuous aeration, aeration rate is 2.5L/h, processes 1h；Process is filtered after terminating, and regulate the pH value of filtrate to 4, add 4.8g sodium peroxydisulfate, passing into air and carry out continuous aeration, aeration rate is 2.5L/h, regulates pH to 12 by NaOH solution after reaction 2h, terminate reaction and produce precipitation simultaneously, regulate the pH to 6.5 of filtrate after filtration, add the 2.5ml hydrolysis acidification antibacterial activated, after processing 48h, collect water outlet.
Effluent index: CODCrFor 54342mg/L, colourity 512 times, B/C is 0.42, and water outlet can be directly entered biochemical system and process.
Embodiment 4
The Raw performance of rifamycin wastewater: CODCrFor 212250mg/L, colourity 8192 times, B/C is 0.08.
Take 500ml rifamycin wastewater, regulate pH value to 3, add 500g Fe-C micro electrolysis filler, be simultaneously introduced 7gCaO2, passing into air and carry out continuous aeration, aeration rate is 1.5L/h, regulates pH to 10 by NaOH solution after reaction 2h, terminates reaction and produces precipitation simultaneously, regulates the pH to 6.5 of filtrate after filtration, adds the 2.5ml hydrolysis acidification antibacterial activated, and collects water outlet after processing 24h.
Effluent index: CODCrFor 55716mg/L, colourity 512 times, B/C is 0.42, and water outlet can be directly entered biochemical system and process.
Comparative example
The Raw performance of rifamycin wastewater: CODCrFor 212250mg/L, colourity 8192 times, B/C is 0.08.
Taking 500ml rifamycin wastewater, regulate pH value to 3, add 500g Fe-C micro electrolysis filler, pass into air and carry out continuous aeration, aeration rate is 1.5L/h, collects water outlet after processing 2h.
Effluent index: CODCrFor 207540mg/L, colourity 512 times, B/C is 0.2, and containing part biological toxicant in liquid-phase chromatographic analysis waste water, water outlet not directly enters biochemical system and processes.
From the above with comparative example it can be seen that for improve high concentration rifamycin wastewater biodegradability, independent micro-electrolysis method does not reach the treatment effect of embodiment 1 to 4.It should be noted that, owing to bio-toxicity is stronger in high concentration rifamycin wastewater, if being directly added into hydrolysis acidification antibacterial, hydrolysis acidification antibacterial can be killed by bio-toxicity material, so can not directly adopt hydrolysis acidification method to process for high concentration rifamycin wastewater.And the biochemical pre-treating method of a kind of rifamycin wastewater provided by the invention, first pass through light electrolysis catalysis reduction-oxidation and two kinds of chemical methodes of oxidant synergistic oxidation reduce the bio-toxicity of waste water, destroy difficult degradation macromole simultaneously, improve the biodegradability of waste water；Improve the biodegradability of waste water further again through the biological method of hydrolysis acidification, pre-treatment water outlet can be directly entered biochemical treatment system, solves the problem that high concentration rifamycin wastewater biodegradability improves difficulty.
Above the biochemical pre-treating method of a kind of rifamycin wastewater provided by the present invention is described in detail.Principles of the invention and embodiment are set forth by specific embodiment used herein, and the explanation of above example is only intended to help to understand method and the central idea thereof of the present invention.It should be pointed out that, for the person of ordinary skill of the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify the protection also falling into the claims in the present invention.
Claims (8)
1. a biochemical pre-treating method for rifamycin wastewater, the COD of described rifamycin wastewaterCrBeing 10000～300000mg/L, colourity is more than 2048 times, it is characterised in that comprise the following steps:
1), the pH value of rifamycin wastewater is adjusted to 1～5, adds light electrolysis catalysis reduction-oxidation filler, carry out continuous aeration, filter after processing 0.5～3h, collect filtrate；The pH value of the filtrate of acquisition being adjusted to 2～5, adds Cooperative oxidant, carry out continuous aeration, synergistic oxidation processes 0.5～6h；
Or
The pH value of rifamycin wastewater being adjusted to 1～5, adds light electrolysis catalysis reduction-oxidation filler, be simultaneously introduced Cooperative oxidant, carry out continuous aeration, synergistic oxidation processes 0.5～6h；
The mass volume ratio of described light electrolysis catalysis reduction-oxidation filler and described rifamycin wastewater is 0.5:1～3:1g/ml；
Described Cooperative oxidant includes: one or more in hydrogen peroxide, chlorine dioxide, calper calcium peroxide, ozone, sodium hypochlorite, sodium peroxydisulfate；
The addition of described Cooperative oxidant is COD in described rifamycin wastewaterCrThe 5%～50% of quality；
2), by step 1) process the pH value of liquid obtained and be adjusted to 9～12, filter, collect filtrate；
3), by step 2) pH value of filtrate that obtains is adjusted to 6～8, adds hydrolysis acidification antibacterial, collects water outlet after processing 12～48h, and water outlet is pre-treatment water outlet.
2. pre-treating method as claimed in claim 1, it is characterised in that step 1) in the pH value of rifamycin wastewater is adjusted to 2～5.
3. pre-treating method as claimed in claim 1, it is characterised in that described light electrolysis catalysis reduction-oxidation filler is Fe-C micro electrolysis filler.
4. pre-treating method as claimed in claim 1, it is characterised in that the air water volume ratio of the gas of described continuous aeration and described rifamycin wastewater is 3:1～10:1.
5. pre-treating method as claimed in claim 1, it is characterised in that step 1) in synergistic oxidation to process the time be 1～3h.
6. pre-treating method as claimed in claim 1, it is characterised in that the addition of described Cooperative oxidant is COD in described rifamycin wastewaterCrThe 10%～25% of quality.
7. pre-treating method as claimed in claim 1, it is characterised in that step 2) in by step 1) pH value that processes the liquid obtained is adjusted to 10.
8. the pre-treating method as according to any one of claim 1 to 7, it is characterised in that step 3) in by step 2) pH value of filtrate that obtains is adjusted to 6.5～7.5.
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| 朱浩: "杀虫双农药生产废水处理技术开发与工程实践", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑（月刊）》 * |
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