CN106477786B - A kind of composite intensified light electrolysis simulation process method - Google Patents
A kind of composite intensified light electrolysis simulation process method Download PDFInfo
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- 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
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- 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
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- 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
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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- C02F1/722—Oxidation by peroxides
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- 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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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
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- 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
- C02F2103/343—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 pharmaceutical industry, e.g. containing antibiotics
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- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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Abstract
The present invention relates to a kind of composite intensified light electrolysis simulation process methods, first successively acid adding, hydrogen peroxide and copper ion into pharmacy waste water and simulated wastewater containing phenyl ring respectively, and are uniformly mixed；Then it is passed through direct current into waste water, and iron carbon ball is added, sufficiently adds adjusting PH with base after reaction, and PAM and PAC is added and accelerates wastewater sedimentation, obtains supernatant after the completion of precipitating.The present invention has the advantages that composite intensified light electrolysis simulation process method is added to hydrogen peroxide simultaneously on the basis of existing technology and is powered into waste water；While not only cleverly increasing iron-carbon micro-electrolysis treatment effeciency, to the effect of hydrogen peroxide during using the power on, more hydroxyl radical free radicals are generated；In addition, being correspondingly formed electric Fenton mechanism since ferroelectricity light electrolysis can generate a large amount of ferrous ion；Under the action of a variety of recombination mechanisms, a possibility that phenyl ring open loop scission of link, is greatly increased, to improve the removal rate to benzene homologues.
Description
Technical field
The present invention relates to a kind of micro-electrolysis treatment method, in particular to a kind of composite intensified light electrolysis simulation process side
Method.
Background technique
For pharmacy corporation during producing the drugs such as fluorine urine pyridine, workshop must be using toluene as the solvent of cyclization reaction
Higher yield could be obtained, and then can be generated containing the benzene homologues waste water based on toluene.In order to ensure subsequent biochemical processing
Stable operation needs enhancing degradation benzene homologues, to mitigate subsequent biochemical burden, it is ensured that biochemical system runs well.
Benzene homologues refer to the monocyclic aromatic volatile containing one kind including benzene, toluene, ethylbenzene, dimethylbenzene etc.
Close object.Because having " three cause benefit ", benzene homologues are determined as strong carcinogen by the World Health Organization, have been put into excellent in China's water
Pollutant blacklist is first controlled, the waste water of species containing benzene series could discharge after needing strict control up to standard.As industrial solvent and production
Raw material, benzene homologues are widely used in chemical industry such as pharmaceutical industry, produce great environmental toxicity in use.This
Outside, benzene homologues may generate certain influence to waste water treatment system, and the benzene homologues of water middle and high concentration can be in biochemical system
Microorganism generates certain bio-toxicity, it is abnormal to frequently result in low, sludge decomposition of wastewater degradation rate etc., and then influence wastewater treatment
The stability of system operation.Therefore, when handling waste water containing benzene homologues, pretreatment stage should be realized as far as possible to waste water containing benzene homologues
Dual treatment remerges other waste water integrated treatments.
At present in industry " iron-carbon micro-electrolysis-Fenton processing-biochemical process " be pharmacy waste water exemplary process technique, generally
Its treatment effeciency, COD(COD are judged by COD removal rate and benzene homologues removal rate) it is under certain condition, to use
Certain strong oxidizer handles consumed oxidant content when water sample, and the calculation formula of COD removal rate are as follows:
But traditional processing method is low to benzene homologues reaction efficiency；It only reacts in acid condition, under alkaline condition
Reaction rate is then greatly reduced, and causes the use scope of its pH smaller, there are significant limitations；In addition to this Patent No.
201360482321.5 patent of invention in just refer to a kind of reverse osmosis thick water treatment method, comprising the following steps: adjust anti-
Permeate the pH to 2.0~4.0 of concentrated water, catalytic and oxidative electrolysis technology；Catalytic and oxidative electrolysis technology water outlet iron made of filling iron and carbon sintering
Redox reaction occurs in the electrolysis reactor of carbon filler；Then plus hydrogen peroxide, further it is oxidized decomposition；Adjust pH to
6.0~8.0, add flocculant flocculation sedimentation；Supernatant after flocculation sedimentation enters aeration and biological pond, and co-substrate, biology drop is added
Solution.By the poor COD of the biodegradability obtained after biochemical treatment is up to standard through reverse osmosis Treatment for Reuse in 70~200mg/L
Reverse osmosis concentrated water process is to 50mg/L hereinafter, to meet most stringent of local discharge standard.Such processing method passes through dioxygen
The strong oxidation of water carries out oxygenolysis, although accelerating W-response rate to a certain extent, hydrogen peroxide itself oxygen
It is still relatively slow to change the rate decomposed, and is affected by pH, working efficiency still has the space further promoted；Therefore the present invention
Have developed that a kind of pH is applied widely, reaction rate is fast and high-efficient composite intensified light electrolysis simulation process method, through examining
Rope is not found and the same or similar technical solution of the present invention.
Summary of the invention
That the technical problem to be solved in the present invention is to provide a kind of pH is applied widely, reaction rate is fast and high-efficient compound
Type pharmaceutics wastewater simulation process method.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of composite intensified light electrolysis simulation process side
Method, innovative point are: the processing method is specific as follows:
(1) waste water needed for choosing treatment process, mainly includes pharmacy waste water and simulated wastewater containing phenyl ring；The simulation is useless
Water is obtained by adding benzene homologues into pharmacy waste water, and the benzene homologues include benzene, toluene, ethylbenzene, dimethylbenzene and styrene, are added
Dosage is 45~55mg/L；
(2) it is 2~5 that successively into pharmacy waste water and simulated wastewater containing phenyl ring, acid adding, which adjusts its pH, is then successively added again
Enter hydrogen peroxide and copper ion, and is stirred evenly respectively using stirring rod；
(3) anode titanium plate and cathode titanium plates are inserted into respectively in pharmacy waste water and simulated wastewater, and in anode titanium plate and yin
D.C. regulated power supply is set between the titanium plate of pole；Then continue into pharmacy waste water and simulated wastewater be added be sintered made of iron carbon
Ball makes the volume of iron carbon ball and the ratio 1:1 of water volume, and sufficiently reacts in the case where D.C. regulated power supply work with waste water
120~180min；
(4) adding alkali to adjust pH value into pharmacy waste water and simulated wastewater respectively after the reaction was completed is 7~8, and is sequentially added
PAC and PAM, standing after stirring makes wastewater sedimentation, and obtains supernatant.
Further, the concentration of hydrogen peroxide is 1%~3% in the step (2), and the concentration of copper ion is 50~100mg/L.
Further, the voltage that D.C. regulated power supply is passed through in the step (3) be 10V~12V, electric current be 0.01A~
0.1A。
The present invention has the advantages that
(1) composite intensified light electrolysis simulation process method is added to hydrogen peroxide into waste water on the basis of existing technology
Simultaneously and it is powered；While not only cleverly increasing iron-carbon micro-electrolysis treatment effeciency, to hydrogen peroxide during using the power on
Effect, generates more hydroxyl radical free radicals；In addition, being correspondingly formed electricity since ferroelectricity light electrolysis can generate a large amount of ferrous ion
Fenton mechanism；Under the action of a variety of recombination mechanisms, a possibility that phenyl ring open loop scission of link, is greatly increased, to improve to benzene series
The removal rate of object.
(2) iron-carbon micro-electrolysis not only working efficiency in acid condition in composite intensified light electrolysis simulation process method
Height, and the pH value of waste water can constantly rise during the energization, neutral or even alkalinity state be presented, hydrogen peroxide starts at this time
Effect, and the copper ion added plays catalytic action to the strong oxidizing property of hydrogen peroxide in the state of neutral meta-alkalescence, greatly speeds up
Reaction rate, work efficiency is high, while whole process can act under conditions of acid and alkalinity, the scope of application of pH
Extensively.
(3) pharmacy waste water is chosen when sampling and simulated wastewater, simulated wastewater are mainly the mixing of pharmacy waste water and benzene homologues
Object obtains simulated wastewater by addition benzene homologues since actual pharmacy waste water water quality is not sufficiently stable, to obtain more accurate
Processing data, while determining that such processing method is more effective to the removal rate of benzene homologues, therefore reality could be applied to
The pharmacy waste water containing benzene homologues in.
(4) PAC and PAM is added before pharmacy waste water and simulated wastewater precipitating, wherein PAC is aluminium polychloride, is industry
In a kind of flocculation aid for generally using；PAM is polyacrylamide, can build bridge and adsorb with the suspended particles being scattered in solution, have
Extremely strong flocculation；The two is comprehensive using the settling rate that can be improved simulated wastewater, improves working efficiency.
Specific embodiment
Embodiment 1
The invention discloses a kind of composite intensified light electrolysis simulation process method, the processing method is specific as follows:
(1) certain pharmaceutical factory's comprehensive discharge waste water is chosen, water quality situation: without benzene, COD:17000~20000mg/L, B/C
It is 0.05~0.15, irritant smell, wherein B/C is the ratio of BOD and COD；
(2) into comprehensive discharge waste water acid adding adjust its pH be 2~5, then sequentially add 1%~3% hydrogen peroxide and
The copper ion of 50~100mg/L, and stirred evenly respectively using stirring rod；
(3) anode titanium plate and cathode titanium plates are inserted into comprehensive discharge waste water, and between anode titanium plate and cathode titanium plates
D.C. regulated power supply is set, and the voltage which is passed through is 10V~12V, and electric current is 0.01A~0.1A；Then after
Continue be added into comprehensive discharge waste water be sintered made of iron carbon ball, make the volume of iron carbon ball and the ratio 1:1 of water volume, and
120~180min is sufficiently reacted with simulated wastewater in the case where D.C. regulated power supply work；
(4) adding alkali to adjust pH value into comprehensive discharge waste water after the reaction was completed is 7~8, and sequentially adds PAC and PAM, is stirred
Standing after mixing precipitates simulated wastewater, and obtains supernatant.
Following table is the concentration of copper ion and the relation table of COD removal rate:
Following table is the relation table of the voltage that D.C. regulated power supply is passed through and COD removal rate:
Following table is the relation table in reaction time and COD removal rate:
The present embodiment is process object with the comprehensive discharge waste water without benzene, determines copper ion needed for testing and voltage,
For the concentration of middle copper ion in 0~50mg/L, the removal rate of COD is lower, and when between 100~200mg/L, the removal rate of COD increases
Than more gentle, and in 50~100mg/L, COD removal rate rate of rise is very fast, and connects with addition high concentration copper ion removal rate
Closely.In order to avoid the copper ion of addition excessive concentrations causes secondary pollution, therefore selecting the concentration of copper ion is 50~100mg/
L；For voltage in 8~10V, the removal rate the comparison of the growth of COD is gentle, and in 12~15V, the removal rate of COD declines voltage, and electric
When being pressed in 10~12V, COD removal rate increases comparatively fast, therefore selecting voltage is 10~12V.
Embodiment 2
The invention discloses a kind of composite intensified light electrolysis simulation process method, the processing method is specific as follows:
(1) pharmacy waste water containing phenyl ring is chosen, and addition benzene homologues obtain simulated wastewater thereto, the benzene homologues include
Benzene, toluene, ethylbenzene, dimethylbenzene and styrene, additive amount are 45~55mg/L；
(2) into simulated wastewater acid adding adjust its pH be 2~5, then sequentially add 1%~3% hydrogen peroxide and 50~
The copper ion of 100mg/L, and stirred evenly respectively using stirring rod；
(3) it is inserted into anode titanium plate and cathode titanium plates in simulated wastewater, and is arranged between anode titanium plate and cathode titanium plates
D.C. regulated power supply, the voltage which is passed through are 10V~12V, and electric current is 0.01A~0.1A；Then continue to
Iron carbon ball made of being sintered is added in simulated wastewater, makes the volume of iron carbon ball and the ratio 1:1 of water volume, and in DC voltage-stabilizing
120~180min is sufficiently reacted with simulated wastewater in the case where power work；
(4) adding alkali to adjust pH value into simulated wastewater after the reaction was completed is 7~8, and sequentially adds PAC and PAM, after stirring
Standing precipitates simulated wastewater, and obtains supernatant.
Following table is the relation table in reaction time and COD removal rate:
Following table is the relation table in reaction time and benzene homologues removal rate:
The present embodiment by into pharmacy waste water add benzene homologues obtain simulated wastewater, copper ion concentration be 50~
100mg/L, voltage be 10~15V in the case where, when reacted between more than 110min when, the removal rate of benzene homologues reach 99% with
On, for the removal rate for guaranteeing working efficiency and COD and benzene homologues, will control in the reaction time as 120~180min；This implementation simultaneously
Example has determined that such processing method keeps the removal effect of benzene homologues fine, can be used for handling the pharmacy waste water containing phenyl ring.
Embodiment 3
The invention discloses a kind of composite intensified light electrolysis simulation process method, the processing method is specific as follows:
(1) the practical pharmacy waste water containing benzene homologues, mainly with toluene for main characteristic contamination, concentration range 50 are chosen
In addition~150mg/L also contains a small amount of benzene and ethylbenzene；
(2) into pharmacy waste water acid adding adjust its pH be 2~5, then sequentially add 1%~3% hydrogen peroxide and 50~
The copper ion of 100mg/L, and stirred evenly respectively using stirring rod；
(3) it is inserted into anode titanium plate and cathode titanium plates in simulated wastewater, and is arranged between anode titanium plate and cathode titanium plates
D.C. regulated power supply, the voltage which is passed through are 10V~12V, and electric current is 0.01A~0.1A；Then continue to
Iron carbon ball made of being sintered is added in pharmacy waste water, makes the volume of iron carbon ball and the ratio 1:1 of water volume, and in DC voltage-stabilizing
120~180min is sufficiently reacted with simulated wastewater in the case where power work；
(4) adding alkali to adjust pH value into pharmacy waste water after the reaction was completed is 7~8, and sequentially adds PAC and PAM, after stirring
Standing precipitates simulated wastewater, and obtains supernatant.
Following table is the relation table in reaction time and COD removal rate:
Following table is the relation table in reaction time and benzene homologues removal rate:
By learning that simulation process method of the invention is suitable for handling the waste water containing phenyl ring, therefore this implementation in embodiment 2
Example is by it with into pharmacy waste water of the reality containing phenyl ring, and when reaching certain reaction time, the removal rate of toluene can reach
99.9%, treatment effect is very good.
Basic principles and main features of the invention have been shown and described above.It should be understood by those skilled in the art that
The present invention is not limited to the above embodiments, and the above embodiments and description only illustrate the principle of the present invention, In
Without departing from the spirit and scope, various changes and improvements may be made to the invention, these changes and improvements are all fallen
Enter in scope of the claimed invention.The scope of the present invention is defined by the appended claims and its equivalents.
Claims (3)
1. a kind of composite intensified light electrolysis simulation process method, it is characterised in that: the processing method is specific as follows:
(1) waste water needed for choosing treatment process, mainly includes pharmacy waste water and simulated wastewater containing phenyl ring；The simulated wastewater is logical
It crosses the addition benzene homologues into pharmacy waste water to obtain, the benzene homologues include benzene, toluene, ethylbenzene, dimethylbenzene and styrene, additive amount
It is 45~55mg/L；
(2) it is 2~5 that successively into pharmacy waste water and simulated wastewater containing phenyl ring, acid adding, which adjusts its pH, is then sequentially added double
Oxygen water and copper ion, and stirred evenly respectively using stirring rod；
(3) anode titanium plate and cathode titanium plates are inserted into respectively in pharmacy waste water and simulated wastewater, and in anode titanium plate and cathode titanium
D.C. regulated power supply is set between plate；Then continue into pharmacy waste water and simulated wastewater be added be sintered made of iron carbon ball,
Make the volume of iron carbon ball and the ratio 1:1 of water volume, and sufficiently reacts 120 with waste water in the case where D.C. regulated power supply work
~180min；
(4) after the reaction was completed respectively into pharmacy waste water and simulated wastewater plus alkali adjust pH value be 7~8, and sequentially add PAC and
PAM, standing after stirring makes wastewater sedimentation, and obtains supernatant.
2. a kind of composite intensified light electrolysis simulation process method according to claim 1, it is characterised in that: the step
(2) concentration of hydrogen peroxide is 1%~3% in, and the concentration of copper ion is 50~100mg/L.
3. a kind of composite intensified light electrolysis simulation process method according to claim 1, it is characterised in that: the step
(3) voltage that D.C. regulated power supply is passed through in is 10V~12V, and electric current is 0.01A~0.1A.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145275A (en) * | 2013-03-15 | 2013-06-12 | 中北大学 | Method and device for treating wastewater by intensified micro-electrolysis-Fenton oxidation method |
| CN104355446A (en) * | 2014-11-06 | 2015-02-18 | 台州学院 | Chemical pharmaceutical wastewater pretreatment enhancement device and enhancement treatment method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145275A (en) * | 2013-03-15 | 2013-06-12 | 中北大学 | Method and device for treating wastewater by intensified micro-electrolysis-Fenton oxidation method |
| CN103145275B (en) * | 2013-03-15 | 2015-02-04 | 中北大学 | Method and device for treating wastewater by intensified micro-electrolysis-Fenton oxidation method |
| CN104355446A (en) * | 2014-11-06 | 2015-02-18 | 台州学院 | Chemical pharmaceutical wastewater pretreatment enhancement device and enhancement treatment method thereof |
Non-Patent Citations (3)
| Title |
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| 强化铁碳微电解处理含苯系物制药废水;陈前，等;《江苏农业科学》;20160325;第4卷(第3期);第340页左栏第2段至右栏第2段及结果分析部分 * |
| 强化铁碳微电解预处理制药废水的实验研究;陈前，等;《资源节约与环保》;20160125(第1期);第56页左栏第3段至第57页右栏最后1段 * |
| 微电解-Fenton耦合处理废水的反应机理与研究进展;畅飞，等;《西安文理学院学报：自然科学版》;20140131;第17卷(第1期);第18页第1段至第19页第3段 * |
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