CN110422922A - A method of iron/persulfate is strengthened based on cysteine and removes organic contamination - Google Patents
A method of iron/persulfate is strengthened based on cysteine and removes organic contamination Download PDFInfo
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- CN110422922A CN110422922A CN201910533458.6A CN201910533458A CN110422922A CN 110422922 A CN110422922 A CN 110422922A CN 201910533458 A CN201910533458 A CN 201910533458A CN 110422922 A CN110422922 A CN 110422922A
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- cysteine
- persulfate
- iron
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- chlorobenzene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
-
- 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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Soil Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention provides a kind of method for removing organic contamination based on cysteine reinforcing iron/persulfate, and steps are as follows: persulfate solution being added in system to be repaired, is uniformly mixed；The mixed solution of iron ion and cysteine is added in system to be repaired, is uniformly mixed, organic pollutant of the persulfate under iron ion and the effect of cysteine system in oxidative degradation system to be repaired.Method provided by the invention is simple and easy, low in cost, has a good application prospect to the reparation of earth's surface and body of groundwater and organic contaminants in soil.
Description
Technical field
The present invention relates to environmental pollutions to repair field, more particularly to a kind of cysteine reinforcing iron/persulfate that is based on is gone
Except the method for organic contamination.
Background technique
In recent decades, China's economy has unprecedented development, and incident is a large amount of poisonous and harmful organic
Pollutant emission is into environment, and wherein soil and water pollution problem seriously constrain the sustainable development of Chinese society economy
Exhibition.Therefore, the organic pollutant in contaminated soil and water body repair and be of great significance.In water body and the organic dirt of soil
Main technology has biological degradation method, chemical reduction method and advanced oxidation processes in dye reparation.Its Trends of Advanced Oxidation Process Methods can be with
Generating has high oxidative energy free radical, by organic pollutant oxygenolysis for biodegradable small organic molecule or directly
Mineralising is water and carbon dioxide, has the characteristics that reparation speed is fast, repairing effect is good, range on probation is wide, has wide application
Prospect.
Persulfate oxidation technology refers to by generating strong oxidizer potentiometric titrations (SO4 -) to carry out oxidation processes organic
A kind of oxidation technology of polluter.Persulfate has higher solubility and stability, obtained rapidly in recent years pay attention to and
Using.Most widely used at present is to utilize Fe2+Persulfate is activated, but Fe2+It can be rapidly by oxygen in activation process
Turn to Fe3+, activation is lost, causes activation efficiency not high.The main method for solving the problems, such as this at present is the networks such as addition EDTA
Mixture and Fe2+Complex compound is formed, Fe is reached2+The purpose of sustained release, slows down Fe2+To Fe3+Conversion, but EDTA have certain toxicity,
It is unfavorable for the utilization again of the water body after repairing and soil.In addition, Fe under alkaline condition2+It will form precipitating, influence activation effect
Rate, this makes Fe2+The pH range that/persulfate is applied in water body and soil remediation is relatively narrow, only in acid condition just to having
Machine object has higher removal efficiency.Therefore, researching and developing one kind may be implemented Fe3+To Fe2+Circulation, thus enhance oxidation efficiency, and
The wider persulfate activating technology of applicable pH range is necessary to repair water body and soil pollution.
Summary of the invention
In order to solve Fe2+Activation persulfate removes Fe during removal organic polluter2+It is oxidized to Fe rapidly3+, make to activate
Efficiency reduces；And Fe2+The problem of precipitating leads to pH narrow application range is formed under alkaline condition, and the invention proposes one kind to be based on
Cysteine strengthens iron/persulfate removal organic contamination method, and method provided by the invention is simple and easy, low in cost,
The reparation of earth's surface and body of groundwater and organic contaminants in soil is had a good application prospect.
The present invention provides a kind of method for removing organic contamination based on cysteine reinforcing iron/persulfate, including following
Step:
Persulfate solution is added in system to be repaired by S1, is uniformly mixed；
The mixed solution of iron ion and cysteine is added in the system to be repaired of step S1 by S2, is uniformly mixed, mistake
Organic pollutant of the sulfate under iron ion and the effect of cysteine system in oxidative degradation system to be repaired.
Further, in step S1, persulfate selects sodium persulfate, potassium persulfate, ammonium peroxydisulfate, crosses two sulphur
The mixture of any one or more of sour calcium, permonosulphuric acid sodium, permonosulphuric acid potassium, permonosulphuric acid ammonium, permonosulphuric acid calcium.
Further, the iron ion is ferrous ion, and the ferrous ion derives from ferrous sulfate, frerrous chloride
Any one of or two kinds of mixture.
Further, the iron ion is ferric ion, and the ferric ion is in ferric sulfate, iron chloride
Any one or two kinds of mixtures.
Further, the pH value of the system to be repaired is 2~9, and temperature is 10~40 DEG C, and system to be repaired is to be repaired
Water body or soil to be repaired, water body to be repaired are underground water, surface water, sanitary sewage or industrial wastewater, and soil to be repaired is agriculture
Field soil or industrial sites Polluted Soil.
Further, system to be repaired, cysteine, iron ion, persulfate molar ratio be 0.3:0.1~3:0.5
~15:3~20.
Fe2+It can be oxidized to Fe rapidly during activation persulfate3+, reduce Fe2+Activity function, and cysteine
The sulfydryl contained has reproducibility, can be by Fe3+Again it is reduced to Fe2+, make Fe2+Continue to activate persulfate, in cysteine
Under the action of, Fe2+→Fe3+→Fe2+Circulation is formed, Fe is effectively maintained2+Activity function, if system be just initially added into be
Ferric ion, Fe3+Fe is reduced under the action of cysteine2+Persulfate is activated.
Technical solution provided by the invention has the benefit that
1, method provided by the invention does not need additionally to take heating, ultraviolet lighting, addition poisonous and harmful substance
The removal efficiency of iron ion activation persulfate oxidation removal water body or organic contaminants in soil is improved by a relatively large margin；
2, additive cysteine of the invention is a kind of amino acid common in organism, and production is from eggs such as human hairs
White matter, compared to additives such as EDTA using safe, environmental-friendly, to person poultry harmless；
3, method provided by the invention is simple, applied widely, pollution removal efficiency is high, low in cost, iron cement yield
Less, green safe；
4, compared with the iron/persulfate system for being added without cysteine, pollutant after present invention addition cysteine
Removal rate improves 10~35%, and applicable pH is wide, can also improve pollutant removal by a relatively large margin under alkaline condition.
Detailed description of the invention
Fig. 1 is the removal effect curve graph of chlorobenzene in the embodiment of the present invention 1 and comparative example 1.
Fig. 2 is the removal effect curve graph of chlorobenzene in the embodiment of the present invention 2 and comparative example 2.
Fig. 3 is the removal effect curve graph of chlorobenzene in the embodiment of the present invention 3 and comparative example 3.
Fig. 4 is the removal effect curve graph of chlorobenzene in 4-11 of the embodiment of the present invention and comparative example 4-11.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing to embodiment party of the present invention
Formula is further described.
Water body to be repaired is simulated using chlorobenzene stock solution in following embodiment.
Embodiment 1:
The accurate certain volume ferrous sulfate solution that measures is added in 24mL brown screw socket vial, is added a certain amount of
Then cysteine solution is added the chlorobenzene stock solution of certain volume, is rapidly added certain volume sodium persulfate stock solution and draws
Hair reaction, final solution volume 24mL, chlorobenzene in reaction system, cysteine, iron ion, sodium persulfate molar ratio be
0.3:1:1:15.After sealing, start timing, reacts 180min.It is dense by certain time interval sampling determination reaction solution chlorobenzene
Degree.
Comparative example 1:
Comparative example 1 and the difference of embodiment 1 are only that: being added without cysteine solution；Remaining then with the basic phase of embodiment 1
Together.
The removal effect curve graph of chlorobenzene is as shown in Figure 1, as shown in Figure 1, be added half Guang in embodiment 1 and comparative example 1
The removal efficiency of chlorobenzene significantly improves in the reaction system of propylhomoserin, and with the extension of reaction time, chlorobenzene surplus is constantly reduced, In
After 180min, the surplus of chlorobenzene is 27.4%, and the surplus of chlorobenzene reduces 14.0% when than being added without cysteine.
Embodiment 2:
The accurate certain volume solution of ferrous chloride that measures is added in 24mL brown screw socket vial, is added a certain amount of
Then cysteine solution is added the chlorobenzene stock solution of certain volume, is rapidly added certain volume sodium persulfate stock solution and draws
Hair reaction, final solution volume 24mL, chlorobenzene in reaction system, cysteine, iron ion, sodium persulfate molar ratio be
0.3:0.5:5:15 starts timing after sealing, react 180min.It is dense by certain time interval sampling determination reaction solution chlorobenzene
Degree.
Comparative example 2:
Comparative example 2 and the difference of embodiment 2 are only that: being added without cysteine in comparative example 2；Remaining then with embodiment 2
It is essentially identical.
The removal effect curve graph of 2 chlorobenzene of embodiment 2 and comparative example is as shown in Fig. 2, as shown in Figure 2, be added half Guang ammonia
The removal efficiency of chlorobenzene further increases in the reaction system of acid, and with the extension of reaction time, chlorobenzene surplus is constantly reduced, In
After 180min, chlorobenzene fully reacting, the surplus of chlorobenzene reduces 22.3% when than being added without cysteine.
Embodiment 3:
The accurate certain volume ferrous sulfate solution that measures is added in 24mL brown screw socket vial, is added a certain amount of
Then cysteine solution is added the chlorobenzene stock solution of certain volume, is rapidly added certain volume sodium persulfate stock solution and draws
Hair reaction, final solution volume 24mL, chlorobenzene in reaction system, cysteine, iron ion, sodium persulfate molar ratio be
0.32:0.5:5:15.Start timing after sealing, reacts 180min.By certain time interval sampling determination reaction solution chlorobenzene
Concentration.
Comparative example 3:
Comparative example 3 and the difference of embodiment 3 are only that: being added without cysteine in comparative example 3；Remaining then with embodiment 3
It is essentially identical.
The removal effect curve graph of 3 chlorobenzene of embodiment 3 and comparative example is as shown in Figure 3.From the figure 3, it may be seen that half Guang ammonia is added
The removal efficiency of chlorobenzene further increases in the reaction system of acid, and with the extension of reaction time, chlorobenzene surplus is constantly reduced.In
After 180min, the surplus of chlorobenzene is 47.3%, and the surplus of chlorobenzene reduces 18.4% when than being added without cysteine.
Embodiment 4:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 2.0, then accurately measures certain volume ferrous sulfate solution and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction, final solution volume 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 4:
Comparative example 4 and the difference of embodiment 4 are only that: being added without cysteine in comparative example 4；Remaining then with embodiment 4
It is essentially identical.
Embodiment 5:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 2.5, then accurately measures certain volume solution of ferrous chloride and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction.Final solution volume is 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 5:
Comparative example 5 and the difference of embodiment 5 are only that: being added without cysteine in comparative example 5；Remaining then with embodiment 5
It is essentially identical.
Embodiment 6:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 3.0, then accurately measures certain volume ferrous sulfate solution and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction.Final solution volume is 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 6:
Comparative example 6 and the difference of embodiment 6 are only that: being added without cysteine in comparative example 6；Remaining then with embodiment 6
It is essentially identical.
Embodiment 7:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 4.0, then accurately measures certain volume ferrous sulfate solution and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction.Final solution volume is 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 7:
Comparative example 7 and the difference of embodiment 7 are only that: being added without cysteine in comparative example 7；Remaining then with embodiment 7
It is essentially identical.
Embodiment 8:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 5.5, then accurately measures certain volume ferrous sulfate solution and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction.Final solution volume is 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 8:
Comparative example 8 and the difference of embodiment 8 are only that: being added without cysteine in comparative example 8；Remaining then with embodiment 8
It is essentially identical.
Embodiment 9:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 7.0, then accurately measures certain volume ferrous sulfate solution and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction.Final solution volume is 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 9:
Comparative example 9 and the difference of embodiment 9 are only that: being added without cysteine in comparative example 9；Remaining then with embodiment 9
It is essentially identical.
Embodiment 10:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 8.0, then accurately measures certain volume ferrous sulfate solution and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction.Final solution volume is 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 10:
Comparative example 10 and the difference of embodiment 10 are only that: being added without cysteine in comparative example 10；Remaining then with implementation
Example 10 is essentially identical.
Embodiment 11:
With sulfuric acid and sodium hydroxide respectively by chlorobenzene stock solution, ferrous sulfate solution, cysteine solution and peroxy-disulfuric acid
The initial pH of sodium stock solution is adjusted to 9.0, then accurately measures certain volume ferrous sulfate solution and is added to 24mL brown screw socket
In vial, a certain amount of cysteine solution is added, the chlorobenzene stock solution of certain volume is then added, is rapidly added certain
Volume sodium persulfate stock solution initiation reaction.Final solution volume is 24mL, chlorobenzene in reaction system, cysteine, iron from
Sub, sodium persulfate molar ratio is 0.3:0.5:5:15.Start timing after sealing, reaction 180min post-sampling measurement is anti-
Answer liquid chlorine benzene concentration.
Comparative example 11:
Comparative example 11 and the difference of embodiment 11 are only that: being added without cysteine in comparative example 11；Remaining then with implementation
Example 11 is essentially identical.
Chlorobenzene goes under the conditions of the different initial pH values of embodiment 4 to 11 and under the conditions of the different initial pH values of comparative example 4 to 11
Except effect picture as shown in figure 4, being between 2~9 in pH, chlorobenzene is remaining under conditions of being added without cysteine as shown in Figure 4
Amount is between 25.0%~51.7%；It is between 2~3 in pH, with the raising of pH, chlorobenzene surplus is gradually decreased；In pH value
Between 3~5.5, the variation of chlorobenzene surplus is slow；The surplus rapid increase of chlorobenzene after pH value is greater than 5.5.It is being added
Under conditions of cysteine, chlorobenzene surplus is between 2.4%~19.8%；Surplus variation with the variation chlorobenzene of pH becomes
Gesture and it is added without similar in the case where cysteine, but when pH value is under conditions of neutrality to alkalinity, the surplus of chlorobenzene increases
Amplitude is significantly less than the case where cysteine is not added.Chlorobenzene when the surplus ratio of chlorobenzene is added without cysteine when cysteine is added
Surplus reduce 11.4%~33.3%.
In conclusion method provided by the invention is high to the removal efficiency of organic pollutant, iron/persulfate body is compared
System, applicable pH range is wider, has raising by a relatively large margin to the removal efficiency of pollutant.
In the absence of conflict, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of strengthen iron/persulfate removal organic contamination method based on cysteine, which is characterized in that including following step
It is rapid:
Persulfate solution is added in system to be repaired by S1, is uniformly mixed；
The mixed solution of iron ion and cysteine is added in the system to be repaired of step S1 by S2, is uniformly mixed, persulfuric acid
Organic pollutant of the salt under iron ion and the effect of cysteine system in oxidative degradation system to be repaired.
2. according to claim 1 strengthen iron/persulfate removal organic contamination method, feature based on cysteine
It is, in step S1, persulfate selects sodium persulfate, potassium persulfate, ammonium peroxydisulfate, peroxy-disulfuric acid calcium, crosses a sulphur
The mixture of any one or more of sour sodium, permonosulphuric acid potassium, permonosulphuric acid ammonium, permonosulphuric acid calcium.
3. according to claim 1 strengthen iron/persulfate removal organic contamination method, feature based on cysteine
Be, the iron ion is ferrous ion, the ferrous ion from any one of ferrous sulfate, frerrous chloride or
Two kinds of mixture.
4. according to claim 1 strengthen iron/persulfate removal organic contamination method, feature based on cysteine
It is, the iron ion is ferric ion, and the ferric ion derives from any one of ferric sulfate, iron chloride or two kinds
Mixture.
5. according to claim 1 strengthen iron/persulfate removal organic contamination method, feature based on cysteine
It is, the pH value of the system to be repaired is 2~9, and temperature is 10~40 DEG C.
6. according to claim 1 strengthen iron/persulfate removal organic contamination method, feature based on cysteine
Be, system to be repaired, cysteine, iron ion, persulfate molar ratio be 0.3:0.1~3:0.5~15:3~20.
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| CN114314798A (en) * | 2021-12-30 | 2022-04-12 | 华夏碧水环保科技有限公司 | Method for removing organic pollutants by activating persulfate through diatomite composite loaded with iron and manganese |
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