CN110526310A - Utilize the method for green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer - Google Patents
Utilize the method for green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer Download PDFInfo
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- CN110526310A CN110526310A CN201910844675.7A CN201910844675A CN110526310A CN 110526310 A CN110526310 A CN 110526310A CN 201910844675 A CN201910844675 A CN 201910844675A CN 110526310 A CN110526310 A CN 110526310A
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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
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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
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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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Abstract
A method of persulfate system renovation of organic pollution aquifer is activated using green tea Nanoscale Iron, it is that green tea Nanoscale Iron suspension is sequentially added in organic pollution aquifer to be repaired, persulfate, the green tea Nanoscale Iron release ferrous ion is reacted with the persulfate, generate the free radical with oxidisability, ferric iron is converted to after the ferrous ion activation persulfate, further ferrous iron is reduced to by green tea extractive liquor to continue to activate persulfate, generate oxidative free radical, the part green tea extractive liquor also can direct activation persulfate generate oxidative free radical, the oxidative free radical of the generation is degraded the organic pollutant in the waste water.Present invention significantly reduces ferrous sulfate dosages, and remediation efficiency is high, be used for organic pollution aquifer have the characteristics that efficiently, it is non-selectivity, environmental-friendly, without secondary pollution, solving the problems, such as during existing ferrous ion activation persulfate that molysite dosage is big can not recycle with molysite.
Description
Technical field
It is specifically a kind of to utilize green tea nanometer the present invention relates to a kind of control of Organic Pollutants In Water and restorative procedure
The method that iron activates persulfate system renovation of organic pollution aquifer is suitable for the fields organic pollution aquifers such as underground water, printing and dyeing
Processing.
Background technique
Industrial Rapid Expansion results in the generation of a large amount of indegradable industrial effluents.Organic pollutants are deposited
Serious threat is being brought to human health and ecological environment.Although with H2O2It can for traditional high-level oxidation technology of representative
It realizes the fast degradation of majority of organic pollutants in water body, but equally exists pH in practical applications and require harsh, H2O2Itself
Hydroxyl radical free radical (OH) service life in water body short defect that is unstable and generating.It is, thus, sought for it is a kind of novel and
Efficient high-level oxidation technology realizes efficient, the safe disposal of Organic Pollutants In Water.
Based on potentiometric titrations (SO4-) be oxidant persulfate activating technology be to grow up in recent years
A kind of high-level oxidation technology.SO4-It is more stable in acid and neutral aqueous solution, service life (half-life period 4s) ratio
OH (half-life period is less than 1 μ s) is long, and when reaction increases the time of contact of living radical and organic pollutant, oxidant utilization
It is high.In neutral conditions, SO4-Standard oxidationreduction potential ratio OH it is taller.The SO4 in alkaline aqueous solution-It can be with
Aoxidize H2O or OH-OH is generated, to cause a series of radical reaction.Therefore, persulfate oxidation method is in environmental pollution
Treatment process field has very big application potential.
Key using persulfate high-level oxidation technology is how efficiently to activate persulfate to generate SO4-.It is conventional living
Change method includes the physical means such as ultraviolet light, ultrasound, heat and transition metal ions.Physical means need external energy, required energy
Consumption is high.Transition metal ions (common Fe2+、Co2+、Cu2+、Ag+、Mn2+Deng) persulfate can be activated at normal temperature, without outer
Add energy, has biggish superiority in terms of activating persulfate.Iron is a kind of environmentally friendly metal, using iron ion and phase
It answers compound can be with fast activating persulfate, while farthest reducing the influence to environment, be current research and application
Widest persulfate activator.But there are some problems for tradition Fe (II) activation: (1) Fe (II) is too fast is oxidized to Fe
(III), cause persulfate activation efficiency low；(2) after ferrous ion is oxidized, it is difficult to Fe (III)/Fe (II) circulation occurs, and
And Fe (III) easily generates iron oxide deposits, hinders the progress of reaction；(3) when ferrous ion excess, ferrous ion will be with
Living radical reaction, to reduce the utilization rate of over cure acid group, while generating a large amount of iron cement.
Inventor retrieves following Patents documents: CN105967314A is disclosed a kind of to be activated using ferrous oxalate
The method of the repairing organic polluted water body of sulfate system, this method are that oxalic acid Asia is added in organic pollution water body to be repaired
Iron, persulfate substance carry out the reparation of organic pollution water body, solve the problems, such as that activator cannot recycle and reuse, but
Ferrous oxalate is the substance for being insoluble in water, and water-bearing layer blocking is likely to occur when applied to underground water organic pollution in-situ immobilization
Situation.CN108946907A discloses a kind of Fe (III) collaboration plant polyphenol activation persulfate system and repairs organic wastewater
Method.This method utilizes plant polyphenol, Fe (III) solution and persulfate solution Combined Treatment organic wastewater to be repaired, realizes
To the efficient degradation of target organic pollutant, Fe can be efficiently and rapidly generated using plant polyphenol and Fe (III) concerted reaction
(II), quinone and Semiquinone Radicals can activate persulfate, while Fe (III) can also be reduced to Fe by the invertibity of quinone
(II), multiple activated channels are not only increased, and promote Fe (II) circulation, solve that persulfate activation efficiency is low, Fe
(II) it is difficult to the problem of recycling.But plant polyphenol is the mixing of several compounds, and rehabilitation cost is high, and the ratio of three is wider
General, specific aim is not strong.In order to overcome drawbacks described above, solve the problems, such as that activator can not recycle and be also easy to produce secondary pollution, simultaneously
Contaminant degradation efficiency is improved, Nanoscale Iron is can use instead of ferrous ion and activates over cure acid group.But the agglomeration traits of Nanoscale Iron
It is urgently to be resolved with Fe (III)/Fe (II) circulatory problems.CN102259993A discloses a kind of ferrous activation persulfate of complexing
Oxidation method for treating water includes the following steps: the pH value and COD that measure waste water to be processed firstcrValue；It selects to be complexed according to pH value
Agent is added in waste water, then ferrous ion is added into waste water and is sufficiently mixed；According to CODcrIt is worth and is added into the waste water of step (2)
Persulfate arrives purified waste water sufficiently after reaction.
How the above technology accomplishes renovation of organic pollution aquifer to can significantly reduce ferrous sulfate dosage, and remediation efficiency
Height does not provide specific guidance program.
Summary of the invention
Persulfate system renovation of organic pollution water is activated using green tea Nanoscale Iron the purpose of the present invention is to provide a kind of
The method of body, it can significantly reduce ferrous sulfate dosage, and remediation efficiency is high, be used for organic pollution aquifer efficiently, without choosing
Selecting property, environmental-friendly, without secondary pollution, to solve, molysite dosage during existing ferrous ion activation persulfate is big and molysite
The problem of can not recycling,
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
A method of persulfate system renovation of organic pollution aquifer is activated using green tea Nanoscale Iron, it is characterised in that it
It is that green tea Nanoscale Iron suspension, persulfate are sequentially added in organic pollution aquifer to be repaired, in green tea Nanoscale Iron suspension
Additive amount (molar concentration of iron) of the iron in water body (system) be 0.033mM~0.15mM, mM, that is, mmol/L, persulfate with
The molar ratio of iron is 30~155:1 in green tea Nanoscale Iron suspension, the green tea Nanoscale Iron release ferrous ion and the over cure
Hydrochlorate reaction generates the free radical with oxidisability, is converted to ferric iron after the ferrous ion activation persulfate, further
Ferrous iron is reduced to by green tea extractive liquor to continue to activate persulfate, generates oxidative free radical, the part green tea extractive liquor
Also can direct activation persulfate generate oxidative free radical, the oxidative free radical of the generation is degraded having in the waste water
Machine pollutant；
The preparation method of above-mentioned green tea Nanoscale Iron suspension comprises the technical steps that: 1. preparing green tea extractive liquor: will be green
Tea is add to deionized water, and the additional amount of green tea is 40~60g in every liter of deionized water, reacts 20 under 80 DEG C of air-proof conditions
~25min is stood to room temperature, and vacuum filtration obtains green tea extractive liquor；2. preparing ferrous sulfate solution: solid seven is hydrated sulphur
Sour ferrous iron is dissolved into deionized water, obtains 0.1~0.15mol/L ferrous sulfate solution；3. preparing green tea Nanoscale Iron suspension:
Green tea extractive liquor is added dropwise in the ferrous sulfate solution, the volume ratio of green tea extractive liquor and ferrous sulfate solution is 2~
4:1, and continue 5~10min of stirring, the ferrous ion in the ferrous sulfate solution is reduced, and obtains the suspension of green tea Nanoscale Iron
Liquid is sealed.
In above-mentioned technical proposal, preferred technical solution be can be, and the persulfate can be sodium peroxydisulfate, over cure
One of sour potassium, ammonium persulfate or several combinations, its proportion is arbitrary when combination.Certainly, persulfate and not only
It is limited to these three raw materials, can also is other raw materials.The green tea Nanoscale Iron that is added in organic pollution aquifer to be repaired hangs
It is stirred after supernatant liquid, persulfate (starting reaction) is added after being sufficiently mixed solution.Above-mentioned organically-polluted water to be repaired
After sequentially adding green tea Nanoscale Iron suspension, persulfate in body, the pH value of the water body is controlled between 3~12.It is above-mentioned to have
Machine object includes but is not limited to rhodamine B, trichloro ethylene, 1,2,3- trichloropropane.Iron is in water in above-mentioned green tea Nanoscale Iron suspension
Additive amount in body can be 0.075mM, and the molar ratio of iron can be 66.67 in persulfate and green tea Nanoscale Iron suspension:
1.In above-mentioned green tea Nanoscale Iron suspension additive amount of the iron in water body can also be 0.1mM, persulfate, that is, sodium peroxydisulfate with
The molar ratio of iron is that can sequentially add green tea in above-mentioned organic pollution aquifer to be repaired with 30:1 in green tea Nanoscale Iron suspension
After Nanoscale Iron suspension, persulfate, the pH value of the water body be can control between 8~9.Above-mentioned green tea Nanoscale Iron suspension
Preparation method preferably include following processing step: 1. prepare green tea extractive liquor: green tea be add to deionized water, every liter is gone
The additional amount of green tea is 40g in ionized water, and 20min is reacted under 80 DEG C of air-proof conditions, is stood to room temperature, vacuum filtration obtains
Green tea extractive liquor；2. preparing ferrous sulfate solution: solid green vitriol being dissolved into deionized water, is obtained
0.1mol/L ferrous sulfate solution；3. preparing green tea Nanoscale Iron suspension: the ferrous sulfate is added dropwise in green tea extractive liquor
In solution, the volume ratio of green tea extractive liquor and ferrous sulfate solution is 2~4:1, and continues to stir 5min, and the ferrous sulfate is molten
Ferrous ion in liquid is reduced, and is obtained green tea Nanoscale Iron suspension, is sealed.Above-mentioned green tea extractive liquor and ferrous sulfate are molten
The volume ratio of liquid is preferably 3:1.
Technical principle of the invention is that Nanoscale Iron can activate persulfate, but Nanoscale Iron preparation cost is high, easy to reunite,
And Fe (III)/Fe (II) can not be recycled.Present invention introduces green tea extractive liquors, restore iron-containing liquor using green tea extractive liquor, can
To prepare Nanoscale Iron (Nanoscale Iron suspension, green tea Nanoscale Iron suspension), and the reproducibility based on green tea extractive liquor, it both can be direct
Persulfate is activated, Fe can also be brought back to life2+, promote Fe (III)/Fe (II) circulation.The present invention activates persulfuric acid using green tea Nanoscale Iron
Salt significantly reduces ferrous sulfate dosage, and ferrous sulfate is only the 1/155~1/30 of persulfate dosage, with congenic method phase
Than ferrous (ferrous sulfate) dosage reduces 95% or more, and the reproducibility of Tea Polyphenols promotes Fe (III)/Fe
(II) it recycles, so that processed waste water salt content be made to substantially reduce, avoids adverse effect of the molysite to water body environment.
Compared with prior art, the invention has the following beneficial effects: (1) green tea extractive liquors as chelating agent and sealing end
Agent can protect its not oxidized and reunite, itself also has with green syt Nanoscale Iron while reduction generates Nanoscale Iron
There is excellent resurrection Fe2+Ability, and with direct activation over cure acid group generate potentiometric titrations ability.(2) of the invention
The persulfate activator used is environmental-friendly, and ferrous dosage reduces 95% or more, avoids a large amount of molysite to the bad of water body
It influences, green tea extractive liquor, by oxidative degradation therewith, not will cause secondary pollution during repairing polluted-water.(3) item is reacted
Part is mild, normal temperature and pressure can fast reaction, be not necessarily to complex appts, easy to operate, no risk, without engaging professional to grasp
Make.(4) the problems such as this method solve activator levels in conventional activation persulfate system greatly, pollution environment, and repair effect
Rate is high.
In conclusion present invention significantly reduces ferrous sulfate dosage, and remediation efficiency is high, is used for organically-polluted water
Body have the characteristics that efficiently, it is non-selectivity, environmental-friendly, without secondary pollution, solve existing ferrous ion activation persulfate
The problem of molysite dosage is greatly in the process and molysite can not recycle.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is that the green tea Nanoscale Iron in the case where adding different green tea nanometer concentration of iron (in terms of iron) of the embodiment of the present invention 1 activates
Persulfate repairs rhodamine B polluted-water effect picture.
Fig. 3 is that the green tea Nanoscale Iron under different persulfate concentration of the embodiment of the present invention 2 activates persulfate reparation sieve
Red bright B polluted-water effect picture.
Fig. 4 is that the green tea Nanoscale Iron under different rhodamine B concentration of the embodiment of the present invention 3 activates persulfate reparation Luo Dan
Bright B polluted-water effect picture.
Fig. 5 is that the embodiment of the present invention 4 is imitated using trichloro ethylene in green tea Nanoscale Iron activation persulfate reparation underground water
Fruit figure.
Fig. 6 is that the embodiment of the present invention 5 utilizes 1,2,3- trichlorine in green tea Nanoscale Iron activation persulfate reparation underground water
Propane effect picture.
Specific embodiment
To keep goal of the invention of the invention, technical solution and advantage clearer, below in conjunction with embodiment to the present invention
Technical solution carry out clear, complete description.Obviously, described embodiments are some of the embodiments of the present invention, Er Feiquan
Portion's embodiment.Based on the embodiment in invention, those of ordinary skill in the art are obtained without making creative work
The every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1: as shown in Figure 1, appended drawing reference 1 is " to sequentially add green tea nanometer in organic pollution aquifer to be repaired
Iron suspension, persulfate "；Appended drawing reference 2 be " the green tea Nanoscale Iron discharges ferrous ion and reacts with the persulfate,
The free radical with oxidisability is generated, ferric iron is converted to after the ferrous ion activation persulfate, is further mentioned by green tea
It takes liquid to be reduced to ferrous iron to continue to activate persulfate, generates oxidative free radical, the part green tea extractive liquor also can be direct
It activates persulfate and generates oxidative free radical "；Appended drawing reference 3 is " the oxidative free radical degradation waste water of the generation
In organic pollutant ".
It (one) using the method for green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer is had to be repaired
Green tea Nanoscale Iron suspension, persulfate (sodium peroxydisulfate), iron in green tea Nanoscale Iron suspension are sequentially added in machine polluted-water
Additive amount in water body (system) is 0.075mM, mM, that is, mmol/L, and persulfate rubs with iron in green tea Nanoscale Iron suspension
, than being 66.67:1, the green tea Nanoscale Iron release ferrous ion react with the persulfate for you, generate with oxidisability certainly
By base, be converted to ferric iron after ferrous ion activation persulfate, further by green tea extractive liquor be reduced to ferrous iron after
Continuous activation persulfate, generates oxidative free radical, and the part green tea extractive liquor also can direct activation persulfate generation oxygen
Change free love base, the oxidative free radical of the generation is degraded the organic pollutant in the waste water.Above-mentioned green tea Nanoscale Iron is outstanding
The preparation method of supernatant liquid comprises the technical steps that: 1. preparing green tea extractive liquor: green tea is add to deionized water, every liter is gone
The additional amount of green tea is 40g in ionized water, and 20min is reacted under 80 DEG C of air-proof conditions, is stood to room temperature, vacuum filtration obtains
Green tea extractive liquor；2. preparing ferrous sulfate solution: solid green vitriol being dissolved into deionized water, is obtained
0.1mol/L ferrous sulfate solution；3. preparing green tea Nanoscale Iron suspension: the ferrous sulfate is added dropwise in green tea extractive liquor
In solution, the volume ratio of green tea extractive liquor and ferrous sulfate solution is 3:1, and continues to stir 5min, the ferrous sulfate solution
In ferrous ion be reduced, obtain green tea Nanoscale Iron suspension, be sealed.
It (two) is present invention green tea under different green tea Nanoscale Irons (green tea Nanoscale Iron suspension) concentration (in terms of iron) below
Nanoscale Iron activates the method that persulfate repairs rhodamine B polluted-water.
Rhodamine B containing 50mg/L in the water body (reaction system) of 100mL, be separately added into system 0.133mL,
0.3mL, 0.6mL green tea Nanoscale Iron suspension (volume ratio of green tea extractive liquor and ferrous sulfate solution is 3:1) and 0.5mmol
Sodium peroxydisulfate, so that the molar concentration of Fe is respectively 0.033mM, 0.075mM, 0.15mM in solution.5min, 15min,
30min, 60min, 120min are separately sampled, are measured in solution at setting wavelength 554nm using ultraviolet-uisible spectrophotometer
The concentration of rhodamine B.The degradation curve for drawing rhodamine B, as shown in Fig. 2, the degradation rate of rhodamine B reaches in 120min
98% or more, that is to say, that green tea Nanoscale Iron is added on a small quantity can reach satisfied degradation effect.
Embodiment 2:(mono-) utilize the method and reality of green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
(1) applied in example 1 is similar, except that in the present embodiment in green tea Nanoscale Iron suspension iron in water body (system)
Additive amount is 0.033mM, and mM, that is, mmol/L, the concentration of persulfate (potassium peroxydisulfate) is 5mM, persulfate and green tea Nanoscale Iron
The molar ratio of iron is 151:1 in suspension, and the volume ratio of green tea extractive liquor and ferrous sulfate solution is 4:1, prepares green tea extraction
In liquid step, the additional amount of green tea is 50g in every liter of deionized water.
It (two) is that present invention green tea Nanoscale Iron activation persulfate under different persulfate concentration repairs rhodamine B below
The method of polluted-water.
Rhodamine B containing 50mg/L, 0.033mM iron (green tea Nanoscale Iron, with iron in the water body (reaction system) of 100mL
Meter), potassium peroxydisulfate is separately added into system so that in reaction system the ultimate density of potassium peroxydisulfate be respectively 0mM, 1mM,
5mM,10mM.It is separately sampled in 5min, 15min, 30min, 60min, 120min, 240min, using UV, visible light spectrophotometric
Count the concentration that rhodamine B in solution is measured at setting wavelength 554nm.The degradation curve of rhodamine B is drawn, as shown in figure 3, with
The increase of persulfate concentration, degradation rate be gradually increased.In addition to 0mM persulfate, other several groups of experiments sieve in 240min
The degradation rate of red bright B reaches 98% or more.
Embodiment 3:(mono-) utilize the method and reality of green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
(1) applied in example 1 is similar, except that in the present embodiment in green tea Nanoscale Iron suspension iron in water body (system)
Additive amount is 0.033mM, and mM, that is, mmol/L, the concentration of persulfate (sodium peroxydisulfate) is 5mM, persulfate and green tea Nanoscale Iron
The molar ratio of iron is 151:1 in suspension, and the volume ratio of green tea extractive liquor and ferrous sulfate solution is 2.5:1, prepares green tea and mentions
It takes in liquid step, the additional amount of green tea is 55g in every liter of deionized water.
It (two) is that present invention green tea Nanoscale Iron activation persulfate under different rhodamine B concentration repairs rhodamine B below
The method of polluted-water.
Contain 0.033mM iron (green tea Nanoscale Iron, in terms of iron), 5mM sodium peroxydisulfate in the water body (reaction system) of 100mL,
Rhodamine B is added into system so that in reaction system the ultimate density of rhodamine B be respectively 50mg/L, 100mg/L,
500mg/L.It is separately sampled in 5min, 15min, 30min, 60min, 120min, 240min, using ultraviolet-uisible spectrophotometer
The concentration of rhodamine B in solution is measured at setting wavelength 554nm.The degradation curve of rhodamine B is drawn, as shown in figure 4, with
The increase of rhodamine B concentration, degradation rate decrease.But in 240min, the rhodamine B degradation rate of 500mg/L is 80%, explanation
For the rhodamine B of high concentration, green tea Nanoscale Iron activation persulfate still has extraordinary degradation effect.
Embodiment 4:(mono-) utilize the method and reality of green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
(1) applied in example 1 is similar, except that in the present embodiment in green tea Nanoscale Iron suspension iron in water body (system)
Additive amount is 0.1mM, and the concentration of mM, that is, mmol/L, persulfate are 3mM, and persulfate is sodium peroxydisulfate, this technical solution drop
Solution rate is high (up to 99%, referring to following test).The molar ratio of iron is 30:1 in persulfate and green tea Nanoscale Iron suspension,
The volume ratio of green tea extractive liquor and ferrous sulfate solution is 3:1, is prepared in green tea extractive liquor step, green tea in every liter of deionized water
Additional amount be 40g.After sequentially adding green tea Nanoscale Iron suspension, persulfate in above-mentioned organic pollution aquifer to be repaired, institute
The pH value for stating water body controls between 8~9.
(2) it is the method that green tea Nanoscale Iron activation persulfate of the invention repairs trichloro ethylene in underground water below, repairs
Multiple effect is as shown in Figure 5.
Using concentration for 0.46mM trichloro ethylene as simulated wastewater, take 320mL simulated wastewater to be divided in 8 40mL browns small
In bottle, green tea Nanoscale Iron and persulfate are added thereto, making final persulfate concentration 3mM, Fe concentration is 0.1mM, is set
In on oscillator with 25 DEG C of 150rpm oscillating reactions, and 0,5,10,15,20,25,30,60min sampling, finally use gas phase color
Trichloro ethylene content in spectrum measurement solution.The check experiment of sodium peroxydisulfate degradation trichloro ethylene is only added in setting simultaneously, as a result
As shown in figure 5, in 30min, green tea Nanoscale Iron+persulfate system tce degradation rate reaches 96%, and the reaction time
Degradation rate is up to 99% when extending to 60min, and the final degradation rate of 60min has only reached 32% in persulfate system.
Embodiment 5:(mono-) utilize the method and reality of green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
(1) applied in example 1 is similar.
It (two) is that green tea Nanoscale Iron activation persulfate of the invention repairs 1,2,3- trichloropropane in underground water below
Method, repairing effect are as shown in Figure 6.Organic contamination underground water is derived from the underground water in certain discarded chemical plant, after sampling, impurely under
Water determines that the main organic pollutant of polluted underground water is 1,2,3- trichloropropane by Mass Spectrometer Method.For 1,2,3- trichlorine
0.6mL green tea Nanoscale Iron is added into 100mL underground water, ammonium persulfate is then added for the reparation of propane polluted underground water, so that
Concentration of iron is 0.075mM and persulfate concentration is 5mM.Without adjusting pH, stand.Simultaneously only to add persulfate to be control examination
It tests, the concentration of persulfate is 5mM in check experiment, detects the degradation situation of 1,2,3- trichloropropane.As a result such as Fig. 6, adding
In the system for entering green tea Nanoscale Iron, react 12 hours, 1,2,3- trichloropropane degradation rates reach 65% in underground water；Only adding
In the system of sulfate, react 12 hours, 1,2,3- trichloropropane degradation rates are only 3% in underground water.
Compared with prior art, (the above various embodiments) of the invention has the following beneficial effects: that (1) green tea extractive liquor is made
For chelating agent and end-capping reagent, can with green syt Nanoscale Iron, protect its not oxidized while reduction generates Nanoscale Iron and
Reunite, itself also there is excellent resurrection Fe2+Ability, and generate potentiometric titrations with direct activation over cure acid group
Ability.(2) the persulfate activator that the present invention uses is environmental-friendly, and ferrous dosage reduces 95% or more, avoids a large amount of iron
Adverse effect of the salt to water body, green tea extractive liquor, by oxidative degradation therewith, not will cause secondary during repairing polluted-water
Pollution.(3) reaction condition is mild, normal temperature and pressure can fast reaction, be not necessarily to complex appts, easy to operate, no risk is not necessarily to
Engage professional's operation.(4) this method solve activator levels in conventional activation persulfate system greatly, pollutes environment etc.
Problem, and remediation efficiency is high.
In conclusion present invention significantly reduces ferrous sulfate dosage, and remediation efficiency is high, is used for organically-polluted water
Body have the characteristics that efficiently, it is non-selectivity, environmental-friendly, without secondary pollution, solve existing ferrous ion activation persulfate
The problem of molysite dosage is greatly in the process and molysite can not recycle.
Claims (9)
1. a kind of method using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer, it is characterised in that it is
Green tea Nanoscale Iron suspension, persulfate, iron in green tea Nanoscale Iron suspension are sequentially added in organic pollution aquifer to be repaired
Additive amount in water body is 0.033mM~0.15mM, mM, that is, mmol/L, iron in persulfate and green tea Nanoscale Iron suspension
Molar ratio is 30~155:1, and the green tea Nanoscale Iron release ferrous ion is reacted with the persulfate, and generating has oxidisability
Free radical, be converted to ferric iron after ferrous ion activation persulfate, divalent be further reduced to by green tea extractive liquor
Iron continues to activate persulfate, generates oxidative free radical, and the part green tea extractive liquor also can the production of direct activation persulfate
Raw oxidative free radical, the oxidative free radical of the generation are degraded the organic pollutant in the waste water；
The preparation method of above-mentioned green tea Nanoscale Iron suspension comprises the technical steps that: 1. prepare green tea extractive liquor: by green tea plus
Enter into deionized water, in every liter of deionized water the additional amount of green tea be 40~60g, under 80 DEG C of air-proof conditions react 20~
25min is stood to room temperature, and vacuum filtration obtains green tea extractive liquor；2. preparing ferrous sulfate solution: by seven hydrated sulfuric acid of solid
Ferrous iron is dissolved into deionized water, obtains 0.1~0.15mol/L ferrous sulfate solution；3. preparing green tea Nanoscale Iron suspension: will
Green tea extractive liquor is added dropwise in the ferrous sulfate solution, and the volume ratio of green tea extractive liquor and ferrous sulfate solution is 2~
4:1, and continue 5~10min of stirring, the ferrous ion in the ferrous sulfate solution is reduced, and obtains the suspension of green tea Nanoscale Iron
Liquid is sealed.
2. the side according to claim 1 using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
Method, it is characterised in that above-mentioned persulfate be one of sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate or several combinations,
Its proportion is arbitrary when combination.
3. the side according to claim 1 using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
Method, it is characterised in that be stirred after green tea Nanoscale Iron suspension is added in above-mentioned organic pollution aquifer to be repaired, fill solution
Persulfate is added after dividing mixing.
4. the side according to claim 1 using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
Method, it is characterised in that described after sequentially adding green tea Nanoscale Iron suspension, persulfate in above-mentioned organic pollution aquifer to be repaired
The pH value of water body controls between 3~12.
5. the side according to claim 1 using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
Method, it is characterised in that above-mentioned organic matter includes but is not limited to rhodamine B, trichloro ethylene, 1,2,3- trichloropropanes.
6. the side according to claim 1 using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
Method, it is characterised in that additive amount of the iron in water body is 0.075mM, persulfate and green tea in above-mentioned green tea Nanoscale Iron suspension
The molar ratio of iron is 66.67:1 in Nanoscale Iron suspension.
7. the side according to claim 1 using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
Method, it is characterised in that additive amount of the iron in water body is 0.1mM, persulfate, that is, persulfuric acid in above-mentioned green tea Nanoscale Iron suspension
The molar ratio of iron is 30:1 in sodium and green tea Nanoscale Iron suspension, sequentially adds green tea in above-mentioned organic pollution aquifer to be repaired and receives
After rice iron suspension, persulfate, the pH value of the water body is controlled between 8~9.
8. the side according to claim 1 using green tea Nanoscale Iron activation persulfate system renovation of organic pollution aquifer
Method, it is characterised in that the preparation method of above-mentioned green tea Nanoscale Iron suspension comprises the technical steps that: green tea extractive liquor is 1. prepared:
Green tea is add to deionized water, the additional amount of green tea is 40g in every liter of deionized water, is reacted under 80 DEG C of air-proof conditions
20min is stood to room temperature, and vacuum filtration obtains green tea extractive liquor；2. preparing ferrous sulfate solution: by seven hydrated sulfuric acid of solid
Ferrous iron is dissolved into deionized water, obtains 0.1mol/L ferrous sulfate solution；3. preparing green tea Nanoscale Iron suspension: green tea is mentioned
Liquid is taken to be added dropwise in the ferrous sulfate solution, the volume ratio of green tea extractive liquor and ferrous sulfate solution is 2~4:1, and
5min is persistently stirred, the ferrous ion in the ferrous sulfate solution is reduced, and obtains green tea Nanoscale Iron suspension, and sealing is protected
It deposits.
9. activating persulfate system using green tea Nanoscale Iron described according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8
The method of renovation of organic pollution aquifer, it is characterised in that the volume ratio of above-mentioned green tea extractive liquor and ferrous sulfate solution is 3:1.
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