CN104609636A - Method for removing endocrine disruptors in water by using iron and manganese double-phase-doped graphene to activate single persulfate - Google Patents
Method for removing endocrine disruptors in water by using iron and manganese double-phase-doped graphene to activate single persulfate Download PDFInfo
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- CN104609636A CN104609636A CN201510074022.7A CN201510074022A CN104609636A CN 104609636 A CN104609636 A CN 104609636A CN 201510074022 A CN201510074022 A CN 201510074022A CN 104609636 A CN104609636 A CN 104609636A
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Abstract
The invention discloses a method for removing endocrine disruptors in water by using iron and manganese double-phase-doped graphene to activate a single persulfate and relates to a method for removing the endocrine disruptors in the water. The invention aims at solving the problems of low removal efficiency and high cost of the existing method for removing the endocrine disruptors in the water. The method comprises the following steps: 1) mixing the single persulfate with the water after pretreatment; 2) regulating a reaction pH value; 3) preparing iron and manganese double-phase-doped graphene; 4) putting iron and manganese double-phase-doped graphene; and 5) separating iron and manganese double-phase-doped graphene by adopting an external magnetic field, thereby completing the method for removing the endocrine disruptors in the water by using iron and manganese double-phase-doped graphene to activate the single persulfate. By using the method disclosed by the invention, the removal rate in removal of the endocrine disruptors in the water can achieve 85%-96%. By using the method disclosed by the invention, the endocrine disruptors in the water can be removed.
Description
Technical field
The present invention relates to a kind of method removing endocrine disrupter in water.
Background technology
Endocrine disrupter (Endocrine disrupting chemicals, EDCs) be by entering water surrounding without the sanitary sewage processed completely, pharmacy waste water or livestock water industry muck runoff, and in water body after enrichment concentration can increase hundreds of times.Even and other EDCs of trace level also can produce carcinogenic, mutagenesis and harm such as interference reproductive system and hormone secretion etc. to long-term exposure human body wherein and organism.Be used frequently due to above-mentioned substance and enter in environment water, causing it to form " false lasting " (pseudo-persistent) phenomenon, and then long-term potential hazard is formed to HUMAN HEALTH and the whole ecosystem.
In current process water, micro quantity organic pollutant (endocrine disrupter, microbiotic etc.) mainly applies chlorination, ozone and advanced oxidation processes, and endocrine disrupter poor effect in these method process water and multistage technology is set processing cost will be caused to increase.
Summary of the invention
The removal efficiency that the object of the invention is to solve endocrine disrupter in existing method removal water is low, the problem that cost is high, and provides a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water.
Utilize ferrimanganic two-phase doped graphene to activate a method for endocrine disrupter in single persulphate removal water, complete according to the following steps:
One, single persulphate is mixed with pretreated water: single persulphate is mixed with pretreated water, be at room temperature stir 20min ~ 45min under the condition of 160r/min ~ 250r/min again with stirring velocity, obtain the mixing solutions of single persulphate and pretreated water;
Single persulphate described in step one is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;
In pretreated water described in step one, the concentration of endocrine disrupter is 0.02mg/L ~ 100mg/L;
The quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:(1000 ~ 10000);
Two, pH value in reaction is regulated: low whipping speed is use the perchloric acid of 0.1mol/L ~ 100mol/L and the sodium hydroxide solution of 0.1mol/L ~ 100mol/L that the pH value of the mixing solutions of single persulphate and pretreated water is adjusted to 6.5 ~ 7.5, the single persulphate after adjusted pH value and the mixing solutions of pretreated water under the condition of 150r/min ~ 200r/min;
Three, ferrimanganic two-phase doped graphene is prepared:
1., by graphene oxide joining massfraction is in the ethylene glycol solution of 97% ~ 99%, re-uses ultrasonic oscillation instrument concussion dispersion 3h ~ 4h, obtains the mixing solutions of graphene oxide and ethylene glycol;
Step 3 1. described in the quality of graphene oxide and massfraction be the volume ratio of the ethylene glycol solution of 97% ~ 99% be (0.001g ~ 10g): 1mL;
2., by the mixing solutions of Trisodium Citrate and ethylene glycol at temperature is 60 DEG C ~ 75 DEG C, heat 20min ~ 45min, obtain the mixing solutions of the Trisodium Citrate after heating and ethylene glycol; Again to heating after Trisodium Citrate and ethylene glycol mixing solutions in add FeCl
36H
2o, urea and MnCl
26H
2o, then stir 2h ~ 4h at the condition lower magnetic force that room temperature and magnetic agitation speed are 100r/min ~ 250r/min, obtain the mixing solutions of Trisodium Citrate containing ferrimanganic and ethylene glycol;
Step 3 2. described in Trisodium Citrate and ethylene glycol mixing solutions in the concentration of Trisodium Citrate be 60mg/mL ~ 200mg/mL;
Step 3 2. described in heating after Trisodium Citrate and the volume of mixing solutions of ethylene glycol and FeCl
36H
2the mass ratio of O is (1mL ~ 1000mL): 1g;
Step 3 2. described in FeCl
36H
2the mass ratio of O and urea is (0.01 ~ 100): 1;
Step 3 2. described in FeCl
36H
2o and MnCl
26H
2the mass ratio of O is (0.01 ~ 1000): 1;
3., the mixing solutions of graphene oxide and ethylene glycol is mixed with the mixing solutions of the Trisodium Citrate containing ferrimanganic and ethylene glycol, joining liner is again in the stainless steel autoclave of tetrafluoroethylene, again stainless steel autoclave is sealed, again the stainless steel autoclave of sealing is reacted 12h ~ 48h at temperature is 200 DEG C ~ 230 DEG C, naturally cool to room temperature again, obtain black suspension;
Step 3 3. described in graphene oxide and the mixing solutions of ethylene glycol be (0.1 ~ 50) with the volume ratio containing the Trisodium Citrate of ferrimanganic and the mixing solutions of ethylene glycol: 1;
4., by black suspension under centrifugal speed is 6500r/min ~ 8000r/min, carry out centrifugation 10min ~ 30min, obtain the sedimentable matter after centrifugation; Use sedimentable matter after methyl alcohol and washed with de-ionized water centrifugation respectively 5 times ~ 10 times, then at temperature is-18 DEG C ~ 15 DEG C dry 24h ~ 48h, obtain ferrimanganic two-phase doped graphene;
Four, ferrimanganic two-phase doped graphene is added: joined by ferrimanganic two-phase doped graphene in the mixing solutions of the single persulphate after adjust ph and pretreated water, the reaction times is 15min ~ 240min, obtains the water containing ferrimanganic two-phase doped graphene;
The dosage of the ferrimanganic two-phase doped graphene described in step 4 is 1mg/L ~ 200mg/L;
Five, foreign field is adopted to be separated ferrimanganic two-phase doped graphene: to adopt foreign field to be separated the water containing ferrimanganic two-phase doped graphene, reclaim ferrimanganic two-phase doped graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim ferrimanganic two-phase doped graphene filter, again by the ferrimanganic two-phase doped graphene dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the ferrimanganic two-phase doped graphene after regenerating and removal water.
Principle of the present invention:
In the present invention surface of graphene oxide exist active metal iron and manganese by with the HSO in single persulphate
5 -or SO
5 2-there is transfer transport, thus make single persulfate be cracked into SO
4 -with OH
-; On the other hand graphene oxide has huge specific surface area, its can adsorbed target organic while, the aerobic functional group that surface is a large amount of, as carboxyl the polyelectrons group that has can activate single persulphate further, generate SO
4 -with H
2o, thus the oxidative degradation accelerating target organic.
Advantage of the present invention:
One, the inventive method is simple to operate, with low cost, compared with the method removing endocrine disrupter in water, reduces cost 40% ~ 60% with other;
Two, the present invention has lower volatility, colourity and smell taste and can not change before and after reaction, and the ferrimanganic two-phase doped graphene of preparation at normal temperatures and pressures can stable existence;
Three, the ferrimanganic two-phase doped graphene speed of response synthesized by the present invention is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the ferrimanganic two-phase doped graphene synthesized by the present invention can be easier to reclaim and regeneration;
Five, the clearance using method of the present invention to remove endocrine disrupter in water can reach 85% ~ 96%.
The present invention can remove remaining endocrine disrupter in water.
Embodiment
Embodiment one: present embodiment is that a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water completes according to the following steps:
One, single persulphate is mixed with pretreated water: single persulphate is mixed with pretreated water, be at room temperature stir 20min ~ 45min under the condition of 160r/min ~ 250r/min again with stirring velocity, obtain the mixing solutions of single persulphate and pretreated water;
Single persulphate described in step one is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;
In pretreated water described in step one, the concentration of endocrine disrupter is 0.02mg/L ~ 100mg/L;
The quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:(1000 ~ 10000);
Two, pH value in reaction is regulated: low whipping speed is use the perchloric acid of 0.1mol/L ~ 100mol/L and the sodium hydroxide solution of 0.1mol/L ~ 100mol/L that the pH value of the mixing solutions of single persulphate and pretreated water is adjusted to 6.5 ~ 7.5, the single persulphate after adjusted pH value and the mixing solutions of pretreated water under the condition of 150r/min ~ 200r/min;
Three, ferrimanganic two-phase doped graphene is prepared:
1., by graphene oxide joining massfraction is in the ethylene glycol solution of 97% ~ 99%, re-uses ultrasonic oscillation instrument concussion dispersion 3h ~ 4h, obtains the mixing solutions of graphene oxide and ethylene glycol;
Step 3 1. described in the quality of graphene oxide and massfraction be the volume ratio of the ethylene glycol solution of 97% ~ 99% be (0.001g ~ 10g): 1mL;
2., by the mixing solutions of Trisodium Citrate and ethylene glycol at temperature is 60 DEG C ~ 75 DEG C, heat 20min ~ 45min, obtain the mixing solutions of the Trisodium Citrate after heating and ethylene glycol; Again to heating after Trisodium Citrate and ethylene glycol mixing solutions in add FeCl
36H
2o, urea and MnCl
26H
2o, then stir 2h ~ 4h at the condition lower magnetic force that room temperature and magnetic agitation speed are 100r/min ~ 250r/min, obtain the mixing solutions of Trisodium Citrate containing ferrimanganic and ethylene glycol;
Step 3 2. described in Trisodium Citrate and ethylene glycol mixing solutions in the concentration of Trisodium Citrate be 60mg/mL ~ 200mg/mL;
Step 3 2. described in heating after Trisodium Citrate and the volume of mixing solutions of ethylene glycol and FeCl
36H
2the mass ratio of O is (1mL ~ 1000mL): 1g;
Step 3 2. described in FeCl
36H
2the mass ratio of O and urea is (0.01 ~ 100): 1;
Step 3 2. described in FeCl
36H
2o and MnCl
26H
2the mass ratio of O is (0.01 ~ 1000): 1;
3., the mixing solutions of graphene oxide and ethylene glycol is mixed with the mixing solutions of the Trisodium Citrate containing ferrimanganic and ethylene glycol, joining liner is again in the stainless steel autoclave of tetrafluoroethylene, again stainless steel autoclave is sealed, again the stainless steel autoclave of sealing is reacted 12h ~ 48h at temperature is 200 DEG C ~ 230 DEG C, naturally cool to room temperature again, obtain black suspension;
Step 3 3. described in graphene oxide and the mixing solutions of ethylene glycol be (0.1 ~ 50) with the volume ratio containing the Trisodium Citrate of ferrimanganic and the mixing solutions of ethylene glycol: 1;
4., by black suspension under centrifugal speed is 6500r/min ~ 8000r/min, carry out centrifugation 10min ~ 30min, obtain the sedimentable matter after centrifugation; Use sedimentable matter after methyl alcohol and washed with de-ionized water centrifugation respectively 5 times ~ 10 times, then at temperature is-18 DEG C ~ 15 DEG C dry 24h ~ 48h, obtain ferrimanganic two-phase doped graphene;
Four, ferrimanganic two-phase doped graphene is added: joined by ferrimanganic two-phase doped graphene in the mixing solutions of the single persulphate after adjust ph and pretreated water, the reaction times is 15min ~ 240min, obtains the water containing ferrimanganic two-phase doped graphene;
The dosage of the ferrimanganic two-phase doped graphene described in step 4 is 1mg/L ~ 200mg/L;
Five, foreign field is adopted to be separated ferrimanganic two-phase doped graphene: to adopt foreign field to be separated the water containing ferrimanganic two-phase doped graphene, reclaim ferrimanganic two-phase doped graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim ferrimanganic two-phase doped graphene filter, again by the ferrimanganic two-phase doped graphene dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the ferrimanganic two-phase doped graphene after regenerating and removal water.
The principle of present embodiment:
In present embodiment surface of graphene oxide exist active metal iron and manganese by with the HSO in single persulphate
5 --or SO
5 2-there is transfer transport, thus make single persulfate be cracked into SO
4 -with OH
-; On the other hand graphene oxide has huge specific surface area, its can adsorbed target organic while, the aerobic functional group that surface is a large amount of, as carboxyl the polyelectrons group that has can activate single persulphate further, generate SO
4 -with H
2o, thus the oxidative degradation accelerating target organic.
The advantage of present embodiment:
One, present embodiment method is simple to operate, with low cost, compared with the method removing endocrine disrupter in water, reduces cost 40% ~ 60% with other;
Two, present embodiment has lower volatility, colourity and smell taste and can not change before and after reaction, and the ferrimanganic two-phase doped graphene of preparation at normal temperatures and pressures can stable existence;
Three, the ferrimanganic two-phase doped graphene speed of response synthesized by present embodiment is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the ferrimanganic two-phase doped graphene synthesized by present embodiment can be easier to reclaim and regeneration;
Five, the clearance using the method for present embodiment to remove endocrine disrupter in water can reach 85% ~ 96%.
Present embodiment can remove remaining endocrine disrupter in water.
Embodiment two: present embodiment and embodiment one difference are: the endocrine disrupter described in step one is a kind of or wherein several mixture in oestrone, 17 α-lynoral, 17 alpha-estradiols, 17 beta estradiols, trihydroxy-oestrin, stilboestrol, nonyl phenol, dihydroxyphenyl propane and octyl phenol.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: step 3 1. described in the power of ultrasonic oscillation instrument be 100W ~ 1000W.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the external magnetic field strength described in step 4 is 0.01T ~ 1T.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: the quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:(1000 ~ 5000).Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: the quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:(5000 ~ 8000).Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: the dosage of the ferrimanganic two-phase doped graphene described in step 4 is 0.02mg/L ~ 10mg/L.Other steps are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: the dosage of the ferrimanganic two-phase doped graphene described in step 4 is 10mg/L ~ 100mg/L.Other steps are identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: the dosage of the ferrimanganic two-phase doped graphene described in step 4 is 100mg/L ~ 200mg/L.Other steps are identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: step 3 1. described in the particle diameter of graphene oxide be 15nm ~ 500nm.Other steps are identical with embodiment one to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water
One, single persulphate is mixed with pretreated water: single persulphate is mixed with pretreated water, then be at room temperature stir 30min under the condition of 180r/min with stirring velocity, obtain the mixing solutions of single persulphate and pretreated water;
Single persulphate described in step one is Potassium peroxysulfate;
Endocrine disrupter described in step one is trihydroxy-oestrin;
In pretreated water described in step one, the concentration of endocrine disrupter is 5mg/L;
The quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:1500;
Two, pH value in reaction is regulated: low whipping speed is use the perchloric acid of 0.1mol/L and the sodium hydroxide solution of 0.1mol/L that the pH value of the mixing solutions of single persulphate and pretreated water is adjusted to 6.5, the single persulphate after adjusted pH value and the mixing solutions of pretreated water under the condition of 180r/min;
Three, ferrimanganic two-phase doped graphene is prepared:
1., by graphene oxide joining massfraction is in the ethylene glycol solution of 99%, re-uses ultrasonic oscillation instrument concussion dispersion 3h, obtains the mixing solutions of graphene oxide and ethylene glycol;
Step 3 1. described in the particle diameter of graphene oxide be 25nm;
Step 3 1. described in the quality of graphene oxide and massfraction be the volume ratio of the ethylene glycol solution of 99% be 0.005g:1mL;
Step 3 1. described in the power of ultrasonic oscillation instrument be 200W;
2., by the mixing solutions of 50mL Trisodium Citrate and ethylene glycol at temperature is 60 DEG C, heat 20min, obtain the mixing solutions of the Trisodium Citrate after heating and ethylene glycol; Again to heating after Trisodium Citrate and ethylene glycol mixing solutions in add FeCl
36H
2o, urea and MnCl
26H
2o, then stir 2h at the condition lower magnetic force that room temperature and magnetic agitation speed are 200r/min, obtain the mixing solutions of Trisodium Citrate containing ferrimanganic and ethylene glycol;
Step 3 2. described in Trisodium Citrate and ethylene glycol mixing solutions in the concentration of Trisodium Citrate be 60mg/mL;
Step 3 2. described in heating after Trisodium Citrate and the volume of mixing solutions of ethylene glycol and FeCl
36H
2the mass ratio of O is 50mL:1g;
Step 3 2. described in FeCl
36H
2the mass ratio of O and urea is 50:1;
Step 3 2. described in FeCl
36H
2o and MnCl
26H
2the mass ratio of O is 5:1;
The mixing solutions of the Trisodium Citrate and ethylene glycol that 3., the mixing solutions of 50mL graphene oxide and ethylene glycol are contained ferrimanganic with 50mL mixes, joining liner is again in the stainless steel autoclave of tetrafluoroethylene, again stainless steel autoclave is sealed, again the stainless steel autoclave of sealing is reacted 12h at temperature is 200 DEG C, naturally cool to room temperature again, obtain black suspension;
4., by black suspension under centrifugal speed is 6500r/min, carry out centrifugation 10min, obtain the sedimentable matter after centrifugation; Use sedimentable matter after methyl alcohol and washed with de-ionized water centrifugation respectively 6 times, then at temperature is-18 DEG C lyophilize 24h, obtain ferrimanganic two-phase doped graphene;
Four, ferrimanganic two-phase doped graphene is added: joined by ferrimanganic two-phase doped graphene in the mixing solutions of the single persulphate after adjust ph and pretreated water, the reaction times is 60min, obtains the water containing ferrimanganic two-phase doped graphene;
The dosage of the ferrimanganic two-phase doped graphene described in step 4 is 10mg/L;
External magnetic field strength described in step 4 is 0.03T;
Five, foreign field is adopted to be separated ferrimanganic two-phase doped graphene: to adopt foreign field to be separated the water containing ferrimanganic two-phase doped graphene, reclaim ferrimanganic two-phase doped graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim ferrimanganic two-phase doped graphene filter, again by the ferrimanganic two-phase doped graphene dry 24h at temperature is 50 DEG C after filtration, obtain the water of endocrine disrupter in the ferrimanganic two-phase doped graphene after regenerating and removal water.
The advantage of this test:
One, this test method is simple to operate, with low cost, compared with the method removing endocrine disrupter in water, reduces cost 45% with other;
Two, this test has lower volatility, colourity and smell taste and can not change before and after reaction, and the ferrimanganic two-phase doped graphene of preparation at normal temperatures and pressures can stable existence;
Three, the ferrimanganic two-phase doped graphene speed of response synthesized by this test is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the ferrimanganic two-phase doped graphene synthesized by this test can be easier to reclaim and regeneration;
Five, the clearance using the method for this test to remove endocrine disrupter in water can reach 95%.
Test two: use gac to remove the simultaneous test of endocrine disrupter in water, specifically complete according to the following steps:
Use the endocrine disrupter 24h in the ature of coal granulated active carbon absorption pretreated water that particle diameter is 4nm ~ 100nm, obtain the water removing endocrine disrupter in water;
In described pretreated water, endocrine disrupter is trihydroxy-oestrin, and the concentration of trihydroxy-oestrin is 5mg/L.
In the ature of coal granulated active carbon Adsorption pretreated water using particle diameter to be 4nm ~ 100nm in test two, the clearance of endocrine disrupter is 53%.
Test three: use UV-light and H
2o
2remove the simultaneous test of endocrine disrupter in water, specifically complete according to the following steps:
The H that concentration is 10mmol/L is added in pretreated water
2o
2, at ultraviolet light intensity 250uW/cm
2the pretreated water 0.5h of UV-irradiation, obtain the water removing endocrine disrupter in water;
In described pretreated water, endocrine disrupter is trihydroxy-oestrin, and the concentration of trihydroxy-oestrin is 5mg/L;
Test three uses UV-light and H
2o
2the clearance removing endocrine disrupter in pretreated water is 68%.
Test four: use Sodium Persulfate to remove the simultaneous test of endocrine disrupter in water, specifically complete according to the following steps:
In pretreated water, add the Sodium Persulfate of 2mg/L, reaction 2h, obtain the water removing endocrine disrupter in water;
In described pretreated water, endocrine disrupter is trihydroxy-oestrin, and the concentration of trihydroxy-oestrin is 5mg/L;
The clearance that test four uses Sodium Persulfate to remove endocrine disrupter in pretreated water is 9%.
Test two uses ature of coal granulated active carbon to remove endocrine disrupter in pretreated water, test three uses UV-light and H
2o
2remove the clearance that in pretreated water, endocrine disrupter and test four use Sodium Persulfate to remove endocrine disrupter in pretreated water and be respectively 53%, 68% and 9%, and the clearance testing is 95%, prove that test one is for endocrine disrupter excellent in removal pretreated water.
Claims (10)
1. utilize ferrimanganic two-phase doped graphene to activate a method for endocrine disrupter in single persulphate removal water, it is characterized in that a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water completes according to the following steps:
One, single persulphate is mixed with pretreated water: single persulphate is mixed with pretreated water, be at room temperature stir 20min ~ 45min under the condition of 160r/min ~ 250r/min again with stirring velocity, obtain the mixing solutions of single persulphate and pretreated water;
Single persulphate described in step one is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;
In pretreated water described in step one, the concentration of endocrine disrupter is 0.02mg/L ~ 100mg/L;
The quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:(1000 ~ 10000);
Two, pH value in reaction is regulated: low whipping speed is use the perchloric acid of 0.1mol/L ~ 100mol/L and the sodium hydroxide solution of 0.1mol/L ~ 100mol/L that the pH value of the mixing solutions of single persulphate and pretreated water is adjusted to 6.5 ~ 7.5, the single persulphate after adjusted pH value and the mixing solutions of pretreated water under the condition of 150r/min ~ 200r/min;
Three, ferrimanganic two-phase doped graphene is prepared:
1., by graphene oxide joining massfraction is in the ethylene glycol solution of 97% ~ 99%, re-uses ultrasonic oscillation instrument concussion dispersion 3h ~ 4h, obtains the mixing solutions of graphene oxide and ethylene glycol;
Step 3 1. described in the quality of graphene oxide and massfraction be the volume ratio of the ethylene glycol solution of 97% ~ 99% be (0.001g ~ 10g): 1mL;
2., by the mixing solutions of Trisodium Citrate and ethylene glycol at temperature is 60 DEG C ~ 75 DEG C, heat 20min ~ 45min, obtain the mixing solutions of the Trisodium Citrate after heating and ethylene glycol; Again to heating after Trisodium Citrate and ethylene glycol mixing solutions in add FeCl
36H
2o, urea and MnCl
26H
2o, then stir 2h ~ 4h at the condition lower magnetic force that room temperature and magnetic agitation speed are 100r/min ~ 250r/min, obtain the mixing solutions of Trisodium Citrate containing ferrimanganic and ethylene glycol;
Step 3 2. described in Trisodium Citrate and ethylene glycol mixing solutions in the concentration of Trisodium Citrate be 60mg/mL ~ 200mg/mL;
Step 3 2. described in heating after Trisodium Citrate and the volume of mixing solutions of ethylene glycol and FeCl
36H
2the mass ratio of O is (1mL ~ 1000mL): 1g;
Step 3 2. described in FeCl
36H
2the mass ratio of O and urea is (0.01 ~ 100): 1;
Step 3 2. described in FeCl
36H
2o and MnCl
26H
2the mass ratio of O is (0.01 ~ 1000): 1;
3., the mixing solutions of graphene oxide and ethylene glycol is mixed with the mixing solutions of the Trisodium Citrate containing ferrimanganic and ethylene glycol, joining liner is again in the stainless steel autoclave of tetrafluoroethylene, again stainless steel autoclave is sealed, again the stainless steel autoclave of sealing is reacted 12h ~ 48h at temperature is 200 DEG C ~ 230 DEG C, naturally cool to room temperature again, obtain black suspension;
Step 3 3. described in graphene oxide and the mixing solutions of ethylene glycol be (0.1 ~ 50) with the volume ratio containing the Trisodium Citrate of ferrimanganic and the mixing solutions of ethylene glycol: 1;
4., by black suspension under centrifugal speed is 6500r/min ~ 8000r/min, carry out centrifugation 10min ~ 30min, obtain the sedimentable matter after centrifugation; Use sedimentable matter after methyl alcohol and washed with de-ionized water centrifugation respectively 5 times ~ 10 times, then at temperature is-18 DEG C ~ 15 DEG C dry 24h ~ 48h, obtain ferrimanganic two-phase doped graphene;
Four, ferrimanganic two-phase doped graphene is added: joined by ferrimanganic two-phase doped graphene in the mixing solutions of the single persulphate after adjust ph and pretreated water, the reaction times is 15min ~ 240min, obtains the water containing ferrimanganic two-phase doped graphene;
The dosage of the ferrimanganic two-phase doped graphene described in step 4 is 1mg/L ~ 200mg/L;
Five, foreign field is adopted to be separated ferrimanganic two-phase doped graphene: to adopt foreign field to be separated the water containing ferrimanganic two-phase doped graphene, reclaim ferrimanganic two-phase doped graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim ferrimanganic two-phase doped graphene filter, again by the ferrimanganic two-phase doped graphene dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the ferrimanganic two-phase doped graphene after regenerating and removal water.
2. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the endocrine disrupter described in step one is a kind of or wherein several mixture in oestrone, 17 α-lynoral, 17 alpha-estradiols, 17 beta estradiols, trihydroxy-oestrin, stilboestrol, nonyl phenol, dihydroxyphenyl propane and octyl phenol.
3. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the power of the ultrasonic oscillation instrument described in step 3 is 1. 100W ~ 1000W.
4. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the external magnetic field strength described in step 4 is 0.01T ~ 1T.
5. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:(1000 ~ 5000).
6. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the quality of the single persulphate described in step one and the mass ratio of pretreated water are 1:(5000 ~ 8000).
7. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the dosage of the ferrimanganic two-phase doped graphene described in step 4 is 0.02mg/L ~ 10mg/L.
8. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the dosage of the ferrimanganic two-phase doped graphene described in step 4 is 10mg/L ~ 100mg/L.
9. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the dosage of the ferrimanganic two-phase doped graphene described in step 4 is 100mg/L ~ 200mg/L.
10. a kind of method utilizing ferrimanganic two-phase doped graphene to activate endocrine disrupter in single persulphate removal water according to claim 1, is characterized in that the particle diameter of the graphene oxide described in step 3 is 1. 15nm ~ 500nm.
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