CN104609607A - Method for removing endocrine disruptors in water by using cobalt-doped magnetic redox graphene to work in coordination with persulfate - Google Patents
Method for removing endocrine disruptors in water by using cobalt-doped magnetic redox graphene to work in coordination with persulfate Download PDFInfo
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- CN104609607A CN104609607A CN201510074018.0A CN201510074018A CN104609607A CN 104609607 A CN104609607 A CN 104609607A CN 201510074018 A CN201510074018 A CN 201510074018A CN 104609607 A CN104609607 A CN 104609607A
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Abstract
The invention discloses a method for removing endocrine disruptors in water by using cobalt-doped magnetic redox graphene to work in coordination with a persulfate and relates to a method for removing the endocrine disruptors in the water. The invention aims at solving the problems of poor removal effect, high cost and production of toxic byproducts of the existing method for removing the endocrine disruptors in the water. The method comprises the following steps: 1) mixing the persulfate with the water after pretreatment; 2) regulating a reaction pH value; 3) preparing cobalt-doped magnetic redox graphene; 4) putting cobalt-doped magnetic redox graphene; and 5) separating cobalt-doped magnetic redox graphene by adopting an external magnetic field, thereby completing the method for removing the endocrine disruptors in the water by using cobalt-doped magnetic redox graphene to work in coordination with the persulfate. By using the method disclosed by the invention, the removal rate in removal of the endocrine disruptors in the water can achieve 88%-95%. 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
Along with the development of science and technology, the chronic pollution of water resources is day by day serious, and meanwhile, growth in the living standard also makes people require increasingly stringent to the safety control of tap water.The exploitation of novel material new technology makes the pollutent in water surrounding day by day increase, water pollutant is as 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.
Oxidating chemicals conventional in current water treatment is primarily of liquid chlorine, dioxide peroxide, ozone and potassium permanganate etc.Compared to other several oxidating chemicals, potassium permanganate can not produce poisonous and hazardous disinfection byproduct (DBP), its reduzate Manganse Dioxide has absorption and helps the effects such as solidifying, the removal of pollutent in water body can be strengthened, and be easy to be separated, but the oxidation efficiency of potassium permanganate is low, obtain the removal effect that liquid chlorine, dioxide peroxide or ozone are identical, the oxidization time needed and dosage can increase, and therefore just bring the increase of capital construction cost and working cost.
Summary of the invention
The object of the invention is the method poor removal effect that will solve endocrine disrupter in existing removal water, the high problem with producing harmful by-products of cost, and a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water is provided.
Utilize the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with a method for endocrine disrupter in persulphate removal water, complete according to the following steps:
One, persulphate is mixed with pretreated water: 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 persulphate and pretreated water;
Persulphate described in step one is a kind of or wherein several mixture in Potassium Persulphate, ammonium persulphate, Sodium Persulfate and 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 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 persulphate and pretreated water is adjusted to 6.5 ~ 7.5, the mixing solutions of the persulphate after adjusted pH value and pretreated water under the condition of 150r/min ~ 200r/min;
Three, the magnetic oxygenated reduced graphene of cobalt doped 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 CoCl
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 iron cobalt 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
3.6H
2the mass ratio of O and urea is (0.01 ~ 100): 1;
Step 3 2. described in FeCl
36H
2o and CoCl
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 iron cobalt 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 iron cobalt 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 the magnetic oxygenated reduced graphene of cobalt doped;
Four, the magnetic oxygenated reduced graphene of cobalt doped is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by magnetic oxygenated for cobalt doped reduced graphene, reaction times is 15min ~ 240min, obtains the water containing the magnetic oxygenated reduced graphene of cobalt doped;
The dosage of the magnetic oxygenated reduced graphene of the cobalt doped described in step 4 is 1mg/L ~ 200mg/L;
Five, foreign field separation of cobalt doped magnetic redox Graphene is adopted: adopt foreign field to be separated the water containing the magnetic oxygenated reduced graphene of cobalt doped, Call Provision doped magnetic redox Graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim the magnetic oxygenated reduced graphene of cobalt doped filter, again by the magnetic oxygenated reduced graphene of the cobalt doped dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the magnetic oxygenated reduced graphene of cobalt doped after regenerating and removal water.
Principle of the present invention:
The active metal iron existed in surface of graphene oxide in the present invention and cobalt by with cross sulfide linkage generation transfer transport in persulphate, destroy the structure of over cure double bond, thus activating reaction occur, generate SO
4 -, active metal iron and cobalt self are then oxidized; On the other hand graphene oxide has huge specific surface area, its can adsorbed target organic while, a large amount of aerobic functional group in surface, as carboxyl the polyelectrons group that has can activate persulphate further, generate SO
4 -with HSO
4 -, thus accelerate the oxidative degradation of endocrine disrupter in water.
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 45% ~ 60% with other;
Two, the present invention has lower volatility, colourity and smell taste and can not change before and after reaction, and the magnetic oxygenated reduced graphene of cobalt doped of preparation at normal temperatures and pressures can stable existence;
Three, the magnetic oxygenated reduced graphene speed of response of the cobalt doped synthesized by the present invention is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the magnetic oxygenated reduced graphene of the cobalt doped 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 88% ~ 95%.
The present invention can remove remaining endocrine disrupter in water.
Embodiment
Embodiment one: a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water completes according to the following steps:
One, persulphate is mixed with pretreated water: 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 persulphate and pretreated water;
Persulphate described in step one is a kind of or wherein several mixture in Potassium Persulphate, ammonium persulphate, Sodium Persulfate and 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 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 persulphate and pretreated water is adjusted to 6.5 ~ 7.5, the mixing solutions of the persulphate after adjusted pH value and pretreated water under the condition of 150r/min ~ 200r/min;
Three, the magnetic oxygenated reduced graphene of cobalt doped 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 CoCl
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 iron cobalt 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 CoCl
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 iron cobalt 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 iron cobalt 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 the magnetic oxygenated reduced graphene of cobalt doped;
Four, the magnetic oxygenated reduced graphene of cobalt doped is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by magnetic oxygenated for cobalt doped reduced graphene, reaction times is 15min ~ 240min, obtains the water containing the magnetic oxygenated reduced graphene of cobalt doped;
The dosage of the magnetic oxygenated reduced graphene of the cobalt doped described in step 4 is 1mg/L ~ 200mg/L;
Five, foreign field separation of cobalt doped magnetic redox Graphene is adopted: adopt foreign field to be separated the water containing the magnetic oxygenated reduced graphene of cobalt doped, Call Provision doped magnetic redox Graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim the magnetic oxygenated reduced graphene of cobalt doped filter, again by the magnetic oxygenated reduced graphene of the cobalt doped dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the magnetic oxygenated reduced graphene of cobalt doped after regenerating and removal water.
Principle of the present invention:
The active metal iron existed in surface of graphene oxide in the present invention and cobalt by with cross sulfide linkage generation transfer transport in persulphate, destroy the structure of over cure double bond, thus activating reaction occur, generate SO
4 -, active metal iron and cobalt self are then oxidized; On the other hand graphene oxide has huge specific surface area, its can adsorbed target organic while, a large amount of aerobic functional group in surface, as carboxyl the polyelectrons group that has can activate persulphate further, generate SO
4 -with HSO
4 -, thus accelerate the oxidative degradation of endocrine disrupter in water.
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 45% ~ 60% with other;
Two, present embodiment has lower volatility, colourity and smell taste and can not change before and after reaction, and the magnetic oxygenated reduced graphene of cobalt doped of preparation at normal temperatures and pressures can stable existence;
Three, the magnetic oxygenated reduced graphene speed of response of the cobalt doped synthesized by present embodiment is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the magnetic oxygenated reduced graphene of the cobalt doped 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 88% ~ 95%.
The present invention 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 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 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 magnetic oxygenated reduced graphene of the cobalt doped 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 magnetic oxygenated reduced graphene of the cobalt doped 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 magnetic oxygenated reduced graphene of the cobalt doped 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 the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water completes according to the following steps:
One, persulphate is mixed with pretreated water: 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 persulphate and pretreated water;
Persulphate described in step one is Sodium Persulfate;
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 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 persulphate and pretreated water is adjusted to 6.5, the mixing solutions of the persulphate after adjusted pH value and pretreated water under the condition of 180r/min;
Three, the magnetic oxygenated reduced graphene of cobalt doped 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 CoCl
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 iron cobalt 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 CoCl
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 iron cobalt 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 the magnetic oxygenated reduced graphene of cobalt doped;
Four, the magnetic oxygenated reduced graphene of cobalt doped is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by magnetic oxygenated for cobalt doped reduced graphene, reaction times is 60min, obtains the water containing the magnetic oxygenated reduced graphene of cobalt doped;
The dosage of the magnetic oxygenated reduced graphene of the cobalt doped described in step 4 is 10mg/L;
External magnetic field strength described in step 4 is 0.03T;
Five, foreign field separation of cobalt doped magnetic redox Graphene is adopted: adopt foreign field to be separated the water containing the magnetic oxygenated reduced graphene of cobalt doped, Call Provision doped magnetic redox Graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim the magnetic oxygenated reduced graphene of cobalt doped filter, again by the magnetic oxygenated reduced graphene of the cobalt doped dry 24h at temperature is 50 DEG C after filtration, obtain the water of endocrine disrupter in the magnetic oxygenated reduced graphene of cobalt doped 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 48% with other;
Two, this test has lower volatility, colourity and smell taste and can not change before and after reaction, and the magnetic oxygenated reduced graphene of cobalt doped of preparation at normal temperatures and pressures can stable existence;
Three, the magnetic oxygenated reduced graphene speed of response of the cobalt doped synthesized by this test is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the magnetic oxygenated reduced graphene of the cobalt doped 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 93%.
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 93%, prove that test one is for endocrine disrupter excellent in removal pretreated water.
Claims (10)
1. utilize the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with a method for endocrine disrupter in persulphate removal water, it is characterized in that a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water completes according to the following steps:
One, persulphate is mixed with pretreated water: 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 persulphate and pretreated water;
Persulphate described in step one is a kind of or wherein several mixture in Potassium Persulphate, ammonium persulphate, Sodium Persulfate and 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 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 persulphate and pretreated water is adjusted to 6.5 ~ 7.5, the mixing solutions of the persulphate after adjusted pH value and pretreated water under the condition of 150r/min ~ 200r/min;
Three, the magnetic oxygenated reduced graphene of cobalt doped 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 CoCl
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 iron cobalt 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 CoCl
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 iron cobalt 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 iron cobalt 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 the magnetic oxygenated reduced graphene of cobalt doped;
Four, the magnetic oxygenated reduced graphene of cobalt doped is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by magnetic oxygenated for cobalt doped reduced graphene, reaction times is 15min ~ 240min, obtains the water containing the magnetic oxygenated reduced graphene of cobalt doped;
The dosage of the magnetic oxygenated reduced graphene of the cobalt doped described in step 4 is 1mg/L ~ 200mg/L;
Five, foreign field separation of cobalt doped magnetic redox Graphene is adopted: adopt foreign field to be separated the water containing the magnetic oxygenated reduced graphene of cobalt doped, Call Provision doped magnetic redox Graphene, re-use aperture be 0.45 μm glass fibre membrane to reclaim the magnetic oxygenated reduced graphene of cobalt doped filter, again by the magnetic oxygenated reduced graphene of the cobalt doped dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the magnetic oxygenated reduced graphene of cobalt doped after regenerating and removal water.
2. a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in 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 the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in 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 the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in 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 the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water according to claim 1, is characterized in that the quality of the persulphate described in step one and the mass ratio of pretreated water are 1:(1000 ~ 5000).
6. a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water according to claim 1, is characterized in that the quality of the persulphate described in step one and the mass ratio of pretreated water are 1:(5000 ~ 8000).
7. a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water according to claim 1, is characterized in that the dosage of the magnetic oxygenated reduced graphene of cobalt doped described in step 4 is 0.02mg/L ~ 10mg/L.
8. a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water according to claim 1, is characterized in that the dosage of the magnetic oxygenated reduced graphene of cobalt doped described in step 4 is 10mg/L ~ 100mg/L.
9. a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in persulphate removal water according to claim 1, is characterized in that the dosage of the magnetic oxygenated reduced graphene of cobalt doped described in step 4 is 100mg/L ~ 200mg/L.
10. a kind of method utilizing the magnetic oxygenated reduced graphene of cobalt doped to work in coordination with endocrine disrupter in 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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| CN107754807A (en) * | 2017-12-01 | 2018-03-06 | 四川大学 | A kind of method that estrogen in water removal is removed using sodium peroxydisulfate and magnetic photocatalyst |
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