CN104609607B - A kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water - Google Patents
A kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water Download PDFInfo
- Publication number
- CN104609607B CN104609607B CN201510074018.0A CN201510074018A CN104609607B CN 104609607 B CN104609607 B CN 104609607B CN 201510074018 A CN201510074018 A CN 201510074018A CN 104609607 B CN104609607 B CN 104609607B
- Authority
- CN
- China
- Prior art keywords
- persulfate
- redox graphene
- cobalt doped
- water
- doped magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Water Treatment By Sorption (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Utilize the collaborative persulfate of cobalt doped magnetic redox Graphene to remove a method for incretion interferent in water, it relates to a kind of method of removing incretion interferent in water. The object of the invention is to solve the method poor removal effect of incretion interferent in existing removal water, cost height and generation have the problem of toxic byproduct. Method: one, persulfate is mixed with pretreated water; Two, regulate pH value in reaction; Three, prepare cobalt doped magnetic redox Graphene; Four, add cobalt doped magnetic redox Graphene; Five, adopt external magnetic field separation of cobalt doped magnetic redox Graphene, complete a kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water. The clearance that uses method of the present invention to remove incretion interferent in water can reach 88%～95%. The present invention can remove remaining incretion interferent in water.
Description
Technical field
The present invention relates to a kind of method of removing incretion interferent in water.
Background technology
Along with scientific and technical development, the chronic pollution of water resource is day by day serious, and meanwhile, growth in the living standard alsoMake people require increasingly stringent to the safety guarantee of drinking water. The exploitation of new material new technology makes the pollutant day in water environmentBenefit increases, water pollutant as incretion interferent (Endocrinedisruptingchemicals, EDCs) be by notEnter water environment through sanitary sewage, pharmacy waste water or the livestock aquatic products industry muck runoff processed completely, and in water body after enrichmentConcentration can increase hundreds of times. Even and other EDCs of trace level also can cause long term exposure human body and organism generation whereinThe harm such as cancer, mutagenesis and interference reproductive system and hormone secretion.
Oxidation medicament conventional in water treatment is at present mainly by liquid chlorine, chlorine dioxide, ozone and potassium permanganate etc. ThanOther several oxidation medicaments, potassium permanganate can not produce poisonous and hazardous DBPs, and its reduzate manganese dioxide hasAdsorb and help the effects such as solidifying, can strengthen the removal of pollutant in water body, and being easy to separate, but the oxidation efficiency of potassium permanganateLow, obtain the removal effect that liquid chlorine, chlorine dioxide or ozone are identical, the oxidization time and the dosage that need can increase, because ofThis has just brought the increase of capital construction cost and operating cost.
Summary of the invention
The object of the invention is to solve the method poor removal effect of incretion interferent in existing removal water, cost high andGeneration has the problem of toxic byproduct, and provides one to utilize the collaborative persulfate of cobalt doped magnetic redox Graphene to remove waterThe method of middle incretion interferent.
A kind of side that utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in waterMethod, completes according to the following steps:
One, persulfate is mixed with pretreated water: persulfate is mixed with pretreated water, more at room temperature andMixing speed is to stir 20min～45min under the condition of 160r/min～250r/min, obtains persulfate and pretreated waterMixed solution;
Persulfate described in step 1 is the one in potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and persulfuric acid calciumOr several mixture wherein;
In pretreated water described in step 1, the concentration of incretion interferent is 0.02mg/L～100mg/L;
The quality of the persulfate described in step 1 and the mass ratio of pretreated water are 1:(1000～10000);
Two, regulate pH value in reaction: under the condition that low whipping speed is 150r/min～200r/min, use 0.1mol/L～The perchloric acid of 100mol/L and the sodium hydroxide solution of 0.1mol/L～100mol/L are mixed by persulfate and pretreated waterThe pH value of closing solution is adjusted to 6.5～7.5, the persulfate after adjusted pH value and the mixed solution of pretreated water;
Three, prepare cobalt doped magnetic redox Graphene:
1., graphene oxide is joined to mass fraction is in 97%～99% ethylene glycol solution, re-uses ultrasonic waveThe concussion of concussion instrument disperses 3h～4h, obtains the mixed solution of graphene oxide and ethylene glycol;
The quality of the graphene oxide of step 3 described in 1. and the ethylene glycol solution that mass fraction is 97%～99%Volume ratio is (0.001g～10g): 1mL;
2., be to heat 20min～45min at 60 DEG C～75 DEG C by the mixed solution of natrium citricum and ethylene glycol in temperature,Obtain heating after natrium citricum and the mixed solution of ethylene glycol; Again to heating after natrium citricum and the mixed solution of ethylene glycolIn add FeCl3·6H2O, urea and CoCl2·6H2O, then be 100r/min～250r/min in room temperature and magnetic agitation speedCondition lower magnetic force stir 2h～4h, the natrium citricum that obtains containing iron cobalt and the mixed solution of ethylene glycol;
In the mixed solution of the natrium citricum of step 3 described in 2. and ethylene glycol the concentration of natrium citricum be 60mg/mL～200mg/mL；
Volume and the FeCl of the natrium citricum after the heating of step 3 described in 2. and the mixed solution of ethylene glycol3·6H2OMass ratio be (1mL～1000mL): 1g;
The FeCl of step 3 described in 2.3.6H2The mass ratio of O and urea is (0.01～100): 1;
The FeCl of step 3 described in 2.3·6H2O and CoCl2·6H2The mass ratio of O is (0.01～1000): 1;
3., that the mixed solution of graphene oxide and ethylene glycol is molten with mixing of the natrium citricum that contains iron cobalt and ethylene glycolLiquid mixes, then joins in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), then by the sealing of stainless steel autoclave,Be to react 12h～48h at 200 DEG C～230 DEG C by the stainless steel autoclave of sealing in temperature again, then naturally cool to chamberTemperature, obtains black suspension;
The mixed solution of the graphene oxide of step 3 described in 3. and ethylene glycol and the natrium citricum and the second that contain iron cobaltThe volume ratio of the mixed solution of glycol is (0.1～50): 1;
4., by black suspension centrifugal speed be under 6500r/min～8000r/min, carry out centrifugation 10min～30min, obtains the deposit after centrifugation; Use respectively the deposit after methyl alcohol and washed with de-ionized water centrifugation5 times～10 times, then be dry 24h～48h at-18 DEG C～15 DEG C in temperature, cobalt doped magnetic redox Graphene obtained;
Four, add cobalt doped magnetic redox Graphene: cobalt doped magnetic redox Graphene is joined to adjustingIn persulfate after pH value and the mixed solution of pretreated water, the reaction time is 15min～240min, obtains containing cobalt and mixesThe water of assorted magnetic oxygenated reduced graphene;
The dosage of the cobalt doped magnetic redox Graphene described in step 4 is 1mg/L～200mg/L;
Five, adopt external magnetic field separation of cobalt doped magnetic redox Graphene: adopt external magnetic field to containing cobalt doped magneticThe water of redox Graphene separates, and reclaims cobalt doped magnetic redox Graphene, and re-using aperture is 0.45 μ m'sGlass fibre membrane filters the cobalt doped magnetic redox Graphene reclaiming, then by the cobalt doped magnetic oxidation after filteringReduced graphene is dry 12h～48h at 50 DEG C～75 DEG C in temperature, obtains the cobalt doped magnetic redox graphite after regenerationThe water of incretion interferent in alkene and removal water.
Principle of the present invention:
The active metal iron existing on graphene oxide surface in the present invention and cobalt by with persulfate in the sulfide linkage of crossing send outRaw electronics shifts, and destroys the structure of the two keys of over cure, thereby activating reaction occurs, and generates SO4 -, and active metal iron and cobalt selfBe oxidized; Graphene oxide has huge specific area on the other hand, and it can adsorb the organic while of target, tableThe a large amount of aerobic of face functional group, as the polyelectron group that carboxyl had can further activate persulfate, generates SO4 -WithHSO4 -Thereby, accelerate the oxidative degradation of incretion interferent in water.
Advantage of the present invention:
One, the inventive method is simple to operate, with low cost, compared with other methods of removing incretion interferent in water,Reduce cost 45%～60%;
Two, the present invention has lower volatility, reacts front and back colourity and smell taste can not change the cobalt doping of preparationMagnetic oxygenated reduced graphene at normal temperatures and pressures can stable existence;
Three, the cobalt doped magnetic redox Graphene reaction speed of synthesized of the present invention is fast, and accessory substance nontoxicity, canEffectively remove incretion interferent in water;
Four, the cobalt doped magnetic redox Graphene of synthesized of the present invention can be easier to reclaim and regeneration;
Five, the clearance that uses method of the present invention to remove incretion interferent in water can reach 88%～95%.
The present invention can remove remaining incretion interferent in water.
Detailed description of the invention
Detailed description of the invention one: in one is utilized in the collaborative persulfate removal of cobalt doped magnetic redox Graphene waterThe method of secretion chaff interference completes according to the following steps:
One, persulfate is mixed with pretreated water: persulfate is mixed with pretreated water, more at room temperature andMixing speed is to stir 20min～45min under the condition of 160r/min～250r/min, obtains persulfate and pretreated waterMixed solution;
Persulfate described in step 1 is the one in potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and persulfuric acid calciumOr several mixture wherein;
In pretreated water described in step 1, the concentration of incretion interferent is 0.02mg/L～100mg/L;
The quality of the persulfate described in step 1 and the mass ratio of pretreated water are 1:(1000～10000);
Two, regulate pH value in reaction: under the condition that low whipping speed is 150r/min～200r/min, use 0.1mol/L～The perchloric acid of 100mol/L and the sodium hydroxide solution of 0.1mol/L～100mol/L are mixed by persulfate and pretreated waterThe pH value of closing solution is adjusted to 6.5～7.5, the persulfate after adjusted pH value and the mixed solution of pretreated water;
Three, prepare cobalt doped magnetic redox Graphene:
1., graphene oxide is joined to mass fraction is in 97%～99% ethylene glycol solution, re-uses ultrasonic waveThe concussion of concussion instrument disperses 3h～4h, obtains the mixed solution of graphene oxide and ethylene glycol;
The quality of the graphene oxide of step 3 described in 1. and the ethylene glycol solution that mass fraction is 97%～99%Volume ratio is (0.001g～10g): 1mL;
2., be to heat 20min～45min at 60 DEG C～75 DEG C by the mixed solution of natrium citricum and ethylene glycol in temperature,Obtain heating after natrium citricum and the mixed solution of ethylene glycol; Again to heating after natrium citricum and the mixed solution of ethylene glycolIn add FeCl3·6H2O, urea and CoCl2·6H2O, then be 100r/min～250r/min in room temperature and magnetic agitation speedCondition lower magnetic force stir 2h～4h, the natrium citricum that obtains containing iron cobalt and the mixed solution of ethylene glycol;
In the mixed solution of the natrium citricum of step 3 described in 2. and ethylene glycol the concentration of natrium citricum be 60mg/mL～200mg/mL；
Volume and the FeCl of the natrium citricum after the heating of step 3 described in 2. and the mixed solution of ethylene glycol3·6H2OMass ratio be (1mL～1000mL): 1g;
The FeCl of step 3 described in 2.3·6H2The mass ratio of O and urea is (0.01～100): 1;
The FeCl of step 3 described in 2.3·6H2O and CoCl2·6H2The mass ratio of O is (0.01～1000): 1;
3., that the mixed solution of graphene oxide and ethylene glycol is molten with mixing of the natrium citricum that contains iron cobalt and ethylene glycolLiquid mixes, then joins in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), then by the sealing of stainless steel autoclave,Be to react 12h～48h at 200 DEG C～230 DEG C by the stainless steel autoclave of sealing in temperature again, then naturally cool to chamberTemperature, obtains black suspension;
The mixed solution of the graphene oxide of step 3 described in 3. and ethylene glycol and the natrium citricum and the second that contain iron cobaltThe volume ratio of the mixed solution of glycol is (0.1～50): 1;
4., by black suspension centrifugal speed be under 6500r/min～8000r/min, carry out centrifugation 10min～30min, obtains the deposit after centrifugation; Use respectively the deposit after methyl alcohol and washed with de-ionized water centrifugation5 times～10 times, then be dry 24h～48h at-18 DEG C～15 DEG C in temperature, cobalt doped magnetic redox Graphene obtained;
Four, add cobalt doped magnetic redox Graphene: cobalt doped magnetic redox Graphene is joined to adjustingIn persulfate after pH value and the mixed solution of pretreated water, the reaction time is 15min～240min, obtains containing cobalt and mixesThe water of assorted magnetic oxygenated reduced graphene;
The dosage of the cobalt doped magnetic redox Graphene described in step 4 is 1mg/L～200mg/L;
Five, adopt external magnetic field separation of cobalt doped magnetic redox Graphene: adopt external magnetic field to containing cobalt doped magneticThe water of redox Graphene separates, and reclaims cobalt doped magnetic redox Graphene, and re-using aperture is 0.45 μ m'sGlass fibre membrane filters the cobalt doped magnetic redox Graphene reclaiming, then by the cobalt doped magnetic oxidation after filteringReduced graphene is dry 12h～48h at 50 DEG C～75 DEG C in temperature, obtains the cobalt doped magnetic redox graphite after regenerationThe water of incretion interferent in alkene and removal water.
Principle of the present invention:
The active metal iron existing on graphene oxide surface in the present invention and cobalt by with persulfate in the sulfide linkage of crossing send outRaw electronics shifts, and destroys the structure of the two keys of over cure, thereby activating reaction occurs, and generates SO4 -, and active metal iron and cobalt selfBe oxidized; Graphene oxide has huge specific area on the other hand, and it can adsorb the organic while of target, tableThe a large amount of aerobic of face functional group, as the polyelectron group that carboxyl had can further activate persulfate, generates SO4 -WithHSO4 -Thereby, accelerate the oxidative degradation of incretion interferent in water.
The advantage of present embodiment:
One, present embodiment method is simple to operate, with low cost, with the method phase of incretion interferent in other removal waterRatio, has reduced cost 45%～60%;
Two, present embodiment has lower volatility, reacts front and back colourity and smell taste can not change the cobalt of preparationDoped magnetic redox Graphene at normal temperatures and pressures can stable existence;
Three, the cobalt doped magnetic redox Graphene reaction speed of present embodiment synthesized is fast, accessory substance nontoxicity,Can effectively remove incretion interferent in water;
Four, the cobalt doped magnetic redox Graphene of present embodiment synthesized can be easier to reclaim and regeneration;
Five, in the method removal water of use present embodiment, the clearance of incretion interferent can reach 88%～95%.
The present invention can remove remaining incretion interferent in water.
Detailed description of the invention two: present embodiment and detailed description of the invention one difference are: interior point described in step 1Secrete chaff interference and be oestrone, 17 α-ethinyl estradiol, 17 alpha-estradiols, 17 beta estradiols, estriol, diethylstilbestrol, nonyl phenol,A kind of in bisphenol-A and octyl phenol or wherein several mixture. Other steps are identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two difference is: step 3 1. inThe power of described ultrasonic oscillation instrument is 100W～1000W. Other steps are identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three difference is: institute in step 4The external magnetic field intensity of stating is 0.01T～1T. Other steps are identical with detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four difference is: institute in step 1The quality of the persulfate of stating and the mass ratio of pretreated water are 1:(1000～5000). Other steps and detailed description of the inventionOne to four is identical.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five difference is: institute in step 1The quality of the persulfate of stating and the mass ratio of pretreated water are 1:(5000～8000). Other steps and detailed description of the inventionOne to five is identical.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six difference is: institute in step 4The dosage of the cobalt doped magnetic redox Graphene of stating is 0.02mg/L～10mg/L. Other steps and detailed description of the inventionOne to six is identical.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven difference is: institute in step 4The dosage of the cobalt doped magnetic redox Graphene of stating is 10mg/L～100mg/L. Other steps and detailed description of the inventionOne to seven is identical.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight difference is: institute in step 4The dosage of the cobalt doped magnetic redox Graphene of stating is 100mg/L～200mg/L. Other steps and detailed description of the inventionOne to eight is identical.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine difference is: step 3 1. inThe particle diameter of described graphene oxide is 15nm～500nm. Other steps are identical with detailed description of the invention one to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: one is utilized the collaborative persulfate of cobalt doped magnetic redox Graphene to remove endocrine in water and disturbedThe method of thing completes according to the following steps:
One, persulfate is mixed with pretreated water: persulfate is mixed with pretreated water, more at room temperature andMixing speed is to stir 30min under the condition of 180r/min, obtains the mixed solution of persulfate and pretreated water;
Persulfate described in step 1 is sodium peroxydisulfate;
Incretion interferent described in step 1 is estriol;
In pretreated water described in step 1, the concentration of incretion interferent is 5mg/L;
The quality of the persulfate described in step 1 and the mass ratio of pretreated water are 1:1500;
Two, regulate pH value in reaction: under the condition that low whipping speed is 180r/min, use 0.1mol/L perchloric acid andThe sodium hydroxide solution of 0.1mol/L is adjusted to 6.5 by the pH value of the mixed solution of persulfate and pretreated water, is adjustedPersulfate after joint pH value and the mixed solution of pretreated water;
Three, prepare cobalt doped magnetic redox Graphene
1., graphene oxide is joined to mass fraction is in 99% ethylene glycol solution, re-uses ultrasonic oscillation instrumentConcussion disperses 3h, obtains the mixed solution of graphene oxide and ethylene glycol;
The particle diameter of the graphene oxide of step 3 described in is 1. 25nm;
The quality of graphene oxide and the volume ratio of ethylene glycol solution that mass fraction be 99% of step 3 described in 1.For 0.005g:1mL;
The power of the ultrasonic oscillation instrument of step 3 described in is 1. 200W;
2. be, to heat 20min at 60 DEG C by the mixed solution of 50mL natrium citricum and ethylene glycol in temperature, after obtaining heatingNatrium citricum and the mixed solution of ethylene glycol; In the natrium citricum after heating and the mixed solution of ethylene glycol, add againFeCl3·6H2O, urea and CoCl2·6H2O, then the condition lower magnetic force that is 200r/min in room temperature and magnetic agitation speed stirs2h, the natrium citricum that obtains containing iron cobalt and the mixed solution of ethylene glycol;
In the mixed solution of the natrium citricum of step 3 described in 2. and ethylene glycol, the concentration of natrium citricum is 60mg/mL;
Volume and the FeCl of the natrium citricum after the heating of step 3 described in 2. and the mixed solution of ethylene glycol3·6H2OMass ratio be 50mL:1g;
The FeCl of step 3 described in 2.3·6H2The mass ratio of O and urea is 50:1;
The FeCl of step 3 described in 2.3·6H2O and CoCl2·6H2The mass ratio of O is 5:1;
3. the natrium citricum and the ethylene glycol that, the mixed solution of 50mL graphene oxide and ethylene glycol and 50mL are contained to iron cobaltMixed solution mix, then join in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), then by anti-stainless steel high pressureAnswer still sealing, then be to react 12h at 200 DEG C by the stainless steel autoclave of sealing in temperature, then naturally cool to room temperature,To black suspension;
4., be under 6500r/min, to carry out centrifugation 10min by black suspension in centrifugal speed, obtain centrifugationAfter deposit; Use respectively deposit after methyl alcohol and washed with de-ionized water centrifugation 6 times, then be-18 in temperatureFreeze drying 24h at DEG C, obtains cobalt doped magnetic redox Graphene;
Four, add cobalt doped magnetic redox Graphene: cobalt doped magnetic redox Graphene is joined to adjustingIn persulfate after pH value and the mixed solution of pretreated water, the reaction time is 60min, obtains containing cobalt doped magnetic oxygenChange the water of reduced graphene;
The dosage of the cobalt doped magnetic redox Graphene described in step 4 is 10mg/L;
External magnetic field intensity described in step 4 is 0.03T;
Five, adopt external magnetic field separation of cobalt doped magnetic redox Graphene: adopt external magnetic field to containing cobalt doped magneticThe water of redox Graphene separates, and reclaims cobalt doped magnetic redox Graphene, and re-using aperture is 0.45 μ m'sGlass fibre membrane filters the cobalt doped magnetic redox Graphene reclaiming, then by the cobalt doped magnetic oxidation after filteringReduced graphene is dry 24h at 50 DEG C in temperature, obtains the cobalt doped magnetic redox Graphene after regeneration and removes waterThe water of middle incretion interferent.
The advantage of this test:
One, this test method is simple to operate, with low cost, compared with other methods of removing incretion interferent in water,Reduce cost 48%;
Two, this test has lower volatility, reacts front and back colourity and smell taste can not change the cobalt doping of preparationMagnetic oxygenated reduced graphene at normal temperatures and pressures can stable existence;
Three, the cobalt doped magnetic redox Graphene reaction speed of this test synthesized is fast, and accessory substance nontoxicity, canEffectively remove incretion interferent in water;
Four, the cobalt doped magnetic redox Graphene of this test synthesized can be easier to reclaim and regeneration;
Five, use the method for this test to remove the clearance of incretion interferent in water and can reach 93%.
Test two: use active carbon to remove the contrast test of incretion interferent in water, specifically complete according to the following steps:
Use the incretion interferent 24h in the ature of coal granular activated carbon absorption pretreated water that particle diameter is 4nm～100nm,Obtain removing the water of incretion interferent in water;
In described pretreated water, incretion interferent is estriol, and the concentration of estriol is 5mg/L.
In test two, use endocrine in the ature of coal granular activated carbon Adsorption pretreated water that particle diameter is 4nm～100nmThe clearance of chaff interference is 53%.
Test three: use ultraviolet light and H2O2Remove the contrast test of incretion interferent in water, specifically according to the following stepsComplete:
In pretreated water, add the H that concentration is 10mmol/L2O2, at ultraviolet light intensity 250uW/cm2UV-irradiationPretreated water 0.5h, obtains removing the water of incretion interferent in water;
In described pretreated water, incretion interferent is estriol, and the concentration of estriol is 5mg/L;
Test three is used ultraviolet light and H2O2The clearance of removing incretion interferent in pretreated water is 68%.
Test four: use sodium peroxydisulfate to remove the contrast test of incretion interferent in water, specifically complete according to the following stepsBecome:
To the sodium peroxydisulfate that adds 2mg/L in pretreated water, reaction 2h, obtains removing the water of incretion interferent in water;
In described pretreated water, incretion interferent is estriol, and the concentration of estriol is 5mg/L;
The clearance that test four is used sodium peroxydisulfate to remove incretion interferent in pretreated water is 9%.
Test two use ature of coal granular activated carbons remove incretion interferent in pretreated waters, test three use ultraviolet lights andH2O2Removing incretion interferent and test four in pretreated water uses sodium peroxydisulfates to remove incretion interferent in pretreated watersClearance is respectively 53%, 68% and 9%, and the clearance of test one is 93%, proves that test one is for removing pretreated waterMiddle incretion interferent effect is splendid.
Claims (10)
1. utilize the collaborative persulfate of cobalt doped magnetic redox Graphene to remove a method for incretion interferent in water,It is characterized in that a kind of collaborative persulfate of cobalt doped magnetic redox Graphene that utilizes removes incretion interferent in waterMethod completes according to the following steps:
One, persulfate is mixed with pretreated water: persulfate is mixed with pretreated water, more at room temperature and stirSpeed is to stir 20min～45min under the condition of 160r/min～250r/min, obtains the mixed of persulfate and pretreated waterClose solution;
Persulfate described in step 1 is a kind of in potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate and persulfuric acid calcium or itsIn several mixtures;
In pretreated water described in step 1, the concentration of incretion interferent is 0.02mg/L～100mg/L;
The quality of the persulfate described in step 1 and the mass ratio of pretreated water are 1:(1000～10000);
Two, regulate pH value in reaction: under the condition that low whipping speed is 150r/min～200r/min, use 0.1mol/L～The perchloric acid of 100mol/L and the sodium hydroxide solution of 0.1mol/L～100mol/L are mixed by persulfate and pretreated waterThe pH value of closing solution is adjusted to 6.5～7.5, the persulfate after adjusted pH value and the mixed solution of pretreated water;
Three, prepare cobalt doped magnetic redox Graphene:
1., graphene oxide is joined to mass fraction is in 97%～99% ethylene glycol solution, re-uses ultrasonic oscillationInstrument concussion disperses 3h～4h, obtains the mixed solution of graphene oxide and ethylene glycol;
The quality of graphene oxide and the volume of ethylene glycol solution that mass fraction be 97%～99% of step 3 described in 1.Than being (0.001g～10g): 1mL;
2., be to heat 20min～45min at 60 DEG C～75 DEG C by the mixed solution of natrium citricum and ethylene glycol in temperature, obtainNatrium citricum after heating and the mixed solution of ethylene glycol; In the natrium citricum after heating and the mixed solution of ethylene glycol, add againEnter FeCl3.6H2O, urea and CoCl2·6H2O, then the bar that is 100r/min～250r/min in room temperature and magnetic agitation speedPart lower magnetic force stirs 2h～4h, the natrium citricum that obtains containing iron cobalt and the mixed solution of ethylene glycol;
In the mixed solution of the natrium citricum of step 3 described in 2. and ethylene glycol the concentration of natrium citricum be 60mg/mL～200mg/mL；
Volume and the FeCl of the natrium citricum after the heating of step 3 described in 2. and the mixed solution of ethylene glycol3.6H2The quality of OThan being (1mL～1000mL): 1g;
The FeCl of step 3 described in 2.3.6H2The mass ratio of O and urea is (0.01～100): 1;
The FeCl of step 3 described in 2.3.6H2O and CoCl2·6H2The mass ratio of O is (0.01～1000): 1;
3., that the mixed solution of graphene oxide and ethylene glycol is mixed with the mixed solution of the natrium citricum that contains iron cobalt and ethylene glycolClose, then join in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), then by the sealing of stainless steel autoclave, then willThe stainless steel autoclave of sealing is to react 12h～48h at 200 DEG C～230 DEG C in temperature, then naturally cools to room temperature,To black suspension;
The mixed solution of the graphene oxide of step 3 described in 3. and ethylene glycol and the natrium citricum and the ethylene glycol that contain iron cobaltThe volume ratio of mixed solution be (0.1～50): 1;
4., by black suspension centrifugal speed be under 6500r/min～8000r/min, carry out centrifugation 10min～30min, obtains the deposit after centrifugation; Use respectively the deposit after methyl alcohol and washed with de-ionized water centrifugation5 times～10 times, then be dry 24h～48h at-18 DEG C～15 DEG C in temperature, cobalt doped magnetic redox Graphene obtained;
Four, add cobalt doped magnetic redox Graphene: cobalt doped magnetic redox Graphene is joined and regulates pH valueAfter persulfate and the mixed solution of pretreated water in, the reaction time is 15min～240min, obtains containing cobalt doping magneticThe water of property redox Graphene;
The dosage of the cobalt doped magnetic redox Graphene described in step 4 is 1mg/L～200mg/L;
Five, adopt external magnetic field separation of cobalt doped magnetic redox Graphene: adopt external magnetic field to containing the oxidation of cobalt doped magneticThe water of reduced graphene separates, and reclaims cobalt doped magnetic redox Graphene, re-uses the glass that aperture is 0.45 μ mTunica fibrosa filters the cobalt doped magnetic redox Graphene reclaiming, then by the cobalt doped magnetic redox after filteringGraphene is dry 12h～48h at 50 DEG C～75 DEG C in temperature, obtain cobalt doped magnetic redox Graphene after regeneration andRemove the water of incretion interferent in water.
2. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, is characterized in that the incretion interferent described in step 1 is oestrone, 17 α-acetenyl female twoOne in alcohol, 17 alpha-estradiols, 17 beta estradiols, estriol, diethylstilbestrol, nonyl phenol, bisphenol-A and octyl phenol or wherein severalThe mixture of planting.
3. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, the power that it is characterized in that the ultrasonic oscillation instrument described in step 3 is 1. 100W～1000W.
4. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, is characterized in that the external magnetic field intensity described in step 5 is 0.01T～1T.
5. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, is characterized in that the quality of the persulfate described in step 1 and the mass ratio of pretreated waterFor 1:(1000～5000).
6. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, is characterized in that the quality of the persulfate described in step 1 and the mass ratio of pretreated waterFor 1:(5000～8000).
7. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, is characterized in that the dosage of the cobalt doped magnetic redox Graphene described in step 4 is0.02mg/L～10mg/L。
8. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, is characterized in that the dosage of the cobalt doped magnetic redox Graphene described in step 4 is10mg/L～100mg/L。
9. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove in waterThe method of incretion interferent, is characterized in that the dosage of the cobalt doped magnetic redox Graphene described in step 4 is100mg/L～200mg/L。
10. one according to claim 1 utilizes the collaborative persulfate of cobalt doped magnetic redox Graphene to remove waterThe method of middle incretion interferent, the particle diameter that it is characterized in that the graphene oxide described in step 3 is 1. 15nm～500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510074018.0A CN104609607B (en) | 2015-02-11 | 2015-02-11 | A kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510074018.0A CN104609607B (en) | 2015-02-11 | 2015-02-11 | A kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104609607A CN104609607A (en) | 2015-05-13 |
| CN104609607B true CN104609607B (en) | 2016-05-11 |
Family
ID=53144305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510074018.0A Expired - Fee Related CN104609607B (en) | 2015-02-11 | 2015-02-11 | A kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104609607B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693976B (en) * | 2016-12-23 | 2019-08-13 | 四川大学 | A kind of preparation of the heterogeneous organo-metallic catalyst containing Ni for active oxidation agent degradation of dye waste water |
| 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 |
| CN109019580A (en) * | 2018-09-27 | 2018-12-18 | 深圳天元羲王材料科技有限公司 | A kind of graphene purifying plant and method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811696A (en) * | 2010-04-28 | 2010-08-25 | 东南大学 | Graphene-supported cobaltosic oxide nano composite material and preparation method thereof |
| CN103012786A (en) * | 2012-11-12 | 2013-04-03 | 南昌航空大学 | Preparation method of graphene/CoFe2O4/polyaniline composite absorbing material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000246277A (en) * | 1999-03-04 | 2000-09-12 | Nichibaku:Kk | Water purifying material using waste containing magnetic component and water purifying method using the same |
-
2015
- 2015-02-11 CN CN201510074018.0A patent/CN104609607B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811696A (en) * | 2010-04-28 | 2010-08-25 | 东南大学 | Graphene-supported cobaltosic oxide nano composite material and preparation method thereof |
| CN103012786A (en) * | 2012-11-12 | 2013-04-03 | 南昌航空大学 | Preparation method of graphene/CoFe2O4/polyaniline composite absorbing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104609607A (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dehghani et al. | Adsorptive removal of endocrine disrupting bisphenol A from aqueous solution using chitosan | |
| CN103342410B (en) | Water treatment method for removing arsenic by strengthening zero-valent iron | |
| US9969640B2 (en) | Sludge drying composite conditioner and application method thereof | |
| CN104667870A (en) | Method for removing endocrine disrupter in water by utilizing persulfate and ferro-manganese loaded dual-phase compound graphene oxide | |
| CN106000297B (en) | A kind of graphene-supported zirconium oxide composite material, preparation method and its application as desulfuration adsorbent | |
| CN103877953B (en) | A kind of hydrogel for sewage disposal and preparation method thereof | |
| CN104609607B (en) | A kind of method of utilizing the collaborative persulfate of cobalt doped magnetic redox Graphene to remove incretion interferent in water | |
| CN107008745A (en) | A kind of petroleum hydrocarbon contaminated soil repairs medicament and application method | |
| CN102266749B (en) | Dispersive composite nano adsorbent and preparation method thereof applied to arsenic underwater removal | |
| CN105314728A (en) | Method for degrading organic pollutant in water through activated persulfate | |
| Xiong et al. | A review on efficient removal of phthalic acid esters via biochars and transition metals-activated persulfate systems | |
| CN105967266A (en) | Efficient sewage treatment agent and preparation method thereof | |
| CN110203994A (en) | Utilize the method for multi-layer hole charcoal activation persulfate degradable organic pollutant | |
| CN104609636B (en) | A kind of method of utilizing ferrimanganic two-phase doped graphene to activate incretion interferent in single persulfate removal water | |
| CN102601108B (en) | Method for treating arsenic polluted soil | |
| CN105293852B (en) | The method of the synchronous coupling odor purification of sludge organism leaching conditioning | |
| CN105540726A (en) | Method for removing pentavalent arsenic from wastewater by adopting magnetic chitosan/biochar composite material | |
| CN104667869B (en) | A kind of single persulfate and load ferro-cobalt two-phase combined oxidation Graphene is utilized to remove the method for incretion interferent in water | |
| CN104628211B (en) | A kind of method of utilizing the collaborative magnetic oxygenated reduced graphene catalyzing activation persulfate of metallic cerium to remove incretion interferent in water | |
| CN107857328A (en) | A kind of method that tetracycline in water removal is removed using two-dimensional nano lamella composite selective absorption | |
| CN104667871B (en) | Method for eliminating endocrine disrupter in water by activating monopersulfate with ferro-cerium dual-phase loaded graphene oxide | |
| CN107233926B (en) | A kind of preparation method of carbon nanotube loaded heterogeneous Fenton System Catalyst | |
| CN103880265B (en) | A kind of method for processing sludge | |
| CN105036285B (en) | Aniline sewage decolorization treatment agent, and preparation method and application method thereof | |
| CN106824066A (en) | Modified zirconium hydroxide composite adsorbing material of the 3D Graphenes of fluorine ion and preparation method thereof in a kind of removal rural potable water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160511 Termination date: 20180211 |