A kind of persulfate and load ferrimanganic two-phase combined oxidation Graphene is utilized to remove incretion interferent in water
Method
Technical field
The present invention relates to a kind of remove the method for incretion interferent in water.
Background technology
Incretion interferent (Endocrine disrupting chemicals, EDCs) is by dirty without the life processed completely
Water, pharmacy waste water or domestic animal aquatic products industry muck runoff enter water environment, and after enrichment, concentration can increase hundreds of times in water body.
Even and the other EDCs of trace level also can expose human body therein and organism carcinogenic, the mutagenesis of generation and interference to long-term
Reproductive system endangers with hormone secretion etc..It is used frequently due to above-mentioned substance and enters in environment water, causing it to be formed
" false lasting " (pseudo-persistent) phenomenon, and then health and whole ecosystem are constituted long-term potential hazard.
Existing conventional drinking water treatment technique, as extremely limited to the removal of EDCs in coagulation, the method that precipitates, filter and sterilize,
Need badly and research and develop the drinking water safety hidden danger that new and effective water treatment technology reply above-mentioned substance is caused.
The method conventional for EDCs removed the most both at home and abroad in water environment includes bioanalysis, physico-chemical process, electrochemical process and thin film
Filtration.Owing to EDCs is to biological toxic action so that without special acclimated microorganism, its removal effect is extremely had
Limit;Electrochemical process is more efficient to the removal of such material, but is also difficult to large-scale use due to relatively costly;Membrane technology is made
For 21 century the most promising water technology, though being widely used in drinking water treatment, but higher membrane module equipment
Make it be difficult to extensive removal in specific organic pollution with operating cost to use;Oxidation in physico-chemical process and absorption, due to
Simple to operate, removal efficiency is high, cost is controlled and is widely applied in drinking water treatment, but individually oxidation technology
Or absorbing process exist relatively costly, the problems such as by-product is more, adsorbent difficulty recovery so that it is still have in applied research
There is certain limitation.
Summary of the invention
It is low that present disclosure is intended to solve the method removal efficiency of incretion interferent in existing removal water, and cost is high, by-product
Thing is many, and adsorbent difficulty reclaims and can not remove the problem of specific organic pollution on a large scale, and provides one to utilize persulfate
And the method for incretion interferent in load ferrimanganic two-phase combined oxidation Graphene removal water.
A kind of utilize persulfate and load ferrimanganic two-phase combined oxidation Graphene to remove the method for incretion interferent in water, be
Complete according to the following steps:
One, persulfate is mixed with the water of pretreatment: persulfate is mixed with the water of pretreatment, more at room temperature and stir
Mixing speed is stirring 20min~45min under conditions of 160r/min~250r/min, obtains the water of persulfate and pretreatment
Mixed solution;
Persulfate described in step one be the one in potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate and persulfuric acid calcium or its
In several mixture;
In the water of the pretreatment described in step one, the concentration of incretion interferent is 0.02mg/L~100mg/L;
The quality of the persulfate described in step one is 1:(1000~10000 with the mass ratio of the water of pretreatment);
Two, regulation pH value in reaction: low whipping speed is use under conditions of 150r/min~200r/min
The perchloric acid of 0.1mol/L~100mol/L and the sodium hydroxide solution of 0.1mol/L~100mol/L are by persulfate and pretreatment
The pH value of mixed solution of water regulate to 6.5~7.5, persulfate after adjusted pH value and the water of pretreatment
Mixed solution;
Three, preparation load ferrimanganic two-phase combined oxidation Graphene:
1., add graphene oxide in the ethylene glycol solution that mass fraction is 97%~99%, re-use ultrasonic wave concussion
Instrument concussion dispersion 3h~4h, obtains the mixed solution of graphene oxide and ethylene glycol;
Step 3 1. described in the volume ratio of the ethylene glycol solution that quality and mass fraction are 97%~99% of graphene oxide
For (0.001g~10g): 1mL;
2. at temperature is 60 DEG C~75 DEG C, by the mixed solution of sodium citrate and ethylene glycol heats 20min~45min, obtains
Sodium citrate after heating and the mixed solution of ethylene glycol;Again to heating after sodium citrate and ethylene glycol mixed solution in add
Enter FeCl3.6H2O, carbamide and MnCl2·6H2O, then at room temperature and bar that magnetic agitation speed is 100r/min~250r/min
Magnetic agitation 2h~4h under part, obtain the mixed solution of the sodium citrate containing ferrimanganic and ethylene glycol;
Step 3 2. described in sodium citrate and ethylene glycol mixed solution in the concentration of sodium citrate be 60
Mg/mL~200mg/mL;
Step 3 2. described in heating after sodium citrate and the volume of mixed solution of ethylene glycol and FeCl3.6H2The matter of O
Amount ratio is (1mL~1000mL): 1g;
Step 3 2. described in FeCl3.6H2O is (0.01~100) with the mass ratio of carbamide: 1;
Step 3 2. described in FeCl3.6H2O and MnCl2·6H2The mass ratio of O is (0.01~1000): 1;
3., the mixed solution of the mixed solution of graphene oxide and ethylene glycol with the sodium citrate containing ferrimanganic and ethylene glycol is mixed
Close, be then added in the rustless steel autoclave that liner is politef, then rustless steel autoclave is sealed, then
The rustless steel autoclave of sealing is reacted at temperature is 200 DEG C~230 DEG C 12h~48h, then naturally cools to room temperature,
Obtain black suspension;
Step 3 3. described in graphene oxide and the mixed solution of ethylene glycol and the sodium citrate containing ferrimanganic and ethylene glycol
The volume ratio of mixed solution be (0.1~50): 1;
4., by black suspension it is centrifuged separating 10min~30min under centrifugal speed is 6500r/min~8000r/min,
Obtain the deposit after centrifugation;Deposit after use methanol and deionized water clean centrifugation respectively 5 times
~10 times, then at temperature is-18 DEG C~15 DEG C, it is dried 24h~48h, obtain loading ferrimanganic two-phase combined oxidation Graphene;
Four, load ferrimanganic two-phase combined oxidation Graphene is added: load ferrimanganic two-phase combined oxidation Graphene is joined regulation
In persulfate after pH value and the mixed solution of the water of pretreatment, the response time is 15min~240min, is contained
The water of load ferrimanganic two-phase combined oxidation Graphene;
The dosage of the load ferrimanganic two-phase combined oxidation Graphene described in step 4 is 1mg/L~200mg/L;
Five, external magnetic field separating load ferrimanganic two-phase combined oxidation Graphene is used: use external magnetic field to containing load ferrimanganic two-phase
The water of combined oxidation Graphene separates, and reclaims load ferrimanganic two-phase combined oxidation Graphene, and re-using aperture is 0.45 μm
Glass fibre membrane to reclaim load ferrimanganic two-phase combined oxidation Graphene filter, then will filter after load ferrimanganic two-phase
Combined oxidation Graphene is dried 12h~48h, the load ferrimanganic two-phase composite oxygen after being regenerated at temperature is 50 DEG C~75 DEG C
The water of incretion interferent in functionalized graphene and removal water.
The principle of the present invention:
In the present invention, active metal ferrum and manganese in surface of graphene oxide existence will occur electricity with the sulfide linkage of crossing in persulfate
Son transfer, destroys the structure of over cure double bond, thus activating reaction occurs, and generates SO4 -, and active metal metallic iron and manganese
Self is then aoxidized;On the other hand graphene oxide has huge specific surface area, its can adsorbed target organic with
Time, surface a large amount of aerobic functional group, the polyelectron group being had such as carboxyl can activate persulfate further, generate SO4 -
With HSO4 -, thus accelerate the oxidative degradation of incretion interferent in water.
Advantages of the present invention:
One, the inventive method is simple to operate, with low cost, removes with other in water compared with the method for incretion interferent, fall
Low cost 40%~60%;
Two, the present invention has relatively low volatility, and before and after reaction, colourity and odor will not change, the load ferrimanganic of preparation
Two-phase combined oxidation Graphene at normal temperatures and pressures can stable existence;
Three, the load ferrimanganic two-phase combined oxidation Graphene response speed synthesized by the present invention is fast, by-product avirulence, it is possible to
Effectively remove incretion interferent in water;
Four, the load ferrimanganic two-phase combined oxidation Graphene synthesized by the present invention can be easier to reclaim and regeneration;Five, use
In the method removal water of the present invention, the clearance of incretion interferent is up to 85%~95%.
The present invention can remove remaining incretion interferent in water.
Detailed description of the invention
Detailed description of the invention one: present embodiment is that one utilizes persulfate and load ferrimanganic two-phase combined oxidation Graphene to go
Except in water, the method for incretion interferent completes according to the following steps:
One, persulfate is mixed with the water of pretreatment: persulfate is mixed with the water of pretreatment, more at room temperature and stir
Mixing speed is stirring 20min~45min under conditions of 160r/min~250r/min, obtains the water of persulfate and pretreatment
Mixed solution;
Persulfate described in step one be the one in potassium peroxydisulfate, Ammonium persulfate., sodium peroxydisulfate and persulfuric acid calcium or its
In several mixture;
In the water of the pretreatment described in step one, the concentration of incretion interferent is 0.02mg/L~100mg/L;
The quality of the persulfate described in step one is 1:(1000~10000 with the mass ratio of the water of pretreatment);
Two, regulation pH value in reaction: low whipping speed is use under conditions of 150r/min~200r/min
The perchloric acid of 0.1mol/L~100mol/L and the sodium hydroxide solution of 0.1mol/L~100mol/L are by persulfate and pretreatment
The pH value of mixed solution of water regulate to 6.5~7.5, persulfate after adjusted pH value and the water of pretreatment
Mixed solution;
Three, preparation load ferrimanganic two-phase combined oxidation Graphene:
1., add graphene oxide in the ethylene glycol solution that mass fraction is 97%~99%, re-use ultrasonic wave concussion
Instrument concussion dispersion 3h~4h, obtains the mixed solution of graphene oxide and ethylene glycol;
Step 3 1. described in the volume ratio of the ethylene glycol solution that quality and mass fraction are 97%~99% of graphene oxide
For (0.001g~10g): 1mL;
2. at temperature is 60 DEG C~75 DEG C, by the mixed solution of sodium citrate and ethylene glycol heats 20min~45min, obtains
Sodium citrate after heating and the mixed solution of ethylene glycol;Again to heating after sodium citrate and ethylene glycol mixed solution in add
Enter FeCl3.6H2O, carbamide and MnCl2·6H2O, then at room temperature and bar that magnetic agitation speed is 100r/min~250r/min
Magnetic agitation 2h~4h under part, obtain the mixed solution of the sodium citrate containing ferrimanganic and ethylene glycol;
Step 3 2. described in sodium citrate and ethylene glycol mixed solution in the concentration of sodium citrate be 60
Mg/mL~200mg/mL;
Step 3 2. described in heating after sodium citrate and the volume of mixed solution of ethylene glycol and FeCl3.6H2The matter of O
Amount ratio is (1mL~1000mL): 1g;
Step 3 2. described in FeCl3.6H2O is (0.01~100) with the mass ratio of carbamide: 1;
Step 3 2. described in FeCl3.6H2O and MnCl2·6H2The mass ratio of O is (0.01~1000): 1;
3., the mixed solution of the mixed solution of graphene oxide and ethylene glycol with the sodium citrate containing ferrimanganic and ethylene glycol is mixed
Close, be then added in the rustless steel autoclave that liner is politef, then rustless steel autoclave is sealed, then
The rustless steel autoclave of sealing is reacted at temperature is 200 DEG C~230 DEG C 12h~48h, then naturally cools to room temperature,
Obtain black suspension;
Step 3 3. described in graphene oxide and the mixed solution of ethylene glycol and the sodium citrate containing ferrimanganic and ethylene glycol
The volume ratio of mixed solution be (0.1~50): 1;
4., by black suspension it is centrifuged separating 10min~30min under centrifugal speed is 6500r/min~8000r/min,
Obtain the deposit after centrifugation;Deposit after use methanol and deionized water clean centrifugation respectively 5 times
~10 times, then at temperature is-18 DEG C~15 DEG C, it is dried 24h~48h, obtain loading ferrimanganic two-phase combined oxidation Graphene;
Four, load ferrimanganic two-phase combined oxidation Graphene is added: load ferrimanganic two-phase combined oxidation Graphene is joined regulation
In persulfate after pH value and the mixed solution of the water of pretreatment, the response time is 15min~240min, is contained
The water of load ferrimanganic two-phase combined oxidation Graphene;
The dosage of the load ferrimanganic two-phase combined oxidation Graphene described in step 4 is 1mg/L~200mg/L;
Five, external magnetic field separating load ferrimanganic two-phase combined oxidation Graphene is used: use external magnetic field to containing load ferrimanganic two-phase
The water of combined oxidation Graphene separates, and reclaims load ferrimanganic two-phase combined oxidation Graphene, and re-using aperture is 0.45 μm
Glass fibre membrane to reclaim load ferrimanganic two-phase combined oxidation Graphene filter, then will filter after load ferrimanganic two-phase
Combined oxidation Graphene is dried 12h~48h, the load ferrimanganic two-phase composite oxygen after being regenerated at temperature is 50 DEG C~75 DEG C
The water of incretion interferent in functionalized graphene and removal water.
The principle of present embodiment:
In present embodiment, active metal ferrum and manganese in surface of graphene oxide existence will be sent out with the sulfide linkage of crossing in persulfate
Raw electron transfer, destroys the structure of over cure double bond, thus activating reaction occurs, and generates SO4 -, and active metal metallic iron
Then aoxidized with manganese self;On the other hand graphene oxide has huge specific surface area, and it can adsorbed target Organic substance
While, surface a large amount of aerobic functional group, the polyelectron group being had such as carboxyl can activate persulfate further, raw
Become SO4 -With HSO4 -, thus 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, removes with other in water compared with the method for incretion interferent,
Reduce cost 40%~60%;
Two, present embodiment has relatively low volatility, and before and after reaction, colourity and odor will not change, the load of preparation
Ferrimanganic two-phase combined oxidation Graphene at normal temperatures and pressures can stable existence;
Three, the load ferrimanganic two-phase combined oxidation Graphene response speed synthesized by present embodiment is fast, by-product avirulence,
Can effectively remove incretion interferent in water;
Four, the load ferrimanganic two-phase combined oxidation Graphene synthesized by present embodiment can be easier to reclaim and regeneration;
Five, the method using present embodiment removes in water the clearance of incretion interferent up to 85%~95%.
Present embodiment can remove remaining incretion interferent in water.
Detailed description of the invention two: present embodiment with detailed description of the invention one difference is: the endocrine described in step one is done
Disturb thing be estrone, 17 α-ethinyl estradiol, 17 alpha-estradiols, 17 beta estradiols, estriol, diethylstilbestrol, nonyl phenol,
A kind of or the most several mixture in bisphenol-A and octyl phenol.Other steps are identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment with one of detailed description of the invention one or two difference is: step 3 1. described in
The power of ultrasonic wave concussion instrument be 100W~1000W.Other steps are identical with detailed description of the invention one or two.
Detailed description of the invention four: present embodiment with one of detailed description of the invention one to three difference is: described in step 4
External magnetic field strength is 0.01T~1T.Other steps are identical with detailed description of the invention one to three.
Detailed description of the invention five: present embodiment with one of detailed description of the invention one to four difference is: described in step one
The quality of persulfate is 1:(1000~5000 with the mass ratio of the water of pretreatment).Other steps and detailed description of the invention one to
Four is identical.
Detailed description of the invention six: present embodiment with one of detailed description of the invention one to five difference is: described in step one
The quality of persulfate is 1:(5000~8000 with the mass ratio of the water of pretreatment).Other steps and detailed description of the invention one to
Five is identical.
Detailed description of the invention seven: present embodiment with one of detailed description of the invention one to six difference is: described in step 4
The dosage of load ferrimanganic two-phase combined oxidation Graphene is 0.02mg/L~10mg/L.Other steps and detailed description of the invention one
Identical to six.
Detailed description of the invention eight: present embodiment with one of detailed description of the invention one to seven difference is: described in step 4
The dosage of load ferrimanganic two-phase combined oxidation Graphene is 10mg/L~100mg/L.Other steps and detailed description of the invention one
Identical to seven.
Detailed description of the invention nine: present embodiment with one of detailed description of the invention one to eight difference is: described in step 4
The dosage of load ferrimanganic two-phase combined oxidation Graphene is 100mg/L~200mg/L.Other steps and detailed description of the invention
One to eight is identical.
Detailed description of the invention ten: present embodiment with one of detailed description of the invention one to nine difference is: step 3 1. described in
The particle diameter of graphene oxide be 15nm~500nm.Other steps are identical with detailed description of the invention one to nine.
Employing tests below checking beneficial effects of the present invention:
Test one: a kind of utilize persulfate and load ferrimanganic two-phase combined oxidation Graphene to remove incretion interferent in water
Method completes according to the following steps:
One, persulfate is mixed with the water of pretreatment: persulfate is mixed with the water of pretreatment, more at room temperature and stir
Mixing speed is stirring 30min under conditions of 180r/min, obtains the mixed solution of the water of persulfate and pretreatment;
Persulfate described in step one is sodium peroxydisulfate;
Incretion interferent described in step one is estriol;
In the water of the pretreatment described in step one, the concentration of incretion interferent is 5mg/L;
The quality of the persulfate described in step one is 1:1500 with the mass ratio of the water of pretreatment;
Two, regulation pH value in reaction: low whipping speed be use under conditions of 180r/min 0.1mol/L perchloric acid and
The pH value of persulfate and the mixed solution of the water of pretreatment is regulated to 6.5 by the sodium hydroxide solution of 0.1mol/L, obtains
Persulfate after regulation pH value and the mixed solution of the water of pretreatment;
Three, preparation load ferrimanganic two-phase combined oxidation Graphene:
1., add graphene oxide in the ethylene glycol solution that mass fraction is 99%, re-use the shake of ultrasonic wave concussion instrument
Swing dispersion 3h, obtain the mixed solution 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 with the volume ratio of the ethylene glycol solution that mass fraction is 99% be
0.005g:1mL;
Step 3 1. described in the power of ultrasonic wave concussion instrument be 200W;
2. at temperature is 60 DEG C, 20min, by the mixed solution of 50mL sodium citrate and ethylene glycol is heated, after being heated
Sodium citrate and the mixed solution of ethylene glycol;Again to heating after sodium citrate and ethylene glycol mixed solution in add
FeCl3.6H2O, carbamide and MnCl2·6H2O, then magnetic force stirs under conditions of room temperature and magnetic agitation speed are 200r/min
Mix 2h, obtain the mixed solution of the sodium citrate containing ferrimanganic and ethylene glycol;
Step 3 2. described in sodium citrate and ethylene glycol mixed solution in the concentration of sodium citrate be 60mg/mL;
Step 3 2. described in heating after sodium citrate and the volume of mixed solution of ethylene glycol and FeCl3.6H2The matter of O
Amount ratio is 50mL:1g;
Step 3 2. described in FeCl3.6H2O is 50:1 with the mass ratio of carbamide;
Step 3 2. described in FeCl3.6H2O and MnCl2·6H2The mass ratio of O is 5:1;
3., the mixed solution of 50mL graphene oxide and ethylene glycol and 50mL are contained sodium citrate and the ethylene glycol of ferrimanganic
Mixed solution mixing, be then added in the rustless steel autoclave that liner is politef, then by anti-for rustless steel high pressure
Answer still to seal, then the rustless steel autoclave of sealing reacted at temperature is 200 DEG C 12h, then naturally cool to room temperature,
Obtain black suspension;
4., by black suspension it is centrifuged separating 10min, after obtaining centrifugation under centrifugal speed is 6500r/min
Deposit;Deposit after use methanol and deionized water clean centrifugation respectively 6 times, then in temperature be
Lyophilization 24h at-18 DEG C, obtains loading ferrimanganic two-phase combined oxidation Graphene;
Four, load ferrimanganic two-phase combined oxidation Graphene is added: load ferrimanganic two-phase combined oxidation Graphene is joined regulation
In persulfate after pH value and the mixed solution of the water of pretreatment, the response time is 60min, obtains containing load ferrimanganic
The water of two-phase combined oxidation Graphene;
The dosage of the load ferrimanganic two-phase combined oxidation Graphene described in step 4 is 10mg/L;
External magnetic field strength described in step 4 is 0.03T;
Five, external magnetic field separating load ferrimanganic two-phase combined oxidation Graphene is used: use external magnetic field to containing load ferrimanganic two-phase
The water of combined oxidation Graphene separates, and reclaims load ferrimanganic two-phase combined oxidation Graphene, and re-using aperture is 0.45 μm
Glass fibre membrane to reclaim load ferrimanganic two-phase combined oxidation Graphene filter, then will filter after load ferrimanganic two-phase
Combined oxidation Graphene at temperature is 50 DEG C be dried 24h, the load ferrimanganic two-phase combined oxidation Graphene after regenerate with
Remove the water of incretion interferent in water.
The advantage of this test:
One, the inventive method is simple to operate, with low cost, removes with other in water compared with the method for incretion interferent, fall
Low cost 40%;
Two, the present invention has relatively low volatility, and before and after reaction, colourity and odor will not change, the load ferrimanganic of preparation
Two-phase combined oxidation Graphene at normal temperatures and pressures can stable existence;
Three, the load ferrimanganic two-phase combined oxidation Graphene response speed synthesized by the present invention is fast, by-product avirulence, it is possible to
Effectively remove incretion interferent in water;
Four, the load ferrimanganic two-phase combined oxidation Graphene synthesized by the present invention can be easier to reclaim and regeneration;Five, use
In the method removal water of the present invention, the clearance of incretion interferent is up to 92%.
Test two: use activated carbon to remove the contrast test of incretion interferent in water, be specifically realized by the following steps:
Incretion interferent 24h in the ature of coal granular active carbon absorption pretreated water using particle diameter to be 4nm~100nm,
To 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 the ature of coal granular active carbon Adsorption pretreated water using particle diameter to be 4nm~100nm in test two, endocrine is done
The clearance disturbing thing is 53%.
Test three: use ultraviolet light and H2O2Remove the contrast test of incretion interferent in water, the most according to the following steps
Complete:
The H that concentration is 10mmol/L is added in the water of pretreatment2O2, at ultraviolet light intensity 250 μ W/cm2Ultraviolet lighting
Penetrate the water 0.5h of pretreatment, 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;
Test three use ultraviolet light and H2O2Removing the clearance of incretion interferent in pretreated water is 68%.
Test four: use sodium peroxydisulfate to remove the contrast test of incretion interferent in water, be specifically realized by the following steps:
In pretreated water, add the sodium peroxydisulfate of 2mg/L, react 2h, 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;
It is 9% that test four use sodium peroxydisulfate removes the clearance of incretion interferent in pretreated water.
Test two use ature of coal granular active carbon remove incretion interferent in pretreated waters, test three use ultraviolet lights and
H2O2Remove incretion interferent and test four use sodium peroxydisulfate in pretreated water and remove incretion interferent in pretreated water
Clearance be respectively 53%, 68% and 9%, and testing the clearance of is 92%, it was demonstrated that test one is for removing pre-place
Incretion interferent excellent in reason water.