CN104628211A - Method for removing endocrine disrupters in water by activating persulfate under synergic catalytic actions of metal cerium and magnetic reduced graphene oxide - Google Patents

Method for removing endocrine disrupters in water by activating persulfate under synergic catalytic actions of metal cerium and magnetic reduced graphene oxide Download PDF

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CN104628211A
CN104628211A CN201510073688.0A CN201510073688A CN104628211A CN 104628211 A CN104628211 A CN 104628211A CN 201510073688 A CN201510073688 A CN 201510073688A CN 104628211 A CN104628211 A CN 104628211A
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reduced graphene
persulphate
magnetic oxygenated
water
cerium
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CN104628211B (en
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郭洪光
石碧
张永丽
梁大山
程鑫
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Sichuan University
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Sichuan University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention relates to a method for removing endocrine disrupters in water, particularly a method for removing endocrine disrupters in water by activating persulfate under synergic catalytic actions of metal cerium and magnetic reduced graphene oxide. The invention aims to solve the problems of poor removal effect, high cost and more byproducts in the existing method for removing endocrine disrupters in water. The method comprises the following steps: 1. mixing persulfate with pretreated water; 2. regulating the reaction pH value; 3. preparing a metal cerium/magnetic reduced graphene oxide composite material; 4. adding the metal cerium/magnetic reduced graphene oxide composite material; and 5. separating the metal cerium/magnetic reduced graphene oxide composite material by using an external field. The removal rate of endocrine disrupters in water can reach 89-95%. The method can remove the endocrine disrupters in water.

Description

A kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation persulphate removal water
Technical field
The present invention relates to a kind of method removing endocrine disrupter in water.
Background technology
In recent years, due to the severe exacerbation of source quality, a large amount of hazardous contaminant is constantly detected in water, persistence organic pollutant, three causes thing, endocrine disrupter etc., in numerous organic pollutants, endocrine disrupter using its harm performance different and as one independently environmental problem be suggested, this pollutant water circulation and utilize in process and can produce biological amplification, conventional water treatment process is very limited to its processing power, is difficult to the drinking water standard reaching country's formulation.And along with industry and agriculture development, the wastewater discharge containing a large amount of endocrine disrupter increases year by year, and kind increases year by year, enters in water cause even more serious pollution without dealing carefully with, and therefore must process this type of trade effluent.
The method that the domestic and international EDCs removed in water surrounding is conventional at present comprises biological process, physico-chemical process, electrochemical process and membrane-filter procedure.Because EDCs is to the toxic action of biology, make without special acclimated microorganism very limited to its removal effect; Electrochemical process is comparatively efficient to the removal of such material, but is also difficult to extensive use because cost is higher; Membrane technique is as 21 century the most promising water technology, though be widely used in drinking water treatment, but higher membrane module equipment and running cost make it be difficult to use extensive removal in specific organic pollutant; Oxidation in physico-chemical process and absorption, due to simple to operate, removal efficiency is high, cost is controlled and be widely applied in drinking water treatment, but the cost of oxidizing process or absorbing process existence is higher separately, by product is more, the problems such as the difficult recovery of sorbent material, make it in applied research, still have certain limitation.
Summary of the invention
The method removal effect that the object of the invention is to solve endocrine disrupter in existing removal water is not good, the problem that cost is high and by product is many, and a kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation persulphate removal water is provided.
Utilize metallic cerium to work in coordination with a method for endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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, metallic cerium/magnetic oxygenated reduced graphene matrix material 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 3 .6H 2o, urea and CeCl 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 cerium 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 3 .6H 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 3 .6H 2o and CeCl 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 cerium 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 cerium 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 metallic cerium/magnetic oxygenated reduced graphene matrix material;
Four, metallic cerium/magnetic oxygenated reduced graphene matrix material is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by metallic cerium/magnetic oxygenated reduced graphene matrix material, reaction times is 15min ~ 240min, obtains the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material;
The dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is 1mg/L ~ 200mg/L;
Five, adopt foreign field separating metal cerium/magnetic oxygenated reduced graphene matrix material: adopt foreign field to be separated the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material, Footwall drift cerium/magnetic oxygenated reduced graphene matrix material, re-use aperture be 0.45 μm glass fibre membrane to reclaim metallic cerium/magnetic oxygenated reduced graphene matrix material filter, again by the metallic cerium/magnetic oxygenated reduced graphene matrix material dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the metallic cerium/magnetic oxygenated reduced graphene matrix material 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 cerium 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 metallic iron and cerium 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 40% ~ 60% with other;
Two, the present invention has lower volatility, colourity and smell taste and can not change before and after reaction, and the metallic cerium/magnetic oxygenated reduced graphene matrix material of preparation at normal temperatures and pressures can stable existence;
Three, the metallic cerium synthesized by the present invention/magnetic oxygenated reduced graphene matrix material speed of response is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the metallic cerium synthesized by the present invention/magnetic oxygenated reduced graphene matrix material can be easier to reclaim and regeneration;
Five, the clearance using method of the present invention to remove endocrine disrupter in water can reach 89% ~ 95%.
The present invention can remove remaining endocrine disrupter in water.
Embodiment
Embodiment one: present embodiment is that a kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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, metallic cerium/magnetic oxygenated reduced graphene matrix material 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 3 .6H 2o, urea and CeCl 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 cerium 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 3 .6H 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 3 .6H 2o and CeCl 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 cerium 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 cerium 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 metallic cerium/magnetic oxygenated reduced graphene matrix material;
Four, metallic cerium/magnetic oxygenated reduced graphene matrix material is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by metallic cerium/magnetic oxygenated reduced graphene matrix material, reaction times is 15min ~ 240min, obtains the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material;
The dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is 1mg/L ~ 200mg/L;
Five, adopt foreign field separating metal cerium/magnetic oxygenated reduced graphene matrix material: adopt foreign field to be separated the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material, Footwall drift cerium/magnetic oxygenated reduced graphene matrix material, re-use aperture be 0.45 μm glass fibre membrane to reclaim metallic cerium/magnetic oxygenated reduced graphene matrix material filter, again by the metallic cerium/magnetic oxygenated reduced graphene matrix material dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the metallic cerium/magnetic oxygenated reduced graphene matrix material after regenerating and removal water.
The principle of present embodiment:
The active metal iron existed in surface of graphene oxide in present embodiment and cerium 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 metallic iron and cerium 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 40% ~ 60% with other;
Two, present embodiment has lower volatility, colourity and smell taste and can not change before and after reaction, and the metallic cerium/magnetic oxygenated reduced graphene matrix material of preparation at normal temperatures and pressures can stable existence;
Three, the metallic cerium synthesized by present embodiment/magnetic oxygenated reduced graphene matrix material speed of response is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the metallic cerium synthesized by present embodiment/magnetic oxygenated reduced graphene matrix material can be easier to reclaim and regeneration;
Five, the clearance using the method for present embodiment to remove endocrine disrupter in water can reach 89% ~ 95%.
Present embodiment can remove remaining endocrine disrupter in water.
Embodiment two: present embodiment and embodiment one difference are: the endocrine disrupter described in step one is a kind of or wherein several mixture in oestrone, 17 α-lynoral, 17 alpha-estradiols, 17 beta estradiols, trihydroxy-oestrin, stilboestrol, nonyl phenol, dihydroxyphenyl propane and octyl phenol.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: step 3 1. described in the power of ultrasonic oscillation instrument be 100W ~ 1000W.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the external magnetic field strength described in step 4 is 0.01T ~ 1T.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: the quality of the 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: present embodiment with one of embodiment one to six difference is: the dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is that other steps of 0.02mg/L ~ 10mg/L are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: the dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material 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 metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material 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 metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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, metallic cerium/magnetic oxygenated reduced graphene matrix material:
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 3 .6H 2o, urea and CeCl 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 cerium 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 3 .6H 2the mass ratio of O is 50mL:1g;
Step 3 2. described in FeCl 3 .6H 2the mass ratio of O and urea is 50:1;
Step 3 2. described in FeCl 3 .6H 2o and CeCl 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 cerium 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 metallic cerium/magnetic oxygenated reduced graphene matrix material;
Four, metallic cerium/magnetic oxygenated reduced graphene matrix material is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by metallic cerium/magnetic oxygenated reduced graphene matrix material, reaction times is 60min, obtains the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material;
The dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is 10mg/L;
External magnetic field strength described in step 4 is 0.03T;
Five, adopt foreign field separating metal cerium/magnetic oxygenated reduced graphene matrix material: adopt foreign field to be separated the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material, Footwall drift cerium/magnetic oxygenated reduced graphene matrix material, re-use aperture be 0.45 μm glass fibre membrane to reclaim metallic cerium/magnetic oxygenated reduced graphene matrix material filter, again by the metallic cerium/magnetic oxygenated reduced graphene matrix material dry 24h at temperature is 50 DEG C after filtration, obtain the water of endocrine disrupter in the metallic cerium/magnetic oxygenated reduced graphene matrix material 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 40% with other;
Two, this test has lower volatility, colourity and smell taste and can not change before and after reaction, and the metallic cerium/magnetic oxygenated reduced graphene matrix material of preparation at normal temperatures and pressures can stable existence;
Three, the metallic cerium synthesized by this test/magnetic oxygenated reduced graphene matrix material speed of response is fast, and by product nontoxicity, can effectively remove endocrine disrupter in water;
Four, the metallic cerium synthesized by this test/magnetic oxygenated reduced graphene matrix material 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 metallic cerium to work in coordination with a method for endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation persulphate removal water, it is characterized in that a kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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, metallic cerium/magnetic oxygenated reduced graphene matrix material 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 CeCl 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 cerium 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 CeCl 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 cerium 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 cerium 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 metallic cerium/magnetic oxygenated reduced graphene matrix material;
Four, metallic cerium/magnetic oxygenated reduced graphene matrix material is added: join in the mixing solutions of the persulphate after adjust ph and pretreated water by metallic cerium/magnetic oxygenated reduced graphene matrix material, reaction times is 15min ~ 240min, obtains the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material;
The dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is 1mg/L ~ 200mg/L;
Five, adopt foreign field separating metal cerium/magnetic oxygenated reduced graphene matrix material: adopt foreign field to be separated the water containing metallic cerium/magnetic oxygenated reduced graphene matrix material, Footwall drift cerium/magnetic oxygenated reduced graphene matrix material, re-use aperture be 0.45 μm glass fibre membrane to reclaim metallic cerium/magnetic oxygenated reduced graphene matrix material filter, again by the metallic cerium/magnetic oxygenated reduced graphene matrix material dry 12h ~ 48h at temperature is 50 DEG C ~ 75 DEG C after filtration, obtain the water of endocrine disrupter in the metallic cerium/magnetic oxygenated reduced graphene matrix material after regenerating and removal water.
2. a kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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 metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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 metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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 metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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 metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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 metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation persulphate removal water according to claim 1, is characterized in that the dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is 0.02mg/L ~ 10mg/L.
8. a kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation persulphate removal water according to claim 1, is characterized in that the dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is 10mg/L ~ 100mg/L.
9. a kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation persulphate removal water according to claim 1, is characterized in that the dosage of the metallic cerium described in step 4/magnetic oxygenated reduced graphene matrix material is 100mg/L ~ 200mg/L.
10. a kind of method utilizing metallic cerium to work in coordination with endocrine disrupter in magnetic oxygenated reduced graphene catalyzing activation 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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107082483A (en) * 2017-05-02 2017-08-22 四川大学 The method that a kind of utilization persulfate and carbon based nano-material remove water pollutant
CN111252848A (en) * 2020-02-25 2020-06-09 中国电建集团成都勘测设计研究院有限公司 Using CeO2Method for removing tetracycline hydrochloride in water by catalytically activating sodium persulfate under visible light of composite BiOI material
CN113041997A (en) * 2021-03-05 2021-06-29 佛山科学技术学院 Modified magnetic biochar and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003236375A (en) * 2002-02-18 2003-08-26 Jsr Corp Endocrine disrupting chemical removing agent and its using method
CN101550003A (en) * 2009-04-22 2009-10-07 湖南大学 Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same
CN103030208A (en) * 2013-01-08 2013-04-10 哈尔滨工业大学 Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters
CN103342405A (en) * 2013-07-23 2013-10-09 哈尔滨工业大学 Method for degrading organic pollutants in water through electrochemical cathodic activation of persulfate
US20140117273A1 (en) * 2009-07-06 2014-05-01 Halosource, Inc. Use of a dual polymer system for enhanced water recovery and improved separation of suspended solids and other substances from an aqueous media

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003236375A (en) * 2002-02-18 2003-08-26 Jsr Corp Endocrine disrupting chemical removing agent and its using method
CN101550003A (en) * 2009-04-22 2009-10-07 湖南大学 Nano-graphite alkenyl composite wave-absorbing material and method of preparing the same
US20140117273A1 (en) * 2009-07-06 2014-05-01 Halosource, Inc. Use of a dual polymer system for enhanced water recovery and improved separation of suspended solids and other substances from an aqueous media
CN103030208A (en) * 2013-01-08 2013-04-10 哈尔滨工业大学 Application of spinel ferrite catalyst and method for urging persulfate to generate free radicals to catalytically degrade organic matters
CN103342405A (en) * 2013-07-23 2013-10-09 哈尔滨工业大学 Method for degrading organic pollutants in water through electrochemical cathodic activation of persulfate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
银洲等: "二氧化钛光催化降解环境内分泌干扰物技术的研究进展", 《水处理技术》, vol. 39, no. 1, 10 January 2013 (2013-01-10), pages 24 - 28 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107082483A (en) * 2017-05-02 2017-08-22 四川大学 The method that a kind of utilization persulfate and carbon based nano-material remove water pollutant
CN111252848A (en) * 2020-02-25 2020-06-09 中国电建集团成都勘测设计研究院有限公司 Using CeO2Method for removing tetracycline hydrochloride in water by catalytically activating sodium persulfate under visible light of composite BiOI material
CN113041997A (en) * 2021-03-05 2021-06-29 佛山科学技术学院 Modified magnetic biochar and preparation method and application thereof

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