CN109453807A - It is a kind of to utilize chelating agent MODIFIED Fe3O4The method of sulfa drugs in material catalytic degradation water body - Google Patents
It is a kind of to utilize chelating agent MODIFIED Fe3O4The method of sulfa drugs in material catalytic degradation water body Download PDFInfo
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- CN109453807A CN109453807A CN201811063334.8A CN201811063334A CN109453807A CN 109453807 A CN109453807 A CN 109453807A CN 201811063334 A CN201811063334 A CN 201811063334A CN 109453807 A CN109453807 A CN 109453807A
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000002738 chelating agent Substances 0.000 title claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000015556 catabolic process Effects 0.000 title claims abstract description 10
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 10
- 239000003814 drug Substances 0.000 title abstract description 18
- 229940079593 drug Drugs 0.000 title abstract description 16
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 229940124530 sulfonamide Drugs 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 10
- 150000003456 sulfonamides Chemical class 0.000 claims abstract 7
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims abstract 4
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 claims description 20
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical group [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 2
- 229940030275 epigallocatechin gallate Drugs 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 41
- 150000003839 salts Chemical class 0.000 description 20
- 239000002253 acid Substances 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 16
- 229960004306 sulfadiazine Drugs 0.000 description 16
- 238000006555 catalytic reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical compound [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- -1 sulphuric acid free radical Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种利用螯合剂改性Fe3O4材料催化降解水体中磺胺类药物的方法，其具体操作步骤如下：1）制备Fe3O4MNPs材料；2）制备螯合剂改性Fe3O4材料；3）催化剂与含磺胺类药物的水溶液混合；4）加入过氧单硫酸盐溶液；5）用外加磁场分离催化剂材料，采用本发明的方法对典型磺胺类药物的去除效果提高明显，并且可通过外加磁场实现负荷催化材料的回收再利用，节约成本，用于解决水环境中日益严峻的抗生素类药物污染问题。
The invention discloses a method for catalyzing degradation of sulfonamide drugs in water by utilizing chelating agent modified Fe 3 O 4 material. The specific operation steps are as follows: 1) preparing Fe 3 O 4 MNPs material; 2) preparing chelating agent modified Fe 3 O 4 material; 3) the catalyst is mixed with the aqueous solution containing sulfonamide drugs; 4) the peroxymonosulfate solution is added; 5) the catalyst material is separated by an external magnetic field, and the removal effect of the typical sulfonamide drugs by the method of the present invention is improved It is obvious, and the recovery and reuse of the loaded catalytic material can be realized by applying an external magnetic field, which can save costs and be used to solve the increasingly serious problem of antibiotic drug pollution in the water environment.
Description
Technical field
The present invention relates to water-treatment technology field more particularly to a kind of chelate modified Fe of utilization3O4Material is catalyzed peroxosulphuric
The method of sulfa drugs in salt degradation water body.
Background technique
The raw medicine output of China's drug and personal care articles (PPCPs) just increases with the development of economy and rapidly.According to
Statistics, drug raw medicine yield increases to 2,710,000 tons within 2013.Currently, drug type organic is in drinking water source area, waterworks
It is frequently detected in output water and sewage treatment plant tail water, long-term potential hazard is caused to human health and the ecosystem,
Huge threat is also formed to the utilization of water resource.Therefore, it needs to seek in efficient, economic control method solution water environment
Increasingly serious drug contamination problem.
Heterogeneous catalysis persulfate oxidation technology is that have the persistent organic pollutants oxidation removal of development potentiality new
Technology makes persulfate decompose the sulphuric acid free radical (SO for generating high oxidation activity using solid material as catalyst4-), with
Realize the efficient removal of organic pollutants.As novel magnetic materials, spinel type ferrite is in heterogeneous catalysis over cure
Favor of the hydrochlorate field by researchers.Ferroferric oxide magnetic nanoparticle (Fe3O4MNPs material) externally-applied magnetic field can be passed through
Quick separating shows good stability and reuse in use.However, Fe3O4MNPs material is in the solution because magnetic
Apparent particle agglomeration phenomenon occurs for effect, and has certain Fe2+Oxidation and iron leakage, it is anti-for resulting in recycling
Answer being substantially reduced for efficiency.Therefore, how Fe is further improved3O4MNPs constructs highly efficient, stable heterogeneous catalysis system
System is the key subject that potentiometric titrations oxidative system engineer application is promoted.
Chelating agent is a kind of substance that can provide electronics pair and form complex or chelate with metal ion, chelating
Ji Shang electron group is usually that may replace the acidic-group of hydrogen, metal ion can with the hydrogen atom on substituent group, thus with
Electron donating group is combined in a manner of covalent bond.Chelate, which can be stablized, to be stored in water, and the hydrolytic precipitation reaction of metal ion is alleviated.
Organic sequestering agent divides competitive reaction, and the remaining possible secondary pollution of organic sequestering agent to ask with free radical in the solution
Topic, limits their further apply.The research and development of chelating agent at present and with start to tend to it is environmentally friendly can biology drop
Solve chelating agent.As can modifying biodegradable chelating agent in Fe3O4MNPs catalysis material surface is then guaranteeing catalysis material
It is stable and while facilitate recycling with chelator frameworks, it solves catalysis material particle agglomeration, organic sequestering agent secondary pollution etc. and asks
Topic alleviates Fe3O4Oxidation and pass through the minimum of iron the amount of dissolution in chelation realization system.Develop chelating agent dressed states
Fe3O4The MNPs material catalytic activity highly efficient to permonosulphuric acid salt, this hardly degraded organic substance, guarantee drink in control water
The research field of water safety will be a full new breakthrough.
Summary of the invention
In view of the above problems, present invention aims at solve existing Fe3O4 MNPs catalysis material is in catalysis peroxide
The relatively low problem of catalytic efficiency during monosulfate provides a kind of utilization chelating agent MODIFIED Fe3O4Material catalytic degradation water body
The method of middle sulfa drugs.
In order to achieve the above object, The technical solution adopted by the invention is as follows: a kind of utilize chelating agent MODIFIED Fe3O4Material
Technique, the technique is as follows:
1) ferric chloride hexahydrate and green vitriol are instilled in alkaline solution, heating reaction, vacuum drying is cooled to room
Temperature obtains Fe3O4 The black powder of MNPs；Wherein, the molar concentration rate of ferric chloride hexahydrate and green vitriol is calculated as
1:1.(molar concentration rate range in 1:1 ~ 1:2, obtained Fe3O4The content of saturation magnetization intensity and magnetic material is all very high,
The magnetic Fe of better performances can be prepared3O4Material works as Fe2+/Fe3+Molar ratio it is bigger, obtained Fe3O4Material particle size is bigger.
To obtain catalytic efficiency with high small particle Fe3O4Material, this patent select 1:1 for reaction condition).
2) by Fe obtained in chelating agent EGCG and step 1)3O4 MNPs black powder is scattered in deoxidized water, at ultrasound
Reason, is separated by solid-liquid separation using magnet, removes supernatant, and vacuum drying is cooled to room temperature, obtains catalyst: what chelating agent was modified
Fe3O4Powder, wherein chelating agent EGCG and Fe3O4 The mass ratio of MNPs is 1:1.(mass ratio can be right at this time in 0.6 ~ 1 range
The removal effect of sulphadiazine is best in water；When chelating agent EGCG content is very few, the removal rate of sulphadiazine in water is had
It is apparent to reduce；When EGCG content is excessive, the removal rate of sulphadiazine will not improve again, cause the waste of material).
A kind of chelating agent MODIFIED Fe3O4The method of sulfa drugs, the method are as follows in material catalytic degradation water body:
1) Fe that chelating agent is modified3O4Powder and the water mixing containing sulfa drugs, obtain mixed solution.
2) the permonosulphuric acid salt of prescribed concentration is added into mixed solution, reaction immediately begins to timing, every a timing
Between, a certain amount of sample is drawn by syringe, is filtered immediately through 0.22 μm of glass fibre membrane；Filtered filtrate investment contains
In the liquid solution of quencher ethyl alcohol, subsequent detection analysis is carried out.
3) utilize external magnetic field separating step 2) in remaining solid after filtering, cleaned with distilled water and ethyl alcohol, vacuum drying,
Obtain the modified Fe of regenerated chelating agent3O4Powder.
Permonosulphuric acid salt of the present invention is potassium hydrogen persulfate (KHSO5).
Step 2) the permonosulphuric acid salt dosage of the present invention is 0.3mM, catalyst chelators MODIFIED Fe3O4
The dosage of material is 0.8 g/L.
The present invention has the advantages that the catalyst that method of the invention obtains: the modified Fe of chelating agent3O4Powder is recyclable
Regeneration also reduces cost, and the Fe that chelating agent is modified while improving reaction speed3O4The stability of powder is good, operation
Simply, it is easy to accomplish；Simultaneously, the chelating agent low toxicity of present invention production catalyst is degradable, is not in secondary pollution, adopts
The sulphadiazine that can be effectively removed with method of the invention, removal efficiency is high, can be used for the net of the water body of amic metadiazine drug contamination
Chemical industry is made.
Detailed description of the invention
Fig. 1 is sulphadiazine removal rate and time history in Examples 1 and 2.
Wherein, in figure one,Indicate Fe in embodiment 23O4 MNPs catalysis permonosulphuric acid salt removes sulphadiazine
Except rate and time relationship；Indicate chelating agent MODIFIED Fe in embodiment 13O4It is phonetic to sulfanilamide (SN) that material is catalyzed permonosulphuric acid salt
The removal rate and time relationship of pyridine, EGCG@Fe3O4MNPs is chelating agent MODIFIED Fe3O4Material.
Fig. 2 is different catalysts EGCG@Fe in embodiment 33O4 Under the conditions of the throwing amount of MNPs, sulphadiazine removal rate and when
Between graph of relation.
Wherein, in Fig. 2, Respectively indicate catalyst EGCG@in embodiment 3
Fe3O4 When the throwing amount of MNPs is 0,0.2,0.4,0.6,0.8,1.0 g/L, EGCG@Fe3O4Permonosulphuric acid salt is catalyzed to sulfanilamide (SN)
The removal rate and time relationship of pyrimidine；
Fig. 3 is sulphadiazine removal rate and time history in embodiment 4 under the conditions of different oxidant dosages.
Wherein, in Fig. 3, Respectively indicating oxidant dosage in embodiment 4 is
When 0.1 mM, 0.3 mM, 0.6 mM, 0.8 mM, 1.0 mM, Fe3O4 MNPs catalysis permonosulphuric acid salt removes sulphadiazine
Except rate and time relationship；
Specific embodiment
The present invention is described in further detail with specific embodiment for explanation with reference to the accompanying drawing.
The EGCG@Fe referred in embodiment3O4MNPs is chelating agent MODIFIED Fe3O4Material.
A kind of embodiment 1: chelating agent MODIFIED Fe3O4The method of sulfa drugs, is by following in material catalytic degradation water body
What step was completed:
1) Fe is prepared3O4 MNPs material: 2.7030 g ferric chloride hexahydrates and 2.7902 g green vitriols are added drop-wise to
In NaOH solution (4M), 80 DEG C of temperature, 18 min, total reaction time 1.5 is added dropwise.Solution is placed on to 40 DEG C of baking after having reacted
It is dried in vacuo 12 h in case, in cooled to room temperature, obtains black solid, is ground to black powder.
2) EGCG@Fe is prepared3O4 MNPs material: deoxidation is dispersed by 1 g chelating agent EGCG and 1 g self-control ferroso-ferric oxide
In 50 mL of water, mixed solution is ultrasonically treated the h of 1 h ~ 1.5.Obtained material is separated by solid-liquid separation using magnet, is stood 10 minutes and is outwelled
Supernatant is placed in 40 DEG C of baking oven and is dried in vacuo 12 h, in cooled to room temperature, obtains black solid, is ground to black
Powder.
3) catalyst is mixed with antibiotic aqueous solution: catalyst and 10 mg/L sulphadiazines are sufficiently mixed 30
Min, the dosage of catalyst are 0.8 g/L.
4) permonosulphuric acid salt is added: the permonosulphuric acid of prescribed concentration being added into the middle mixed container of step 3)
Salt, permonosulphuric acid salt throwing amount is 0.3 mmol/L；Reaction immediately begins to timing, and interval passes through injection at the appointed time
Device is drawn 2 mL samples and is filtered immediately by 0.22 μm of glass fibre membrane.Take the filtered filtrate of 0.8 mL to having shifted to an earlier date
Progress subsequent detection analysis in the liquid-phase inlet bottle of 0.2 mL quencher ethyl alcohol is added.
5) it uses externally-applied magnetic field separating catalyst material: separating EGCG@Fe with externally-applied magnetic field3O4 MNPs material, recycling catalysis
Agent material is cleaned up with distilled water and ethyl alcohol, is placed in 60 DEG C of baking oven and is dried in vacuo 12 h, and regenerated Fe is obtained3O4
MNPs material.
Embodiment 2: comparative test；Use spinelle Fe3O4 MNPs catalysis permonosulphuric acid salt goes the sulfanilamide (SN) in water removal phonetic
Pyridine is specifically realized by the following steps:
1) Fe is prepared3O4 MNPs material: 2.7030 g ferric chloride hexahydrates and 2.7902 g green vitriols are added drop-wise to
In NaOH solution (4 M), 80 DEG C of temperature, 18 min, total reaction time 1.5 is added dropwise.Solution is placed on 40 DEG C after having reacted
It is dried in vacuo 12 h in baking oven, in cooled to room temperature, obtains black solid, is ground to black powder.
2) catalyst is mixed with antibiotic aqueous solution: by catalyst obtained in step 1): Fe3O4 MNPs material with
10 mg/L sulphadiazines are sufficiently mixed 30 min；The dosage of catalyst is 0.8 g/L.
3) permonosulphuric acid salt is added: the permonosulphuric acid salt of prescribed concentration being added to the middle mixed container of step 2,
Permonosulphuric acid salt throwing amount is 0.3 mmol/L；Reaction immediately begins to timing, and interval passes through syringe at the appointed time
It draws 2 mL samples and is filtered immediately by 0.22 μm of glass fibre membrane；Take the filtered filtrate of 0.8 mL in advance plus
Enter progress subsequent detection analysis in the liquid-phase inlet bottle of 0.2 mL quencher ethyl alcohol.
Obtained result is as shown in Figure 1: in embodiment 2 in step 3), Fe3O4 MNPs is catalyzed permonosulphuric acid salt in water
Sulphadiazine removal rate be 37.94 %.
In the step 4) of embodiment 1, EGCG Fe3O4 MNPs is catalyzed permonosulphuric acid salt
68.28%, the catalyst in embodiment 1: chelating agent MODIFIED Fe is proved by comparison3O4Material to the removal effect of sulphadiazine more
It is good.
Embodiment 3: comparative test；Change catalyst EGCG@Fe3O4Dosage, different catalysts dosage is in water
Sulphadiazine removal rate influences according to Fig.2,.
EGCG@Fe as we can see from the figure3O4Catalyst amounts are smaller, also smaller to the removal rate of sulphadiazine in water；
EGCG@Fe3O4When catalyst amounts are 0.2 g/L, the removal rate of sulphadiazine is about 30 %；EGCG@Fe simultaneously3O4Catalysis
When agent dosage is 1.0 g/L when being 0.2 g/L, catalytic rate is most fast, only just reaches maximum material removal rate in 30 min.Therefore it urges
Agent dosage is that 0.2 g/L is throwing amount ratio under optimum operating condition.
Embodiment 4: comparative test；Change the dosage of permonosulphuric acid salt, different oxidant dosages are to the sulphur in water
Amic metadiazine removal rate influences according to Fig.3,.
The dosage of permonosulphuric acid salt is different as we can see from the figure, also different to the removal rate of sulphadiazine in water
Sample；When oxidant dosage is 0.3 mM, the removal rate highest of sulphadiazine, oxidation rate is most fast, is the throwing amount of optimum operating condition
Than.
It should be noted that above-mentioned is only presently preferred embodiments of the present invention, protection model not for the purpose of limiting the invention
It encloses, any combination or equivalents made on the basis of the above embodiments all belong to the scope of protection of the present invention.
Claims (6)
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