CN110152689A - A kind of synthetic method and its application of special graceful stone of showing severity - Google Patents
A kind of synthetic method and its application of special graceful stone of showing severity Download PDFInfo
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- CN110152689A CN110152689A CN201910387492.7A CN201910387492A CN110152689A CN 110152689 A CN110152689 A CN 110152689A CN 201910387492 A CN201910387492 A CN 201910387492A CN 110152689 A CN110152689 A CN 110152689A
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- severity
- special graceful
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- graceful stone
- showing severity
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- 239000004575 stone Substances 0.000 title claims abstract description 116
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- 239000004098 Tetracycline Substances 0.000 claims abstract description 55
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 55
- 229960002180 tetracycline Drugs 0.000 claims abstract description 53
- 229930101283 tetracycline Natural products 0.000 claims abstract description 53
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 230000001376 precipitating effect Effects 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 230000010355 oscillation Effects 0.000 claims abstract description 5
- 239000011949 solid catalyst Substances 0.000 claims abstract description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 36
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 18
- 229910052742 iron Inorganic materials 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000009777 vacuum freeze-drying Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229940040944 tetracyclines Drugs 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000011953 bioanalysis Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- -1 high-efficient Substances 0.000 description 4
- 229910052603 melanterite Inorganic materials 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000383 hazardous chemical Substances 0.000 description 2
- 239000013056 hazardous product Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical group [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910001608 iron mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the synthetic methods and its application of a kind of special graceful stone of showing severity, belong to water-treatment technology field.The synthesis step that the present invention prepares special graceful stone of showing severity includes: step 1: FeSO is added in the aqueous solution that pH is 2~74·7H2O is stirred evenly, and then adds H2O2, there is precipitating to generate after then carrying out oscillation treatment；Step 2: the precipitating of generation being collected by filtration, is washed using acid solution, then, then is washed with deionized, and solid catalyst is obtained after vacuum freeze drying and is showed severity special graceful stone；It is high using the graceful special stone yield of showing severity of the method for the present invention preparation.It is heterogeneous Fenton reaction iron-based material in the carry out class Fenton oxidation reaction treatment to tetracycline using the special graceful masonry of showing severity being prepared, can fast and effectively removes tetracycline in water removal；And secondary pollution will not be generated to environment, easy to operate, at low cost, Tetracyclines pollutant has a good application prospect in degradation water.
Description
Technical field
The invention belongs to water-treatment technology field, a kind of synthetic method more specifically to special graceful stone of showing severity and its
Using.
Background technique
Tetracycline antibiotics belong to a kind of typical drug and personal care articles (PPCPs) pollutant, are widely answered
In human disease treatment and Animal husbandry production, largely remained in water environment so as to cause it.Remain in water environment
Tetracycline (TC) can seriously destroy water ecology balance, bring a variety of adverse effects, such as can lead to bacterial dissociation and generate largely
Drug-fast bacteria endangers aquatic animal vital movement and human health.So the Treatment process of TC pollution is with important in research water body
Meaning.
Currently, the common processing method of tetracycline antibiotics has physisorphtion, anaerobic biodegradation and chemical oxidation
Method etc..If wherein physical absorption goes the adsorbent in water removal after tetracycline that cannot effectively be handled, still can be to environment
Cause serious harm.Due to antibiotic waste water high organic content, pollutant component is complicated, has and sterilizes and inhibit microorganism
The characteristics such as active function, bioanalysis is also difficult to effectively degrade to antibiotic waste water and microorganism is easily dead.Furthermore it is general
Chemical oxidization method processing cost is higher, generates a large amount of iron cements, it is difficult to recycle, therefore, Fenton's reaction comes into being.
Review literature defines Fe2+/H2O2System is Fenton's reaction.But Fenton's reaction condition is harsh, it is desirable that pH2~3.5
Acidic environment is unfavorable for practical water pollutant processing, so there is class Fenton's reaction (heterogeneous catalysis).Heterogeneous catalysis
Water treatment technology is a kind of method of effective degradation organic pollutants.Compared to homogeneous Fenton's reaction, it is responded with pH
Range is wide, does not generate iron cement and is easy to the advantages that being separated by solid-liquid separation.
Special graceful stone (Sch) of showing severity is a kind of sulfovinic acid iron mineral, chemical component Fe, S, O, H, since its surface contains
There is Fe (III), can produce hydroxyl free free radical (OH) and handled organic pollutants as heterogeneous catalysis.
Researcher mostly synthesizes special graceful stone of showing severity using bioanalysis at present.Such as Zhou Lixiang et al. (Song Yongwei, Zhao Bowen, Huo Minbo, Cui Chun
Red, Zhou Lixiang environmental science .2013 (34): 3264-3271) Acidithiobacillus ferrooxidans and ferrous oxide are utilized
Activity has successfully prepared special graceful stone of showing severity.Li et al. people (Li et al., Journal of Hazardous Materials
(" hazardous material magazine ") 344 (2018) 689-697) use ferrous oxide for raw material, by FeSO4Biooxidation reactions
The Man Teshi that shows severity is synthesized.But showed severity special graceful stone using bioanalysis synthesis, there is a problem of one it is maximum: strain pole used
Vulnerable to the influence of external environmental condition, such as the excessively cold oxidation activity that can then inhibit strain of temperature, special graceful stone of showing severity is influenced
Prepare rate.
And compared with bioanalysis, it is then the quick process of comparison that special graceful stone of showing severity is synthesized using chemical method, can
It greatly reduces time-consuming and small by such environmental effects.Such as Wang et al. (Wang et al., Journal of
Hazardous Materials (" hazardous material magazine ") 262 (2013) 412-419), it has been synthesized showed severity using hydro-thermal method for the first time
Special graceful stone, and for the first time as novel Fenton class catalyst application.However, discovery biosynthesis is showed severity Te Man under study for action
Time-consuming for stone (about twice of chemical method), and microorganism closes the oxidation rate in reaction system, relatively chemistry in synthesis process
Architectonical is slowly more, improves the control environment of microorganism, just can improve and stablize the phase change of Schwertmannite, guarantees enough
Special graceful stone of showing severity accordingly can be made in the long reaction time.And chemical method synthesizes during showing severity special graceful stone, reaction is general
Compare rapidly, the yield of special graceful stone of showing severity interior for 24 hours is basicly stable, and with the extension of reaction time, yield is difficult to occur again
Variation.Therefore, it is limited by above-mentioned reason, the application that special graceful stone of showing severity is synthesized using chemical method is not extensive.
Summary of the invention
1. to solve the problems, such as
For the problem that in the prior art, being chemically synthesized special graceful stone low yield of showing severity, an object of the present invention is
A kind of synthetic method of the special graceful stone of showing severity of high yield is provided；For in the prior art, in water body, the removal effect of tetracycline is not
Good problem, the second object of the present invention is in order to provide a kind of minimizing technology of tetracycline in water body.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows:
A kind of synthetic method for special graceful stone of showing severity, comprising the following steps:
Step 1: FeSO is added in acidic aqueous solution4·7H2O is stirred evenly, and then adding mass fraction is 30%
H2O2Reaction system is obtained, has precipitating to generate afterwards for a period of time as oscillation treatment in reciprocal shaker reaction system；Acid water
Solution is preferably the aqueous solution that pH is 2~7；
Step 2: the precipitating generated in reaction system is collected by filtration, and is washed using the acid solution that pH is 2.0~2.5,
Then, it then is washed with deionized, solid catalyst is obtained after vacuum freeze drying and is showed severity special graceful stone.
Preferably, in the step 1, on the basis of the total volume of reaction system, H2O2Addition concentration be 1.0~
5.0g/L, FeSO4·7H2The addition concentration and H of O2O2The ratio between addition concentration be (5~11): 1.
Preferably, in the step 1, by reaction system as reciprocal shaker vibration temperature be 28~35 DEG C, reaction 20~
25 hours.
Preferably, in the step 1, H is utilized2SO4To adjust the pH of aqueous solution.
Preferably, in the step 2, precipitating is carried out using the filter membrane that aperture is 0.22~0.45 μm and is collected by filtration；It is acid
Solution is H2SO4Aqueous solution.
Application of the special graceful stone in water process of showing severity obtained using above-mentioned synthetic method, for removing four in water body
Ring element.
Preferably, include the following steps:
Step 1: the pH of the target water body containing tetracycline is adjusted to neutral (preferably pH=7)；
Step 2: the special graceful stone that will show severity is added in target water body, waiting show severity special graceful stone and tetracycline it is flat up to adsorption/desorption
Weighing apparatus；
Step 3: H is added after special graceful stone of showing severity is balanced with tetracycline up to adsorption/desorption2O2, it is anti-to carry out class Fenton oxidation
It answers, is preferably reacted under dark condition；
Preferably, in the first step, the concentration of tetracycline is 1~50mg/L in target water body.
Preferably, in the second step, on the basis of the volume of target water body, the addition concentration for special graceful stone of showing severity is 0.8
~1.5g/L.
Preferably, in the third step, on the basis of the volume of target water body, H2O2Addition concentration be 300~
1000mg/L。
3. beneficial effect
Compared with the prior art, the invention has the benefit that
(1) synthetic method of special graceful stone provided by the invention of showing severity, it is creative in the initial aqueous solution that pH is 2~7
Synthesis material (FeSO is added4·7H2O and H2O2), the synthesis yield that can be improved special graceful stone of showing severity is showed severity in pH=5
The yield highest of special graceful stone, is equivalent to 1g FeSO4·7H2O about generates 0.14g and shows severity special graceful stone；And pass through grinding for inventor
Study carefully, when pH < 2.0, the yield for special graceful stone of showing severity is almost nil, because will lead to the dissolution for graceful special stone of showing severity under acidic environment；When
The yield of pH excessively high (when pH > 7), special graceful stone of showing severity can equally reduce.
(2) synthetic method provided by the invention for showing severity special graceful stone passes through adjusting in the aqueous solution of suitable pH
FeSO4·7H2O and H2O2Addition concentration ratio, the specific surface area for special graceful stone of showing severity can not only be changed, while will affect its table
The OH content in face, and then improve special graceful stone point-of-zero charge of showing severity.The pKa value of tetracycline is 3.3, therefore, special graceful stone zero of showing severity
Point charge is higher, since electrostatic attraction acts on, more facilitates the absorption of tetracycline, and then reach the effect of fast degradation；
It is worth noting that the pH of initial aqueous solution is 5, FeSO4·7H2O and H2O2Addition concentration ratio be 10.81 when, by the spy that shows severity
The point-of-zero charge of graceful stone has been promoted to 6.2.
(3) the special graceful masonry of showing severity synthesized using the present invention is for heterogeneous catalytic reaction and to handle the dirt containing tetracycline
Water body is contaminated, due to showing severity, special graceful stone point-of-zero charge is higher, and help for tetracycline to be adsorbed to its surface, increases catalytic performance,
And it just can be in the height of 30min realization tetracycline without additional energy auxiliary (applying ultraviolet light, carry out photocatalysis induction)
Effect degradation；And the special graceful stone of showing severity that the present invention synthesizes passes through condition optimizing (pH, FeSO of initial aqueous solution4·7H2O and H2O2's
Add concentration ratio), have the stable advantage of large specific surface area, performance, during degrading tetracycline, high-efficient, iron dissolution
Amount is few, and easy recycling and reusing after degradation, so will not generate pollution to environment, and processing cost is low, the reaction time is short.
Detailed description of the invention
Fig. 1 is the sample schematic diagram of the special graceful stone of showing severity synthesized in the embodiment of the present invention 1；
Fig. 2 is scanning electron microscope (SEM) spectrogram of the special graceful stone of showing severity synthesized in the embodiment of the present invention 1；
Fig. 3 is the X-ray photoelectron spectroscopic analysis (XPS) of the special graceful stone catalyst of showing severity synthesized in the embodiment of the present invention 1
Spectrogram, in figure abscissa Binding energy indicate to combine can, ordinate Intensity indicates relative intensity；
Fig. 4 is the Fourier Transform Infrared Spectroscopy (FT-IR) of the special graceful stone catalyst of showing severity synthesized in the embodiment of the present invention 1
Spectrogram, abscissa Wavenumber indicates wave number in figure, and ordinate Transmittance indicates relative permeability；
Fig. 5 is X-ray diffraction (XRD) spectrogram of the special graceful stone catalyst of showing severity synthesized in the embodiment of the present invention 1, cross in figure
CoordinateIt indicates the angle of diffraction (i.e. deflection angle of the reflection light relative to incident ray), ordinate Intensity indicates that diffraction is strong
Degree；
Fig. 6 is to utilize the degradation speed that special graceful masonry is catalyst degradation tetracycline of showing severity synthesized in the embodiment of the present invention 1
Rate figure；
Fig. 7 is that special graceful stone iron dissolution during degrading tetracycline of showing severity synthesized in the embodiment of the present invention 1 contains spirogram；
It is catalyst recycling figure that Fig. 8, which is using the special graceful masonry of showing severity synthesized in the embodiment of the present invention 1,.
Specific embodiment
The present invention is further described below combined with specific embodiments below.
Embodiment 1
Being showed severity in the present embodiment using chemical method preparation, specific step is as follows for special graceful stone catalyst:
Step 1: the aqueous solution (adjusting using sulfuric acid) of pH5 is added in triangular flask, the FeSO of 43.2g is then added4·
7H2O is stirred evenly, and the H that 7mL mass fraction is 30% is added in property again2O2It (is not added dropwise, has disposably been directly added into
Conducive to obtaining bigger serface and the smooth Man Teshi that shows severity in surface), finally keeping reaction system total volume is 600mL；At this time
H in reaction system2O2Addition concentration be 4.0g/L, FeSO4·7H2The addition concentration and H of O2O2Concentration ratio be 10.8；
Then, it in shaking table reaction system back and forth rocked as 180r/min, at a temperature of 28 DEG C, reacts 24 hours,
There is precipitating to generate in reaction system；
Step 2: the membrane filtration that the precipitating aperture generated in reaction system is 0.45 μm is collected, and is 2.0 using pH
~2.5 sulfuric acid solution washs 4 times, then, then is washed with deionized 3 times, solid catalyst is obtained after vacuum freeze drying
It shows severity special graceful stone.
It will be seen from figure 1 that the graceful special stone of showing severity of preparation is powdered；As can be seen that synthesis from the SEM spectrogram of Fig. 2
Special graceful stone of showing severity be solid particle, in smooth spherical appearance.The spy that shows severity of the XPS elemental analysis spectrogram display synthesis of Fig. 3
Graceful stone only contains Fe, O, S element, and the infrared analysis spectrogram in Fig. 4 is shown, the special graceful stone of showing severity of synthesis contains a large amount of-OH,
SO4 2-, Fe-O functional group is the element and functional group that special graceful stone itself has of showing severity, without other elements and miscellaneous
Matter illustrates that product purity height, impurity are few.The XRD diagram of Fig. 5 be even more demonstrate synthesis be show severity special graceful stone (26.26 °,
35.16 °, 46.53 ° and 61.34 ° of characteristic peak is corresponding with the standard card of special graceful stone of showing severity respectively).And obtain after tested,
The specific surface area for the graceful special stone of showing severity being prepared is up to 54.9m2/g。
Utilize graceful special stone catalytic degradation tetracycline manufactured in the present embodiment of showing severity, the specific steps are as follows:
It is utilized step 1: the target water body (tetracycline concentration 50mg/L) containing tetracycline is added in reaction flask
The pH of target water body is adjusted to 7 by 0.1mol/LNaOH.
Step 2: the special graceful stone of showing severity of 1g is added in target water body, move in photo catalysis reactor, dark condition, room
Temperature is lower to wait the special graceful stone that makes for 1 hour to show severity to balance with tetracycline up to adsorption/desorption；(sentenced by the peak area value that liquid phase HPLC is tested
Break its adsorption equilibrium, peak area value, which is stabilized, may be degraded experiment as adsorption equilibrium)
Step 3: H is added after special graceful stone of showing severity is balanced with tetracycline up to adsorption/desorption2O2, carried out under dark condition
Degradation reaction is stirred under conditions of revolving speed is 350r/min using the agitating function of photo catalysis reactor；H2O2Plus
Entering concentration is 300mg/L；
Step 4: taking primary degradation sample every 5 minutes, it is measured.
Wherein, tetracycline removal rate calculation formula in water: η=[(C0-Ct)/C0] × 100%；
In formula: C0And CtThe respectively initial tetracycline concentration in water after the reaction t time of experiment.
As can be seen from Figure 6, after 30 minutes, the removal of tetracycline almost all, removal rate is up to 95%.Illustrate special graceful catalysis of showing severity
Agent shows good catalytic activity under the conditions of initial pH is 7, can produce great amount of hydroxy group free radical, to reach effective drop
Solve tetracycline.
Embodiment 2
The present embodiment is substantially the same manner as Example 1, the difference is that only:
It is prepared in the step of showing severity special graceful stone catalyst one using chemical method: overall reaction system is reciprocal as 180r/min
In the shaking table rocked, at a temperature of 30 DEG C, when reacting 20, there is precipitating to generate in reaction system；
In step 2: the membrane filtration that the precipitating aperture generated in reaction system is 0.22 μm being collected, is using pH
2.0~2.5 sulfuric acid solution washs 3 times, then, then is washed with deionized 3 times, solid catalysis is obtained after vacuum freeze drying
Agent is showed severity special graceful stone.
Catalytic degradation is carried out using the target water body that graceful special stone manufactured in the present embodiment of showing severity is 1 to tetracycline concentration,
In:
In second step: additional amount of the special graceful stone in target water body of showing severity is 0.8, is moved in photo catalysis reactor, dark
Condition waits special graceful stone of showing severity to balance with tetracycline up to adsorption/desorption at room temperature；
In third step: after special graceful stone of showing severity is balanced with tetracycline up to adsorption/desorption, H is added2O2, under dark condition into
Row degradation reaction is stirred under conditions of revolving speed is 350r/min using the agitating function of photo catalysis reactor；H2O2's
Addition concentration is 600mg/L；
Step 4: taking primary degradation sample every 3 minutes, it is measured.
Embodiment 3
The present embodiment is substantially the same manner as Example 1, the difference is that only:
It is prepared in the step of showing severity special graceful stone catalyst one using chemical method: overall reaction system is reciprocal as 180r/min
In the shaking table rocked, at a temperature of 35 DEG C, when reacting 25, there is precipitating to generate in reaction system；
In step 2: the membrane filtration that the precipitating aperture generated in reaction system is 0.32 μm being collected, is using pH
2.0~2.5 sulfuric acid solution washs 3 times, then, then is washed with deionized 3 times, solid catalysis is obtained after vacuum freeze drying
Agent is showed severity special graceful stone.
Catalytic degradation is carried out using the target water body that graceful special stone manufactured in the present embodiment of showing severity is 1 to tetracycline concentration,
In:
In second step: additional amount of the special graceful stone in target water body of showing severity is 1.5g, is moved in photo catalysis reactor, dark
Condition waits special graceful stone of showing severity to balance with tetracycline up to adsorption/desorption at room temperature；(sentenced by the peak area value that liquid phase HPLC is tested
Break its adsorption equilibrium, peak area value, which is stabilized, may be degraded experiment as adsorption equilibrium)
In third step: after special graceful stone of showing severity is balanced with tetracycline up to adsorption/desorption, H is added2O2, under dark condition into
Row degradation reaction is stirred under conditions of revolving speed is 350r/min using the agitating function of photo catalysis reactor；H2O2's
Addition concentration is 1000mg/L；
Step 4: taking primary degradation sample every 10 minutes, it is measured.
The catalytic degradation of tetracycline equally may be implemented using the graceful special stone of showing severity prepared in the present embodiment.Utilize this implementation
The catalytic degradation of tetracycline equally may be implemented in the graceful special stone of showing severity prepared in example.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, the difference is that only:
It is prepared in the step of showing severity special graceful stone catalyst one: being added in triangular flask different using chemical method in the present embodiment
The aqueous solution (being adjusted using sulfuric acid) of pH, pH is respectively 2,5,6,7.
Finally, obtaining the special graceful stone of showing severity of different output accordingly:
When pH is 2, the special graceful stone yield of showing severity being prepared is 1.0g；
When pH is 5, the special graceful stone yield of showing severity being prepared is 3.8g；
When pH is 6, the special graceful stone yield of showing severity being prepared is 3.4g；
When pH is 7, the special graceful stone yield of showing severity being prepared is 3.44g；
It is worth noting that when pH < 2.0, it may occur that the phenomenon that special graceful stone of showing severity dissolves, iron can dissolve out, therefore last production
Rate is almost 0, and as pH > 7, has sulfate radical dissolution, and hydroxyl substitutes sulfate radical, and the special graceful stone that causes to show severity can not generate.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, the difference is that only:
It is prepared in the step of showing severity special graceful stone catalyst one in the present embodiment using chemical method: FeSO4·7H2The addition of O is dense
DegreeWith H2O2Addition concentrationThe ratio between difference, be respectively as follows:6.0,10.8；Finally, obtaining difference accordingly
The special graceful stone of showing severity of yield:
When, the iron sulphur ratio Fe/S=3.1 for the special graceful stone of showing severity being prepared, molecular formula: Fe8O8(OH)2.8
(SO4)2.6.Specific surface area is 4.4m2/g.Removal rate to tetracycline is 59.7%.
When, the iron sulphur ratio Fe/S=4.4 for the special graceful stone of showing severity being prepared, molecular formula: Fe8O8(OH)4.4
(SO4)1.8.Specific surface area is 12.8m2/g.Removal rate to tetracycline is 62.2%.
When, the iron sulphur ratio Fe/S=7 for the special graceful stone of showing severity being prepared, molecular formula: Fe8O8(OH)5.7
(SO4)1.14.Specific surface area is 54.9m2/ g, the removal rate to tetracycline are 95%.
It is worth noting that FeSO4·7H2O and H2O2Mass concentration ratio without the iron content that will affect special graceful stone of showing severity with
And Fe/S (Fe/S ratio is high, and the point-of-zero charge of mine is with regard to relatively high), it also will affect the hydroxy radical content for special graceful stone of showing severity, and then influence
Isoelectric point,When, the special graceful stone point-of-zero charge of showing severity of preparation is 6.2,
The pKa value of tetracycline is 3.3, and therefore, in pH > 3, since electrostatic attraction acts on, tetracycline can be attracted to it
Surface, and then reach the effect of fast degradation.
Embodiment 6
The present embodiment has carried out showing severity on the basis of embodiment 1 special graceful stone catalyst during degrading tetracycline, molten
The measurement of iron content out takes primary degradation sample at regular intervals, carries out iron dissolution measurement.Specific determination step is as follows:
It takes the filtrate (1mL) to test sample after five minutes in 10mL colorimetric cylinder, 10% NH of 0.2mL is added2OH-HCl
Solution mixes, and stands 2min；
The buffer solution and 1mL Phen solution of 0.8mL sodium acetate are respectively added again, is diluted with water to scale, mixes, puts
Set 10min；
Finally, measuring absorbance value under 510nm wavelength, brings the absorbance measured into standard curve, calculate
The concentration of total iron after a certain period of time.
As can be seen from Figure 7, after 30 minutes tetracyclines all remove, iron the amount of dissolution is only 0.47mg/L.Illustrate special graceful stone of showing severity
Catalyst occurs mainly in superficial degradation during degrading tetracycline, and dissolution iron content is seldom, hardly generates iron cement,
And it may be implemented to recycle.Illustrate to be prepared and show severity special graceful stone with stable structure, therefore in degradation tetracycline
Reaction process in, special graceful stone of showing severity is solid catalyst, less soluble tapping.
Embodiment 7
Show severity special graceful stone catalyst recycling, cycling and reutilization the step of:
The present embodiment has carried out showing severity on the basis of embodiment 1 special graceful stone catalyst after tetracycline of degrading, catalyst
It shows severity the recovery experiment of special graceful stone.Specific step is as follows: after tetracycline all removal, filtering and recycles the special graceful Shi Cuihua that shows severity
Agent reuses after dry at 60 DEG C of baking oven (with embodiment 1).
As can be seen from Figure 8, special graceful stone catalyst tetracycline removal rate after circulation 3 times of showing severity can still keep 90% or more.It says
Bright special graceful stone catalyst of showing severity can be recycled in degradation tetracycline.
Claims (10)
1. a kind of synthetic method for special graceful stone of showing severity, it is characterised in that: the following steps are included:
Step 1: FeSO is added in the aqueous solution that pH value is 2~74·7H2O is stirred evenly, and then adds H2O2, with laggard
Row oscillation treatment has deposit generation；
Step 2: the deposit of generation being collected by filtration, is washed using acid solution, then, then is washed with deionized, very
Solid catalyst is obtained after vacuum freecing-dry to show severity special graceful stone.
2. the synthetic method of special graceful stone according to claim 1 of showing severity, it is characterised in that: in the step 1, H2O2It is dense
Degree is 1.0~5.0g/L, FeSO4·7H2The concentration and H of O2O2The ratio between concentration be (5~11): 1.
3. the synthetic method of special graceful stone according to claim 1 or 2 of showing severity, it is characterised in that: in the step 1, utilize
H2SO4To adjust the pH of aqueous solution.
4. the synthetic method of special graceful stone according to claim 3 of showing severity, it is characterised in that: in the step 1, oscillation temperature
Degree is 28~35 DEG C, and duration of oscillation is 20~25h.
5. the synthetic method of special graceful stone according to claim 3 of showing severity, it is characterised in that: in the step 2, utilize hole
Diameter is that 0.22~0.45 μm of filter membrane carries out precipitating and is collected by filtration；Acid solution is H2SO4Aqueous solution.
6. the application for special graceful stone of showing severity is prepared in a kind of synthetic method of the special graceful stone of showing severity as described in Claims 1 to 5,
It is characterized in that: for removing the tetracycline in water body.
7. the application of special graceful stone according to claim 6 of showing severity, characterized by the following steps:
Step 1: the pH value of the water body containing tetracycline is adjusted to neutrality；
Step 2: the special graceful stone that will show severity is added in water body；
Step 3: H is added after special graceful stone of showing severity is balanced with tetracycline up to adsorption/desorption2O2, carry out the reaction of class Fenton oxidation.
8. the application of special graceful stone according to claim 7 of showing severity, it is characterised in that: in the first step, tetracycline it is dense
Degree is 1~50mg/L.
9. the application of special graceful stone according to claim 8 of showing severity, it is characterised in that: in the second step, special graceful stone of showing severity
Concentration be 0.8~1.5g/L.
10. the application of special graceful stone according to claim 8 of showing severity, it is characterised in that: in the third step, H2O2Concentration
For 300~1000mg/L.
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| CN110732304A (en) * | 2019-10-24 | 2020-01-31 | 山西农业大学 | High-efficiency synthesis process of biogenic Schwertmannite |
| CN111186933A (en) * | 2020-01-08 | 2020-05-22 | 南京农业大学 | Chemical method for quickly forming sea urchin-shaped schneiderian minerals from acid mine wastewater |
| CN112978994A (en) * | 2021-02-25 | 2021-06-18 | 南京农业大学 | Method for treating stainless steel pickling wastewater and synchronously synthesizing secondary iron mineral |
| CN113262804A (en) * | 2021-05-31 | 2021-08-17 | 南京贝克特环保科技有限公司 | Molybdenum disulfide modified Schwertmann stone and preparation method and application thereof |
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| CN114804216A (en) * | 2022-04-28 | 2022-07-29 | 中国地质大学（北京） | Shi mineral for removing hexavalent chromium pollution in wastewater and preparation method thereof |
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| CN110732304A (en) * | 2019-10-24 | 2020-01-31 | 山西农业大学 | High-efficiency synthesis process of biogenic Schwertmannite |
| CN111186933A (en) * | 2020-01-08 | 2020-05-22 | 南京农业大学 | Chemical method for quickly forming sea urchin-shaped schneiderian minerals from acid mine wastewater |
| CN112978994A (en) * | 2021-02-25 | 2021-06-18 | 南京农业大学 | Method for treating stainless steel pickling wastewater and synchronously synthesizing secondary iron mineral |
| CN113262804A (en) * | 2021-05-31 | 2021-08-17 | 南京贝克特环保科技有限公司 | Molybdenum disulfide modified Schwertmann stone and preparation method and application thereof |
| CN113262804B (en) * | 2021-05-31 | 2024-01-19 | 南京贝克特环保科技有限公司 | Molybdenum disulfide modified schweitmann stone and preparation method and application thereof |
| CN113385139A (en) * | 2021-06-21 | 2021-09-14 | 南京贝克特环保科技有限公司 | Schwertmannite prepared by alkali neutralization method and application thereof |
| CN113385138A (en) * | 2021-06-21 | 2021-09-14 | 南京贝克特环保科技有限公司 | Preparation method and application of Schneider mineral |
| CN113385139B (en) * | 2021-06-21 | 2023-06-27 | 南京贝克特环保科技有限公司 | Schweitmann stone prepared by alkali neutralization method and application thereof |
| CN114790010A (en) * | 2022-04-28 | 2022-07-26 | 中国地质大学（北京） | Reduced schlerren mineral, preparation method thereof and application thereof in chromium-contaminated soil |
| CN114804216A (en) * | 2022-04-28 | 2022-07-29 | 中国地质大学（北京） | Shi mineral for removing hexavalent chromium pollution in wastewater and preparation method thereof |
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Application publication date: 20190823 Assignee: NANJING BEIKETE ENVIRONMENTAL PROTECTION TECHNOLOGY CO.,LTD. Assignor: NANJING AGRICULTURAL University Contract record no.: X2023980046863 Denomination of invention: A synthetic method of Schwertmann stone and its application Granted publication date: 20200508 License type: Common License Record date: 20231115 |