CN108479703A - A kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal - Google Patents
A kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal Download PDFInfo
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- CN108479703A CN108479703A CN201810348801.5A CN201810348801A CN108479703A CN 108479703 A CN108479703 A CN 108479703A CN 201810348801 A CN201810348801 A CN 201810348801A CN 108479703 A CN108479703 A CN 108479703A
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- active carbon
- magnetic active
- magnetic
- water removal
- beta estradiols
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- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
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- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of preparation methods for efficiently removing the magnetic active carbon of 17 β estradiol in water removal, for many drawbacks of existing adsorbent, it is high to provide a kind of adsorption capacity, safety is good, recycling is convenient, the repeatable preparation method for removing the adsorbent of 17 β estradiol in water removal utilized, magnetic active carbon prepared by the present invention, it can be used for handling 17 β estradiol in water, and can magnetic force quickly recycle, it repeats and utilizes after regeneration, solve the problems, such as to go the quick recycling and recycling of the adsorbent of 17 β estradiol in water removal at present, with realistic meaning, be conducive to hydro-ecological safety.
Description
Technical field
The present invention relates to sorbing material technical field more particularly to a kind of magnetism for efficiently removing 17 beta estradiols in water removal are living
The preparation method of property charcoal.
Background technology
Non-steroidal estrogenic is mainly generated by the mankind and livestock and poultry animal ovarian follicle and placenta secretion, while testis can also generate greatly
Measure estrogen.These non-steroidal estrogenics are concentrated by excrement and urine through municipal sewage pipe network mostly enters sewage treatment plant,
And as the Chinese effluent of sewage treatment plant enters environment water, 90% non-steroidal estrogenic comes from intensive farm poultry
Poultry manure.Non-steroidal estrogenic source in China's surface water is related with untreated agricultural and the discharge of sanitary sewage.According to
Investigation, although there is some difference for various countries' surface water non-steroidal estrogenic content, its concentration level has still closed on even more than
The risk critical value of toxicological test.
The toxicity of estrogen is mainly shown as the influence to reproductive system, internal system etc., in ng/L grades of concentration water
The flat internal system that may interfere with biology, multiple American-European countries such as Britain will be by limiting emission.When the class in water environment
Sterol estrogen concentrations can then influence the normal function of aquatile sexual gland higher than interference threshold, destroy sex ratio, influence to plant
Population density, and then constituted a threat to the ecosystem by food chain.Female human shifts to an earlier date in puberty, and male reproductive function declines
It is considered related with these substances.With oestrone, estradiol and ethinyl estradiol etc. are that the female vigor estrogens of height of representative are solid
Alcohol estrogen is classified as priority monitoring and the substance of research by European Union.
17 beta estradiols are that most strong sex hormone is acted in many environmental estrogens, and 17 beta estradiols of low concentration are just
Apparent irreversible harm can be generated, murder by poisoning concentration down to 1 ng/L.Such as milter feminisation, break internal system balance etc..
17 beta estradiols are prevalent in all kinds of surrounding mediums, especially in water environment.139 to 30 states in the U.S. such as Kolpin
River water sample is detected the water sample for finding 40% by the different degrees of pollution of 17 beta estradiols.Currently, in surface water, underground
Water and drinking water have the detection of 17 beta estradiols.It can be seen that the harm of 17 beta estradiols is big, pollution range is wide.Therefore in water
Especially the removal of 17 beta estradiols is very necessary in drinking water source.
Currently, the main minimizing technology of 17 beta estradiols is bioanalysis, Physical and chemical method.But there is degradation in bioanalysis
The shortcomings of period is long, degradation is not thorough, is big by environmental influence.Chemical method is higher to experiment condition and material requirements, hardly possible one
17 beta estradiols are mineralized into innocuous substance by secondary property.Absorption method removal estrogen research is more, but both at home and abroad to the suction of estrogen
Attached research has focused largely on activated carbon adsorption and activated sludge absorption, and maximum problem existing for these methods is point of adsorbent
From difficulty, adsorbent cannot recycle.
The present invention is directed to filter out the adsorbent strong to 17 beta estradiol suction-operateds in water first, then altogether using chemistry
The precipitation method are prepared into magnetic active carbon, and study its regeneration method, develop highly effective and safe, the convenient and repeatable profit of recycling
Adsorbent has good application prospect.
Invention content
It is an object of the invention to many drawbacks for existing adsorbent, study it is a kind of efficiently, safety, recycling it is convenient,
The repeatable preparation method for removing the adsorbent of 17 beta estradiols in water removal utilized, solves to go 17 beta estradiols in water removal at present
The recycling difficulty of adsorbent and the problem of cannot reusing, there is realistic meaning, be conducive to hydro-ecological safety.
The present invention is achieved by the following technical solutions：
A kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal, includes the following steps：
（1）Powdered Activated Carbon 20-24 h are impregnated with 5% hydrochloric acid solution, then are washed repeatedly to neutrality with deionized water, and in
104-106 DEG C of drying is for 24 hours；
（2）The accurate 10-20g seven that weighs is hydrated FeSO4And 30-40g tetra- is hydrated FeCl3It is dissolved in 400-800 mL deionized waters
In, 10-20g step 1 gained Powdered Activated Carbons are added, are placed on stirring 20-60 min on magnetic stirring apparatus, are allowed to be sufficiently mixed
It is even, then fast drop 2-10mol/L sodium hydroxides 60-160mL, it is stirring while adding, so that it is fully reacted；
（3）Mixture is placed in 100 DEG C of thermostat water bath and is aged 2-5h, object to be mixed is cooled to room temperature, and uses deionized water
It is rinsed repeatedly to neutrality, dry 20-30h under the conditions of being placed in 105 DEG C can be obtained magnetic active carbon through magnetic force recycling.
Magnetic active carbon pack sealing obtained, is stored at shady and cool drying in the step 3.
The regeneration method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal：
（1）Dry 1h under the conditions of the magnetic active carbon that magnetic force recycles is placed in 104-106 DEG C；
（2）By methanol and ethyl acetate according to volume ratio（30-60）:（40-70）It is hybridly prepared into regeneration leacheate, after drying
Magnetic active carbon to be regenerated put into the glass chromatography column with porous sieve plate, first with regeneration leacheate elution, then with etc. bodies
Product deionized water elution；
（3）The magnetic active carbon in chromatographic column is poured out, dry 1h, packs and be sealed in cool place under the conditions of being placed in 104-106 DEG C
At dry.
The solid-to-liquid ratio of the magnetic active carbon and regeneration leacheate is 1：（5-20）g/mL.
Beneficial effects of the present invention are：
The present invention is by screening Fe2+、Fe3+And the optimal proportion of activated carbon, it prepares magnetic active carbon using chemical precipitation method and removes
17 beta estradiols in water, adsorption effect is good, of low cost, safe and reliable, can quickly recycle magnetic force, with regeneration leacheate elution
The magnetic active carbon of adsorption saturation can be allowed to regenerate afterwards, can be reused 5 times or more, magnetic active carbon can be increased and gone as adsorbent
The popularization and application dynamics of 17 beta estradiols in water removal has significant economic, society and environmental benefit.
Description of the drawings
Fig. 1 show in the present invention magnetic separation pattern in 1min after magnetic active carbon adsorption saturation（A）Before separation
（B）In separation（C）In separation（D）After separation.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
A kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal, includes the following steps：
（1）24 h of Powdered Activated Carbon is impregnated with 5% hydrochloric acid solution, then is washed repeatedly to neutrality with deionized water, and in 105 DEG C
Drying is for 24 hours；
（2）The accurate 19.5g seven that weighs is hydrated FeSO4And 37.8g tetra- is hydrated FeCl3It is dissolved in 500mL deionized waters, is added
16.5g step 1 gained Powdered Activated Carbons, are placed on magnetic stirring apparatus and stir 30min, are allowed to be sufficiently mixed uniformly, then quickly drop
Add 5mol/L sodium hydroxides 100mL, it is stirring while adding, so that it is fully reacted；
（3）Mixture is placed in 100 DEG C of thermostat water bath and is aged 4h, object to be mixed is cooled to room temperature, anti-with deionized water
It is multiple to rinse to neutrality, it is dried under the conditions of being placed in 105 DEG C for 24 hours, can be obtained magnetic active carbon through magnetic force recycling, packed close
Envelope is stored at shady and cool drying.
The regeneration method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal：
（1）Dry 1h under the conditions of the magnetic active carbon that magnetic force recycles is placed in 105 DEG C；
（2）By methanol and ethyl acetate according to volume ratio 50：50 are hybridly prepared into regeneration leacheate, will be to be regenerated after drying
Magnetic active carbon is put into glass chromatography column, and first with regeneration leacheate elution, wherein magnetic active carbon is consolidated with leacheate is regenerated
Liquor ratio is 1：10g/mL, then eluted with isometric deionized water；
（3）The magnetic active carbon in chromatographic column is poured out, dry 1h under the conditions of being placed in 105 DEG C, pack is sealed dry in cool place
Place.
Static Adsorption experiments have shown that, magnetic active carbon produced by the present invention in water 17 beta estradiols adsorption dynamics adsorption kinetics accord with
Pseudo-second order kinetic model is closed, adsorption isotherm more meets Freundlich adsorption isotherm models, satisfies to 17 beta estradiols
It is 430mg/g with adsorption capacity, is 90% or so to the removal rate of 17 beta estradiols in 5min, it can be on the left sides 1min after adsorption saturation
It is right to realize that quick magnetic force recycles such as Fig. 1, have the advantages that the convenient and repeatable utilization of highly effective and safe, recycling.
In five regeneration tests, magnetic active carbon to the removal rates of 17 beta estradiols of initial concentration 2mg/L in water according to
Secondary is 96.3%, 88.5%, 79.4%, 69.3%, 61.2%, it is seen then that magnetic active carbon of the present invention has preferable recycling value.
Claims (4)
1. a kind of preparation method for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal, which is characterized in that including following step
Suddenly：
（1）Powdered Activated Carbon 20-24 h are impregnated with 5% hydrochloric acid solution, then are washed repeatedly to neutrality with deionized water, and in
104-106 DEG C of drying is for 24 hours；
（2）The accurate 10-20g seven that weighs is hydrated FeSO4And 30-40g tetra- is hydrated FeCl3It is dissolved in 400-800 mL deionized waters,
10-20g step 1 gained Powdered Activated Carbons are added, are placed on stirring 20-60 min on magnetic stirring apparatus, are allowed to be sufficiently mixed uniformly,
Fast drop 2-10mol/L sodium hydroxides 60-160mL again, it is stirring while adding, so that it is fully reacted；
（3）Mixture is placed in 100 DEG C of thermostat water bath and is aged 2-5h, object to be mixed is cooled to room temperature, and uses deionized water
It is rinsed repeatedly to neutrality, dry 20-30h under the conditions of being placed in 105 DEG C can be obtained magnetic active carbon through magnetic force recycling.
2. the preparation method according to claim 1 for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal, feature
It is, magnetic active carbon pack sealing obtained, is stored at shady and cool drying in the step 3.
3. a kind of magnetism for efficiently removing 17 beta estradiols in water removal made from claim 1-2 any one of them preparation methods
Activated carbon further includes its regeneration method：
（1）Dry 1h under the conditions of the magnetic active carbon that magnetic force recycles is placed in 104-106 DEG C；
（2）By methanol and ethyl acetate according to volume ratio（30-60）:（40-70）It is hybridly prepared into regeneration leacheate, after drying
Magnetic active carbon to be regenerated put into the glass chromatography column with porous sieve plate, first with regeneration leacheate elution, then with etc. bodies
Product deionized water elution；
（3）The magnetic active carbon in chromatographic column is poured out, dry 1h, packs and be sealed in cool place under the conditions of being placed in 104-106 DEG C
At dry.
4. the regeneration method according to claim 3 for efficiently removing the magnetic active carbon of 17 beta estradiols in water removal, the magnetic
Property activated carbon with regeneration leacheate solid-to-liquid ratio be 1：（5-20）g/mL.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532229A (en) * | 2022-10-18 | 2022-12-30 | 兰州交通大学 | Preparation of magnetic adsorbent material and application of bacterium carrier construction in removing aflatoxin |
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|---|---|---|---|---|
| CN101774576A (en) * | 2010-01-26 | 2010-07-14 | 哈尔滨工程大学 | Modified active carbon and preparation method application thereof |
| CN102240537A (en) * | 2011-06-28 | 2011-11-16 | 中国科学技术大学 | Method for preparing organic dye absorbent |
| CN103406094A (en) * | 2013-06-04 | 2013-11-27 | 北京林业大学 | Method for manufacturing magnetic sludge-based active carbon |
| CN103611496A (en) * | 2013-11-12 | 2014-03-05 | 南京工业大学 | Magnetic carbon-based adsorbent and application thereof |
| CN105126755A (en) * | 2015-09-10 | 2015-12-09 | 哈尔滨工业大学宜兴环保研究院 | Novel magnetic active carbon and preparation method thereof |
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- 2018-04-18 CN CN201810348801.5A patent/CN108479703A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774576A (en) * | 2010-01-26 | 2010-07-14 | 哈尔滨工程大学 | Modified active carbon and preparation method application thereof |
| CN102240537A (en) * | 2011-06-28 | 2011-11-16 | 中国科学技术大学 | Method for preparing organic dye absorbent |
| CN103406094A (en) * | 2013-06-04 | 2013-11-27 | 北京林业大学 | Method for manufacturing magnetic sludge-based active carbon |
| CN103611496A (en) * | 2013-11-12 | 2014-03-05 | 南京工业大学 | Magnetic carbon-based adsorbent and application thereof |
| CN105126755A (en) * | 2015-09-10 | 2015-12-09 | 哈尔滨工业大学宜兴环保研究院 | Novel magnetic active carbon and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532229A (en) * | 2022-10-18 | 2022-12-30 | 兰州交通大学 | Preparation of magnetic adsorbent material and application of bacterium carrier construction in removing aflatoxin |
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