CN103028375A - BC-CuFe2O4 magnetic composite for removing tannic acid in drinking water and preparation method and application thereof - Google Patents
BC-CuFe2O4 magnetic composite for removing tannic acid in drinking water and preparation method and application thereof Download PDFInfo
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- CN103028375A CN103028375A CN2012105748683A CN201210574868A CN103028375A CN 103028375 A CN103028375 A CN 103028375A CN 2012105748683 A CN2012105748683 A CN 2012105748683A CN 201210574868 A CN201210574868 A CN 201210574868A CN 103028375 A CN103028375 A CN 103028375A
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- tannic acid
- bamboo charcoal
- drinking water
- coppe ferrite
- bamboo carbon
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Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a preparation method and an application of a bamboo carbon-copper ferrite (BC-CuFe2O4) magnetic composite for absorbing tannic acid in drinking water. The method comprises the steps of milling cleaned and dried bamboo carbon into powder with a grain size less than 80 meshes with a ball mill, and allowing the bamboo carbon to conduct composite reaction with copper ferrite prepared by a chemical coprecipitation method, to obtain a novel adsorbing material-bamboo carbon-copper ferrite composite which has higher adsorbability and magnetism, wherein when 0.4g/L adsorbent is added to the adsorbing material under neutral and faintly acid conditions of a tannic acid aqueous solution, and the adsorption time is 140min, the maximum adsorption capacity of the adsorbing material can reach 228.86mg/g. According to the preparation method, the adsorption capacity of the bamboo carbon to tannic acid is improved by increasing kinds and quantity of acid-alkali functional groups on the surface of the bamboo carbon according to chemical characteristics of tannic acid, and the prepared bamboo carbon-copper ferrite composite has good magnetism, and can be conveniently recovered by a magnetic separation method. The composite has a wider application prospect for removing a soluble organic matter-tannic acid in the drinking water.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to a kind of bamboo charcoal-coppe ferrite (BC-CuFe for absorption drinking water tannic acid
2O
4) magnetic composite and its preparation method and application.
Background technology
Tannic acid is the typical dissolved organic matter of occurring in nature (DOM), and its molecular structure is similar to humic acid, take polynary phenyl ring as skeleton, contains the functional groups such as hydroxyl, carboxyl in the molecule, and the structure of its polyphenol hydroxyl is given chemical characteristic and the physiologically active of its uniqueness.It is a kind of strong fixative, and fixedly numerous protein and carbohydrate derivative are again a kind of mordants, can strengthen the absorption to some heavy metal.There are some researches show that tannic acid has anti-inflammatory effect, but also be one of paathogenic factor of Kaschin-Beck disease, in drinking water chlorination process can with final chloroform class (THMs) strong carcinogen that generates after the chloropexia.Along with tannic acid extensive use in daily use chemicals, medicine, food service industry, tannic acid waste water is drained into can bring a series of water environment ecological problem in the environment.Therefore, tannic acid has become the drinking water safety control object, and it is significant for drinking water safety control efficiently to remove in the drinking water tannic acid.
At present, the technology of tannic acid has coagulant sedimentation, oxidizing process, absorption method, electrochemical process, the film way of distillation and bioanalysis etc. in the removal water body commonly used.Along with the development of synthetic technology, the advantage such as absorption method is fast because of its processing speed, efficient is high is widely used in removing the organic pollution of hard degradation in the drinking water.The tannic acid that a lot of scholars remove in the water body absorption method is studied, such as Wang Jinnan etc. once in " macromolecule journal " the 1st phase 96-101 page or leaf system research in 2010 absorption behavior of amido modified superhigh cross-linking resin to tannic acid, its saturated extent of adsorption is 24.43mg/g, but is difficult to satisfy the control requirement to numerous organic pollution aldehydes matters in the drinking water.Huang Jianhua etc. once utilized the attapulgite modified absorption tannic acid of OTAC in the 31st volume the 3rd phase 50-54 page or leaf in 2011 at " chemistry of forest product and industry ", and its saturated extent of adsorption can reach 190mg/g.Research mostly relies on the characteristics such as dense holes structure, high-specific surface area of adsorbent for the Adsorption of tannic acid for these, or forms various chemical bonds by the various active groups in surface and adsorbent, finally reaches to have the purpose of adsorbing tannic acid.Yet the lower or cost of adsorbance is higher to be the main restricting factor of this type of adsorbent of restriction during tannic acid is used in removing drinking water.Therefore, it is significant for removing in the drinking water tannic acid to seek efficient, cheap new adsorbent.
Natural porous material---bamboo charcoal (BC) has that specific area is large, porosity is high, is a kind of good porous adsorbent, is widely used in the fields such as industry, agricultural, electronics, health care, environmental protection.But because bamboo charcoal is the low pole material, the ability of removing tannic acid in the drinking water a little less than.For improving its adsorption capacity, the present invention adopts chemical coprecipitation, with the magnetic coppe ferrite (CuFe of tool
2O
4) carry out composite modifiedly with bamboo charcoal, increasing kind and the quantity of bamboo charcoal surface soda acid functional group, thereby improve bamboo charcoal to the adsorption capacity of tannic acid.Simultaneously, the bamboo charcoal that makes-coppe ferrite compound has good magnetic, can utilize easily magnetic separation method to reclaim.
Summary of the invention
The objective of the invention is for the removal of tannic acid in the drinking water and a kind of also magnetic novel absorption material of tool of stronger absorption property---bamboo charcoal-coppe ferrite compound that not only has is provided.For improving the bamboo Charcoal Adsorption ability, the present invention adopts chemical coprecipitation, with the magnetic coppe ferrite (CuFe of tool
2O
4) carry out composite modifiedly with bamboo charcoal, increasing kind and the quantity of bamboo charcoal surface soda acid functional group, thereby improve bamboo charcoal to the adsorption capacity of tannic acid.Simultaneously, the bamboo charcoal that makes-coppe ferrite compound has good magnetic, can utilize easily magnetic separation method to reclaim.
A kind of BC-CuFe for removing the drinking water tannic acid of the present invention
2O
4Magnetic composite it is characterized in that bamboo charcoal-coppe ferrite compound, is that bamboo charcoal is made powder, carries out recombination reaction with the coppe ferrite that makes by chemical coprecipitation and obtains.
Preparation method of the present invention is: be that the bamboo charcoal particle of 10-20mm is prepared into powder with commercial particle diameter, then carry out recombination reaction with the coppe ferrite that makes by chemical precipitation method, obtain again magnetic NEW TYPE OF COMPOSITE sorbing material of existing adsorption function.
The concrete preparation method of the present invention is as follows:
(1) bamboo charcoal preliminary treatment: bamboo charcoal is boiled with distilled water, remove dust and other residue of bamboo charcoal surface attachment, oven dry is that the dry bamboo charcoal particle of 10-20mm becomes particle diameter Powdered for subsequent use less than 80 purposes with grinding of ball grinder again with particle diameter after filtering;
(2) preparation of bamboo charcoal-coppe ferrite compound: prepare coppe ferrite by chemical coprecipitation, CuSO
45H
2O and Fe
2(SO
4)
3Mol ratio be 1:1, rear adding bamboo charcoal powder, making the mass ratio of itself and coppe ferrite is 1:2, carries out recombination reaction, namely obtains bamboo charcoal-coppe ferrite compound BC-CuFe
2O
4
Step (2) is specifically: take by weighing a certain amount of CuSO
45H
2O and Fe
2(SO
4)
3Put into conical flask, so that n (CuSO
45H
2O): n (Fe
2(SO
4)
3)=1:1 adds the 150mL ultra-pure water and is placed on magnetic stirring apparatus and makes it abundant dissolving, rear adding bamboo charcoal powder, and making the mass ratio of itself and coppe ferrite is 1:2, rapid stirring drips the NaOH solution of 4mol/L so that the pH of suspension is 11, continues to stir 30min; Then still aging 120min in 95 ℃ bath temperature outwells the upper strata stillness of night after the taking-up cooling, suction filtration, and repeatedly be washed with distilled water to neutrality, the gained solid namely obtains bamboo charcoal-coppe ferrite compound BC-CuFe 105 ℃ of lower oven dry
2O
4
Bamboo charcoal described in the present invention is commercial, and particle diameter is 10-20mm usually, and the minimum-value aperture is 1nm, and specific area is about 200m
2/ g.
The invention also discloses the method that described magnetic composite is used for removing the drinking water tannic acid, is with bamboo charcoal-coppe ferrite compound, adopts the tannic acid in the absorption method Drinking Water; The aqueous solution adds 20mg bamboo charcoal-coppe ferrite compound adsorbent in 50mL tool plug PA tube under neutrality and solutions of weak acidity, can reach the best Static Adsorption effect of removing tannic acid when adsorption time is 140min.
Adsorption experiment: in a series of 50mL tool plug PA tubes, add respectively a certain amount of BC-CuFe
2O
4Contain the tannic acid solution that initial concentration is 100mg/L with 50mL, its ionic strength that contains tannic acid solution is 0.1mol/LNaNO
3Behind solution mixing in the pipe, be fixed in 25 ± 1 ℃ the constant-temperature shaking incubator and vibrate with the 150r/min rotating speed, take out behind the 1440min and be rapidly the pin type filter PES-poly (ether sulfone) film filtration of 0.22 μ m with the aperture.Utilize at last AAS under the 277nm wavelength, to measure absorbance and calculate the concentration of tannic acid in the filtrate.
Mechanism of the present invention: the present invention utilizes chemical coprecipitation, with Fe
3+With divalent metal Cu
2+React at alkali condition, make coppe ferrite suspension, the valence state that exists of the Fe in this complex is+3 valencys, FeO
2 -Exist with anionic form.Recycling direct combination method, under alkali condition, coppe ferrite enters and carries out hybrid reaction generation BC-CuFe in the bamboo charcoal hole
2O
4, and be coated on the surfaces externally and internally in bamboo charcoal aperture.
Cu
2++2Fe
3++8OH
-→Cu(FeO
2)
2+4H
2O
Product B C-CuFe
2O
4In contain a large amount of Fe
3+, and Fe
3+May there be BC-CuFe in tannic acid iron complex with tannin-reaction generation black simultaneously
2O
4Carrier catalysis effect in reaction makes finally that tannic acid is able to effective removal in the water body, and its possible chemical equation is as follows:
Wherein
Represent the tannic acid molecule.
The present invention have the preparation method simple, process that energy consumption is low, the novel absorption material of efficient high, can make that tannic acid content obviously descends in the drinking water, dissolved organic matter---tannic acid has more wide application prospect in the drinking water for removing.
The specific embodiment
The concrete technical scheme of the present invention is as follows:
Take by weighing 2.50gCuSO
45H
2O and 4.00gFe
2(SO
4)
3Put into conical flask, add the 150mL ultra-pure water and be placed on magnetic stirring apparatus and make it abundant dissolving, add the 3g bamboo charcoal powder, rapid stirring drips the NaOH solution of 4mol/L so that the pH of suspension is 11, continues to stir 30min.Then still aging 120min in 95 ℃ bath temperature, outwell the upper strata stillness of night after taking out cooling, the turbid liquid of gained is washed with distilled water to neutrality repeatedly with 0.45 μ m water system membrane filtration, the gained solid namely makes composite adsorbing material BC-CuFe 105 ℃ of lower oven dry
2O
4
Take by weighing respectively 5-35mgBC-CuFe
2O
4In a series of 50mL tool plug PA tubes, namely in 1L solution, add the BC-CuFe of 0.1-0.7g
2O
4Composite adsorbing material, and contain the tannic acid solution that initial concentration is 100mg/L toward wherein adding respectively 50mL, it contains 0.1mol/LNaNO
3Background ions intensity.The pH of tannic acid solution is controlled to be 3-11.Behind solution mixing in the pipe, be fixed in 25 ± 1 ℃ the constant-temperature shaking incubator and vibrate with the 150r/min rotating speed, adsorption time is set is to take out behind the 10-1440min and be rapidly the pin type filter PES-poly (ether sulfone) film filtration of 0.22 μ m with the aperture.Utilize AAS to measure absorbance under the 277nm wavelength, calculate the concentration of tannic acid in each filtrate, the high energy of its adsorption capacity reaches 228.86mg/g, and under the same conditions, unmodified bamboo charcoal is up to 20.43mg/g to the adsorption capacity of tannic acid.
Below in conjunction with embodiment the present invention is further elaborated, but institute of the present invention protection domain is not limited only to this.
Embodiment 1
Quantity of sorbent is on the impact of adsorption effect
Take by weighing respectively 5mg, 15mg, 20mg, 25mg, 30mg, 35mgBC-CuFe
2O
4In a series of 50mL tool plug PA tubes, namely in 1L solution, add respectively the BC-CuFe of 0.1g, 0.3g, 0.4g, 0.5g, 0.6g, 0.7g
2O
4Composite adsorbing material, and contain the tannic acid solution that initial concentration is 100mg/L toward wherein adding 50mL respectively, it contains 0.1mol/LNaNO
3Background ions intensity.The pH of tannic acid solution is 5.Behind solution mixing in the pipe, be fixed in 25 ± 1 ℃ the constant-temperature shaking incubator and vibrate with the 150r/min rotating speed, adsorption time is set is to take out behind the 1440min and be rapidly the pin type filter PES-poly (ether sulfone) film filtration of 0.22 μ m with the aperture.The concentration of utilizing AAS to measure its absorbance under the 277nm wavelength and calculating tannic acid in each filtrate shows, when the adsorbent dosage is 5mg, clearance to tannic acid is 68.18%, its saturated extent of adsorption is 170.45mg/g, and adsorbent dosage amount is when being 20mg, clearance to tannic acid reaches 92.27%, and its saturated adsorption capacity reaches 230.68mg/g.When dosage is increased to 35mg from 20mg, tannic acid clearance in the solution is all remained on about 92%.Therefore, in 50mL tool plug PA tube, add the 20mg adsorbent as BC-CuFe
2O
4Sorbing material is removed the best Static Adsorption agent consumption of tannic acid.
Embodiment 2
The pH value is on the impact of adsorption effect
Take by weighing respectively 20mgBC-CuFe
2O
4In a series of 50mL tool plug PA tubes, and contain the tannic acid solution that initial concentration is 100mg/L toward wherein adding 50mL respectively, it contains 0.1mol/L NaNO
3Background ions intensity.The pH that tannic acid solution is set is 3-11.Behind solution mixing in the pipe, be fixed in 25 ± 1 ℃ the constant-temperature shaking incubator and vibrate with the 150r/min rotating speed, adsorption time is set is to take out behind the 1440min and be rapidly the pin type filter PES-poly (ether sulfone) film filtration of 0.22 μ m with the aperture.Utilize AAS under the 277nm wavelength, to measure its absorbance, the concentration of calculating tannic acid in each filtrate shows, when tannic acid solution pH is 3-8, its saturated extent of adsorption is all more than 218.36mg/g, clearance to tannic acid all is higher than 87.34%, wherein, its saturated extent of adsorption reaches maximum during pH=5, is 230.55mg/g.When pH is 9-11, along with the rising of pH, the clearance of tannic acid there is downward trend, pH is 11 o'clock, is 68.08% to the clearance of tannic acid.Hence one can see that, the aqueous solution under neutrality and solutions of weak acidity, BC-CuFe
2O
4Compound adsorbent has more excellent adsorption effect to tannic acid.
Embodiment 3
Adsorption time is on the impact of adsorption effect
Take by weighing respectively 20mgBC-CuFe
2O
4In a series of 50mL tool plug PA tubes, and contain the tannic acid solution that initial concentration is 100mg/L toward wherein adding 50mL respectively, it contains 0.1mol/LNaNO
3Background ions intensity.The pH of tannic acid solution is 5, behind solution mixing in the pipe, be fixed in 25 ± 1 ℃ the constant-temperature shaking incubator and vibrate with the 150r/min rotating speed, adsorption time is set is to take out behind the 10-1440min and be rapidly the pin type filter PES-poly (ether sulfone) film filtration of 0.22 μ m with the aperture.The concentration of utilizing AAS to measure tannic acid in each filtrate under the 277nm wavelength shows that along with the increase of adsorption time, compound adsorbent also increases gradually to the adsorbance of tannic acid.When adsorption time was 10min, its adsorbance was 131.29mg/g, and be 52.52% to the clearance of tannic acid this moment.When adsorption time during at 140-1440min, its adsorbance increase to tannic acid is comparatively slow, its adsorbance all about 225mg/g, this moment to the clearance of tannic acid all about 90%.Therefore, 140min can be used as BC-CuFe
2O
4Adsorbent reaches the minimum adsorption time of maximum adsorption capacity.
Claims (4)
1. BC-CuFe who be used for to remove the drinking water tannic acid
2O
4The preparation method of magnetic composite is characterized in that bamboo charcoal is made powder, carries out recombination reaction with the coppe ferrite that makes by chemical coprecipitation, obtains bamboo charcoal-coppe ferrite compound BC-CuFe
2O
4
2. preparation method according to claim 1 is characterized in that concrete steps are as follows:
(1) bamboo charcoal preliminary treatment: bamboo charcoal is boiled with distilled water, remove dust and other residue of bamboo charcoal surface attachment, oven dry is that the dry bamboo charcoal particle of 10-20mm becomes particle diameter Powdered for subsequent use less than 80 purposes with grinding of ball grinder again with particle diameter after filtering;
(2) preparation of bamboo charcoal-coppe ferrite compound: prepare coppe ferrite by chemical coprecipitation, CuSO
4* 5H
2O and Fe
2(SO
4)
3Mol ratio be 1:1, rear adding bamboo charcoal powder, making the mass ratio of itself and coppe ferrite is 1:2, carries out recombination reaction, namely obtains bamboo charcoal-coppe ferrite compound BC-CuFe
2O
4
3. BC-CuFe who be used for to remove the drinking water tannic acid
2O
4Magnetic composite it is characterized in that bamboo charcoal-coppe ferrite compound, is that bamboo charcoal is made powder, carries out recombination reaction with the coppe ferrite that makes by chemical coprecipitation and obtains.
4. the described magnetic composite of claim 3 is used for removing the method for drinking water tannic acid, is with bamboo charcoal-coppe ferrite compound, adopts the tannic acid in the absorption method Drinking Water; The aqueous solution adds 20 mg bamboo charcoal-coppe ferrite compound adsorbent in 50 mL tool plug PA tubes under neutrality and solutions of weak acidity, can reach the best Static Adsorption effect of removing tannic acid when adsorption time is 140 min.
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|---|---|---|---|
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|---|---|---|---|
| CN2012105748683A CN103028375A (en) | 2012-12-26 | 2012-12-26 | BC-CuFe2O4 magnetic composite for removing tannic acid in drinking water and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263890A (en) * | 2013-05-24 | 2013-08-28 | 中国计量学院 | Magnetic bamboo charcoal material and preparation method thereof |
| CN103831108A (en) * | 2014-03-18 | 2014-06-04 | 南京大学 | Copper ferrite-loaded activated carbon fiber, preparation method and application of fiber, and method for degrading activated azo dye wastewater |
| CN111185137A (en) * | 2020-01-22 | 2020-05-22 | 青岛农业大学 | Method for preparing biological carbon with magnetism and photocatalysis simultaneously by using pepper straws |
| CN111229162A (en) * | 2020-01-22 | 2020-06-05 | 青岛农业大学 | Method for preparing magnetic biochar from garlic straws |
| CN111229161A (en) * | 2020-01-22 | 2020-06-05 | 青岛农业大学 | Using CuFeO2Method for adsorbing oxytetracycline by/BC composite magnetic material |
-
2012
- 2012-12-26 CN CN2012105748683A patent/CN103028375A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 彭扬飞: "竹炭-铁酸盐复合物的制备及其性能研究", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263890A (en) * | 2013-05-24 | 2013-08-28 | 中国计量学院 | Magnetic bamboo charcoal material and preparation method thereof |
| CN103831108A (en) * | 2014-03-18 | 2014-06-04 | 南京大学 | Copper ferrite-loaded activated carbon fiber, preparation method and application of fiber, and method for degrading activated azo dye wastewater |
| CN111185137A (en) * | 2020-01-22 | 2020-05-22 | 青岛农业大学 | Method for preparing biological carbon with magnetism and photocatalysis simultaneously by using pepper straws |
| CN111229162A (en) * | 2020-01-22 | 2020-06-05 | 青岛农业大学 | Method for preparing magnetic biochar from garlic straws |
| CN111229161A (en) * | 2020-01-22 | 2020-06-05 | 青岛农业大学 | Using CuFeO2Method for adsorbing oxytetracycline by/BC composite magnetic material |
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Application publication date: 20130410 |