CN109179554A - Utilize the method for fortimicin in manganese dioxide load biological carbon materials removal water body - Google Patents
Utilize the method for fortimicin in manganese dioxide load biological carbon materials removal water body Download PDFInfo
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- CN109179554A CN109179554A CN201811175979.0A CN201811175979A CN109179554A CN 109179554 A CN109179554 A CN 109179554A CN 201811175979 A CN201811175979 A CN 201811175979A CN 109179554 A CN109179554 A CN 109179554A
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- manganese dioxide
- fortimicin
- carbon materials
- biological carbon
- dioxide load
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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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- 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
-
- 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
Abstract
The application that the present invention relates to biological carbon materials in water treatment field, disclose a kind of method using fortimicin in manganese dioxide load biological carbon materials removal water body, method summarizes following steps, composite material preparation: loading manganese dioxide in biomass, then fires manganese dioxide load biological carbon materials by compound biomass；Minimizing technology is vibrated the following steps are included: by manganese dioxide load biological carbon materials addition fortimicin solution, completes the Adsorption to fortimicin.The present invention efficiently eliminates fortimicin in water by using manganese dioxide load biological carbon materials adsorbent, reduces harm of the fortimicin to aquatic ecological environment.
Description
Technical field
The application that the present invention relates to manganese dioxide composite materials in water treatment field is related to a kind of negative using manganese dioxide
Carry the application of fortimicin in biological carbon materials removal water body.
Background technique
Tetracycline antibiotics are a kind of broad-spectrum antibiotics, develop and application be 20th century medical science it is great at
Just, it can control and treat infectious diseases, be widely used in fields such as medicine, animal-breeding and agriculturals.Fortimicin is made
It for main tetracycline antibiotics, is widely used also and many negative effects and problem occurs, in soil, plant, food
Residue in product is finally pooled in water body by biodegrade and rain drop erosion, then is migrated by water body to animals and plants and people
Body seriously threatens the balance of the nature ecosystem.In production and application, a small amount of fortimicin remained in the environment is
Aqueous bio, animal and people's life bring very big security risk.It is attributed to the growth inhibition and breeding effect of fortimicin
It answers, Doxycycline Wastewater becomes traditional biological wastewater treatment and is difficult to one of waste water coped with.Therefore, it removes strong in aquatic environment
Power mycin is necessary and urgent.The testing result of domestic and international many water bodys shows the antibiotic using fortimicin as representative
Be prevalent in urban water-body and concentration be higher than interference threshold more, and these major parts because of sewage treatment plant to this substance
Incomplete removal.This results in fish and other aquatiles in river water to there are potential risks at low concentrations.At present
Common minimizing technology mainly has biological treatment, advanced oxidation processes and absorption method.Absorption method is substantially adsorbent activity table
In face of the attraction of antibiotic, and because the advantages that it is efficient, low price and recuperability are strong receives more and more attention, absorption is commonly used
The active charcoal of agent, multi-walled carbon nanotube etc..
In recent years, the application of charcoal receives significant attention.Charcoal organic material due to it is loose porous, be arranged with
The structures such as the aromatic rings lamella of sequence, so that charcoal has in terms of adsorbing the pollutants such as heavy metal, organic matter, dyestuff in waste water
Very big potentiality.Furthermore, it is possible to improve the adsorption capacity of charcoal by using subsequent processing.Nano-manganese dioxide conduct
One kind of adsorbent has many advantages, such as the extensive concern that cheap and environment is friendly, by domestic and international expert.Its specific surface area
Greatly, partial size is small, adsorb, aoxidize and catalytic performance is high, and having to heavy metal ion, phenol, organic dye waste water etc. in water has
Stronger removal ability.Furthermore the use scope of composite material is also concerned, they have removal efficiency height, operating cost
The features such as low, function modification is easy.More than accordingly, it is considered to, manganese dioxide is loaded in husk biomass, fires two with tube furnace
Manganese oxide load biological carbon materials, with this come increase biological carbon surface fortimicin adsorption site and functional group quantity and
Type, to improve its adsorption capacity to fortimicin.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of at low cost, adsorption efficiency
Height, recycling property are strong and are removed in water body strongly to contaminant removal capacity is strong using manganese dioxide load biological carbon materials
The method of mycin.
In order to solve the above technical problems, technical solution proposed by the present invention is to be gone using manganese dioxide load biological carbon materials
Except the method for fortimicin in water body, comprising the following steps: manganese dioxide is loaded in biomass, then by compound biomass
Prepare manganese dioxide load biological carbon materials；The obtained composite material completes the Adsorption to fortimicin.
Above-mentioned is gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials, the manganese dioxide
Biological carbon materials are loaded through the following steps that being prepared:
(1) biomass is added by continuing nitrogen purification, and stir 1h in the manganese chloride solution after nitrogen purification,
Obtain biomass-Mn2+Mixture
(2) biomass-Mn in (1) is added dropwise into the solution containing potassium permanganate and sodium hydroxide2+Mixture, after
Biomass-MnO is generated after continuous stirring 20min2Mixture is dried at 70 DEG C.
(3) by biomass-MnO after drying in (2)2It fires in tube furnace, then thoroughly washes it with deionized water
It washs repeatedly, filtering obtains manganese dioxide load biological carbon materials after drying.
Above-mentioned is gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials, the manganese dioxide
In the preparation step (1) for loading biological carbon materials, the manganese chloride solution concentration is 0.1mol/L, the manganese chloride solution nitrogen
Purification time is 20min, and stirring uses magnetic stirring apparatus, revolving speed 300rpm.
Above-mentioned is gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials, the manganese dioxide
In the preparation step (2) for loading biological carbon materials, potassium permanganate concentration is 0.1mol/L in the solution, and naoh concentration is
0.2mol/L, the biomass and MnO2Ratio is 2:1.
Above-mentioned is gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials, the manganese dioxide
In the preparation step (3) for loading biological carbon materials, the firing temperature of the tube furnace is 500 DEG C, fire-bar in the drying box
Part: temperature is 70 DEG C.
Above-mentioned is gone in water removal in the method for fortimicin, in the water body using manganese dioxide load biological carbon materials
The concentration control of fortimicin is in 10-400mg/L, and pH control is in 2.0-10.0, and temperature control is at 25 DEG C, revolving speed 180rpm.
Above-mentioned is gone in water removal in the method for fortimicin, in the water body using manganese dioxide load biological carbon materials
The equilibrium adsorption capacity of fortimicin reaches 104mg/g.
Compared with the prior art, the advantages of the present invention are as follows:
1. leading to the present invention provides a kind of method for removing fortimicin in water removal using manganese dioxide load biological carbon materials
It crosses using in charcoal area load manganese dioxide, changes charcoal surface characteristics, realize and fortimicin is effectively gone
It removes；
2. manganese dioxide load biological carbon materials of the invention have, easy to operate, operating cost is low, surface functionalities group
The characteristics of mostly and easily in conjunction with fortimicin molecule, and removal efficiency is high, has environment friendly, is fortimicin in water body
Removal propose new method；
3. raw material sources of the invention are abundant, at low cost, and preparation method and simple process, work can be effectively realized
Industry metaplasia produces.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of primitive organism charcoal
Fig. 2 is the scanning electron microscope (SEM) photograph that charcoal loads manganese dioxide composite material in present example 1
Fig. 3 is that charcoal loads manganese dioxide composite material to fortimicin under the differential responses time in present example 2
Absorption variation
Fig. 4 is that charcoal loads manganese dioxide composite material to fortimicin under different initial concentrations in present example 3
Absorption variation
Fig. 5 is that charcoal loads manganese dioxide composite material to fortimicin under condition of different pH in present example 4
Absorption variation
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Embodiment 1
The method for removing fortimicin in water removal using manganese dioxide load biological carbon materials, comprising the following steps:
(1) manganese dioxide load biological carbon materials are prepared
(1.1) biomass is added by continuing nitrogen purification, and stir in the manganese chloride solution after nitrogen purification
1h obtains biomass-Mn2+Mixture
(1.2) biomass-Mn in (1.1) is added dropwise into the solution containing potassium permanganate and sodium hydroxide2+Mixing
Object continues to generate biomass-MnO after stirring 20min2Mixture is dried at 70 DEG C.
(1.3) by biomass-MnO after drying in (1.2)2It is fired in tube furnace, it is then that it is thorough with deionized water
Repeatedly, filtering obtains manganese dioxide load biological carbon materials after drying for bottom washing.As shown in Figure 2.Fig. 2 is in the present embodiment
Activate the electron scanning electron microscope of montmorillonite biology carbon composite.Comparison diagram 1 and Fig. 2 are it is found that activation montmorillonite of the invention
Charcoal composite material surface has one layer of charcoal package, rough surface, aggregation extent height.
(2) in water body fortimicin Adsorption
(2.1) it prepares the stock solution of 1g/L fortimicin: weighing fortimicin 0.5g and be dissolved in 500mL deionized water, hide
Light is stored in 4 DEG C of refrigerators.
(2.2) stock solution in (2.1) is diluted to aimed concn, the manganese dioxide of 10mg step (1.3) preparation is added
Biological carbon materials are loaded, are placed in 25 DEG C of constant temperature oscillations, water-bath constant temperature oscillator revolving speed is 180rpm, and duration of oscillation is for 24 hours, instead
Ying Hou, solution sedimentation, using 0.45 μm of Teflon filtration (syringe type).
(2.3) solution concentration after being reacted (2.2) is measured with ultraviolet specrophotometer.
Embodiment 2
A kind of method that manganese dioxide load biological carbon materials remove fortimicin in water removal, step and 1 water body of embodiment
The Adsorption of middle fortimicin is identical, is different only in that: sorption reaction time is 0-24h in embodiment 2.
Concentration is the fortimicin solution of 50mg/L after taking 25mL to dilute, and manganese dioxide made from 10mg embodiment 1 is added
Load biological carbon materials, be placed in 25 DEG C of constant temperature oscillations, water-bath constant temperature oscillator revolving speed be 180rpm, duration of oscillation 0-24h,
After reaction, solution sedimentation, using 0.45 μm of Teflon filtration (syringe type).After ultraviolet specrophotometer measurement reaction
The adsorbance result of the concentration of fortimicin in solution, calculating is shown in Fig. 3.The result shows that being inhaled in manganese dioxide load biological carbon materials
During attached fortimicin, the incipient rate of adsorption is most fast, as the incremental rate of adsorption of time gradually tends towards stability,
For 24 hours close to adsorption equilibrium.
Embodiment 3
A kind of method that manganese dioxide load biological carbon materials remove fortimicin in water removal, step and 1 water body of embodiment
The Adsorption of middle fortimicin is identical, is different only in that: it is 10.0-400.0mg/L that initial concentration is adsorbed in embodiment 3.
Concentration is 10.0,40.0,80.0,120.0,180.0,240.0,300.0,360.0 Hes after taking 25mL to dilute
The fortimicin solution of 400.0mg/L is added manganese dioxide load biological carbon materials made from 10mg embodiment 1, is placed in 25 DEG C
In constant temperature oscillation, water-bath constant temperature oscillator revolving speed is 180rpm, and duration of oscillation is that for 24 hours, after reaction, solution is settled, using 0.45 μ
M Teflon filtration (syringe type).With the concentration of fortimicin in solution after ultraviolet specrophotometer measurement reaction, calculate
Adsorbance result see Fig. 4.The result shows that with the increase of initial concentration, adsorbance also increases.It is 400mg/L in initial concentration
When, manganese dioxide load biological carbon materials reach 899mg/g to the adsorbance maximum of fortimicin.
Embodiment 4
A kind of method that manganese dioxide load biological carbon materials remove fortimicin in water removal, step and 1 water body of embodiment
The Adsorption of middle fortimicin is identical, is different only in that: the pH value that solution is adjusted in embodiment 4 is 2.0-10.0.
Concentration is the fortimicin solution of 50mg/L after taking 25mL to dilute, and with concentration be 1M NaOH and HCl solution adjusting is molten
The pH value of liquid is manganese dioxide made from 2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0 and 10.0 addition 10mg embodiments 1
Biological carbon materials are loaded, are placed in 25 DEG C of constant temperature oscillations, water-bath constant temperature oscillator revolving speed is 180rpm, and duration of oscillation is for 24 hours, instead
Ying Hou, solution sedimentation, using 0.45 μm of Teflon filtration (syringe type).It is molten after being reacted with ultraviolet specrophotometer measurement
The adsorbance result of the concentration of fortimicin in liquid, calculating is shown in Fig. 5.The result shows that pH is 3.0 or so, manganese dioxide load is raw
Object Carbon Materials reach maximum to the adsorbance of fortimicin.
Claims (7)
1. a kind of method using fortimicin in manganese dioxide load biological carbon materials removal water body, comprising the following steps:
Manganese dioxide is loaded in biomass, and manganese dioxide load biological carbon materials are then prepared by compound biomass；It is described to obtain
Composite material completes the Adsorption to fortimicin.
2. the method according to claim 1 for removing fortimicin in water removal using manganese dioxide load biological carbon materials,
It is characterized in that, the manganese dioxide load biological carbon materials are through the following steps that be prepared:
(1) biomass is added by continuing nitrogen purification, and stir 1h, obtaining in the manganese chloride solution after nitrogen purification
Biomass-Mn2+Mixture
(2) biomass-Mn in step (1) is added dropwise into the solution containing potassium permanganate and sodium hydroxide2+Mixture, after
Biomass-MnO is generated after continuous stirring 20min2Mixture is dried at 70 DEG C.
(3) by biomass-MnO after drying in step (2)2It fires in tube furnace, then thoroughly washes it with deionized water
It washs repeatedly, filtering obtains manganese dioxide load biological carbon materials after drying.
3. according to claim 2 gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials,
In the preparation step (1) of the manganese dioxide load biological carbon materials, the manganese chloride solution concentration is 0.1mol/L, the chlorine
The change manganese solution nitrogen purification time is 20min, and stirring uses magnetic stirring apparatus, revolving speed 300rpm.
4. according to claim 2 gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials,
In the preparation step (2) of the manganese dioxide load biological carbon materials, potassium permanganate concentration is 0.1mol/L, hydrogen in the solution
Oxidation na concn is 0.2mol/L, the biomass and MnO2Ratio is 2:1.
5. according to claim 2 gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials,
In the preparation step (3) of the manganese dioxide load biological carbon materials, the firing temperature of the tube furnace is 500 DEG C, the baking
Heating condition in dry case: temperature is 70 DEG C.
6. according to claim 2 gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials,
The concentration control of fortimicin in the water body is in 10-400mg/L, and in 2.0-10.0, temperature is controlled at 25 DEG C for pH control, turns
Speed is 180rpm.
7. according to claim 2 gone in water removal in the method for fortimicin using manganese dioxide load biological carbon materials,
The equilibrium adsorption capacity of fortimicin in the water body reaches 104mg/g.
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Cited By (7)
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| CN110898804A (en) * | 2019-11-25 | 2020-03-24 | 湖南第一师范学院 | Biochar composite material and preparation method and application thereof |
| CN111266084A (en) * | 2020-01-08 | 2020-06-12 | 江苏大学 | Porous aquatic plant-based biomass charcoal material and application thereof |
| CN112973629A (en) * | 2021-02-06 | 2021-06-18 | 中国农业大学 | Pig manure biogas residue adsorbent and method for quickly removing doxycycline in water body |
| CN113262758A (en) * | 2021-06-02 | 2021-08-17 | 重庆交通大学 | Preparation method and application of trivalent manganese modified biomass charcoal |
| CN113683152A (en) * | 2021-09-16 | 2021-11-23 | 合肥工业大学 | Method for removing oxytetracycline in water body by utilizing alkali modified manganese-doped charcoal adsorption |
| CN115138332A (en) * | 2022-06-23 | 2022-10-04 | 华中农业大学 | Preparation method and application of manganese-acid-modified composite biochar passivation material |
| WO2024022299A1 (en) * | 2022-07-26 | 2024-02-01 | 青岛理工大学 | Manganese-loaded biochar catalyst, preparation method therefor, and use thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110898804A (en) * | 2019-11-25 | 2020-03-24 | 湖南第一师范学院 | Biochar composite material and preparation method and application thereof |
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| CN112973629A (en) * | 2021-02-06 | 2021-06-18 | 中国农业大学 | Pig manure biogas residue adsorbent and method for quickly removing doxycycline in water body |
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| CN113262758A (en) * | 2021-06-02 | 2021-08-17 | 重庆交通大学 | Preparation method and application of trivalent manganese modified biomass charcoal |
| CN113683152A (en) * | 2021-09-16 | 2021-11-23 | 合肥工业大学 | Method for removing oxytetracycline in water body by utilizing alkali modified manganese-doped charcoal adsorption |
| CN115138332A (en) * | 2022-06-23 | 2022-10-04 | 华中农业大学 | Preparation method and application of manganese-acid-modified composite biochar passivation material |
| WO2024022299A1 (en) * | 2022-07-26 | 2024-02-01 | 青岛理工大学 | Manganese-loaded biochar catalyst, preparation method therefor, and use thereof |
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