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CN109110863A - Utilize the method for fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body - Google Patents

Utilize the method for fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body Download PDF

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Publication number
CN109110863A
CN109110863A CN201811099673.1A CN201811099673A CN109110863A CN 109110863 A CN109110863 A CN 109110863A CN 201811099673 A CN201811099673 A CN 201811099673A CN 109110863 A CN109110863 A CN 109110863A
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activation
biochar
fortimicin
water
micro
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CN201811099673.1A
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Inventor
刘思佳
刘云国
谭小飞
曾光明
刘少博
李美芳
田思溶
尹志红
周雅惠
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Hunan University
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Hunan University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3085Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The application that the present invention relates to biological carbon materials in water treatment field, disclose a kind of method using fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body, method summarizes following steps, composite material preparation: biological carbon composite is activated with NaOH, then obtains activation charcoal after carrying out micro-wave digestion activation to gained mixed liquor;Minimizing technology is vibrated the following steps are included: by chemical activation/micro-wave digestion activation biological carbon materials addition fortimicin solution, completes the Adsorption to fortimicin.The present invention activates biological carbon materials adsorbent by using chemical activation/micro-wave digestion, efficiently eliminates fortimicin in water, reduces harm of the fortimicin to aquatic ecological environment.

Description

It is mould using strength in chemical activation/micro-wave digestion activation biological carbon materials removal water body The method of element
Technical field
The present invention relates to application of the activation charcoal in water treatment field, it is related to a kind of disappearing using chemical activation/microwave The application of fortimicin in solution activation 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.Chemical activation is with chemistry Reagent such as ZnCl2, KOH and H3PO4Etc. come the method that activates charcoal.It can improve the physicochemical property of charcoal significantly.Chemistry Activation can improve the hole property of charcoal by removing the impurity of biological carbon surface, and introduce and permitted on biological carbon surface Polyfunctional group.Microwave-assisted firing is a kind of very novel processing technique.Compared with tradition fires charcoal, microwave heating activation Heating can be directly provided charcoal inside, different pore structure and specific surface area are thus obtained.For going in water removal Pollutant, modification biological charcoal have a good application prospect.More than accordingly, it is considered to, at the same using two methods (chemical activation and Microwave-assisted activation) the fortimicin adsorption site of biological carbon surface and the value volume and range of product of functional group increased with this, from And 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 Utilization chemical activation/micro-wave digestion high and strong to contaminant removal capacity activates fortimicin in biological carbon materials removal water body Method.
In order to solve the above technical problems, technical solution proposed by the present invention is using the charcoal after chemical activation by micro- The method of fortimicin in water body is removed after wave resolution activation, comprising the following steps: the carbonization of husk biomass by hydro-thermal, then to it NaOH is activated and is carried out micro-wave digestion;The obtained material completes the Adsorption to fortimicin.
Above-mentioned is gone in water removal in the method for fortimicin using chemical activation/micro-wave digestion activation biological carbon materials, institute Chemical activation/micro-wave digestion activation biological carbon materials are stated through the following steps that being prepared:
(1) charcoal is added in NaOH solution and is activated, be dissolved in 40mL ultrapure water, this suspension is placed in In 100mL conical flask, shaken in concussion case.
(2) NaOH and charcoal mixed liquor that step (1) obtains are placed in counteracting tank, activation are cleared up in micro-wave oven, It is cooling, then it is thoroughly washed repeatedly with deionized water, it filters, drying, the biological carbon composite after being activated.
Above-mentioned is gone in water removal in the method for fortimicin using chemical activation/micro-wave digestion activation biological carbon materials, institute It states in chemical activation/micro-wave digestion activation biological carbon materials preparation step (1), the ratio that NaOH and charcoal is added is 30%, the concussion time is that for 24 hours, revolving speed 170rpm, temperature is controlled at 25 DEG C.
Above-mentioned is gone in water removal in the method for fortimicin using chemical activation/micro-wave digestion activation biological carbon materials, institute It states in chemical activation/micro-wave digestion activation biological carbon materials preparation step (2), the micro-wave oven resolution is using power 600w, time 10min, heating condition in the drying box: temperature is 80 DEG C.
Above-mentioned is gone in water removal in the method for fortimicin using chemical activation/micro-wave digestion activation biological carbon materials, institute The concentration control of the fortimicin in water body is stated in 5.0-100.0mg/L, in 2.0-10.0, temperature is controlled at 25 DEG C for pH control, Revolving speed is 180rpm.
Above-mentioned is gone in water removal in the method for fortimicin using chemical activation/micro-wave digestion activation biological carbon materials, institute The equilibrium adsorption capacity for stating the fortimicin in water body reaches 78mg/g.
Compared with the prior art, the advantages of the present invention are as follows:
1. removing fortimicin in water removal using chemical activation/micro-wave digestion activation biological carbon materials the present invention provides a kind of Method, by activate charcoal, change charcoal surface characteristics, realize and fortimicin is effectively removed;
2. chemical activation of the invention/micro-wave digestion activation biological carbon materials have, easy to operate, operating cost is low, surface The characteristics of more than functional group and easily in conjunction with fortimicin molecule, and removal efficiency is high, has environment friendly, is in water body The removal of fortimicin proposes 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 chemical activation/micro-wave digestion activates biological carbon materials in present example 1
Fig. 3 is that chemical activation/micro-wave digestion activates biological carbon materials to strength under the differential responses time in present example 2 The absorption of mycin changes
Fig. 4 is that chemical activation/micro-wave digestion activates biological carbon materials to strength under different initial concentrations in present example 3 The absorption of mycin changes
Fig. 5 is that chemical activation/micro-wave digestion activates biological carbon materials to strongly mould under condition of different pH in present example 4 The absorption variation of element
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
Embodiment 1
A kind of method that chemical activation/micro-wave digestion activation biological carbon materials remove fortimicin in water removal, including following step It is rapid:
(1) chemical activation/micro-wave digestion activation biological carbon materials are prepared
(1.1) charcoal (Fig. 1) is added in the NaOH solution of 2mol/L, the mass fraction ratio of NaOH and charcoal is 30%.This suspension is placed in conical flask, concussion is for 24 hours.
(1.2) NaOH and charcoal mixed liquor that step (1.1) obtains are placed in counteracting tank, with 600W in micro-wave oven Power resolution activation 10min.
(1.3) NaOH obtained after step (1.2) resolution and charcoal mixed liquor are thoroughly washed into deionized water Property, filtering, for 24 hours in 80 DEG C of drying box drying, grinding obtain chemical activation/micro-wave digestion activation biological carbon materials, such as Fig. 2 institute Show.Fig. 2 is chemical activation/micro-wave digestion activation biological carbon materials electron scanning electron microscope in the present embodiment.1 He of comparison diagram Fig. 2 is it is found that biological carbon surface before modified contains a large amount of ash content and mineralogical composition, block pores;And activation of the invention is raw Object carbon surface newly forms many bigger pore structures.
(2) in water body estrogen Adsorption
(2.1) it prepares the stock solution of 1g/mL 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 activation biology of 10mg step (1.3) preparation is added Carbon Materials are placed in 25 DEG C of constant temperature oscillations, water-bath constant temperature oscillator revolving speed be 180rpm, duration of oscillation be for 24 hours, it is molten after reaction Liquid 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 chemical activation/micro-wave digestion activation biological carbon materials remove fortimicin in water removal, step and reality The Adsorption for applying fortimicin in 1 water body of example 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 the activation biology obtained of 10mg embodiment 1 is added Carbon Materials are placed in 25 DEG C of constant temperature oscillations, and water-bath constant temperature oscillator revolving speed is 180rpm, duration of oscillation 0-24h, after reaction, Solution sedimentation, using 0.45 μm of Teflon filtration (syringe type).With in solution after ultraviolet specrophotometer measurement reaction The adsorbance result of the concentration of fortimicin, calculating is shown in Fig. 3.The result shows that activating biological raw material of wood-charcoal in chemical activation/micro-wave digestion During material absorption fortimicin, the incipient rate of adsorption is most fast, as the incremental rate of adsorption of time gradually tends to be flat It is slow, for 24 hours close to adsorption equilibrium.
Embodiment 3
A kind of method that chemical activation/micro-wave digestion activation biological carbon materials remove fortimicin in water removal, step and reality The Adsorption for applying fortimicin in 1 water body of example is identical, is different only in that: it is 5.0- that initial concentration is adsorbed in embodiment 3 100.0mg/L。
Concentration is 5.0,10.0,20.0,30.0,40.0,50.0,60.0,70.0,80.0,90.0 Hes after taking 25mL to dilute The fortimicin solution of 100.0mg/L is added chemical activation made from 10mg embodiment 1/micro-wave digestion and activates biological carbon materials, It being placed in 25 DEG C of constant temperature oscillations, water-bath constant temperature oscillator revolving speed is 180rpm, and duration of oscillation is that for 24 hours, after reaction, solution is settled, Using 0.45μmTeflon filtration (syringe type).With fortimicin in solution after ultraviolet specrophotometer measurement reaction The adsorbance result of concentration, calculating is shown in Fig. 4.The result shows that with the increase of initial concentration, adsorbance also increases.In initial concentration When for 100mg/L, activation montmorillonite biology carbon composite reaches 126mg/g to the adsorbance maximum of estradiol and ethinyloestradiol.
Embodiment 4
A kind of method that chemical activation/micro-wave digestion activation biological carbon materials remove fortimicin in water removal, step and reality The Adsorption for applying fortimicin in 1 water body of example 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 estrogen solution of 50mg/L after taking 25mL to dilute, and with concentration be 1M NaOH and HCl solution adjusts solution PH value be 2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0 and 10.0 chemical activation/micro- made from 10mg embodiments 1 to be added Wave resolution activation biological carbon materials, 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, after reaction, solution sedimentation, using 0.45 μm of Teflon filtration (syringe type).It is anti-with ultraviolet specrophotometer measurement The concentration of fortimicin in rear solution is answered, the adsorbance result of calculating is shown in Fig. 5.The result shows that pH is 4.0 or so, activation is covered de- Stone biology carbon composite reaches maximum to the adsorbance of estrogen.

Claims (6)

1.一种利用化学活化/微波消解活化生物炭材料去除水体中强力霉素的方法,其特征在于,包括以下步骤:将生物炭复合材料用NaOH活化,再对所得混合液进行微波消解活化后得到活化生物炭;所述得到的生物炭材料完成对强力霉素的吸附去除。1. a method utilizing chemical activation/microwave digestion and activation biochar material to remove doxycycline in water, is characterized in that, comprises the following steps: biochar composite material is activated with NaOH , then gained mixed solution is carried out microwave digestion After activation, activated biochar is obtained; the obtained biochar material completes the adsorption and removal of doxycycline. 2.根据权利要求1所述的利用化学活化/微波消解活化生物炭材料去除水体中强力霉素的方法,其特征在于,所述化学活化/微波消解活化生物炭材料是通过以下步骤制备得到:2. the method for utilizing chemical activation/microwave digestion and activation biochar material to remove doxycycline in water body according to claim 1, is characterized in that, described chemical activation/microwave digestion and activation biochar material is prepared through the following steps: (1)将生物炭加入NaOH溶液中进行活化,溶于40mL超纯水中,将此悬浮液置于100mL锥形瓶内,于震荡箱中震荡。(1) Add biochar to NaOH solution for activation, dissolve it in 40mL ultrapure water, place the suspension in a 100mL conical flask, and shake it in a shaking box. (2)将步骤(1)得到的NaOH与生物炭混合液置于消解罐中,于微波炉中消解活化,冷却,再将其用去离子水彻底洗涤多次,过滤,烘干,得到活化后的生物炭复合材料。(2) placing the NaOH and biochar mixture obtained in step (1) in a digestion tank, digesting and activating in a microwave oven, cooling, thoroughly washing it with deionized water for many times, filtering, drying, and obtaining the activated of biochar composites. 3.根据权利要求2所述的利用化学活化/微波消解活化生物炭材料去除水中强力霉素的方法中,所述化学活化/微波消解活化生物炭材料的制备步骤(1)中,加入NaOH和生物炭的比例为30%,震荡时间为24h,转速为170rpm,温度控制在25℃。3. in the method for removing doxycycline in water using chemical activation/microwave digestion and activation biochar material according to claim 2, in the preparation step (1) of the chemical activation/microwave digestion and activation biochar material, add NaOH and The proportion of biochar was 30%, the shaking time was 24h, the rotation speed was 170rpm, and the temperature was controlled at 25°C. 4.根据权利要求2所述的利用化学活化/微波消解活化生物炭材料去除水中强力霉素的方法中,所述化学活化/微波消解活化生物炭材料的制备步骤(2)中,所述微波炉消解使用功率为600w,时间为10min,所述烘干箱内加热条件:温度为80℃。4. in the method for removing doxycycline in water using chemical activation/microwave digestion and activation biochar material according to claim 2, in the preparation step (2) of the chemical activation/microwave digestion and activation biochar material, the microwave oven The power used for digestion was 600w, the time was 10min, and the heating conditions in the drying box: the temperature was 80°C. 5.根据权利要求2所述的利用化学活化/微波消解活化生物炭材料去除水中强力霉素的方法中,所述水体中的强力霉素的浓度控制在5.0-100.0mg/L,pH控制在2.0-10.0,温度控制在25℃,转速为180rpm。5. In the method for removing doxycycline in water using chemical activation/microwave digestion and activation biochar material according to claim 2, the concentration of doxycycline in the water body is controlled at 5.0-100.0mg/L, and the pH is controlled at 5.0-100.0mg/L. 2.0-10.0, the temperature is controlled at 25°C, and the speed is 180rpm. 6.根据权利要求2所述的利用化学活化/微波消解活化生物炭材料去除水中强力霉素的方法中,所述水体中的强力霉素的平衡吸附量达到78mg/g。6. In the method for removing doxycycline in water by chemical activation/microwave digestion and activation of biochar material according to claim 2, the equilibrium adsorption amount of doxycycline in the water body reaches 78 mg/g.
CN201811099673.1A 2018-09-20 2018-09-20 Utilize the method for fortimicin in chemical activation/micro-wave digestion activation biological carbon materials removal water body Pending CN109110863A (en)

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CN110327882A (en) * 2019-07-11 2019-10-15 江西省科学院 The preparation method and application of multidigit activation and modified reed-south reed charcoal
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
CN115608318A (en) * 2022-09-21 2023-01-17 江苏省生态环境评估中心(江苏省排污权登记与交易管理中心) Reed biochar material synthesized by phosphoric acid activation modification
CN116786082A (en) * 2023-07-27 2023-09-22 大同同星抗生素有限责任公司 Specific adsorbent for oxytetracycline and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110327882A (en) * 2019-07-11 2019-10-15 江西省科学院 The preparation method and application of multidigit activation and modified reed-south reed charcoal
CN110327882B (en) * 2019-07-11 2020-03-27 江西省科学院 Preparation method and application of multiposition activated and modified reed-triarrhena sacchariflora biochar
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
CN112973629B (en) * 2021-02-06 2022-05-17 中国农业大学 A kind of pig manure digester adsorbent and method for rapidly removing doxycycline in water body
CN115608318A (en) * 2022-09-21 2023-01-17 江苏省生态环境评估中心(江苏省排污权登记与交易管理中心) Reed biochar material synthesized by phosphoric acid activation modification
CN116786082A (en) * 2023-07-27 2023-09-22 大同同星抗生素有限责任公司 Specific adsorbent for oxytetracycline and preparation method thereof
CN116786082B (en) * 2023-07-27 2024-05-28 大同同星抗生素有限责任公司 Specific adsorbent for oxytetracycline and preparation method thereof

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Application publication date: 20190101