CN108998439A - The preparation of microbial immobilized gel ball and its removal to Norfloxacin in water and tetracycline - Google Patents

The preparation of microbial immobilized gel ball and its removal to Norfloxacin in water and tetracycline Download PDF

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Publication number
CN108998439A
CN108998439A CN201810902793.4A CN201810902793A CN108998439A CN 108998439 A CN108998439 A CN 108998439A CN 201810902793 A CN201810902793 A CN 201810902793A CN 108998439 A CN108998439 A CN 108998439A
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microorganism
gel ball
antibiotic
water
added
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单然然
何媛
刘秀玉
朱英
邵艳秋
田超
闫良国
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NEW MATERIAL INSTITUTE OF SHANDONG ACADEMY OF SCIENCES
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NEW MATERIAL INSTITUTE OF SHANDONG ACADEMY OF SCIENCES
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/14Enzymes or microbial cells immobilised on or in an inorganic carrier
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • 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
    • C02F2101/34Organic compounds containing oxygen
    • 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
    • C02F2101/36Organic compounds containing halogen
    • 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
    • C02F2101/38Organic compounds containing nitrogen

Abstract

Removal the present invention provides the preparation of microbial immobilized gel ball and its to Norfloxacin in water and tetracycline.Calcined hydrotalcite (CLDH) good absorption property will be utilized, nontoxicity, adsorptivity and the good forming ability of sodium alginate (SA) and the degradation capability synthesizing new water treatment agent of microorganism, the removal for antibiotic such as Norfloxacin in water and tetracyclines.The microorganism of degradable antibiotic is fixed in gel ball by the present invention by gel technique, immobilized microorganism is not only increased to the tolerance and degradation capability of noxious material, microorganism can also be avoided to be lost with water outlet, higher microorganism concn can be maintained for a long time, enhance the anti-interference ability and stability of water treatment system.

Description

The preparation of microbial immobilized gel ball and its to Norfloxacin in water and tetracycline Removal
Technical field
The present invention relates to the preparation methods of microbial immobilized gel ball, belong at water treatment agent preparation and pharmaceutical wastewater Manage technical field.
Background technique
In recent years, antibiotic is widely used in the disease treatment of human and animal, and Norfloxacin and tetracycline are because of tool Broad-spectrum antibacterial action and be widely used.However since the mankind and animal are all very poor to the metabolism and absorption of most antibiotics, Most of antibiotic is excreted by urine and excrement.Scientist has detected in soil, surface water, underground water anti-at present The presence of raw element has human and animal slow even if the antibiotic of low concentration can result in the generation and propagation of resistant gene Property toxicity, can reduce the immunity of human body and animal and improve drug resistance, seriously endanger the health of human and animal.Therefore, it goes Antibiotic in water removal is extremely urgent.
Currently, the removal of antibiotic is of increasing concern in water environment, wherein absorption method because its small investment, it is easy to operate, Quickly and it is easy to be widely applied and the method as main use.But antibiotic is only transferred to solid phase from water phase by absorption method In, it cannot be completely removed, absorption method is used alone and easily causes secondary pollution.Biodegrade is that antibiotic is degraded in the environment Most important approach, the antibiotic being biodegradable can be converted into the inorganic or small organic molecule of not bio-toxicity.
Summary of the invention
In order to overcome above-mentioned deficiency, the present invention provides that a kind of preparation process is simple, raw material is environmentally protective and can become waste material The preparation method for the microbial immobilized gel ball that waste be changed into values.The object of the invention is also to provide a kind of microbial immobilized solidifying The method that glueballs removes antibiotic in water removal.
To achieve the goals above, the present invention adopts the following technical scheme:
The present invention provides the preparation sides of the microbial immobilized gel ball of a kind of can degrade Norfloxacin and/or tetracycline Method, comprising:
Domestication is cultivated from cow dung, the microorganism for (the Norfloxacin and/or tetracycline) antibiotic that obtains capable of degrading;
Under anaerobic, mentioned microorganism, calcined hydrotalcite CLDH are added in sodium alginate soln, mixing is equal It is even, form suspension;
Under anaerobic, above-mentioned suspension is added to CaCl2In solution, reaction, solidification form gel ball, washing, To obtain the final product;
In some embodiments, anaerobic condition can obtain in the following manner: microorganism is trained in branch mouth conical flask It supports, wherein a mouth is used to change water, and a mouth is used to connect a three-way valve, the mouth connection gas collection dress of three-way valve It sets, gas collecting apparatus is that a big plastic bottle make-up once forms, and measures gas production using drainage.It is anaerobism shape in whole device State.As shown in Figure 2.
The mass ratio of the microorganism, CLDH and SA is 10~20:6~8:1.5~2.
In order to improve tolerance and degradation of the microorganism obtained from cow dung domestication, culture to Norfloxacin and tetracycline Ability, the application attempt that gel ball for the microorganism (anti-norfloxacin and tetracycline) is made, but study discovery: due to microorganism To different fixation supports formed microenvironment adaptability and to the difference of carrier adhesive ability, immobilization is to microorganism Structure of community produces bigger effect.In order to guarantee that microorganism (anti-norfloxacin and tetracycline) has preferable absorption effect after embedding Fruit and bioactivity, the application system research microorganism tolerances of a variety of occlusion vehicles to anti-norfloxacin and tetracycline With the influence of degradation capability, grope to find by large scale experiment: using calcined hydrotalcite (CLDH) good absorption property, lead to Sodium alginate is crossed as embedding medium, calcium chloride as crosslinking agent, microorganism (anti-norfloxacin and tetracycline) embedding is formed Gel ball has preferable adsorptivity and biological stability.
Different for main occlusion vehicle from sodium alginate, the main component of gel ball is calcined hydrotalcite in the application (CLDH), it adds a small amount of sodium alginate and primarily serves crosslinking, solidification, make calcined hydrotalcite (CLDH) molding purpose, therefore, The application also has mechanical strength and mechanical stability much higher than sodium alginate base gel ball.
In some embodiments, the suspension is added to CaCl2The specific steps of solution are as follows: use peristaltic pump by micro- life The CaCl that the mixed solution of object, calcined hydrotalcite CLDH and sodium alginate is added dropwise to 20-40 DEG C of water-bath, is stirred continuously2It is molten In liquid, 1~6h is stirred, after complete reaction, 12~48h of stirring solidification, takes out gel ball, use deionized water under room temperature state Wash away extra Ca2+To get arrive microbial immobilized gel ball.
In some embodiments, the reaction temperature, reaction time and curing time are 40 DEG C: 2h:24h.
In some embodiments, can degrade antibiotic microculture domestication comprise the concrete steps that excrement is added to it is close In the production gas culture apparatus of envelope, and be added the waste water containing Norfloxacin or tetracycline carry out culture domestication, daily to supernatant into Row changes water and adds the corresponding antibiotic of 1mg/L, convenient for generating the dominant bacteria that can resist the antibiotic.Routine observation gas produces Raw situation illustrates the microorganism for having filtered out the resistance antibiotic when generating methane, continues culture to system in device and stablizes, Microorganism when microorganism is enough in withdrawing device immobilizes experiment, and content of microorganisms is 30% in device at this time, it may be assumed that The strain concentration of microbial inoculum is 2.1 × 108cells/mL。
In some embodiments, the antibiotic is Norfloxacin and/or tetracycline.
Since the intensity of sodium alginate is lower, especially easily it is decomposed by the microorganisms under anaerobic.Therefore, the application exists A small amount of medical stone is added in calcined hydrotalcite (CLDH), using its spongy porous structure to the biology under anaerobism of microorganism Activity is regulated and controled, and the decomposition of sodium alginate is inhibited.The result shows that: gel ball mechanical stability is improved, is more conducive to Nuo Fosha The removal of star or tetracycline and the holding of bioactivity.Therefore, in some embodiments, the gel ball further include: 0.1~ 0.3% medical stone, partial size are 40-70 mesh.
The second object of the present invention is to provide the immobilization gel ball of any above-mentioned method preparation.
Present invention also provides a kind of gel balls that can be used for handling Norfloxacin and/or tetracycline, by CLDH and SA Composition, the mass ratio of the two are 6~8:1.5~2;The preparation method is as follows:
Calcined hydrotalcite CLDH is added in sodium alginate soln, is uniformly mixed, suspension is formed;
Above-mentioned suspension is added to CaCl2In solution, reaction, solidification, formed gel ball, washing to get.
There is provided a kind of using above-mentioned microbial immobilized gel ball to antibiotic in water for the third object of the present invention Removal method characterized by comprising
The oscillation that microbial immobilized gel ball carries out 4-48h is added to antibiotic solution.
In some embodiments, the concentration of the antibiotic solution is 8-12mg/L.
In some embodiments, the antibiotic is Norfloxacin and/or tetracycline.
A kind of water treatment agent, comprising: any above-mentioned gel ball.
Beneficial effects of the present invention
(1) microorganism of degradable antibiotic is fixed in gel ball by the present invention by gel technique, is not only increased Immobilized microorganism can also avoid microorganism from being lost with water outlet the tolerance and degradation capability of noxious material, can be with Higher microorganism concn is maintained for a long time, enhances the anti-interference ability and stability of water treatment system.
(2) the efficient removal of antibiotic can be realized in the present invention under lesser gel ball dosage, and removal rate highest can Reach 100%.
(3) suction of the microbial immobilized gel ball of CLDH to Norfloxacin and tetracycline is not added with prepared by this method Attached effect is higher by 10% or more adsorption effect compared with the gel ball for being not added with CLDH and unlocked microorganism;In addition, this method institute The microbial immobilized gel ball of the addition CLDH of preparation is to the adsorption effect of Norfloxacin and tetracycline and addition CLDH and not The gel ball of fixation of microbe is suitable.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the removal effect figure of microbial immobilized gel ball of the invention to Norfloxacin and tetracycline.Wherein, 1- 5 successively are as follows: 0% microorganism -0%CLDH-SA gel ball, 15% microorganism -0%CLDH-SA gel ball, 20% microorganism -0% CLDH-SA gel ball, 0% microorganism -8%CLDH-SA gel ball, 15% microorganism -8%CLDH-SA gel ball.
Fig. 2 is the anaerobic culture device of the application.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field The identical meanings of understanding.
Method of the invention is to obtain the microorganism of degradable antibiotic using the method for culture domestication, and pass through gel skill Microorganism is fixed in SA gel ball by art, so that microbial immobilized gel ball be made, and is used for antibiotic in water body Removal.
The preparation of microbial immobilized gel ball and its removal to Norfloxacin in water and tetracycline, including following step It is rapid:
(1) excrement for choosing ox carries out the culture domestication of microorganism.Comprise the concrete steps that the production gas that excrement is added to sealing In culture apparatus, and the waste water containing Norfloxacin or tetracycline is added and carries out culture domestication, change water simultaneously to supernatant daily The corresponding antibiotic of 1mg/L is added, convenient for generating the dominant bacteria that can resist the antibiotic.Routine observation gas production, Illustrate to have filtered out the microorganism for resisting the antibiotic when generating methane, continues culture to system in device and stablize, microorganism Microorganism when enough in withdrawing device immobilizes experiment, and content of microorganisms is 30% in device at this time.
(2) SA is dissolved in deionized water and is stirred continuously simultaneously ultrasonic disperse, obtain homogeneous and transparent colloidal solution;
(3) under anaerobic, the microorganism filtered out and CLDH are added in the solution of step (2), are stirred continuously, Standing and defoaming obtains uniform suspension;
(4) by CaCl2It is dissolved in deionized water and obtains transparent and homogeneous solution;
(5) under anaerobic, the solution of step (3) is added dropwise to by 20-40 DEG C of water-bath using peristaltic pump, constantly stirred In the step of mixing (4) solution, 1~6h is stirred, after complete reaction, 12~48h of stirring solidification, takes out gel under room temperature state Extra Ca is washed with deionized water in ball2+To get arrive microbial immobilized gel ball.
Preparation method of the invention is using SA as embedding medium, CaCl2For crosslinking agent, microorganism and CLDH are effective component, at Function synthesized micro-organism immobilization gel ball.When by the content of control microorganism and CLDH, reaction temperature, reaction time and solidification Between obtain the microbial immobilized gel ball of superior performance.
Wherein, CLDH can not only play good absorption property, moreover it is possible to improve the internal structure of gel ball.In order to improve Combined coefficient obtains high performance microbial immobilized gel ball simultaneously, and the content of microorganism and CLDH are preferably 15%:8%; Reaction temperature, reaction time and curing time are preferably 40 DEG C: 2h:24h.
The CLDH is additionally added the medical stone of 0.1~0.3wt%, and partial size is 40-70 mesh.
Steps are as follows for removal of the microbial immobilized gel ball to antibiotic in water:
Pipetting concentration is the antibiotic solution 20mL of 10mg/L in 50mL centrifuge tube, and addition 20 is microbial immobilized solidifying Glueballs carries out the oscillation of 4-48h, the concentration of supernatant detection antibiotic is taken after standing, according to the initial concentration of antibiotic in solution The removal rate of antibiotic is calculated with the residual concentration after absorption.
Above-mentioned antibiotic is selected from one of following: Norfloxacin and tetracycline.
A kind of embodiment 1: preparation method of microbial immobilized gel ball
(1) 0.4g SA is dissolved in 20mL deionized water, is stirred continuously simultaneously ultrasonic disperse, obtaining quality volume fraction is The homogeneous and transparent colloidal solution of 2% SA;
(2) by 1g CaCl2It is dissolved in and obtains the CaCl that quality volume fraction is 2% in 50mL deionized water2Transparent and homogeneous is molten Liquid;
(3) the step of solution of step (1) being added dropwise to 20 DEG C of water-baths, be stirred continuously by peristaltic pump (2) solution In, 1h is persistently stirred, after complete reaction, stirring solidification 12h, takes out gel ball, be washed with deionized water under room temperature state Extra Ca2+To get arrive microbial immobilized gel ball 1:0% microorganism -0%CLDH-SA gel ball.
At room temperature, 20 microbial immobilized gel balls in 4h, for 24 hours with removal when 48h to the Norfloxacin of 10mg/L Rate is respectively 37.2%, 51.6% and 56.6%, and the removal rate to tetracycline is respectively 27.6%, 38.3% and 45.6%.
A kind of embodiment 2: preparation method of microbial immobilized gel ball
(1) excrement for choosing ox carries out the culture domestication of microorganism.Comprise the concrete steps that the excrement for taking ox is added to sealing It produces in gas culture apparatus, culture domestication, culture domestication phase temperature is carried out using the simulated wastewater containing Norfloxacin or tetracycline 37 DEG C are maintained at, antibiotic antibiotic (Nuo Fosha star or tetracycline) the simulated wastewater concentration replaced daily is 1mg/L.It is early daily Late routine observation gas production tames by the culture of 7d, has collected methane gas about 10-20mL in gas production mouth, say It is bright to have filtered out the microorganism that resist the antibiotic, continue culture tame the microorganism and daily monitoring pH value, gas production and Antibiotic concentration.By the domestication culture of about 30d or so, pH stable is in 7.5 or so, gas production 110-130mL/d, water inlet Antibiotic (Nuo Fosha star or tetracycline) removal rate is 80% or so, i.e. state in culture apparatus has been held essentially constant, and is said Bright culture domestication is completed, and microbial biomass meets subsequent experimental needs, and content of microorganisms is about 30% in mixed liquor in device at this time.
(2) 0.4g SA is dissolved in 10mL deionized water, is stirred continuously simultaneously ultrasonic disperse, obtains homogeneous and transparent SA glue Shape solution;
(3) under anaerobic, the microbial solution for taking 10mL step (1) to filter out is into the solution of step (2), constantly Stirring, standing and defoaming, obtaining microorganism concn is the uniform suspension that 15%, SA mass fraction is 2%;
(4) by 1g CaCl2It is dissolved in and obtains the CaCl that quality volume fraction is 2% in 50mL deionized water2Transparent and homogeneous is molten Liquid;
(5) under anaerobic, the solution of step (3) is added dropwise to by 40 DEG C of water-baths using peristaltic pump, be stirred continuously The step of (4) solution in, stir 2h, after complete reaction, under room temperature state stirring solidification for 24 hours, take out gel ball, spend from Extra Ca is removed in son washing2+To get arrive microbial immobilized gel ball 2:15% microorganism -0%CLDH-SA gel ball.
At room temperature, 20 microbial immobilized gel balls in 4h, for 24 hours with removal when 48h to the Norfloxacin of 10mg/L Rate is respectively 47.1%, 59.7% and 60.9%, and the removal rate to tetracycline is respectively 24.2%, 29.7% and 43.5%.
A kind of embodiment 3: preparation method of microbial immobilized gel ball
(1) excrement for choosing ox carries out the culture domestication of microorganism.Comprise the concrete steps that the production gas that excrement is added to sealing In culture apparatus, and the waste water containing Norfloxacin or tetracycline is added and carries out culture domestication, change water simultaneously to supernatant daily The corresponding antibiotic of 1mg/L is added, convenient for generating the dominant bacteria that can resist the antibiotic.Routine observation gas production, Illustrate to have filtered out the microorganism for resisting the antibiotic when generating methane, continues culture to system in device and stablize, microorganism Microorganism when enough in withdrawing device immobilizes experiment, and content of microorganisms is 30% in mixed liquor in device at this time.
(2) 0.4g SA is dissolved in 6.7mL deionized water, is stirred continuously simultaneously ultrasonic disperse, obtains homogeneous and transparent SA glue Shape solution;
(3) under anaerobic, the microbial solution for taking 13.3mL step (1) to filter out is into the solution of step (2), no Disconnected stirring, standing and defoaming, obtaining microorganism concn is the uniform suspension that 20%, SA mass fraction is 2%;
(4) by 1g CaCl2It is dissolved in and obtains the CaCl that quality volume fraction is 2% in 50mL deionized water2Transparent and homogeneous is molten Liquid;
(5) under anaerobic, the solution of step (3) is added dropwise to by 40 DEG C of water-baths using peristaltic pump, be stirred continuously The step of (4) solution in, stir 2h, after complete reaction, under room temperature state stirring solidification for 24 hours, take out gel ball, spend from Extra Ca is removed in son washing2+To get arrive microbial immobilized gel ball 3:20% microorganism -0%CLDH-SA gel ball.
At room temperature, 20 microbial immobilized gel balls in 4h, for 24 hours with removal when 48h to the Norfloxacin of 10mg/L Rate is respectively 35.3%, 47.4% and 49.2%, and the removal rate to tetracycline is respectively 32.8%, 46.3% and 60.5%.
A kind of embodiment 4: preparation method of microbial immobilized gel ball
(1) 0.4g SA is dissolved in 20mL deionized water, is stirred continuously simultaneously ultrasonic disperse, obtaining quality volume fraction is The homogeneous and transparent colloidal solution of 2% SA;
(2) 1.6g CLDH is added in the colloidal solution of step (1), is stirred continuously and ultrasonic disperse, standing and defoaming, Obtain uniform suspension;
(3) by 1g CaCl2It is dissolved in and obtains the CaCl that quality volume fraction is 2% in 50mL deionized water2Transparent and homogeneous is molten Liquid;
(4) the step of solution of step (2) being added dropwise to 30 DEG C of water-baths, be stirred continuously by peristaltic pump (3) solution In, 6h is persistently stirred, after complete reaction, stirring solidification 48h, takes out gel ball, be washed with deionized water under room temperature state Extra Ca2+To get arrive microbial immobilized gel ball 4:0% microorganism -8%CLDH-SA gel ball.
At room temperature, 20 microbial immobilized gel balls in 4h, for 24 hours with removal when 48h to the Norfloxacin of 10mg/L Rate is respectively 66.7%, 84.9% and 91.7%, and the removal rate to tetracycline is respectively 74.3%, 92.6% and 100%.
A kind of embodiment 5: preparation method of microbial immobilized gel ball
(1) excrement for choosing ox carries out the culture domestication of microorganism.Comprise the concrete steps that the production gas that excrement is added to sealing In culture apparatus, and the waste water containing Norfloxacin or tetracycline is added and carries out culture domestication, change water simultaneously to supernatant daily The corresponding antibiotic of 1mg/L is added, convenient for generating the dominant bacteria that can resist the antibiotic.Routine observation gas production, Illustrate to have filtered out the microorganism for resisting the antibiotic when generating methane, continues culture to system in device and stablize, microorganism Microorganism when enough in withdrawing device immobilizes experiment, and content of microorganisms is 30% in mixed liquor in device at this time.
(2) 0.4g SA is dissolved in 10mL deionized water, is stirred continuously simultaneously ultrasonic disperse, obtains homogeneous and transparent SA glue Shape solution;
(3) under anaerobic, the microbial solution and 1.6g CLDH for taking 10mL step (1) to filter out are to step (2) It in solution, is stirred continuously, standing and defoaming, it is that 8%, SA mass fraction is that obtain microorganism concn, which be 15%, CLDH mass fraction, 2% uniform suspension;
(4) by 1g CaCl2It is dissolved in and obtains the CaCl that quality volume fraction is 2% in 50mL deionized water2Transparent and homogeneous is molten Liquid;
(5) under anaerobic, the solution of step (3) is added dropwise to by 40 DEG C of water-baths using peristaltic pump, be stirred continuously The step of (4) solution in, stir 2h, after complete reaction, under room temperature state stirring solidification for 24 hours, take out gel ball, spend from Extra Ca is removed in son washing2+To get arrive microbial immobilized gel ball 5:15% microorganism -8%CLDH-SA gel ball.
At room temperature, 20 microbial immobilized gel balls in 4h, for 24 hours with removal when 48h to the Norfloxacin of 10mg/L Rate is respectively 61.2%, 79.3% and 85.8%, and the removal rate to tetracycline is respectively 71.9%, 89.5% and 97.8%.
A kind of embodiment 6: preparation method of microbial immobilized gel ball
(1) excrement for choosing ox carries out the culture domestication of microorganism.Comprise the concrete steps that the production gas that excrement is added to sealing In culture apparatus, and the waste water containing Norfloxacin or tetracycline is added and carries out culture domestication, change water simultaneously to supernatant daily The corresponding antibiotic of 1mg/L is added, convenient for generating the dominant bacteria that can resist the antibiotic.Routine observation gas production, Illustrate to have filtered out the microorganism for resisting the antibiotic when generating methane, continues culture to system in device and stablize, microorganism Microorganism when enough in withdrawing device immobilizes experiment, and content of microorganisms is 30% in mixed liquor in device at this time.
(2) 0.4g SA is dissolved in 10mL deionized water, is stirred continuously simultaneously ultrasonic disperse, obtains homogeneous and transparent SA glue Shape solution;
(3) under anaerobic, the microbial solution and 1.6g medical stone for taking 10mL step (1) to filter out are to step (2) Solution in, be stirred continuously, standing and defoaming, obtain microorganism concn be 15%, medical stone mass fraction be 8%, SA mass divide The uniform suspension that number is 2%;
(4) by 1g CaCl2It is dissolved in and obtains the CaCl that quality volume fraction is 2% in 50mL deionized water2Transparent and homogeneous is molten Liquid;
(5) under anaerobic, the solution of step (3) is added dropwise to by 40 DEG C of water-baths using peristaltic pump, be stirred continuously The step of (4) solution in, stir 2h, after complete reaction, under room temperature state stirring solidification for 24 hours, take out gel ball, spend from Extra Ca is removed in son washing2+To get arrive microbial immobilized -8% medical stone-SA gel ball of gel ball 5:15% microorganism.
At room temperature, 20 microbial immobilized gel balls in 4h, for 24 hours with removal when 48h to the Norfloxacin of 10mg/L Rate is respectively 60.1%, 76.3% and 81.4%, and the removal rate to tetracycline is respectively 61.3%, 77.6% and 84.8%.
A kind of embodiment 7: preparation method of microbial immobilized gel ball
(1) excrement for choosing ox carries out the culture domestication of microorganism.Comprise the concrete steps that the production gas that excrement is added to sealing In culture apparatus, and the waste water containing Norfloxacin or tetracycline is added and carries out culture domestication, change water simultaneously to supernatant daily The corresponding antibiotic of 1mg/L is added, convenient for generating the dominant bacteria that can resist the antibiotic.Routine observation gas production, Illustrate to have filtered out the microorganism for resisting the antibiotic when generating methane, continues culture to system in device and stablize, microorganism Microorganism when enough in withdrawing device immobilizes experiment, and content of microorganisms is 30% in mixed liquor in device at this time.
(2) 0.4g SA is dissolved in 10mL deionized water, is stirred continuously simultaneously ultrasonic disperse, obtains homogeneous and transparent SA glue Shape solution;
(3) under anaerobic, microbial solution and 1.12g CLDH, the 0.48g wheat meal for taking 10mL step (1) to filter out Stone is stirred continuously, standing and defoaming into the solution of step (2), and it is 8% that obtain microorganism concn, which be 15%, CLDH mass fraction, The uniform suspension that SA mass fraction is 2%;
(4) by 1g CaCl2It is dissolved in and obtains the CaCl that quality volume fraction is 2% in 50mL deionized water2Transparent and homogeneous is molten Liquid;
(5) under anaerobic, the solution of step (3) is added dropwise to by 40 DEG C of water-baths using peristaltic pump, be stirred continuously The step of (4) solution in, stir 2h, after complete reaction, under room temperature state stirring solidification for 24 hours, take out gel ball, spend from Extra Ca is removed in son washing2+To get arrive microbial immobilized gel ball 5:15% microorganism -8%CLDH-SA gel ball.
At room temperature, 20 microbial immobilized gel balls in 4h, for 24 hours with removal when 48h to the Norfloxacin of 10mg/L Rate is respectively 64.5%, 78.8% and 87.8%, and the removal rate to tetracycline is respectively 65.2%, 79.5% and 88.6%.
Analysis of conclusion:
1) by the comparison of embodiment 2,3 it is found that when the additive amount of microorganism is 15%, adsorption effect is best, this explanation The microbial biomass of degradation antibiotic also has suitable concentration, is more than this concentration, will affect the adsorption effect of microorganism instead.
2) by the comparison of embodiment 4,5 it is found that " CLDH-SA gel ball " has compared with " microorganism-CLDH-SA gel ball " Preferably adsorption effect, this explanation: CLDH itself is just fine to the adsorption effect of antibiotic, and microbes has been added to decrease.
3) " microorganism-CLDH- can be further improved it is found that adding suitable medical stone by the comparison of embodiment 6,7 Adsorption effect of the SA gel ball " to antibiotic.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for the skill of this field For art personnel, various changes and changes are possible in this application.Within the spirit and principles of this application, made any to repair Change, equivalent replacement, improvement etc., should be included within the scope of protection of this application.

Claims (10)

1. a kind of preparation method of the microbial immobilized gel ball of can degrade Norfloxacin and/or tetracycline, which is characterized in that Include:
Domestication is cultivated from cow dung, the microorganism for the antibiotic that obtains capable of degrading;
Under anaerobic, mentioned microorganism, calcined hydrotalcite CLDH are added in sodium alginate soln, are uniformly mixed, shape At suspension;
Under anaerobic, above-mentioned suspension is added to CaCl2In solution, reaction, solidification, formed gel ball, washing to get;
The mass ratio of the microorganism, CLDH and SA is 10~20:6~8:1.5~2.
2. the method as described in claim 1, which is characterized in that be additionally added the medical stone of 0.1~0.3wt% in the CLDH.
3. the method as described in claim 1, which is characterized in that the suspension is added to CaCl2The specific steps of solution are as follows: The mixed solution of microorganism, calcined hydrotalcite CLDH and sodium alginate is added dropwise to by 20-40 DEG C of water-bath, no using peristaltic pump The CaCl of disconnected stirring2In solution, 1~6h is stirred, after complete reaction, 12~48h of stirring solidification under room temperature state takes out solidifying Extra Ca is washed with deionized water in glueballs2+To get arrive microbial immobilized gel ball.
4. the method as described in claim 1, which is characterized in that the reaction temperature, reaction time and curing time are 40 DEG C: 2h:24h.
5. the method as described in claim 1, which is characterized in that the specific steps of the microculture domestication for the antibiotic that can degrade It is to be added to excrement in the production gas culture apparatus of sealing, and waste water of the addition containing Norfloxacin or tetracycline carries out culture and tames and dociles Change, daily supernatant is carried out changing water and add the corresponding antibiotic of 1mg/L, convenient for generating the dominant bacteria that can resist the antibiotic Kind.Routine observation gas production illustrates to have filtered out the microorganism for resisting the antibiotic when generating methane, continues to cultivate System is stablized in device, and microorganism when microorganism is enough in withdrawing device immobilizes experiment, micro- in device at this time Biological content is 30%.
6. the immobilization gel ball of the described in any item method preparations of claim 1-5.
7. a kind of preparation method of the gel ball of can degrade Norfloxacin and/or tetracycline characterized by comprising
Calcined hydrotalcite CLDH is added in sodium alginate soln, is uniformly mixed, suspension is formed;
Above-mentioned suspension is added to CaCl2In solution, reaction, solidification, formed gel ball, washing to get;
The mass ratio of the CLDH and SA is 6~8:1.5~2.
8. a kind of remove Norfloxacin in water and/or tetracycline using microbial immobilized gel ball as claimed in claim 7 The method removed characterized by comprising
The oscillation that microbial immobilized gel ball carries out 4-48h is added to antibiotic solution.
9. method according to claim 8, which is characterized in that the concentration of the antibiotic solution is 8-12mg/L.
10. a kind of water treatment agent of the removal for Norfloxacin in water and/or tetracycline characterized by comprising right It is required that the gel ball of method preparation described in the claim of any one of 1-5,7.
CN201810902793.4A 2018-08-09 2018-08-09 The preparation of microbial immobilized gel ball and its removal to Norfloxacin in water and tetracycline Pending CN108998439A (en)

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