CN102531084B - Method for treating tetracycline waste water with iron-modified attapulgite adsorbent - Google Patents
Method for treating tetracycline waste water with iron-modified attapulgite adsorbent Download PDFInfo
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Abstract
The invention relates to a method for treating tetracycline waste water with an iron-modified attapulgite adsorbent, which is characterized in that concentration of tetracycline in the waste water is 5-150mg/L. The iron-modified attapulgite adsorbent is added in the tetracycline waste water, and mass ratio of the tetracycline waste water to the adsorbent is 1: (4-6). The adsorption process adopts a static mode of action and/or an oscillating and stirring mode of action at the temperature of 0-50 DEG C. The method aims at the waste water polluted by tetracycline and removes tetracycline by adding the iron-modified attapulgite adsorbent in the waste water for adsorption. The method has the advantages of having high adsorption efficiency for tetracycline compounds, simple operational process, low requirements for adsorption conditions, low cost of adsorption materials and high regeneration efficiency and being easy to popularize. The method is used for removing tetracycline compounds in a water body and has good economic and environmental benefits.
Description
Technical field
The present invention relates to the adsorption treatment method of tetracycline compound in a kind of waste water, particularly relate to and utilize iron modified attapulgite adsorbent tetracycline compound in medical sewage to be carried out to the method for Adsorption.
Background technology
Tetracycline antibiotics (tetracycline antibiotics, TCs, hereinafter to be referred as tetracyclines) is the class Broad spectrum antibiotics being produced by streptomycete, and frequency of utilization is high, scope is wide.It is reported, this type of production of antibiotics and usage quantity world rankings the second, China ranks the first.Tetracyclines comprises natural tetracyclines and semi-synthetic tetracyclines, and natural tetracyclines is to extract from Streptomyces nutrient solution, and tsiklomitsin (Tetracycline) is the one of natural tetracyclines.There is antimicrobial spectrum widely, the microorganisms such as Gram-positive, Gram-negative bacteria, mycoplasma, rickettsia and chlamydozoan are had to activity.
China since early 1990s, tsiklomitsin widespread use in the industries such as medicine, livestock industry and aquaculture, its output and consumption are always in rising trend.But its production in above-mentioned industry and use and a large amount of waste water of producing are unprocessed or process and thoroughly do not make tsiklomitsin enter ecotope with water, therefore, the content of tsiklomitsin in water surrounding grows with each passing day, and the negative effect of the mankind and ecotope is also highlighted day by day.
For the ecosystem, abuse tsiklomitsin can directly cause individual resistance.More and more data shows simultaneously, and more natural bacteriums are more much higher than what expect to the resistance of tsiklomitsin, and the drug resistance gene of bacterium may transfer occur at occurring in nature.The resistance of tsiklomitsin may pass to malignant bacteria from non-pathogenic bacteria, even may further propagate, and develops into the resistance on ecological level, and makes the individuality that does not directly touch tsiklomitsin also produce resistance.The World Health Organization points out in the report of 2000: the phenomenon of resistance pathogen propagation is on the rise, and is the 21 century huge challenge that faces of human health.
Residual composition and the activity that can affect microorganisms in water of tsiklomitsin in water surrounding, thus microbial ecological structure changed, affect nitrated, the mineralization of soil and Nutrient Cycling of soil etc.In addition, the residual meeting of tsiklomitsin impacts plant, hydrobiont and soil organisms, because the difference of residual concentration produces harm such as suppressing growth or variation and teratogenesis.Because tetracycline compound can be through the lipophilic group of cytolemma, and there is higher stability, therefore, be easy to biological accumulation and long-term stable existence etc. in environment.
For reducing the ecological risk of tetracycline compound in water surrounding, need to remove the tetracycline compound in sewage or high density surface water body.Conventional water treatment method has at present: the combination treatment method of physics, chemistry and biological process and aforesaid method, but due to tetracycline compound complex structure, its toxicity and resistance concentration can affect the effect of biochemical treatment, and the conventional water treatment process of Sewage Plant is difficult to its removal.Compared with the complicated technology such as various advanced oxidations, catalyzed oxidation, absorbing process has the advantages such as technique is simple, treatment effect stable, relative low price.
Conventional sorbing material has gac, active sludge, clay class etc., gac is a kind of high-performance sorbing material, patent publication No. CN101333011 has introduced a kind of method of utilizing tsiklomitsin in mesoporous carbon Adsorption water, patent publication No. CN101337706 utilizes Powdered Activated Carbon to process the method for water body containing tetracycline antibiotics, two kinds of methods all have higher eliminating rate of absorption to tetracycline compound, absolutely proved the high absorption property of gac, but this sorbing material preparation cost is higher, the economic situation current according to China, can not be widely used.Active sludge is the conventional treatment process of sewage work, but activated sludge process can not thoroughly be removed tetracycline compound, along with the increase of tsiklomitsin concentration in water, eliminating rate of absorption reduces and treating processes has drug-fast microorganism in a large number by generation, will form potentially dangerous after entering environment.Therefore, exploitation is a kind of novel, cheap clay class sorbing material is very necessary, at present both at home and abroad about the absorption research of tsiklomitsin adopts natural soil sorbing materials as black grid soil more, oceanic sediment, cinnamon soil, red soil etc., also there is the modification of employing composite adsorbing material as montmorillonite, wilkinite, corn straw modification, ferrate etc., but natural soil sorbing material exists loading capacity low, adsorption concentration is limited in scope, be not suitable for removing the tetracycline compound in high density water body, and modification composite adsorbing material montmorillonite, wilkinite, corn straw modification, ferrate is limited to water body middle and high concentration tsiklomitsin removal efficiency, as ferrate can only reach 75.4% to tetracycline compound clearance under optimal adsorption condition, corn straw modification is up to 93.4% to tetracycline compound clearance.
Attapulgite is a kind of natural clay mineral, owing to having unique layer chain crystalline structure and very tiny ((internal surface area can be up to 300-400m for bar-shaped, fibrous crystals form m) of approximately 0.01 μ m × 1 μ and larger specific surface area
2/ g, and outer surface area depends on the size of attapulgite crystal grain, according to actual measurement, Soviet Union's Anhui attapulgite outer surface area is about 23m
2/ g), determined that it has good absorption property.According to existing bibliographical information attapulgite, be heavy metal and organic strong sorbing material, and processing costs is only the 5-10% of gac, and regenerative operation is simple, and regeneration rate is high, the non-metal kind clay mineral that belongs to a kind of efficient, economy, environmental protection class, has broad prospect of application.Current document has been reported the removal of attapulgite to COD of sewage, and clearance can be up to more than 90%, and what have even reaches 100%, and regeneration rate is high, reusable, but the Adsorption that attapulgite is applied to tetracycline compound is not appeared in the newspapers.
Summary of the invention
The object of this invention is to provide the method for tetracycline compound in a kind of economy, the waste water of iron modified attapulgite adsorbent absorption efficiently.
Iron modified attapulgite adsorbent of the present invention is processed the method for tetracycline wastewater, it is characterized in that:
The concentration of described tsiklomitsin in waste water is 5-150mg/L;
At described tetracycline wastewater, add iron modified attapulgite adsorbent, the mass ratio of described tetracycline wastewater and described sorbent material is 1: (4-6), and preferably 1: 5;
Described adsorption process in temperature is under the condition of 0-50 ℃, adopt static state and/or vibration, stirring action mode is carried out.
In concrete enforcement,
The pH value scope of described tetracycline wastewater is 3-7.
Described adsorption time is 3-24h.
The method of described iron modified attapulgite adsorbent processing tetracycline wastewater also comprises the regeneration of sorbent material;
The regeneration of described sorbent material be by the saturated sorbent material of absorption mix with NaOH, immersion, clear water wash, wherein
Described NaOH concentration is 5%-15%, preferably 5%;
Described soak time is 2-3h.
Iron modified attapulgite adsorbent of the present invention is a kind of novel absorption material generating for the modification of attapulgite raw ore, and this material is higher to the adsorption efficiency of tsiklomitsin, after regeneration, can reuse, and economy is strong, simple to operate.
The preparation process of described iron modified attapulgite adsorbent is:
(1) attapulgite is purified
A. former attapulgite pulverizing, grinding are obtained to particle diameter≤100 object powder;
B. in concave and convex rod stone powder, add water, be made into the suspension that concentration is 5-10wt%, stir, concave and convex rod stone powder is uniformly dispersed;
C. in the suspension after dispersion treatment, add Sodium hexametaphosphate 99, the mass ratio of itself and attapulgite is 1-5: 100, stir 0.5h, and ultrasonic 1h, standing 2h, dewaters to mud cake shape, and 105 ℃ of dry 3h, obtain Concavo-convex stick after purifying stone;
(2) Concavo-convex and excellent after purifying stone modification
A. will in 5g Concavo-convex stick after purifying stone, add 150-200mL water, stir, Concavo-convex stick after purifying stone powder is uniformly dispersed,
B. add the FeCl of 0.2-5.0g
36H
2o,
C. add the HCl of appropriate 1mol/L or the NaOH of 1mol/L that pH value is adjusted to neutrality,
D. magnetic agitation 2-3h, centrifuge washing 2-3 time, dries 36-48h for 40 ℃, grinds and obtains particle diameter≤100 object iron modified attapulgite adsorbent.
Described absorption is subject to the molecular structure feature limits of tsiklomitsin own, and tsiklomitsin, under acid, alkali condition, reaction of degeneration all easily occurs, and known pH value value has material impact to absorption, experimental results show that the preferred pH value of tetracycline scope is 3-7.It is little that absorption is affected by temperature, hunting speed, can select according to practical situation, and adsorbing the preferred time is 3-24h, and adsorption effect increases along with the growth of time, after absorption 24h, reaches adsorption equilibrium completely, and after balance, eliminating rate of absorption reaches more than 98%.
Described iron modified attapulgite regeneration, NaOH concentration is 5%-15%, and preferably NaOH concentration is 5%, soaks 2-3h, after clear water washing, can continue on for tsiklomitsin in planar water, and after regeneration, eliminating rate of absorption reaches 61.8%.
The present invention is directed to the waste water that polluted by tsiklomitsin, by adding iron modified attapulgite adsorbent to carry out Adsorption in waste water, beneficial effect of the present invention:
1. the adsorption efficiency of pair tetracycline compound is high,
2. operating process is simple,
3. adsorption conditions requirement is low,
4. sorbing material is with low cost, regeneration efficiency is high, be easy to popularization.
Therefore, the present invention is applied to and removes tetracycline compound in water body and have good economy and environmental benefit.
Accompanying drawing explanation
The impact of Fig. 1 time on eliminating rate of absorption
The impact of Fig. 2 tsiklomitsin starting point concentration on eliminating rate of absorption
The impact of Fig. 3 temperature on eliminating rate of absorption
The impact of Fig. 4 oscillation rate on eliminating rate of absorption
The impact of Fig. 5 pH on eliminating rate of absorption
The impact of the different iron amount of Fig. 6 modified attapulgite adsorbent on eliminating rate of absorption
Embodiment
Below in conjunction with specific examples, invention is described in detail.Scope of the present invention is not limited with embodiment, but is limited by the scope of claim.
Embodiment
Embodiment 1
Take 5g Concavo-convex stick after purifying stone and be placed in 500mL beaker, add 250mL distilled water, after magnetic agitation 0.5h, add the FeCl of 0.724g
36H
2o (being equivalent to 0.15gFe), magnetic agitation 30min, guarantees FeCl
36H
2o dissolves completely, regulates pH value=7, continues stirring 1h, after centrifuge washing 3 times, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 order, makes iron modified attapulgite adsorbent.
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, the rate oscillation of 150r/min at 25 ℃ of temperature, at 1h, 3h, 6h, 12h, 24h, get supernatant liquor and cross respectively the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, tsiklomitsin eliminating rate of absorption is respectively 70.3%, 88.8%, 95.3%, 98.1%, 98.7%.Accompanying drawing 1, the impact of time on eliminating rate of absorption.
Visible, be adsorbed on 3h clearance and approach 90%, growth in time, clearance increases gradually, and after adsorption equilibrium, clearance reaches more than 98%.Adsorbing the preferred time is 3-24h.
With embodiment 1, make iron modified attapulgite adsorbent.
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug Erlenmeyer flask, add that 20mL concentration is respectively 10,20,50, in the tetracycline of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, the rate oscillation 24h of 150r/min is to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, tsiklomitsin eliminating rate of absorption is respectively 100.0%, 99.4%, 99.4%, 98.7%.Accompanying drawing 2, the impact of tsiklomitsin starting point concentration on eliminating rate of absorption.
Visible, iron modified attapulgite adsorbent has very high clearance to the tsiklomitsin polluted-water of 5-150mg/L concentration.
Embodiment 3
With embodiment 1, make iron modified attapulgite adsorbent.
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, respectively at 5,15,25,40 ℃ of temperature the rate oscillation 24h of 150r/min to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, tsiklomitsin eliminating rate of absorption is respectively 96.6%, 97.4%, 98.7%, 99.7%.Accompanying drawing 3, the impact of temperature on eliminating rate of absorption.
Visible, iron modified attapulgite adsorbent absorption tetracycline compound temperature influence is little, is applicable to the removal that the 0-50 ℃ of water body tsiklomitsin under temperature condition pollutes.
Embodiment 4
With embodiment 1, make iron modified attapulgite adsorbent.
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, respectively with 0,50,100,150, the rate oscillation 24h of 200r/min is to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculates standard deviation, guarantees measuring accuracy.As calculated, tsiklomitsin eliminating rate of absorption is respectively 97.6%, 98.9%, 98.9%, 98.7%, 98.7%.Accompanying drawing 4, the impact of oscillation rate on eliminating rate of absorption.
Visible, the service requirements of iron modified attapulgite adsorbent absorption tetracycline compound is low, can directly add use.
With embodiment 1, make iron modified attapulgite adsorbent.
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g (± 0.0005g), be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, regulator solution pH value is respectively 1,3,5,7,9 and is placed in constant temperature oscillator, at 25 ℃ of temperature, the rate oscillation 24h of 150r/min is to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy.As calculated, tsiklomitsin eliminating rate of absorption is respectively 70.1%, 98.7%, 97.2%, 91.5%, 73.6%.Accompanying drawing 5, the impact of pH on eliminating rate of absorption.
Visible, pH is larger to Adsorption Effect, and preferred solution pH value scope is 3-7.
Take 5g Concavo-convex stick after purifying stone and be placed in 500mL beaker, add 250mL distilled water, after magnetic agitation 0.5h, add respectively the FeCl of 0.241g, 0.483g, 0.724g, 1.207g, 2.414g, 3.620g
36H
2o (being equivalent to respectively 0.05g, 0.10g, 0.15g, 0.25g, 0.50g, 0.75gFe), magnetic agitation 30min, guarantees FeCl
36H
2o dissolves completely, regulates pH value=7, continues stirring 1h, after centrifuge washing 3 times, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 order, makes the iron modified attapulgite adsorbent of different iron amounts.
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g (± 0.0005g) respectively, be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, with the rate oscillation 24h of 150r/min to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculates standard deviation, guarantees measuring accuracy.As calculated, tsiklomitsin eliminating rate of absorption is respectively 96.8%, 98.3%, 98.7%, 97.8%, 95.3%, 96.4%.Accompanying drawing 6, the impact of different iron amount modified attapulgite adsorbents on eliminating rate of absorption.
Claims (2)
1. iron modified attapulgite adsorbent is processed a method for tetracycline wastewater, it is characterized in that:
The preparation process of described iron modified attapulgite adsorbent is:
Take 5g Concavo-convex stick after purifying stone and be placed in 500mL beaker, add 250mL distilled water, after magnetic agitation 0.5h, add the FeCl of 0.724g
36H
2o, magnetic agitation 30min, guarantees FeCl
36H
2o dissolves completely, regulates pH value=7, continues stirring 1h, after centrifuge washing 3 times, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 order, makes iron modified attapulgite adsorbent;
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g ± 0.0005g, be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, the rate oscillation of 150r/min at 25 ℃ of temperature, at 1h, 3h, 6h, 12h, 24h, get supernatant liquor and cross respectively the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy;
Or, making as mentioned above after iron modified attapulgite adsorbent,
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g ± 0.0005g, be placed in 250mL tool plug Erlenmeyer flask, add that 20mL concentration is respectively 10,20,50, in the tetracycline of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, the rate oscillation 24h of 150r/min is to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy;
Or, making as mentioned above after iron modified attapulgite adsorbent,
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g ± 0.0005g, be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, respectively at 5,15,25,40 ℃ of temperature the rate oscillation 24h of 150r/min to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy;
Or, making as mentioned above after iron modified attapulgite adsorbent,
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g ± 0.0005g, be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, respectively with 0,50,100,150, the rate oscillation 24h of 200r/min is to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculates standard deviation, guarantees measuring accuracy;
Or, making as mentioned above after iron modified attapulgite adsorbent,
Accurate weighing is through iron modified attapulgite adsorbent 0.1000g ± 0.0005g, be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, regulator solution pH value is respectively 1,3,5,7,9 and is placed in constant temperature oscillator, at 25 ℃ of temperature, the rate oscillation 24h of 150r/min is to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, test residual tsiklomitsin concentration by liquid chromatography, three groups of each experiment settings are parallel, result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy;
Or adopt following methods to make the iron modified attapulgite adsorbent of different iron amounts:
Take 5g Concavo-convex stick after purifying stone and be placed in 500mL beaker, add 250mL distilled water, after magnetic agitation 0.5h, add respectively the FeCl of 0.241g, 0.483g, 0.724g, 1.207g, 2.414g, 3.620g
36H
2o, magnetic agitation 30min, guarantees FeCl
36H
2o dissolves completely, regulates pH value=7, continues stirring 1h, after centrifuge washing 3 times, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 order;
Afterwards, accurate weighing is through iron modified attapulgite adsorbent 0.1000g ± 0.0005g respectively, be placed in 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L, be placed in constant temperature oscillator, at 25 ℃ of temperature, with the rate oscillation 24h of 150r/min to adsorption equilibrium, get supernatant liquor and cross the millipore filtration of 0.45 μ m, by liquid chromatography, test residual tsiklomitsin concentration, three groups of each experiment settings are parallel, and result is with arithmetical mean value representation, and calculate standard deviation, guarantee measuring accuracy;
The method of described iron modified attapulgite adsorbent processing tetracycline wastewater also comprises the regeneration of sorbent material;
The regeneration of described sorbent material be by the saturated sorbent material of absorption mix with NaOH, immersion, clear water wash, wherein
Described NaOH concentration is 5%-15%; Described soak time is 2-3h.
2. iron modified attapulgite adsorbent as claimed in claim 1 is processed the method for tetracycline wastewater, it is characterized in that:
Described NaOH concentration is 5%.
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| CN103145212A (en) * | 2013-03-20 | 2013-06-12 | 中国科学院高能物理研究所 | Method for treating tetracycline-containing wastewater |
| CN105080472B (en) * | 2014-05-23 | 2017-10-03 | 北京师范大学 | A kind of inorganic organic combined modified attapulgite clay adsorbent and preparation method thereof and its method for handling 6 aminopenicillanic acid waste water |
| CN105080473B (en) * | 2014-05-23 | 2017-10-03 | 北京师范大学 | A kind of inorganic organic combined modified attapulgite clay adsorbent and preparation method thereof and its method for handling ampicillin waste water |
| CN106315810B (en) * | 2016-09-26 | 2020-02-04 | 郑州紫盈节能环保科技有限公司 | Multiple-load type silicon-based phosphorus removal agent, preparation method and application thereof |
| CN107159094B (en) * | 2017-05-26 | 2019-11-01 | 湖南农业大学 | The method of tetracycline in magnetic magnesium hydroxide adsorbent removal waste water |
| CN107159112B (en) * | 2017-05-26 | 2019-11-01 | 湖南农业大学 | The method that magnetic composite adsorbent removes tetracycline in waste water |
| CN109020150B (en) * | 2018-09-15 | 2021-07-09 | 东莞理工学院 | Sludge recovery harmless treatment method and device |
| CN109467289A (en) * | 2019-01-16 | 2019-03-15 | 福建省蓝深环保技术股份有限公司 | A kind of processing method of breeding wastewater |
| CN111196618B (en) * | 2020-03-16 | 2022-05-31 | 河北省科学院生物研究所 | Method for removing cobalt ions and/or antibiotics in wastewater |
| CN113772798A (en) * | 2021-09-13 | 2021-12-10 | 华南农业大学 | Method for removing tetracycline in water body |
| CN114314732B (en) * | 2022-01-06 | 2022-12-06 | 绍兴上虞联谊化工有限公司 | Treatment and recycling process of sulfonated para-ester production mother liquor wastewater |
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