CN102531084A - 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 sorbent material tetracycline compound in the medical sewage to be adsorbed the method for removal.
Background technology
TCs (tetracycline antibiotics, TCs is hereinafter to be referred as tetracyclines) is the one type of Broad spectrum antibiotics that is 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 from the Streptomyces nutrient solution, to extract, and tsiklomitsin (Tetracycline) is a kind of of natural tetracyclines.Antimicrobial spectrum is widely arranged, mikrobes such as Gram-positive, Gram-negative bacteria, mycoplasma, rickettsia and chlamydozoan are all had activity.
China since early 1990s, tsiklomitsin widespread use in industries such as medicine, livestock industry and aquaculture, its output and consumption are in rising trend always.But its production and use and great amount of wastewater of producing in above-mentioned industry is unprocessed or handle and thoroughly do not make tsiklomitsin get into ecotope with water; Therefore; The content of tsiklomitsin in water surrounding grows with each passing day, and the negative effect of human and ecotope is also highlighted day by day.
For the ecosystem, the abuse tsiklomitsin can directly cause individual resistance.Increasing data shows simultaneously, and more natural bacteriums are more much higher than what expect to the resistance of tsiklomitsin, and promptly the drug-resistance of bacteria gene possibly transfer take place at occurring in nature.The resistance of tsiklomitsin possibly pass to malignant bacteria from non-pathogenic bacteria, even may further propagate, and develops into the resistance on the ecological level, and makes the individuality that does not directly touch tsiklomitsin also produce resistance.The World Health Organization points out in report in 2000: the phenomenon of resistance pathogen propagation is on the rise, and is the 21 century huge challenge that faces of human health.
The residual composition and the activity that can influence microorganisms in water of tsiklomitsin in the water surrounding, thus the microbial ecological structure changed, influence nitrated, the mineralization of soil and the nutrient of soil and circulate or the like.In addition, the residual meeting of tsiklomitsin impacts plant, hydrobiont and soil organisms, because of the difference generation inhibition growth or the harm such as variation and teratogenesis of residual concentration.Because tetracycline compound can pass the lipophilic group of cytolemma, and has advantages of higher stability, therefore, be easy to biological accumulation and at the medium-term and long-term stable existence of environment etc., thereby aggravate it
For reducing the ecological risk of tetracycline compound in the water surrounding, need to remove the tetracycline compound in sewage or the high density surface water body.Conventional at present water treatment method has: the combination treatment method of physics, chemistry and biological process and aforesaid method; But because tetracycline compound complex structure; Its toxicity and resistance concentration can influence the effect of biochemical treatment, and the conventional water treatment process of Sewage Plant is difficult to its removal.Compare with complicated technologies such as various advanced oxidations, catalyzed oxidations, absorbing process has advantages such as technology is simple, treatment effect stable, relative low price.
Sorbing material commonly used 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 the absorption of mesopore charcoal to remove tsiklomitsin in the water, and patent publication No. CN101337706 utilizes Powdered Activated Carbon to handle the method for water body containing tetracycline antibiotics, and two kinds of methods all have higher eliminating rate of absorption to tetracycline compound; Proved absolutely the high absorption property of gac; But this sorbing material preparation cost is higher, and the economic situation present according to China can not be widely used.Active sludge is sewage work's treatment process commonly used; But activated sludge process can not thoroughly be removed tetracycline compound; Along with the increase of tsiklomitsin concentration in the water, eliminating rate of absorption reduces and treating processes will produce and have drug-fast mikrobe in a large number, will form potentially dangerous after entering environment.Therefore; It is very necessary developing a kind of novel, cheap clay class sorbing material; Adopt natural soil sorbing material such as black grid soil, oceanic sediment, cinnamon soil, red soil etc. at present both at home and abroad about the absorption research of tsiklomitsin; Also have the modification of employing composite adsorbing material if you would take off stone, wilkinite, corn straw modification, perferrate etc., but the natural soil sorbing material exists loading capacity low, adsorption concentration is limited in scope; The unsuitable tetracycline compound of removing in the high density water body; And that modification composite adsorbing material smectite, wilkinite, corn straw modification, perferrate are removed efficient to water body middle and high concentration tsiklomitsin is limited, under the optimal adsorption condition, can only reach 75.4% to the tetracycline compound clearance like perferrate, and corn straw modification is up to 93.4% to the tetracycline compound clearance.
Attapulgite is a kind of natural clay mineral, and (internal surface area can be up to 300-400m owing to have bar-shaped, fibrous crystals form and the bigger specific surface area of unique layer chain crystalline structure and very tiny (about 0.01 μ m * 1 μ m)
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 it to have the good adsorption performance.According to existing bibliographical information attapulgite is heavy metal and organic strong sorbing material; And processing costs is merely the 5-10% of gac, and regenerative operation is simple, and regeneration rate is high; Belong to the non-metal kind clay mineral of a kind of efficient, economy, environmental protection class, have broad prospect of application.Present document has been reported the removal of attapulgite to COD of sewage, and clearance can be up to more than 90%, have in addition reach 100%, and regeneration rate is high, reusable, does not appear in the newspapers but the absorption that attapulgite is applied to tetracycline compound removed.
Summary of the invention
The purpose of this invention is to provide a kind of economy, the method for tetracycline compound in the iron modified attapulgite adsorbents adsorb waste water efficiently.
The method of iron modified attapulgite sorbent treatment tetracycline wastewater of the present invention is characterized in that:
The concentration of described tsiklomitsin in waste water is 5-150mg/L;
Add iron modified attapulgite sorbent material at described tetracycline wastewater, the mass ratio of described tetracycline wastewater and described sorbent material is 1: (4-6), and preferred 1: 5;
Described adsorption process in temperature is under 0-50 ℃ the condition, adopt static state and/or vibration, the stirring action mode is carried out.
In practical implementation,
The pH value scope of described tetracycline wastewater is 3-7.
Described adsorption time is 3-24h.
The method of described iron modified attapulgite sorbent treatment tetracycline wastewater also comprises the regeneration of sorbent material;
The regeneration of described sorbent material be with the saturated sorbent material of absorption mix with NaOH, immersion, clear water wash and get final product, wherein
Described NaOH concentration is 5%-15%, preferred 5%;
Described soak time is 2-3h.
Iron modified attapulgite sorbent material of the present invention is a kind of novel absorption material that generates to 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, and is simple to operate.
Described iron modified attapulgite preparation of adsorbent process is:
(1) attapulgite is purified
A. former attapulgite pulverizing, grinding are obtained particle diameter≤100 purpose powder;
B. in concave and convex rod stone powder, add water, be made into the suspension-s that concentration is 5-10wt%, stir, concave and convex rod stone powder is uniformly dispersed;
C. add Sodium hexametaphosphate 99 in the suspension-s after dispersion treatment, the mass ratio of itself and attapulgite is 1-5: 100, stir 0.5h, and ultrasonic 1h leaves standstill 2h, dewaters to the 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. with adding 150-200mL water in the 5g Concavo-convex stick after purifying stone, stir, the Concavo-convex stick after purifying stone powder be uniformly dispersed,
B. the FeCl that adds 0.2-5.0g
36H
2O,
C. add the HCl of an amount of 1mol/L or the NaOH of 1mol/L the pH value be adjusted to neutrality,
D. magnetic agitation 2-3h, centrifuge washing 2-3 time, 40 ℃ of oven dry 36-48h grind and obtain particle diameter≤100 purpose iron modified attapulgite sorbent materials.
Described absorption receives the molecular structure feature limits of tsiklomitsin own, and tsiklomitsin all is prone to rd-takes place under acid, alkali condition, can know that pH value value has material impact to absorption, and the preferred pH value of experiment proof tetracycline scope is 3-7.It is little that absorption is influenced 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, reaches adsorption equilibrium fully behind the absorption 24h, and eliminating rate of absorption reaches more than 98% after the balance.
Said iron modified attapulgite regeneration, NaOH concentration is 5%-15%, and preferred NaOH concentration is 5%, soaks 2-3h, can continue on for tsiklomitsin in the planar water after the clear water washing, and regeneration back eliminating rate of absorption reaches 61.8%.
The present invention is directed to the waste water that polluted by tsiklomitsin, adsorb removal, beneficial effect of the present invention through in waste water, adding iron modified attapulgite sorbent material:
1. the adsorption efficiency to tetracycline compound is high,
2. operating process is simple,
3. the 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 remove that tetracycline compound has good economy and environmental benefit in the water body.
Description of drawings
Fig. 1 time is to the influence of eliminating rate of absorption
Fig. 2 tsiklomitsin starting point concentration is to the influence of eliminating rate of absorption
Fig. 3 temperature is to the influence of eliminating rate of absorption
Fig. 4 oscillation rate is to the influence of eliminating rate of absorption
Fig. 5 pH value of solution value is to the influence of eliminating rate of absorption
The different iron amount of Fig. 6 modified attapulgite sorbent material is to the influence of eliminating rate of absorption
Embodiment
Below in conjunction with specific examples invention is described in detail.Scope of the present invention is not exceeded with embodiment, but is limited the scope of claim.
Embodiment
Take by weighing 5g Concavo-convex stick after purifying stone and place the 500mL beaker, add 250mL zero(ppm) water, behind the 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 fully, regulates pH value=7, continues stirring 1h, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 orders behind the centrifuge washing 3 times, makes iron modified attapulgite sorbent material.
Accurately weighing through iron modified attapulgite sorbent material 0.1000g (± 0.0005g), place 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L; Place in the constant temperature oscillator; The rate oscillation of 150r/min is got the millipore filtration that supernatant is crossed 0.45 μ m at 1h, 3h, 6h, 12h, 24h respectively under 25 ℃ of temperature, tests residual tsiklomitsin concentration with liquid chromatography; Three groups of each experiment settings are parallel; The result is with the arithmetical mean value representation, and the base of calculation deviation, guarantees measuring accuracy.Through calculating, the tsiklomitsin eliminating rate of absorption is respectively 70.3%, 88.8%, 95.3%, 98.1%, 98.7%.Accompanying drawing 1, the time is to the influence of eliminating rate of absorption.
It is thus clear that, be adsorbed on the 3h clearance near 90%, growth in time, clearance increases gradually, and clearance reaches more than 98% after the adsorption equilibrium.Adsorbing the preferred time is 3-24h.
Make iron modified attapulgite sorbent material with embodiment 1.
Accurately weighing through iron modified attapulgite sorbent material 0.1000g (± 0.0005g), place 250mL tool plug Erlenmeyer flask, add that 20mL concentration is respectively 10,20,50, in the tetracycline of 100mg/L; Place in the constant temperature oscillator; The rate oscillation 24h of 150r/min gets the millipore filtration that supernatant is crossed 0.45 μ m to adsorption equilibrium under 25 ℃ of temperature, tests residual tsiklomitsin concentration with liquid chromatography; Three groups of each experiment settings are parallel; The result is with the arithmetical mean value representation, and the base of calculation deviation, guarantees measuring accuracy.Through calculating, the tsiklomitsin eliminating rate of absorption is respectively 100.0%, 99.4%, 99.4%, 98.7%.Accompanying drawing 2, the tsiklomitsin starting point concentration is to the influence of eliminating rate of absorption.
It is thus clear that iron modified attapulgite sorbent material all has very high clearance to the tsiklomitsin polluted-water of 5-150mg/L concentration.
Embodiment 3
Make iron modified attapulgite sorbent material with embodiment 1.
Accurately weighing through iron modified attapulgite sorbent material 0.1000g (± 0.0005g), place 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L; Place in the constant temperature oscillator; The rate oscillation 24h of 150r/min gets the millipore filtration that supernatant is crossed 0.45 μ m to adsorption equilibrium under 5,15,25,40 ℃ of temperature respectively, tests residual tsiklomitsin concentration with liquid chromatography; Three groups of each experiment settings are parallel; The result is with the arithmetical mean value representation, and the base of calculation deviation, guarantees measuring accuracy.Through calculating, the tsiklomitsin eliminating rate of absorption is respectively 96.6%, 97.4%, 98.7%, 99.7%.Accompanying drawing 3, temperature is to the influence of eliminating rate of absorption.
It is thus clear that iron modified attapulgite adsorbents adsorb tetracycline compound temperature influence is little, be applicable to the removal that the 0-50 ℃ of water body tsiklomitsin under the temperature condition pollutes.
Make iron modified attapulgite sorbent material with embodiment 1.
Accurately weighing through iron modified attapulgite sorbent material 0.1000g (± 0.0005g), place 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L; Place in the constant temperature oscillator, under 25 ℃ of temperature, respectively with 0,50,100,150, the rate oscillation 24h of 200r/min is to adsorption equilibrium; Get supernatant and cross the millipore filtration of 0.45 μ m; Test residual tsiklomitsin concentration with liquid chromatography, three groups of each experiment settings are parallel, and the result is with the arithmetical mean value representation; And the base of calculation deviation, guarantee measuring accuracy.Through calculating, the tsiklomitsin eliminating rate of absorption is respectively 97.6%, 98.9%, 98.9%, 98.7%, 98.7%.Accompanying drawing 4, oscillation rate is to the influence of eliminating rate of absorption.
It is thus clear that the request for utilization of iron modified attapulgite adsorbents adsorb tetracycline compound is low, can directly add use.
Make iron modified attapulgite sorbent material with embodiment 1.
Accurately weighing through iron modified attapulgite sorbent material 0.1000g (± 0.0005g), place 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 places in the constant temperature oscillator; The rate oscillation 24h of 150r/min gets the millipore filtration that supernatant is crossed 0.45 μ m to adsorption equilibrium under 25 ℃ of temperature, tests residual tsiklomitsin concentration with liquid chromatography; Three groups of each experiment settings are parallel; The result is with the arithmetical mean value representation, and the base of calculation deviation, guarantees measuring accuracy.Through calculating, the tsiklomitsin eliminating rate of absorption is respectively 70.1%, 98.7%, 97.2%, 91.5%, 73.6%.Accompanying drawing 5, the pH value of solution value is to the influence of eliminating rate of absorption.
It is thus clear that the pH value of solution value is bigger to Adsorption Effect, preferred solution pH value scope is 3-7.
Take by weighing 5g Concavo-convex stick after purifying stone and place the 500mL beaker, add 250mL zero(ppm) water, behind the magnetic agitation 0.5h, add the FeCl of 0.241g, 0.483g, 0.724g, 1.207g, 2.414g, 3.620g respectively
36H
2O (being equivalent to 0.05g, 0.10g, 0.15g, 0.25g, 0.50g, 0.75gFe respectively), magnetic agitation 30min guarantees FeCl
36H
2O dissolves fully, regulates pH value=7, continues stirring 1h, in 40 ℃ of dry 36-48h, is ground to particle diameter≤100 orders behind the centrifuge washing 3 times, makes the iron modified attapulgite sorbent material of different iron amounts.
Respectively accurate weighing through iron modified attapulgite sorbent material 0.1000g (± 0.0005g), place 250mL tool plug Erlenmeyer flask, adding 20mL concentration is in the tetracycline of 100mg/L; Place in the constant temperature oscillator, under 25 ℃ of temperature, with the rate oscillation 24h of 150r/min to adsorption equilibrium; Get supernatant and cross the millipore filtration of 0.45 μ m; Test residual tsiklomitsin concentration with liquid chromatography, three groups of each experiment settings are parallel, and the result is with the arithmetical mean value representation; And the base of calculation deviation, guarantee measuring accuracy.Through calculating, the tsiklomitsin eliminating rate of absorption is respectively 96.8%, 98.3%, 98.7%, 97.8%, 95.3%, 96.4%.Accompanying drawing 6, different iron amount modified attapulgite sorbent materials are to the influence of eliminating rate of absorption.
Claims (7)
1. the method for an iron modified attapulgite sorbent treatment tetracycline wastewater is characterized in that:
The concentration of described tsiklomitsin in waste water is 5-150mg/L;
Add iron modified attapulgite sorbent material at described tetracycline wastewater, the mass ratio of described tetracycline wastewater and described sorbent material is 1: (4-6);
Described adsorption process in temperature is under 0-50 ℃ the condition, adopt static state and/or vibration, the stirring action mode is carried out.
2. the method for iron modified attapulgite sorbent treatment tetracycline wastewater as claimed in claim 1 is characterized in that:
The mass ratio of described tetracycline wastewater and described sorbent material is 1: 5.
3. the method for iron modified attapulgite sorbent treatment tetracycline wastewater as claimed in claim 2 is characterized in that:
The pH value scope of described tetracycline wastewater is 3-7.
4. the method for iron modified attapulgite sorbent treatment tetracycline wastewater as claimed in claim 3 is characterized in that:
Described adsorption time is 3-24h.
5. the method for iron modified attapulgite sorbent treatment tetracycline wastewater as claimed in claim 1 is characterized in that:
The method of described iron modified attapulgite sorbent treatment tetracycline wastewater also comprises the regeneration of sorbent material;
The regeneration of described sorbent material be with the saturated sorbent material of absorption mix with NaOH, immersion, clear water wash and get final product, wherein
Described NaOH concentration is 5%-15%; Described soak time is 2-3h.
6. the method for iron modified attapulgite sorbent treatment tetracycline wastewater as claimed in claim 5 is characterized in that:
Described NaOH concentration is 5%.
7. like the method for the iron modified attapulgite sorbent treatment tetracycline wastewater of one of claim 1～6, it is characterized in that described iron modified attapulgite preparation of adsorbent process is:
(1) attapulgite is purified
A. former attapulgite pulverizing, grinding are obtained particle diameter≤100 purpose powder;
B. in concave and convex rod stone powder, add water, be made into the suspension-s that concentration is 5-10wt%, stir, concave and convex rod stone powder is uniformly dispersed;
C. add Sodium hexametaphosphate 99 in the suspension-s after dispersion treatment, the mass ratio of itself and attapulgite is 1-5: 100, stir 0.5h, and ultrasonic 1h leaves standstill 2h, dewaters to the 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. with adding 150-200mL water in the 5g Concavo-convex stick after purifying stone, stir, the Concavo-convex stick after purifying stone powder be uniformly dispersed,
B. the FeCl that adds 0.2-5.0g
36H
2O,
C. add the HCl of an amount of 1mol/L or the NaOH of 1mol/L the pH value be adjusted to neutrality,
D. magnetic agitation 2-3h, centrifuge washing 2-3 time, 40 ℃ of oven dry 36-48h grind and obtain particle diameter≤100 purpose iron modified attapulgite sorbent materials.
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| CN105080473A (en) * | 2014-05-23 | 2015-11-25 | 北京师范大学 | Inorganic-organic co-modified attapulgite adsorbent, preparation method, and method for treating ampicillin wastewater by using adsorbent |
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| CN107159094A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic magnesium hydroxide adsorbent removes tetracycline in waste water |
| CN107159112A (en) * | 2017-05-26 | 2017-09-15 | 湖南农业大学 | The method that magnetic composite adsorbent removes tetracycline in waste water |
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| 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 |
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| 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 |
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| CN113772798A (en) * | 2021-09-13 | 2021-12-10 | 华南农业大学 | Method for removing tetracycline in water body |
| CN114314732A (en) * | 2022-01-06 | 2022-04-12 | 绍兴上虞联谊化工有限公司 | Treatment and recycling process of sulfonated para-ester production mother liquor wastewater |
| 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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