CN105293616A - Method for removing antibiotic residue from the environment - Google Patents
Method for removing antibiotic residue from the environment Download PDFInfo
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- CN105293616A CN105293616A CN201410315708.6A CN201410315708A CN105293616A CN 105293616 A CN105293616 A CN 105293616A CN 201410315708 A CN201410315708 A CN 201410315708A CN 105293616 A CN105293616 A CN 105293616A
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Abstract
The invention provides a method for removing antibiotic residue from the environment. The method comprises the following steps: adding water in to waste organic residue obtained after caustic extraction of weathered coal or brown coal for dissolution, adjusting the pH to be equal to or lower than 7, carrying out centrifugation, removing the supernatant fluid, drying the precipitate, grinding the dried precipitate into powder, sieving the powder with a 200-mesh sieve, weighing 3 to 100 g of treated residue, preparing a chromatographic column (or synthesizing a molecular imprint compound), simply testing the water quality of a sample to be tested with a humate (taking part of the water sample to be tested, adjusting the taken water sample to be weak alkalic, adding a small quantity of humic acid, and observing the flocculation condition), treating the water sample according to a direct loading method when the water sample is easy to flocculate, otherwise loading the water sample after the chromatographic column is reactivated with a calcium chloride aqueous solution, and finally, taking a phosphate buffer-methanol solution of which the pH is 2 or formic acid for elution when elution is required for analysis of enriched antibiotics, otherwise transferring a filling material after the saturated extent of adsorption is reached (the concentration of ciprofloxacin is 129 mg/g), carrying out ashing, and recovering metal ions in ash obtained via ashing.
Description
Technical field
The invention belongs to weathered coal or the discarded organic detritus of brown coal after caustic extraction for applied chemistry field antibiotic in enrichment environment.In recent years, there is serious abuse of antibiotics situation in China, and microbiotic only has 20% can be absorbed in human body or animal body, remaining 80% all enters in environment with the form of urine, ight soil, thus cause the ubiquity of residual antibiotic in environment, its harm existed is exactly resistance, the appearance of such as superbacteria.So, the microbiotic how removed in environment just becomes extremely urgent problem.Rudimentary coal is as contained humic acids in weathered coal, brown coal etc., humic acids in coal can be extracted (less than 60%) after caustic extraction, residue organic detritus (more than 30%) often goes out of use or sells fertilizer plant with extremely low price, and this residue can efficiently concentrating microbiotic.Therefore, the present invention utilizes the microbiotic in organic detritus enrichment environment, eliminates in environment and decreases residue quantity discharged while residual antibiotic, finally reach protection of the environment, improves the object of resource utilization.
Background technology
Show about antibiotic large quantity research: the annual various microbiotic summations used in the whole world, more than 200,000 tons, have detected antibiotic remains all widely at present in water body, food, settling, animal excrement and soil.Antibiotic excessive use can strengthen the resistance of the microorganisms such as some bacteriums, and being on the increase along with drug-resistant microorganism, it becomes the dominant bacteria in environment the most at last and constantly breeds, can eliminate even if the microbiotic in environment pollutes, the drug-resistant microorganism formed still can sustainable existence in the environment, thus threatens the living environment of the mankind.
The rudimentary rich coal resources such as China's weathered coal, but containing a large amount of humic acidss in this rudimentary coal, as described in Figure 1, in factory, conventional alkali lye carries out extracting to the humic acids in coal, but extraction yield is the highest can only reach 60% ~ 70%, the non-humic acid organic substances matter of residue about 30% just becomes waste residue, 60% is also had to be difficult to by the humic acids that extracts or class humic-acid-type substances in these waste residues, and these organic detritus are directly drained with the form of solid waste by enterprise usually or sell with more than 100 yuan of prices per ton, therefore there is serious wasting of resources situation.
Through literature survey, humic acids meeting complexing, chelating, absorption polyvalent metal ion, the microbiotic such as tsiklomitsin also can be combined with polyvalent metal ion, and as shown in Figure 2, the microbiotic in environment and humic acids as bridge, can link together by polyvalent metal ion.The research that humic acids synthetic resins is used for the heavy metal in adsorbed water body is existing many, and result shows, the saturated extent of adsorption of Humic Acid Resin heavy metal ion can reach tens to hundreds of mg/g.In conventional enrichment environment, antibiotic method is solid phase extraction, HLB solid-phase extraction column due to applied widely, bioaccumulation efficiency is high and obtain general application, but this pillar is expensive.Therefore use the organic detritus containing humic acids as sorbent material, carry out enrichment simultaneously to the heavy metal in environment and microbiotic, the efficient circulation realizing residue utilizes, and for environment protection, reduces costs, and realizing turns waste into wealth has important theory and realistic meaning.
Patent CN103611513A discloses a kind of magnetic phenolic aldehyde humic acid resin in March, 2014, and this resin is to Cu
2+ion has good absorption property, can be used for the removal of Cu in waste water ion, and the magnetic that this technology make use of humic acids is separated, but due to actual aqueous body compositions comparatively complicated, therefore, its range of application in actual use may be caused narrower.
Patent CN103739134A discloses a kind of antibiotic method in removal water in April, 2014, and first Sodium Persulfate mixes with pretreated water by the method, then adjust ph, re-uses ultraviolet lighting water jetting body, finally adds hypo solution.The object of this invention will solve antibiotic method in existing removal water to there is the low problem of the higher and clearance of cost, but to there is working conditions comparatively loaded down with trivial details for this technology, and the introducing of Sulfothiorine may cause secondary pollution to water body.
Patent CN103693710A discloses a kind of preparation and oil-water separation method of humic acids modification flying dust magneticsubstance in April, 2014, and the humic acids modification flying dust magneticsubstance obtained by the method has good absorption property and stronger Magneto separate performance.In conjunction with profit magnetism separate method, can dispersed oil, emulsus oil in water body be adsorbed with partial solubility wet goods pollution substance, be separated and removed.The inventive method technique is simple, easy to control, and adapt to large-scale industrial production oily water separation material, the water body after process can reach national wastewater discharge standard, and reaches the object of the treatment of wastes with processes of wastes against one another.Patent CN103739036A discloses a kind of sewage-treating agent be made up of Sodium salts humic acids, bodied ferric sulfate and polyacrylamide in April, 2014,2-4h is reacted after adding sewage-treating agent, by the oil reservoir sucking-off of apparatus for treating sewage upper surface, lower floor's sewage is discharged.The present invention is the humic-acid kind water conditioner that can remove grease in oily(waste)water preferably.
Summary of the invention
Object of the present invention solves this phenomenon of antibiotic remains ubiquity in current environment exactly, provides a kind of low cost, high-level efficiency to remove the method for antibiotic remains in environment.
To the effect that of the present invention, exist mainly with the combined with polyvalent metal ion greatly based on the microbiotic in environment, and a large amount of humic acidss in weathered coal or the brown coal discarded organic detritus after caustic extraction are also easy to chelated polyvalent metal ion, material is thus formed the combination of " humic acids-metal ion-microbiotic " three.Therefore, namely the present invention utilizes this residue to remove the residual antibiotic in environment.Another feature of the present invention be organic detritus eliminating Multiple Classes of Antibiotics in environment while, also by multivalence heavy metal ion also enrichment in the lump, the mode heavy metal of calcination (or charing) can be adopted afterwards to recycle.The present invention has simultaneously accomplished to make full use of resource, and also do not have antibiotic product in cheap removal (enrichment) environment in current industry, therefore the present invention makes the low level coal organic detritus after extracting turn waste into wealth.
The present invention is achieved through the following technical solutions.
Take a certain amount of low level coal organic detritus crossed through caustic extraction to dissolve, adjustment pH, filters, and collects filter residue, then carries out wet method filling, be prepared into column chromatography.For not containing heavy metal and the less waste water of hardness, first should use containing Ca
2+, Mg
2+the aqueous solution Deng polyvalent metal ion activates (otherwise without the need to activation) to pillar, after loading, if afterwards without the need to collecting the microbiotic of enrichment, then the pillar weighting material of the adsorptive capacity that reaches capacity can be carried out ashing; If desired analyze the microbiotic obtained, then carry out wash-out with acidic phosphate buffer or formic acid, elutriant is for subsequent use after drying.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of factory's traditional extraction humic acids;
Fig. 2 is microbiotic-polyvalent metal ion-humic acids residue interaction mechanism figure;
Fig. 3 is simple process figure of the present invention;
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.These embodiments are interpreted as only being not used in for illustration of the present invention limiting the scope of the invention.After having read the content that the present invention records, the various change made the present invention based on principle of the present invention or amendment have fallen into claims of the present invention limited range equally.
Embodiment 1
Antibiotic enrichment in water body: after the residue after weathered coal or brown coal extracting humic acids is dissolved in water by (1), adjustment pH is less than 7, centrifugal rear abandoning supernatant, ground 200 mesh sieves after being dried by throw out.(2) take the residue of 3-100g process, be prepared into chromatographic column.(3) carry out concise and to the point qualification by the water quality situation of humate to testing sample and (take out part water sample to be measured, be adjusted to weakly alkaline, add a small amount of humic acids, observe its flocculation situation) (4) for the water sample of easily flocculation in previous step, then take the method for direct loading; And the water sample do not flocculated, then first with the aqueous solution of calcium-magnesium-containing, chromatographic column is activated, after activation, loading (5) needs wash-out to carry out analyzing for the microbiotic of institute's enrichment again, then adopt pH be 2 phosphate buffered saline buffer-methanol solution or formic acid carry out wash-out; If without the need to wash-out, then after its adsorptive capacity that reaches capacity (Ciprofloxacin is 129mg/g), carry out ashing after being shifted by weighting material, the metal ion in ash content is reclaimed.
Test residue used and take from Xinjiang Shuanglong Humate and Humic Acid Co., Ltd..
Embodiment 2
Antibiotic removal in soil: (1) adopt pH be 2 mixture of acetonitrile-phosphate buffer-disodium ethylene diamine tetraacetate mixing solutions to carry out extracting (2) to microbiotic contaminated soil centrifugal, collect that supernatant liquor (3) calcium ions activated in water solution chromatographic column (4) loading (5) needs wash-out to carry out analyzing for the microbiotic of institute's enrichment, then employing formic acid or methyl alcohol-formic acid mixing solutions carry out wash-out; Otherwise just weighting material is shifted out and carries out ashing.
Test residue used and take from Xinjiang Shuanglong Humate and Humic Acid Co., Ltd..
Embodiment 3
(1) select microbiotic as function monomer; humic acids (organic detritus) is as template molecule; template is 1:5-1:10 with the ratio of monomer; after adding the initiator potassium persulfate of 0.1%-3% and the linking agent sodium bisulfite of 0.01-0.1%; after adopting mass polymerization synthesis humic acids-antibiotics molecular engram compound (2) polymkeric substance drying, grinding; after this polymkeric substance is prepared into packed column by screening 200-400 object particle (3), with methyl alcohol-formic acid solution removing microsphere (4) loading, wash-out with embodiment 2.
Test a residue used and take from Xinjiang Shuanglong Humate and Humic Acid Co., Ltd..
Claims (6)
1. and polyvalent metal ion easy based on the microbiotic in environment combines, and a large amount of humic acidss in weathered coal or the brown coal discarded organic detritus after caustic extraction are also easy to chelating, complexing polyvalent metal ion, therefore, when the microbiotic in environment is to exist with the combined form of polyvalent metal ion, humic acids waste residue just can be directly utilized to adsorb it and remove; And when microbiotic exists with free state, need first to adopt calcium chloride solution to activate humic acids, again enrichment is carried out to microbiotic afterwards; Another feature of the present invention be organic detritus eliminating Multiple Classes of Antibiotics in environment while, also by multivalence heavy metal ion also enrichment in the lump, the mode heavy metal of calcination (or charing) can be adopted afterwards to recycle.
2. the present invention has simultaneously accomplished the utilization of organic detritus being regardless of a kind of form; such as, be prepared into chromatographic column, synthetic molecules trace compound after pickling; can also identify polyvalent metal ion situation in water quality, for the activation method of organic detritus chromatographic column provides foundation.
3. the minimizing technology of antibiotic remains in a kind of environment according to claim 1, is characterized in that: what remove that antibiotic sorbent material selects is weathered coal or the discarded organic detritus of brown coal after caustic extraction.
4. the minimizing technology of antibiotic remains in a kind of environment according to claim 1, is characterized in that: discarded humic acids residue is the interaction based on " humic acids-polyvalent metal ion-microbiotic " three to antibiotic removal.
5. the minimizing technology of antibiotic remains in a kind of environment according to claim 1, is characterized in that: the while that microbiotic being removed, can by and the heavy metal ion of depositing together enrichment.
6. a kind of method improving weathered coal and prepare humate productive rate according to claim 1; it is characterized in that: the utilization of organic detritus being regardless of a kind of form; such as, be prepared into chromatographic column, synthetic molecules trace compound after pickling; can also identify polyvalent metal ion situation in water quality, for the activation method of organic detritus chromatographic column provides foundation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410315708.6A CN105293616A (en) | 2014-07-04 | 2014-07-04 | Method for removing antibiotic residue from the environment |
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| CN201410315708.6A CN105293616A (en) | 2014-07-04 | 2014-07-04 | Method for removing antibiotic residue from the environment |
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| CN105293616A true CN105293616A (en) | 2016-02-03 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558539A (en) * | 2018-06-19 | 2018-09-21 | 中国农业大学 | It is a kind of to promote the auxiliary agent and its application that antibiotic discharges in livestock and poultry solid waste |
| CN111268814A (en) * | 2020-01-07 | 2020-06-12 | 昆明理工大学 | Anthracycline wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
| CN113582427A (en) * | 2021-06-18 | 2021-11-02 | 中国恩菲工程技术有限公司 | Magnetic suspension centrifugal treatment method for wastewater |
-
2014
- 2014-07-04 CN CN201410315708.6A patent/CN105293616A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558539A (en) * | 2018-06-19 | 2018-09-21 | 中国农业大学 | It is a kind of to promote the auxiliary agent and its application that antibiotic discharges in livestock and poultry solid waste |
| CN111268814A (en) * | 2020-01-07 | 2020-06-12 | 昆明理工大学 | Anthracycline wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
| CN111268814B (en) * | 2020-01-07 | 2022-05-24 | 昆明理工大学 | Anthracycline wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
| CN113582427A (en) * | 2021-06-18 | 2021-11-02 | 中国恩菲工程技术有限公司 | Magnetic suspension centrifugal treatment method for wastewater |
| CN113582427B (en) * | 2021-06-18 | 2022-11-25 | 中国恩菲工程技术有限公司 | Magnetic suspension centrifugal treatment method for wastewater |
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Application publication date: 20160203 |