CN105084517A - Method for degrading residual tetracycline in pharmaceutical wastewater - Google Patents
Method for degrading residual tetracycline in pharmaceutical wastewater Download PDFInfo
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- CN105084517A CN105084517A CN201510547424.4A CN201510547424A CN105084517A CN 105084517 A CN105084517 A CN 105084517A CN 201510547424 A CN201510547424 A CN 201510547424A CN 105084517 A CN105084517 A CN 105084517A
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- tsiklomitsin
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- pharmacy waste
- wastewater
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Abstract
The invention discloses a method for degrading residual tetracycline in pharmaceutical wastewater. The method comprises the following steps that the volume of the pharmaceutical wastewater is used as the reference; 11 to 66 weight parts of sodium hypochlorite solutions with the active chlorine content being 10 to 13 percent are added into the pharmaceutical wastewater with the residual tetracycline content being 1 to 3; the materials are stirred and processed for 5 to 30 min; the tetracycline remained in the wastewater can be degraded. The method provided the invention has the advantages that strong-toxicity byproducts cannot be generated; the operation is simple; the effect is stable; the processed wastewater can reach the subsequent biochemical treatment requirements; the method belongs to a simple convenient and efficient tetracycline wastewater processing technology.
Description
Technical field
The present invention relates to sewage disposal control techniques field, particularly in a kind of pharmacy waste water of degrading, remain the method for tsiklomitsin.
Background technology
China is antibiotic use big country, Ye Shi big producing country.But meanwhile, can the waste water of a large amount of residual antibiotic of the row of producing in antibiotic production process.Due to antibiotic antibacterial, fungicidal activity, cause this kind of wastewater biodegradability poor, and there is certain bio-toxicity.Therefore, the residual antibiotic waste water of high density, before entering Sewage treatment systems, must significantly cut down remained microbiotic.
In fermentative Production tsiklomitsin process, in the waste water of generation, tsiklomitsin content is between 200-600mg/L.Because tsiklomitsin antibacterial ability is strong, has a broad antifungal spectrum, adopts traditional aerobic, anaerobism or method that the two combines, is all difficult to realize tetracycline wastewater qualified discharge, because the tsiklomitsin of residual high density can suppress or kill the microorganism of Waste Water Treatment.In recent years, also there is scholar to adopt photocatalytic method process containing tetracycline wastewater, find that the tsiklomitsin of about 75% is degraded, but this method whether proper scale process tetracycline wastewater, remain query, because light can only the antibiotic molecule of catalyzed degradation illuminating surface.Therefore, development is efficient, economical, eco-friendly tetracycline wastewater treatment process, has important practical significance to the Sustainable development of tsiklomitsin manufacturing enterprise and environment protection.
For the outstanding problem run in current tetracycline wastewater process, carry out the research of technique tetracycline wastewater treatment process simple, with low cost.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for residual tsiklomitsin in a kind of pharmacy waste water of degrading, and overcomes the defect of above-mentioned prior art.The present invention has and does not produce supervirulent by product, simple to operate, effect stability, enables the waste water after process reach the requirement of subsequent biochemical process, is a kind of easy, efficient tetracycline wastewater treatment technology.
The present invention is based on following principle:
Tetracycline antibiotics belongs to the derivative of many rings tetracene oxyamide parent nucleus in chemical structure, and beta-lactam, Macrolide and sulfa drugs are soluble in water and can be hydrolyzed.The degradation speed of beta-lactam under slightly acidic to alkaline condition is all quite fast.Can hydrolysis reaction be there is in cephalosporins in the water surrounding of acidity, alkalescence and neutrallty condition.Penicillin medicine is subject to nucleophilic and electrophilic reagent attack, and be easily hydrolyzed and cause molecular transposition, some metal ion, oxygenant and heating etc. can play katalysis to the decomposition of penicillin medicine and molecular transposition.In the basic conditions, the beta-lactam nucleus of penicillin medicine is first destroyed, is decomposed into penicillic acid; When having an Action of Metal Ions, penicillic acid can be decomposed into peniloaldehyde and Trolovol further.Will be unstable when tetracycline antibiotics is in basic solution, facile hydrolysis.And available chlorine content is the chlorine bleach liquor of 10-13%, its sodium hydrate content is between 5%-6%, and pH is about 11, and in alkalescence, the more important thing is, clorox has very strong oxidative degradation to tsiklomitsin.Therefore, know-why of the present invention is based under alkaline condition, and available chlorine content is that the chlorine bleach liquor of 10-13% is to the oxidative degradation of tsiklomitsin residual in pharmacy waste water.
Technical problem to be solved by this invention is achieved through the following technical solutions:
The method of residual tsiklomitsin in a kind of pharmacy waste water of degrading is provided described in the invention provides, comprises the following steps:
(1) chlorine bleach liquor that available chlorine content is 10-13% is configured, for subsequent use;
(2) getting weight part is that the described chlorine bleach liquor of 11-66 adds and remains in the waste water of tsiklomitsin containing 1-3 part;
(3) namely tsiklomitsin is remained described in degradable after stirring and evenly mixing 5-30min.
The weight part content of described chlorine bleach liquor in pharmacy waste water is 22-33; Most preferred weight part content is: 28.
The weight part content of described residual tsiklomitsin in pharmacy waste water: 1-2; Most preferred weight part content is: 1.5;
The described stirring and evenly mixing time is: 10-15min; Most preferably be: 12min.
The beneficial effect that the present invention has after adopting technique scheme:
(1) method is simple: clorox single agents only need be added in the pharmacy waste water of residual tsiklomitsin by the present invention, without the need to adding other chemistry or biological reagent again;
(2) high efficiency and time conservation: chlorine bleach liquor only need be added in the pharmacy waste water of residual tsiklomitsin by a certain amount of by the present invention, stir process 5-30min;
(3) environmental friendliness: chlorine bleach liquor used in the present invention, Chang Zuowei oxygenant is used for the purifying treatment of tap water.So, for other chemical oxidizing agent, agents useful for same environmental friendliness of the present invention;
(4) degradation effect is good: by utilizing the mensuration of high performance liquid chromatography, the residual tsiklomitsin of 96-99% in degradable waste water of the present invention.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, will be described in further detail embodiments of the present invention below:
Embodiment 1
Get the chlorine bleach liquor that available chlorine is 10-13%, it is in the pharmacy waste water of the amount of 1 that the amount being 11 according to weight part is added to residual tsiklomitsin, stir process 5min.Then adopt the content of residual tsiklomitsin in waste water before and after high performance liquid chromatography check processing, the degradation rate that recycling degradation rate formula obtains tsiklomitsin is 99%.
Embodiment 2
Get the chlorine bleach liquor that available chlorine is 10-13%, it is in the pharmacy waste water of the amount of 3 that the amount being 66 according to weight part is added to residual tsiklomitsin, stir process 30min.Then adopt the content of residual tsiklomitsin in waste water before and after high performance liquid chromatography check processing, the degradation rate that recycling degradation rate formula obtains tsiklomitsin is 98%.
Embodiment 3
Get the chlorine bleach liquor that available chlorine is 10-13%, it is in the pharmacy waste water of the amount of 1 that the amount being 22 according to weight part is added to residual tsiklomitsin, stir process 10min.Then adopt the content of residual tsiklomitsin in waste water before and after high performance liquid chromatography check processing, the degradation rate that recycling degradation rate formula obtains tsiklomitsin is 99%.
Embodiment 4
Get the chlorine bleach liquor that available chlorine is 10-13%, it is in the pharmacy waste water of the amount of 2 that the amount being 33 according to weight part is added to residual tsiklomitsin, stir process 15min.Then adopt the content of residual tsiklomitsin in waste water before and after high performance liquid chromatography check processing, the degradation rate that recycling degradation rate formula obtains tsiklomitsin is 97%.
Embodiment 5
Get the chlorine bleach liquor that available chlorine is 10-13%, it is in the pharmacy waste water of the amount of 1.5 that the amount being 28 according to weight part is added to residual tsiklomitsin, stir process 12min.Then adopt the content of residual tsiklomitsin in waste water before and after high performance liquid chromatography check processing, the degradation rate that recycling degradation rate formula obtains tsiklomitsin is 99%.
In described embodiment 1-5, after tsiklomitsin degraded, the measuring method of residual quantity all adopts high performance liquid chromatography, determined wavelength 354nm, and be described for embodiment 1, concrete steps are as follows:
1, tsiklomitsin typical curve drafting.Prepare the tsiklomitsin standardized solution of 250mg/L, 200mg/L, 150mg/L, 100mg/L, 50mg/L, 25mg/L and 0mg/L respectively, by high performance liquid chromatography, with tetracycline concentration, peak area is mapped, thus obtain linear equation and R
2value;
2, to process in front waste water because tsiklomitsin content is higher with chlorine bleach liquor, measure again after therefore needing suitably to dilute with water.And processed waste water, then need to add appropriate oxalic acid till available chlorine not detected with moistening potassium iodide starch test paper.Then the waste water before and after process is crossed 0.22 μm of filter membrane respectively, the content adopting high performance liquid chromatography to detect tsiklomitsin is weight part 0.01;
3, utilize following equation, the degradation rate obtaining residual tsiklomitsin in pharmacy waste water is 99%;
In formula, X is the degradation rate (%) of tsiklomitsin, C
0the weight part of residual tsiklomitsin in the pharmacy waste water without chlorine bleach liquor's process, C
1it is the weight part of residual tsiklomitsin in the pharmacy waste water after chlorine bleach liquor's process.
Described high-efficient liquid phase chromatogram condition: chromatographic column: InertSustainHC-C
18(4.6 × 150mm, 5 μm); Determined wavelength 354nm; Column temperature: 35 DEG C; Sample size: 20 μ L; Moving phase: organic phase [acetonitrile: methyl alcohol=2: 1 (volume ratio)]-aqueous phase (0.01mol/L oxalic acid)=35: 65 (volume ratio); Flow velocity: 0.8mL/min.
Should be understood that, above-mentioned embodiment of the present invention only for exemplary illustration or explain principle of the present invention, and does not form the restriction to invention.Therefore, any amendment made when without departing from the spirit and scope of the present invention, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.In addition, claims of the present invention be intended to contain fall into claims scope and border or this scope and border equivalents in whole change and modification.
Claims (7)
1. to degrade the method for residual tsiklomitsin in pharmacy waste water, comprise the following steps:
(1) chlorine bleach liquor that available chlorine content is 10-13% is configured, for subsequent use;
(2) getting weight part is that the described chlorine bleach liquor of 11-66 adds and remains in the waste water of tsiklomitsin containing 1-3 part;
(3) namely tsiklomitsin is remained described in degradable after stirring and evenly mixing 5-30min.
2. remain the method for tsiklomitsin in a kind of pharmacy waste water of degrading according to claim 1, the weight part content of described chlorine bleach liquor in pharmacy waste water is: 22-33.
3. remain the method for tsiklomitsin in a kind of pharmacy waste water of degrading according to claim 2, the weight part content of described chlorine bleach liquor in pharmacy waste water is: 28.
4. remain the method for tsiklomitsin in a kind of pharmacy waste water of degrading according to claim 1, the weight part content of described residual tsiklomitsin in pharmacy waste water is: 1-2.
5. remain the method for tsiklomitsin in a kind of pharmacy waste water of degrading according to claim 4, the weight part content of described residual tsiklomitsin in pharmacy waste water is: 1.5.
6. remain the method for tsiklomitsin in a kind of pharmacy waste water of degrading according to claim 1, the described stirring and evenly mixing time is: 10-15min.
7. remain the method for tsiklomitsin in a kind of pharmacy waste water of degrading according to claim 6, the described stirring and evenly mixing time is: 12min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262018A (en) * | 2018-01-25 | 2018-07-10 | 宁夏大学 | A kind of method of tetracycline in two-dimensional slice structure Adsorption water using foliaceous |
| CN108993390A (en) * | 2018-08-10 | 2018-12-14 | 宁夏大学 | A method of utilizing residual tetracycline in pharmacy waste water after ZnO support type expanded graphite removal flocculation treatment |
| WO2020124180A1 (en) * | 2018-12-21 | 2020-06-25 | Cristália Produtos Químicos Farmacêuticos Ltda | Industrial process and system for the inactivation of liquid waste |
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| CN101186352A (en) * | 2007-12-21 | 2008-05-28 | 南京大学 | Method for degrading aureomycin in water by using visible light irradiation |
| KR20120051847A (en) * | 2010-11-15 | 2012-05-23 | 서울과학기술대학교 산학협력단 | A degrading material of antibiotics comprising metal nitride oxide |
| CN103739134A (en) * | 2014-01-28 | 2014-04-23 | 四川中洁诺环保科技有限公司 | Method for removing antibiotics in water |
| CN104276651A (en) * | 2014-09-12 | 2015-01-14 | 宁夏大学 | Method for degrading residual oxytetracycline in pharmaceutical wastewater |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| SU1210373A1 (en) * | 1983-10-25 | 1988-01-15 | Всесоюзный научно-исследовательский институт биологического приборостроения | Strain pseudomonas alcaligenes no 11 used for degradation of antibiotics and formaldehyde |
| CN101186352A (en) * | 2007-12-21 | 2008-05-28 | 南京大学 | Method for degrading aureomycin in water by using visible light irradiation |
| KR20120051847A (en) * | 2010-11-15 | 2012-05-23 | 서울과학기술대학교 산학협력단 | A degrading material of antibiotics comprising metal nitride oxide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108262018A (en) * | 2018-01-25 | 2018-07-10 | 宁夏大学 | A kind of method of tetracycline in two-dimensional slice structure Adsorption water using foliaceous |
| CN108993390A (en) * | 2018-08-10 | 2018-12-14 | 宁夏大学 | A method of utilizing residual tetracycline in pharmacy waste water after ZnO support type expanded graphite removal flocculation treatment |
| CN108993390B (en) * | 2018-08-10 | 2021-10-22 | 宁夏大学 | Method for removing residual tetracycline in pharmaceutical wastewater after flocculation treatment by using ZnO-loaded expanded graphite |
| WO2020124180A1 (en) * | 2018-12-21 | 2020-06-25 | Cristália Produtos Químicos Farmacêuticos Ltda | Industrial process and system for the inactivation of liquid waste |
| CN113748090A (en) * | 2018-12-21 | 2021-12-03 | 克里斯泰利亚化学药物产品有限公司 | Industrial method and system for inactivating liquid waste |
| US11591243B2 (en) | 2018-12-21 | 2023-02-28 | Cristalia Produtos Quimicos Farmaceuticos Ltda. | Industrial process and system for the inactivation of liquid waste |
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Application publication date: 20151125 |