CN101570378A - Process for treating antibiotic pharmaceutical wastewater - Google Patents
Process for treating antibiotic pharmaceutical wastewater Download PDFInfo
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- CN101570378A CN101570378A CNA2008101057637A CN200810105763A CN101570378A CN 101570378 A CN101570378 A CN 101570378A CN A2008101057637 A CNA2008101057637 A CN A2008101057637A CN 200810105763 A CN200810105763 A CN 200810105763A CN 101570378 A CN101570378 A CN 101570378A
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Abstract
The invention provides a process for treating antibiotic pharmaceutical wastewater. The process comprises the following steps that: A, pharmaceutical wastewater is subjected to precipitation separation, enters a primary biological oxidation pond, is added with yeast or mould for biochemical treatment, stays in water for 6 to 72 hours, is taken out from the water, and then is subjected to solid-liquid separation; B, the wastewater treated in a step A is oxidized, wherein oxidation conditions are as follows: the pH of the wastewater is regulated to be between 3 and 4.5; hydrogen peroxide and divalent iron reagent are added for oxidation; oxidation time is 1 to 10 hours; the molar ratio of the hydrogen peroxide H2O2 to divalent iron Fe<2+> is 1 to 50; and the hydrogen peroxide is 1 to 10 times the concentration of antibiotics in the wastewater; or the oxidation conditions are as follows: the pH of the wastewater is regulated to be between 7 and 11; ozone is supplied for oxidation; the dosage of the ozone is 30 to 120 mg/L; and the oxidation time is 1 to 10 hours; C, the wastewater treated in a step B is subjected to solid-liquid separation, enters a secondary biological oxidation pond, and then is oxidized to remove substances easy to biodegrade; and D, the wastewater treated in a step C is precipitated, and then supernatant is discharged.
Description
Technical field
The invention belongs to field of waste water treatment, specifically relate to a kind of treatment process that is used for pharmacy waste water.
Background technology
According to incompletely statistics, China's medicine industry waste water year discharging 2 * 10
8～3 * 10
8T, chemical oxygen demand (COD) about 1.5 * 10
5T, average treatment rate＜30%, especially antibiotic factory effluent.According to GB8978-1996 " integrated wastewater discharge standard " secondary standard, must satisfy following requirement the: COD after the wastewater treatment of bio-pharmaceuticals industry
Cr≤ 150mg/L; BOD
5≤ 300mg/L; NH3-N≤50mg/L; SS≤200mg/L.
Microbiotic is through microbial fermentation, filtration, extractive crystallization, chemical extraction, refining forming.Its factory effluent complicated component, mainly contain the microorganism silk thalline that insoluble antibiotic ferment filtrate, fermentation produce in the extraction liquid that extracts residues of antibiotics, the remaining matrix of fermentation and nutrition, solvent leaching process, the water, has COD height (10,000～80,000mg/L), the SS height (500～25,000mg/L), NH
3-N concentration height, BOD
5The characteristics that/COD value is low.Have high concentrated acid, alkali, residual antibiotic etc. in the waste water, bio-toxicity is big; The pH fluctuation is big, temperature is high, colourity is dark, smell is heavy.
Residual antibiotic in the waste water and high-enriched organics make the traditional biological facture be difficult to reach the treatment effect of expection.Because residual antibiotic poisons aerobic bacteria to the strongly inhibited effect of microorganism, cause the aerobic treatment difficulty; And that the organism of anaerobic treatment high density is difficult to satisfy water outlet is up to standard, also needs further to handle.Therefore, for the wastewater treatment of high density production of antibiotics, has certain difficulty.Numerous antibiotic waste water treatment process research of bibliographical information at present nearly all is that the removal with waste water COD is the treatment effect of index evaluation waste water, and do not give enough attention for the high density antibiotics compound that contains in the waste water, still contain the Antibiotique composition of high density in the waste water after treatment.The microbiotic of high residue enters natural water body by discharge of wastewater, because antibiotic character, biology in the environment is exposed to the generation that is easy to cause anti-medicine bacterium in the microbiotic of high density for a long time, will bring serious destruction to water body ecotope and HUMAN HEALTH.The waste water of common bio-pharmaceuticals industry (is example with the terramycin wastewater) water quality sees Table 1.
Table 1 terramycin factory effluent water quality
Summary of the invention
The object of the present invention is to provide a kind of treatment process that is used for antibiotic pharmaceutical wastewater, to reduce disadvantageous effect to environment.
For achieving the above object, the technical solution used in the present invention, be that fungal microbe-yeast or mould that microbiotic can't act on are at first carried out the one-level bio-oxidation, remove the organic compound that readily biodegradable utilizes, thereby save follow-up Fenton oxidising agent and ozone dosage.Fenton oxidation or the ozonation technology microbiotic that can not only destroy or degrade makes it to lose bacteriostatic activity, make and wherein be difficult to biodegradable material and be converted into and be easy to biodegradable small-molecule substance, promptly eliminate the restraining effect of microbiotic to microorganism, improve the biodegradability of waste water, and can kill the anti-medicine bacterium that produces by the one-level biological oxidation process, thereby help follow-up two stage biological oxidation.
Specifically, the treatment process that is used for antibiotic pharmaceutical wastewater provided by the invention, its step is as follows:
A, pharmacy waste water enter the one-level bio-oxidation pond through after the precipitate and separate, carry out biochemical treatment, and general retention time of sewage does not have strict the qualification, grasp getting final product at 6-72 hour, and the preferred residence time is 24-48 hour; Part biological easily biodegradable organics in the waste water is by fungal microbe (yeast or mould) metabolism oxidation; Solid-liquid separation is carried out in water outlet.
The waste water of B, processing of step A carries out oxidation, makes the antibiotics organism of waste water be oxidized to the material of readily biodegradable; Oxidizing condition is:
B1, adjusting wastewater pH are 3-4.5, add hydrogen peroxide then and ferrous iron reagent carries out oxidation, and oxidization time does not have strict the qualification, is generally 1-10 hour, and hydrogen peroxide and ferrous iron mol ratio are H
2O
2: Fe
2+=1-50, preferred hydrogen peroxide and ferrous iron mol ratio are H
2O
2: Fe
2+=5-15; Hydrogen peroxide is disposable adds or gradation adds continuously.Hydrogen peroxide is 1-10 a times of antibiotic concentration in the waste water, and the 3-6 that preferred hydrogen peroxide is an antibiotic concentration in the waste water doubly.Or
B2, adjusting wastewater pH are 7-11, feed ozone then and carry out oxidation.The ozone dosage is 30-120mg/L, and preferred dosage is 60-90mg/L, and oxidization time does not have strict the qualification, is generally 1-10 hour.Be to improve oxidation effectiveness, during ozone oxidation, in addition uviolizing or add hydrogen peroxide.
The waste water that C, step B handle enters the two stage biological oxidation pond after solid-liquid separation, the residence time does not have strict the qualification, is generally the material of oxidation removal readily biodegradable 4-24 hour;
The waste water that D, step C handle precipitates, and discharges supernatant liquor.
Described treatment process, wherein, the waste water after step B1 or the B2 oxidation neutralizes earlier, proceeds step C then.
Innovation part of the present invention and its effect that has:
1) utilizes microbiotic that fungal microbe is not suppressed and killing action, anticipate the biological organic carbon of readily biodegradable in the waste water.Thereby reduce subsequent chemistry oxide treatment cost.
2) not only microbiotic can be removed by chemical oxidation of gold, and anti-medicine bacterium and drug resistant gene can be removed.
3) biological chemistry combined treatment process reaches with lower cost degraded COD and environment is had the microbiotic of great effect.
4) the present invention can make full use of bio-oxidation and remove the organism that readily biodegradable utilizes in the waste water, can effectively remove simultaneously to be difficult to biological degradation and biology is had inhibiting microbiotic.Therefore, in the processing that contains the high density antibiotic waste water, important application prospects is arranged.
Description of drawings
Fig. 1 is the treatment process synoptic diagram that the present invention is used to handle the terramycin factory effluent.
Embodiment
The treatment process that is used for pharmacy waste water provided by the invention as shown in Figure 1, has adopted the combined technology of biochemistry-chemical oxidation-biochemistry, specifically comprises the steps:
1, the terramycin factory effluent enters the one-level bio-oxidation pond through after the precipitate and separate, carries out biochemical treatment, and the part biological easily biodegradable organics in the waste water is by yeast or mould metabolism oxidation; Water outlet is carried out solid-liquid separation through the one-level settling tank.
The water conservancy residence time in the one-level bio-oxidation pond is 6-72 hour, preferred 24-48 hour;
Described biochemical treatment process comprises: active sludge, bio-contact oxidation, microbial film, intermittent activated sludge etc.
2, after above-mentioned technology water outlet, enter the chemical oxidation stage, chemical oxidation treatment can adopt:
1) Fenton (hydrogen peroxide and ferrous mixed solution) retort is difficult to be oxidized to by biodegradable antibiotics organism the material of readily biodegradable in the waste water; Water outlet neutralizes with milk of lime after oxidation, and carries out solid-liquid separation.In the Fenton retort, the pH that regulates waste water is 3-4.5, and the hydrogen peroxide of adding is 1-10 times of antibiotic concentration in the water inlet, and preferred 3-6 doubly.Adding ferrous iron and hydrogen peroxide mol ratio is H
2O
2: Fe
2+=1-50, preferred 5-15.In the Fenton retort, H
2The dosing method of O2 can adopt disposable adding, and also can adopt continuously to add.Oxidization time 1-10 in the Fenton retort hour, preferred 2-6 hour.Perhaps
2) ozone reactor is difficult in the waste water be become the material of readily biodegradable by biodegradable antibiotics organism by ozone oxidation, makes wastewater biodegradability be improved.In the ozone reactor, the adjusting wastewater pH is 3-11, preferred 7-11.Ozone dosage 30-120mg/L, preferred 60-90mg/L.The low pressure ultra violet lamp that can be aided with 17-35W during ozone oxidation.
3, after above-mentioned technology water outlet, waste water enters the two stage biological oxidation pond, and the organism of the readily biodegradable that produces after Fenton oxidation or ozone oxidation obtains removing again; Water outlet is carried out solid-liquid separation through second-level settling pond, and supernatant liquor effluxes.Hydraulic detention time in the secondary oxidation pond is 4-24 hour.
Embodiment 1
Get domestic certain terramycin factory factory effluent, test.Raw water quality sees Table 2: as seen this sewage has higher COD, ammonia nitrogen, sulfate radical and low biodegradability.Adopt the treatment process that is used for pharmacy waste water provided by the invention to handle this waste water.At first through the remaining mycelium of settling tank precipitate and separate, through post precipitation waste water through pump to the one-level bio-oxidation pond, be 24 hours in the water conservancy residence time in this pond, under the effect of mould, the oxidation that is decomposed of the partial organic substances in the sewage; Solid-liquid separation was carried out in the stop of water outlet in the one-level settling tank in 8 hours; The supernatant liquor of telling enters the Fenton retort, and regulating pH is 3.5, though the amount of going into of hydrogen peroxide is that the 1-10 of terramycin concentration in the waste water doubly gets final product, in general, the add-on of hydrogen peroxide for a long time, the reaction times can shorten, on the contrary reaction of propagation time then.Hydrogen peroxide can once add or add for several times, the disposable adding of ferrous sulfate, and by ferrous iron, the mol ratio of hydrogen peroxide and ferrous sulfate is controlled between the 1-50.This routine hydrogen peroxide is twice adding, each add-on is 6mmol/L, each joining day is spaced apart 1 hour, the add-on of ferrous sulfate is 2.4mmol/L, oxidation time 3 hours is difficult to the small-molecule substance that biolytic antibiotics organism is oxidized to readily biodegradable in the sewage; Water outlet after peroxidation neutralizes with milk of lime, and adds the flocculation agent precipitation after 2 hours, carries out solid-liquid separation; Waste water enters the two stage biological oxidation pond and carries out oxidation, and this stage hydraulic detention time is 24 hours, and the organism of the readily biodegradable that produces after the process Fenton oxidation obtains removing again; Water outlet was carried out solid-liquid separation in 2 hours through the second-level settling pond precipitation, and supernatant liquor effluxes.Each cell processing effect sees Table 3.
The water quality analysis of domestic certain the production of antibiotics factory oxytetracycline crystallization mother liquor of table 2
| pH | COD | TN | NH 4 +-N | SO 4 2- | Terramycin |
| 4.0 | 12000mgl -1 | 2100mgl -1 | 1600mgl -1 | 1900mgl -1 | ＞800 |
Table 3 uses the removal process of treatment process provided by the invention at individual unit COD and terramycin
| Former water | The settling tank water outlet | One-level bio-oxidation precipitation | The Fenton oxidation precipitation | The two stage biological oxidation precipitation | |
| CODmgl -1 | 12000 | 5126 | 3020 | 1120 | 120 |
| Terramycin mgl -1 | 900 | 800 | 690 | 0 | 0 |
Embodiment 2
Get domestic certain terramycin factory factory effluent, test.Raw water quality sees Table 2: as seen this sewage has higher COD, ammonia nitrogen, sulfate radical and low biodegradability.Adopt the treatment process that is used for pharmacy waste water provided by the invention to handle this waste water.At first through the remaining mycelium of settling tank precipitate and separate, through post precipitation waste water through pump to the one-level bio-oxidation pond, be 48 hours in the water conservancy residence time in this pond, under saccharomycetic effect, the oxidation that is decomposed of the partial organic substances in the sewage; Solid-liquid separation was carried out in the stop of water outlet in the one-level settling tank in 8 hours; The supernatant liquor of telling enters ozone reactor.Regulate wastewater pH to 7, the ozone dosage in the 30-120mg/L scope, 2 hours ozone oxidation reaction time.When ozone oxidation, can also adopt in the UV-light and shine, to improve the effect of oxidizing reaction under the same conditions.Adopt ozone to add low pressure ultraviolet lamp (17W) irradiation in this example, be difficult to the small-molecule substance that biolytic antibiotics organism is oxidized to readily biodegradable in the sewage; Water outlet after peroxidation enters the two stage biological oxidation pond and carries out oxidation, and this stage hydraulic detention time is 24 hours, and the organism of the readily biodegradable that produces after the process ozone oxidation obtains removing again; Water outlet was carried out solid-liquid separation in 2 hours through the second-level settling pond precipitation, and supernatant liquor effluxes.Each cell processing effect sees Table 4.
Table 4 uses the removal process of treatment process provided by the invention at individual unit COD and terramycin
| Former water | The settling tank water outlet | One-level bio-oxidation precipitation | The Fenton oxidation precipitation | The two stage biological oxidation precipitation | |
| CODmgl -1 | 12000 | 5126 | 3020 | 2120 | 126 |
| Terramycin mgl -1 | 900 | 800 | 690 | 0 | 0 |
Claims (10)
1, a kind of treatment process that is used for antibiotic pharmaceutical wastewater, its step is as follows:
A, pharmacy waste water enter the one-level bio-oxidation pond through after the precipitate and separate, carry out biochemical treatment, and hydraulic detention time is 6-72 hour, and the part biological easily biodegradable organics in the waste water can be tolerated antibiotic fungal microbe metabolism oxidation; Solid-liquid separation is carried out in water outlet;
The waste water of B, processing of step A carries out oxidation, makes antibiotics refractory organic in the waste water be oxidized to the material of readily biodegradable; Oxidizing condition is:
B1, adjusting wastewater pH are 3-4.5, add hydrogen peroxide and ferrous iron reagent and carry out oxidation, and oxidation 1-10 hour, hydrogen peroxide and ferrous iron mol ratio were H
2O
2: Fe
2+=1-50, hydrogen peroxide are 1-10 times of antibiotic concentration in the waste water; Or
B2, adjusting wastewater pH are 7-11, feed ozone and carry out oxidation, and the ozone dosage is 30-120mg/L, oxidation 1-10 hour;
The waste water that C, step B handle enters the two stage biological oxidation pond, the material of oxidation removal readily biodegradable after solid-liquid separation;
The waste water that D, step C handle precipitates, and discharges supernatant liquor.
2, treatment process as claimed in claim 1, wherein, the fungal microbe in the one-level bio-oxidation pond is yeast or mould.
3, treatment process as claimed in claim 1, wherein, hydraulic detention time is 24-48 hour in the one-level bio-oxidation pond.
4, treatment process as claimed in claim 1, wherein, hydrogen peroxide among the step B1 and ferrous iron mol ratio are H
2O
2: Fe
2+=5-15.
5, treatment process as claimed in claim 1, wherein, the hydrogen peroxide among the step B1 is disposable adds or gradation adds continuously.
6, treatment process as claimed in claim 1, wherein, the hydrogen peroxide among the step B1 is 3-6 a times of antibiotic concentration in the waste water.
7, treatment process as claimed in claim 1, wherein, the ozone pH=7-11 among the step B2.
8, treatment process as claimed in claim 1, wherein, the ozone dosage among the step B2 is 60-90mg/L.
9, treatment process as claimed in claim 1, wherein, the ozone oxidation of step B2 is with the low pressure ultra violet lamp of 17-35W.
10, treatment process as claimed in claim 1, wherein, in the waste water after step B 1 or B2 oxidation and after carry out step C.
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|---|---|---|---|
| CN2008101057637A CN101570378B (en) | 2008-04-30 | 2008-04-30 | Process for treating antibiotic pharmaceutical wastewater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101057637A CN101570378B (en) | 2008-04-30 | 2008-04-30 | Process for treating antibiotic pharmaceutical wastewater |
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| CN101570378A true CN101570378A (en) | 2009-11-04 |
| CN101570378B CN101570378B (en) | 2011-08-10 |
Family
ID=41229882
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|---|---|---|---|
| CN2008101057637A Active CN101570378B (en) | 2008-04-30 | 2008-04-30 | Process for treating antibiotic pharmaceutical wastewater |
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| CN101811791A (en) * | 2010-04-29 | 2010-08-25 | 石家庄开发区德赛化工有限公司 | Flocculation pretreatment method for penicillin fermentation waste water |
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| CN102491573A (en) * | 2011-12-23 | 2012-06-13 | 西南大学 | Method for enhancing degradability of antibiotics and hormones in livestock cultivating waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU998382A1 (en) * | 1980-12-22 | 1983-02-23 | Всесоюзный Научно-Исследовательский Институт По Охране Вод | Method of biochemically purifying effluents from organic compounds |
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2008
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| CN107500984A (en) * | 2017-09-21 | 2017-12-22 | 哈尔滨工业大学 | A kind of method for producing organic fertilizer using Fenton process processing antibiotic bacterium dregs |
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| CN108358386A (en) * | 2018-03-02 | 2018-08-03 | 成都知联汇科技有限公司 | A kind for the treatment of process of antibiotic pharmaceutical wastewater |
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