CN102826722B - Treatment method for wastewater generated by producing cephalosporin medicines - Google Patents
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- 239000002351 wastewater Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 229930186147 Cephalosporin Natural products 0.000 title claims abstract description 19
- 229940124587 cephalosporin Drugs 0.000 title claims abstract description 19
- 150000001780 cephalosporins Chemical class 0.000 title claims abstract description 19
- 239000003814 drug Substances 0.000 title claims abstract description 13
- 229940079593 drug Drugs 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000012528 membrane Substances 0.000 claims abstract description 30
- 230000020477 pH reduction Effects 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims description 32
- 238000006460 hydrolysis reaction Methods 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 6
- 239000010802 sludge Substances 0.000 claims description 6
- 230000004907 flux Effects 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 3
- 230000016615 flocculation Effects 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 230000031018 biological processes and functions Effects 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract 2
- 238000005286 illumination Methods 0.000 description 7
- 238000005273 aeration Methods 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WYWFMUBFNXLFJK-UHFFFAOYSA-N [Mo].[Sb] Chemical compound [Mo].[Sb] WYWFMUBFNXLFJK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- -1 electrolysis Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 230000003245 working effect Effects 0.000 description 1
Abstract
The invention provides a treatment method for wastewater generated by producing cephalosporin medicines. The method comprises three treatment steps of as anoxic hydrolytic acidification, electrolysis and membrane bioreactor treatment. Specifically, the method comprises the following steps of: (1) firstly carrying out biological hydrolytic acidification on the wastewater generated by producing cephalosporin synthesis pharmacy in an anaerobic pond, so that the biodegradability of the wastewater can be improved; (2) electrolyzing the discharged water of the step (1) in an electrolytic tank, so that COD (chemical oxygen demand) can be further removed, and the biodegradability of the wastewater can be improved; and (3) enabling the discharged out of the step (2) to flow into the membrane bioreactor for the final aerobiotic biotreatment, wherein the treated wastewater is pumped by a water outlet pump through an ultrafiltration membrane in the membrane bioreactor, and is discharged to an external discharge pipeline or recycled in a production technology after reaching the standard.
Description
Technical field
The present invention relates to and a kind ofly produce the wastewater produced treatment process of medicine, particularly a kind ofly produce the wastewater produced treatment process of cephalosporins medicine.
Background technology
Antibiotic production wastewater is a class high density, organic waste water containing multiple hardly degraded organic substance and bio-toxicity material.When the state such as American-European produces penicillin from the forties in 20th century just process its waste water, but fail good terms of settlement always.20 century 70s rise, and large conventional medicine is produced to developing country's transfer by developed country, and therefore China starts the research and apply about antibiotic production wastewater treatment technology.Compared with other microbiotic, cephalosporin analog antibiotic has the features such as has a broad antifungal spectrum, anti-microbial activity is strong, curative effect is high, side effect is little, in classes of anti-infective drug market, occupy critical role.The production of cephalosporin analog antibiotic adopts microbe fermentation method to obtain cynnematin, then adopt chemosynthesis to carry out the production of intermediate, bulk drug, and consequent synthetic wastewater has the features such as COD is high, complicated component, biodegradability difference.
Can be summarized as following several in the technique of administering the waste water that production cephalosporins medicine produces at present:
(1) materializing strategy technology, comprises flocculation sediment, electrolysis, Fenton reagent oxide treatment, membrane separation technique etc.(2) biologic treating technique, comprises aerobic treatment method (traditional activated sludge process), anaerobic treatment method, anaerobic-aerobic combination process, acidication-aerobic combination technique etc.In addition, membrane bioreactor (MBR) due to its sub-argument effective, microorganism concn can be maintained, to influent load strong adaptability, excess sludge production is few, the features such as floor space is little receive publicity more and more in water treatment field, in the treatment process to cephalosporin waste water, also have the example using MBR technology.
In China Patent Publication No. CN101434437, disclose the treatment process that a kind of cephalosporin synthesis pharmaceutical is wastewater produced, the present invention makes on its basis.
Summary of the invention
In order to reach better water treatment effect, we through test of many times, find that illumination that specific link wherein carries out specific wavelength can significantly improve the effect of water treatment on the basis of the cephalosporin waste water treatment process of routine.Concrete technology is as follows:
By anaerobic hydrolysis acidifying, electrolysis and these three treatment steps of Membrane Bioreactor for Wastewater Treatment are formed.
(1) waste water that cephalosporin synthesis pharmaceutical produces in producing first carries out biological hydrolysis acidifying in anoxic pond, improves the biodegradability of waste water;
(2) water outlet of step (1) carries out electrolysis in electrolyzer, removes COD further, improves the biodegradability of waste water;
(3) water outlet of step (2) flows in membrane bioreactor and carries out final Aerobic biological process, the ultra-filtration membrane of waste water after process in membrane bioreactor, pump out by going out water pump, qualified discharge is to outer discharge pipe or be back to use in production technique.
Specifically, the biological hydrolysis acidifying of above-mentioned steps (1) comprises hydrolysis stage and souring stage, and these two stages complete anaerobic digestion by acidification bacteria.Acidication bacterium utilizes water power to be opened by the carbon bond in organic molecule from hydrogen ion and hydroxide radical in this course, and long-chain can be hydrolyzed to short chain, side chain is hydrolyzed to straight chain, opens ring texture, thus is that the process of ensuing aerobe is ready.
Preferably, at hydrolysis and souring stage, omnidistance illumination is carried out to hydrolysis acidification pool.
More preferably, at hydrolysis and souring stage, omnidistance Infrared irradiation is carried out to hydrolysis acidification pool.
Most preferably, at hydrolysis and souring stage, the Infrared irradiation of omnidistance light wave scope at 1100 ~ 2500nm is carried out to hydrolysis acidification pool.
Electrolysis step in above-mentioned steps (2) takes ferrum-carbon internal electrolysis, iron filings are dropped into also simultaneously to air-blowing in waste water in waste water, can form countless small galvanic cell in waste water like this, there is redox reaction, produce divalence and ferric ion simultaneously, thus in waste water, form colloid generation flocculation sediment effect.After these precipitations being removed, effluent liquid can enter step (3) and process.
Membrane bioreactor in above-mentioned steps (3) is made up of aeration zone and membrane filtration district, aeration zone adopts disc type micro porous aeration head to carry out aeration, ultra-filtration membrane is placed on membrane filtration district, waste water after aerobic contact oxidation, anaerobic hydrolysis acidification, organism is wherein biodegradable substantially, waste water is extracted out in ultra-filtration membrane, and the microorganism in reactor is blocked in reactor.
Inventive point of the present invention is mainly to introduce illumination in the acidication stage, the effect of this Lighting operations to acidication has significant lifting (specific experiment data see below literary composition), and the work-ing life of membrane bioreactor can be increased, reduce the use cost of membrane bioreactor.Thus improve the quality of water treatment on the one hand, reduce the cost of whole technical process on the other hand.
Embodiment
The analytical procedure used in the present invention: adopt potassium dichromate process to measure COD; Dilution inoculation method is adopted to measure BOD
5; Adopt potassium persulfate oxidation---determined by ultraviolet spectrophotometry total nitrogen (TN); Adopt molybdenum-antimony anti-spectrophotometric method to measure total phosphorus (TP), adopt filter paper filtering weighting method to measure suspended substance (SS).
Embodiment 1
Wastewater from cephalosporin synthesis pharmaceutical production 415m
3/ d, the COD value 8000mg/l of water inlet, the BOD of water inlet
5value 740mg/l, the TN value 480mg/l of water inlet, the value 85mg/l of the TP of water inlet, the SS value 110mg/l of water inlet.
After adjust ph, be introduced into hydrolysis acidification pool through equalizing tank balanced water quality and quantity, be 3 hours at the hydraulic detention time of hydrolysis acidification pool, and set up light source above hydrolysis acidification pool, whole process carries out the irradiation that wavelength is 2200nm infrared light.The COD value 4500mg/l of hydrolysis acidification pool water outlet, the BOD of water outlet
5value 550mg/l, the TN value 275mg/l of water outlet, the value 58mg/l of the TP of water outlet, the SS value 50mg/l of water outlet.
Water after acidication process enters electrolyzer, presses iron filings 2kg/m in electrolyzer
3ratio throw in, hydraulic detention time is 10 hours, and in operation process, use gas blower to be blown into air in pond, thus ensures there is sufficient oxygen in the water of electrolyzer.
Membrane bioreactor is entered in water outlet in electrolyzer, and the residence time of waste water in membrane bioreactor is 20 hours, and volumetric loading is 6kgCOD/m
3.d, sludge concentration is 7-11g/l, and membrane flux is 15L/m
2.h, resistance of membrane filtration is less than 25kPa; COD value≤the 50mg/l of water outlet, the BOD of water outlet
5value≤8mg/l, the TN value 156mg/l of water outlet, the value 13mg/l of the TP of water outlet, the SS value of water outlet does not detect.
Embodiment 2
Wastewater from cephalosporin synthesis pharmaceutical production 200m
3/ d, the COD value 13000mg/l of water inlet, the BOD of water inlet
5value 950mg/l, the TN value 625mg/l of water inlet, the value 112mg/l of the TP of water inlet, the SS value 145mg/l of water inlet.
After adjust ph, be introduced into hydrolysis acidification pool through equalizing tank balanced water quality and quantity, be 4.5 hours at the hydraulic detention time of hydrolysis acidification pool, and set up light source above hydrolysis acidification pool, whole process carries out the irradiation that wavelength is 1500nm infrared light.The COD value 6000mg/l of hydrolysis acidification pool water outlet, the BOD of water outlet
5value 440mg/l, the TN value 315mg/l of water outlet, the value 74mg/l of the TP of water outlet, the SS value 90mg/l of water outlet.
Water after acidication process enters electrolyzer, presses iron filings 2kg/m in electrolyzer
3ratio throw in, hydraulic detention time is 10 hours, and in operation process, use gas blower to be blown into air in pond, thus ensures there is sufficient oxygen in the water of electrolyzer.
Membrane bioreactor is entered in water outlet in electrolyzer, and the residence time of waste water in membrane bioreactor is 20 hours, and volumetric loading is 6kgCOD/m
3.d, sludge concentration is 7-11g/l, and membrane flux is 15L/m
2.h, resistance of membrane filtration is less than 25kPa; COD value≤the 70mg/l of water outlet, the BOD of water outlet
5value≤10mg/l, the TN value 146mg/l of water outlet, the value 14mg/l of the TP of water outlet, the SS value of water outlet does not detect.
Embodiment 3
Wastewater from cephalosporin synthesis pharmaceutical production 300m
3/ d, the COD value 3000mg/l of water inlet, the BOD of water inlet
5value 410mg/l, the TN value 380mg/l of water inlet, the value 86mg/l of the TP of water inlet, the SS value 104mg/l of water inlet.
After adjust ph, be introduced into hydrolysis acidification pool through equalizing tank balanced water quality and quantity, be 2.5 hours at the hydraulic detention time of hydrolysis acidification pool, and set up light source above hydrolysis acidification pool, whole process carries out the irradiation that wavelength is 1100nm infrared light.The COD value 1300mg/l of hydrolysis acidification pool water outlet, the BOD of water outlet
5value 270mg/l, the TN value 198mg/l of water outlet, the value 52mg/l of the TP of water outlet, the SS value 61mg/l of water outlet.
Water after acidication process enters electrolyzer, presses iron filings 2kg/m in electrolyzer
3ratio throw in, hydraulic detention time is 10 hours, and in operation process, use gas blower to be blown into air in pond, thus ensures there is sufficient oxygen in the water of electrolyzer.
Membrane bioreactor is entered in water outlet in electrolyzer, and 18 hours residence time in membrane bioreactor of waste water, volumetric loading is 6kgCOD/m
3.d, sludge concentration is 7-11g/l, and membrane flux is 15L/m
2.h, resistance of membrane filtration is less than 25kPa; COD value≤the 45mg/l of water outlet, the BOD of water outlet
5value≤8mg/l, the TN value 108mg/l of water outlet, the value 21mg/l of the TP of water outlet, the SS value of water outlet does not detect.
Table 1 is the experimental data list carrying out illumination experiment in Hydrolysis Acidification.Can see from the data of table 1, COD clearance, BOD after adopting illumination
5clearance and SS clearance are all significantly increased, and the clearance of TN and TP slightly improves.And can find out, when adopting far red light to irradiate, clearance is the highest, and effect is best.Illustrate that photo-irradiation treatment creates significant effect.The reason had effect is analyzed theoretically, may be because illumination creates impact to the microbial growth metabolism of working in Hydrolysis Acidification, create impact to the result of acidication.And the illumination of different wave length is variant to microbial growth metabolic effect, best irradiation optical band therefore can be drawn by experiment.
Table 1, note: above-mentioned data are the mean value and variance that repeat for 4 times to test.
Those skilled in the art can make replacement or modification according to content disclosed by the invention and the art technology grasped to content of the present invention; but these replacements or modification should not be considered as disengaging the present invention design, and these replacements or modification are all in the interest field of application claims protection.
Claims (3)
1. to producing the wastewater produced treatment process of cephalosporins medicine, it is characterized in that the method is by anaerobic hydrolysis acidifying, electrolysis and these three treatment steps of Membrane Bioreactor for Wastewater Treatment are formed,
Step (1) is produced the wastewater produced elder generation of cephalosporins medicine and carry out biological hydrolysis acidifying in anaerobic hydrolysis acidification pool, improves the biodegradability of waste water;
The water outlet of step (1) is carried out electrolysis by step (2) in electrolyzer, removes COD further, improves the biodegradability of waste water;
The water outlet of step (2) flows in membrane bioreactor by step (3) carries out final Aerobic biological process, the ultra-filtration membrane of waste water after process in membrane bioreactor, pump out by going out water pump, qualified discharge is to outer discharge pipe or be back to use in production technique;
Biological hydrolysis acidifying wherein in step (1) comprises hydrolysis stage and souring stage, and at hydrolysis and souring stage, carry out omnidistance far red light photograph to anaerobic hydrolysis acidification pool, the light wave scope of the infrared light used is 1100 ~ 2500nm.
2. a kind of wastewater produced to the production cephalosporins medicine treatment process described in claim 1, it is characterized in that wherein said electrolysis step takes ferrum-carbon internal electrolysis, iron filings are dropped into also simultaneously to air-blowing in waste water in waste water, thus in waste water, form countless small galvanic cell, there is redox reaction, produce divalence and ferric ion simultaneously, in waste water, form colloid produce flocculation sediment effect.
3. a kind of wastewater produced to the production cephalosporins medicine treatment process described in claim 2, is characterized in that wherein iron filings are by 2kg/m
3ratio throw in, the residence time of waste water in membrane bioreactor is 19 hours, and volumetric loading is 6kgCOD/m
3.d, sludge concentration is 7-11g/l, and membrane flux is 15L/m
2.h, resistance of membrane filtration is less than 25kPa.
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| CN104773919B (en) * | 2015-04-08 | 2016-06-29 | 常州大学 | A kind of pharmacy waste water advanced treatment system |
| CN106007186A (en) * | 2016-06-28 | 2016-10-12 | 焦作健康元生物制品有限公司 | 7-aminocephalosporanic acid production wastewater treatment method |
| CN107032495A (en) * | 2017-05-22 | 2017-08-11 | 大连理工大学 | A kind of biological treatment group technology of the high salinity pharmacy waste waters of high COD |
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| JP3635619B2 (en) * | 1999-02-17 | 2005-04-06 | 株式会社荏原製作所 | Water purification method using powdered activated carbon and photocatalyst |
| CN101434437B (en) * | 2008-12-02 | 2011-04-06 | 浙江双益环保科技发展有限公司 | Processing method for wastewater from cephalosporin synthesis pharmaceutical production |
| CN101941749B (en) * | 2010-09-27 | 2012-12-19 | 中国环境科学研究院 | Method for treating high-concentration copper-containing antibiotic wastewater and recovering copper by iron-carbon micro-electrolysis |
| CN102531273A (en) * | 2010-12-31 | 2012-07-04 | 上海轻工业研究所有限公司 | Treatment equipment for ammonia nitrogen and COD (Chemical Oxygen Demand) in surface treatment waste water |
| CN102372401B (en) * | 2011-09-28 | 2013-10-30 | 同济大学 | Iron-carbon micro-electrolysis-dynamic membrane wastewater deep treatment process |
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