CN105036486A - Method for deeply treating antibiotic pharmaceutical wastewater based on magnetic Fenton-like resin - Google Patents
Method for deeply treating antibiotic pharmaceutical wastewater based on magnetic Fenton-like resin Download PDFInfo
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Abstract
The invention discloses a method and a device for deeply treating antibiotic pharmaceutical wastewater based on magnetic Fenton-like resin. The device comprises a coagulative precipitation tank, a Fenton-like reactor, an anaerobic baffle plate reactor, an aerobic biological contact oxidation tank, a sedimentation tank, a magnetic resin Fenton-like oxidation tank and a resin adsorption tower which are sequentially communicated by virtue of pipelines. By using the method and the device, the antibiotic pharmaceutical wastewater can be deeply treated; and effluent obtained after the antibiotic pharmaceutical wastewater is treated by using the method and the device disclosed by the invention can stably reach up to the emission limit regulated by Fermented Pharmaceutical Industrial Water Pollutant Emission Standard (GB21903-2008).
Description
Technical field
The invention belongs to field of waste water treatment, particularly relate to a kind of method based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water and device.
Background technology
Microbiotic is the important chemicals of the various disease of mankind's infection control.In the screening of antibiotic and production, strain improvement etc., still there are many technological difficulties in current production of antibiotics, thus occur that raw material availability is low, refine the problems such as residual fungistatic cellulose content in low, the waste water of purity is high, cause Heavy environmental pollution.The production processes such as antibiotic pharmaceutical wastewater mainly extracts from fermentation, filtration, extractive crystallization, chemical process, refining.COD, BOD and the ammonia nitrogen concentration of this waste water are high, and strongly-acid has very strong bio-toxicity.The treatment process of current antibiotic pharmaceutical wastewater mainly contains the combined treatment etc. of chemical treatment method, materilization freatment method, bioremediation and multiple method.Chemical treatment method needs to add certain class or a few class medicament, the risk of secondary environmental pollution is also there is except operation cost is higher, current chemical treatment be only used to carry out a biological disposal upon pre-treatment, play adjustments, the stabilizing water quality water yield, remove biological inhibition material and raising wastewater biodegradability effect.Biochemical process process antibiotic pharmaceutical wastewater relatively economical, but microbiotic residual in waste water and high-enriched organics make traditional biological process be difficult to reach expection treatment effect, because the strongly inhibited effect of residual antibiotic to microorganism makes aerobic bacteria poisoning, and the organism of anaerobic treatment high density is difficult to the requirement meeting effluent index.Studies in China personnel have carried out many research and practices to microbiotic pharmacy pharmacy waste water for this reason, existing document Patent " a kind for the treatment of process of antibiotic pharmaceutical wastewater and device " (CN201110455026.1), by arranging porous membrane pointedly between the anion and cation exchange membrane that electrodialyzer film is right, thus electrodialysis and membrane filtration process are combined, both utilized the sieving action of porous membrane to realize colloid in waste water, albumen, the macromolecular substance such as mycelia and being effectively separated between microbiotic with the small-molecule substances such as salt ion, ion-exchange membrane can be utilized again under the effect of DC electric field to realize in waste water cloudy to the electro-ionic selective penetrated property of lotus, the isolation and identification of positively charged ion and charged microbiotic ion.Patent " a kind for the treatment of process of antibiotic pharmaceutical wastewater " (CN201210027326.4), disclose a kind for the treatment of process of antibiotic pharmaceutical wastewater, comprise the steps such as the pre-treatment of antibiotic pharmaceutical wastewater, immobilization biological ferment treatment, immobilized active sludge treatment.Enzyme immobilization technology and immobilized active sludge technology are united and applied in the process of antibiotic waste water by this inventive method, than being used alone immobilized microorganism technique or biological reinforcing technology method raising 2 ~ 3 times of effects.Patent " treatment process of pharmacy waste water " (CN201510013714.0) discloses a kind for the treatment of process of pharmacy waste water, comprise the following steps, first pharmacy waste water is carried out an ozone oxidation, the toxin such as process microbiotic, then carry out biochemical degradation through biological bacteria, the waste water after biochemical degradation carries out secondary oxidation again, dissipation biological bacteria and other poisonous and harmful bacteriums, last precipitation process, pharmacy waste water detects direct discharge up to standard or is back to use production process through equipment for reclaiming.Patent " a kind for the treatment of process for antibiotic pharmaceutical wastewater " (CN200810105763.7) discloses a kind for the treatment of process for antibiotic pharmaceutical wastewater: A. pharmacy waste water enters one-level bio-oxidation pond after precipitate and separate, add yeast or mould carries out biochemical treatment, hydraulic detention time is 6-72 hour; Solid-liquid separation is carried out in water outlet; B. the waste water of processing of step A is oxidized, and oxidizing condition is: adjustment wastewater pH is 3-4.5, then adds hydrogen peroxide and ferrous iron reagent is oxidized, and oxidation 1-10 hour, hydrogen peroxide and ferrous iron mol ratio are H
2o
2: Fe
2+=1-50, hydrogen peroxide is 1-10 times of antibiotic concentration in waste water; Or adjustment wastewater pH is 7-11, passes into ozone and is oxidized, ozone dosage is 30-120mg/L, oxidation 1-10 hour; C. the waste water of step B process enters two stage biological oxidation pond after solid-liquid separation, the material of oxidation removal readily biodegradable; D. the waste water of step C process precipitates, and discharges supernatant liquor.
Numerous antibiotic waste water treatment process of current bibliographical information is nearly all with the treatment effect of the removal of waste water COD for metrics evaluation waste water, and do not give enough attention for the antibiotic compound contained in waste water, still containing Antibiotique composition in waste water after treatment.And residual microbiotic enters natural water body by discharge of wastewater, serious destruction is brought by giving water ecological setting and HUMAN HEALTH, so need more perfect technical matters to improve the treatment effect of antibiotic pharmaceutical wastewater, reduce the discharge of antibiotic pharmaceutical wastewater to the harm of ecotope.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of method and apparatus based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water, i.e. coagulation vertical sedimentation basin-class Fenton reactor-anaerobic baffled reactor-aerobic bio-contact oxidation pond-settling tank-tower-coupled technology of magnetic resin class Fenton oxidation pond-resin absorption and device.
For achieving the above object, the present invention is achieved by the following technical solutions.
Based on a device for magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water, comprise use pipeline communication successively coagulative precipitation tank, class Fenton reactor, anaerobic reactor, oxidation pond, settling tank, magnetic resin class Fenton oxidation pond, resin absorption tower.
Four pieces of vertically arranged traverse baffles are provided with further in described anaerobic reactor, be followed successively by traverse baffle on traverse baffle on first time traverse baffle, first, second time traverse baffle, second, anaerobic reactor is divided into the first upstream room, the first downstream room, the second upstream room, the second downstream room, the 3rd upstream room by four pieces of traverse baffles, and upstream room is 4:1 with the ratio of the width of downstream room
Described first time traverse baffle, second time traverse baffle upper end adopt zigzag structure further; The knuckle of the oriented water (flow) direction in the bottom of traverse baffle on traverse baffle, second on first, knuckle angle is 135 °.
Be provided with magnetism macroporous resin extender bed in described magnetic resin class Fenton oxidation pond further, magnetism macroporous resin extender bed virtual height and diameter ratio are 2:1.
Be provided with X-5 type macroporous adsorbent resin bed of packings in described resin absorption tower further, X-5 type macroporous adsorbent resin bed of packings virtual height and diameter ratio are 4:1.Residual organism and antibiotic agents in the further planar water of X-5 type macroporous adsorbent resin energy
A kind of method based on magnetic type Fenton resin advanced treatment antibiotics wastewater from chemical industry, water reuse flow by gravity, enter coagulative precipitation tank, class Fenton reactor, anaerobic baffled reactor, aerobic bio-contact oxidation pond, settling tank, magnetic resin class Fenton oxidation pond, resin absorption tower continuously, specifically comprise the following steps:
(1) first waste water enter coagulative precipitation tank, by 50-100g/m
3amount add coagulating agent, hydraulic detention time controls at 3h-4h;
(2) water outlet of step (1) enters class Fenton reactor, adding Fe-ZSM-5 molecular sieve type class fenton catalyst by the amount of 0.5-0.8g/L, is that carbonic acid gas must be measured and adds H by organism permineralization contained in the waste water entering class Fenton reactor
2o
2, H
2o
2dosage control at 0.5ml/L-5ml/L, hydraulic detention time controls at 0.5-1h;
(3) water outlet of step (2) enters anaerobic baffled reactor, and hydraulic detention time controls at 6-10h;
(4) water outlet of step (3) enters oxidation pond and carries out aeration, and hydraulic detention time controls at 6-8h;
(5) water outlet of step (4) enters settling tank, and hydraulic detention time is 2-3h;
(6) water outlet of step (5) enters magnetic type Fenton resin oxidation pond with downflow system, adds H
2o
2reaction, H
2o
2dosage control at 0.5ml/L-1ml/L, hydraulic detention time controls at 0.5-1h;
(7) water outlet of step (6) enters resin absorption tower with upflowing, and hydraulic detention time controls at 3-5h.
In described step (1), coagulating agent is PAC and PAM further, in mass ratio 2:1 composition.
In described step (2), pH value in reaction controls between 3 and 6 further.
In described step (4), oxidation pond dissolved oxygen DO value controls at 3-5mg/L further.
In described step (5), pH value in reaction controls between 6-7 further.
Beneficial effect: compared with prior art, the invention has the advantages that:
1) antibiotic pharmaceutical wastewater can reach emission limit in " fermentation class pharmaceutical industry pollution discharge standard " (GB21903-2008) after the technology of the present invention process;
2) class Fenton reactor produces hydroxyl radical free radical by class fenton catalyst catalysis hydrogen peroxide, utilize the Strong oxdiative ability of hydroxyl radical free radical, complicated toxic organic pollutant is oxidized to simple organic, realize removing COD and improving the functions such as biodegradable, anaerobic baffled reactor utilizes its distinctive mechanism and anaerobion efficiently to remove organism in waste water, the pollution substances such as the organism in water are removed further by the metabolism of aerobic microbiological in aerobic bio-contact oxidation pond, three, by coupling, realizes the optimization of respective function;
3) microbiotic remained in waste water and organic substance can be carried out further mineralising by magnetic type Fenton resin oxidation pond between pH value 6-7, COD in further reduction waste water and microbiotic, follow-up resin absorption tower then can adsorb residual microbiotic further, ensures water outlet not containing pollution substances such as microbiotic.
Accompanying drawing explanation
Fig. 1 present invention process schema;
Fig. 2 structural representation of the present invention;
Diagram: 1. coagulative precipitation tank, 2. class Fenton reactor, 3. anaerobic baffled reactor, 4. aerobic bio-contact oxidation pond, 5. settling tank, 6. magnetic resin class Fenton oxidation pond, 7. resin absorption tower.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Embodiment 1:
As shown in Figure 1, 2, a kind of device based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water be connect successively with pipeline coagulative precipitation tank 1, class Fenton reactor 2, anaerobic baffled reactor 3, aerobic bio-contact oxidation pond 4, settling tank 5, magnetic resin class Fenton oxidation pond 6, resin absorption tower 7, wherein coagulative precipitation tank 1, settling tank adopt vertical-flow structure, agitator and pH meter are installed in class Fenton reactor 2, four pieces of vertically arranged traverse baffles are provided with in anaerobic baffled reactor 3, be followed successively by first time traverse baffle, traverse baffle on first, second time traverse baffle, traverse baffle on second, anaerobic baffled reactor 3 is divided into the first upstream room by four pieces of traverse baffles, first downstream room, second upstream room, second downstream room, 3rd upstream room, first upstream room and the second upstream room width equal, first downstream room and the second downstream room width equal, first upstream room is 4:1 with the ratio of the width of the first downstream room, the bottom of first time traverse baffle, the bottom of second time traverse baffle is all fixed on bottom anaerobic baffled reactor 3, the upper end of first time traverse baffle, the upper end of second time traverse baffle all adopts zigzag structure, on first traverse baffle upper end, second on the upper end of traverse baffle be all fixed on anaerobic baffled reactor 3 top, on first traverse baffle bottom, second on the knuckle of all oriented water (flow) direction in bottom of traverse baffle, knuckle angle is 135 °, magnetism macroporous resin extender bed is provided with in magnetic resin class Fenton oxidation pond 7, magnetism macroporous resin extender bed virtual height and diameter ratio are 2:1, and magnetism macroporous resin is prepared by patent " a kind of magnetism macroporous adsorbent resin microballon and preparation method thereof " (application number 201310658029.4), be provided with X-5 type macroporous adsorbent resin bed of packings in resin absorption tower, X-5 type macroporous adsorbent resin bed of packings virtual height and diameter ratio are 4:1.
Zhejiang pharmaceutical factory mainly produces antibiotic agents and chemical intermediate, and the water quality of its waste water produced is as shown in table 1.
Table 1 waste water quality
Utilize a kind of above-mentioned waste water of method process based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water of the present invention, the method comprises the steps:
(1) first antibiotic pharmaceutical wastewater enters coagulation vertical sedimentation basin, and vertical sedimentation basin hydraulic detention time controls as 3h, and coagulant charging quantity controls at 80g/m
3, coagulating agent by PAC (polymerize aluminum chloride) and PAM (polyacrylamide) in mass ratio 2:1 form.
(2) water outlet of step (1) enters class Fenton reactor, adds Fe-ZSM-5 molecular sieve type class fenton catalyst and H in class Fenton reactor
2o
2, the dosage of Fe-ZSM-5 is 0.6g/L, H
2o
2dosage according to class Fenton reactor entering organic matter of water mass concentration calculate determine, dosage is 2ml/L, and pH value in reaction controls between 3-4, and hydraulic detention time controls at 1h.
(3) water outlet of step (2) enters anaerobic baffled reactor, and hydraulic detention time is 8h.
(4) water outlet of step (3) enters aerobic bio-contact oxidation pond, and aerobic bio-contact oxidation pond dissolved oxygen DO value controls at 3mg/L, and hydraulic detention time controls at 6h.
(5) water outlet of step (4) enters settling tank, and settling tank adopts vertical-flow, and settling tank hydraulic detention time is 2h.
(6) water outlet of step (5) enters magnetic type Fenton resin oxidation pond, adds H
2o
2reaction, H
2o
2dosage be 0.8ml/L, pH value in reaction controls between 6-7, and hydraulic detention time controls at 0.5h.
(7) water outlet of step (6) enters resin absorption tower, and hydraulic detention time controls at 4h, and the index of water outlet is stable reaches emission limit in " fermentation class pharmaceutical industry pollution discharge standard " (GB21903-2008).
Embodiment 2: substantially the same manner as Example 1, difference is: in step (1), coagulant charging quantity controls at 50g/m
3, hydraulic detention time controls at 3.5h; In step (2), the dosage of Fe-ZSM-5 is 0.5g/L, H
2o
2dosage be 5ml/L, pH value in reaction controls between 4-5, and hydraulic detention time controls at 1h; In step (3), hydraulic detention time controls at 10h; In step (4), dissolved oxygen DO value controls at 4mg/L, and hydraulic detention time controls at 7h; In step (5), hydraulic detention time is 3h; H in step (6)
2o
2dosage be 0.5ml/L, hydraulic detention time controls at 1h, and hydraulic detention time controls at 5h in step (7).
Embodiment 3: substantially the same manner as Example 1, difference is: in step (1), coagulant charging quantity controls at 100g/m
3, hydraulic detention time controls at 3h; In step (2), the dosage of Fe-ZSM-5 is 0.8g/L, H
2o
2dosage be 0.5ml/L, pH value in reaction controls between 5-6, and hydraulic detention time controls at 0.5h; In step (3), hydraulic detention time controls at 6h; In step (4), dissolved oxygen DO value controls at 5mg/L, and hydraulic detention time controls at 8h; In step (5), hydraulic detention time is 2.5h; H in step (6)
2o
2dosage be 1ml/L, hydraulic detention time controls at 1h, and hydraulic detention time controls at 3h in step (7).
Embodiment 4: substantially the same manner as Example 1, difference is: in step (1), coagulant charging quantity controls at 70g/m
3, hydraulic detention time controls at 4h; In step (2), the dosage of Fe-ZSM-5 is 0.7g/L, H
2o
2dosage be 1.5ml/L, pH value in reaction controls between 3-4, and hydraulic detention time controls at 0.8h; In step (3), hydraulic detention time controls at 7h; In step (4), dissolved oxygen DO value controls at 4mg/L, and hydraulic detention time controls at 7h; In step (5), hydraulic detention time is 2.5h; H in step (6)
2o
2dosage be 0.8ml/L, hydraulic detention time controls at 0.7h, and hydraulic detention time controls at 3.5h in step (7).
Concrete treatment technology index is as shown in table 2.
The water outlet situation of table 2 each technique unit COD and terramycin
Note: in table I: coagulation vertical sedimentation basin water outlet, II: the water outlet of class Fenton reactor, III: anaerobic baffled reactor water outlet, IV+V: aerobic bio-contact oxidation pond+settling tank water outlet, VI: the pond water outlet of magnetic resin class Fenton oxidation, VII: the water outlet of resin absorption tower
The present invention is illustrated according to above-described embodiment, should be appreciated that above-described embodiment does not limit the present invention in any form, and all employings are equal to replacement or the technical scheme that obtains of equivalent transformation mode, all drop within protection scope of the present invention.
Claims (10)
1. the device based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water, it is characterized in that, comprise use pipeline communication successively coagulative precipitation tank, class Fenton reactor, anaerobic baffled reactor, aerobic bio-contact oxidation pond, settling tank, magnetic resin class Fenton oxidation pond, resin absorption tower.
2. a kind of device based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 1, it is characterized in that, four pieces of vertically arranged traverse baffles are provided with in described anaerobic reactor, be followed successively by traverse baffle on traverse baffle on first time traverse baffle, first, second time traverse baffle, second, anaerobic reactor is divided into the first upstream room, the first downstream room, the second upstream room, the second downstream room, the 3rd upstream room by four pieces of traverse baffles, and upstream room is 4:1 with the ratio of the width of downstream room.
3. a kind of device based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 2, is characterized in that, described first time traverse baffle, second time traverse baffle upper end adopt zigzag structure; The knuckle of the oriented water (flow) direction in the bottom of traverse baffle on traverse baffle, second on first, knuckle angle is 135 °.
4. a kind of device based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 1, it is characterized in that, be provided with magnetism macroporous resin extender bed in described magnetic resin class Fenton oxidation pond, magnetism macroporous resin extender bed virtual height and diameter ratio are 2:1.
5. a kind of device based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 1, it is characterized in that, be provided with X-5 type macroporous adsorbent resin bed of packings in described resin absorption tower, X-5 type macroporous adsorbent resin bed of packings virtual height and diameter ratio are 4:1.
6. a kind of method based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to any one of claim 1 ~ 5, it is characterized in that, waste water enters coagulative precipitation tank, class Fenton reactor, anaerobic baffled reactor, aerobic bio-contact oxidation pond, settling tank, magnetic resin class Fenton oxidation pond, resin absorption tower continuously, specifically comprises the following steps:
(1) first waste water enter coagulative precipitation tank, by 50-100g/m
3amount add coagulating agent, hydraulic detention time controls at 3h-4h;
(2) water outlet of step (1) enters class Fenton reactor, adds Fe-ZSM-5 molecular sieve type class fenton catalyst by the amount of 0.5-0.8g/L, and the amount being carbonic acid gas by organism permineralization contained in the waste water entering class Fenton reactor adds H
2o
2, H
2o
2dosage control at 0.5ml/L-5ml/L, hydraulic detention time controls at 0.5-1h;
(3) water outlet of step (2) enters anaerobic baffled reactor, and hydraulic detention time controls at 6-10h;
(4) water outlet of step (3) enters aerobic bio-contact oxidation pond and carries out aeration, and hydraulic detention time controls at 6-8h;
(5) water outlet of step (4) enters settling tank, and hydraulic detention time is 2-3h;
(6) water outlet of step (5) enters magnetic type Fenton resin oxidation pond with downflow system, adds H
2o
2reaction, H
2o
2dosage control at 0.5ml/L-1ml/L, hydraulic detention time controls at 0.5-1h;
(7) water outlet of step (6) enters resin absorption tower with upflowing, and hydraulic detention time controls at 3-5h.
7. a kind of method based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 6, is characterized in that, in described step (1), coagulating agent is PAC and PAM, in mass ratio 2:1 composition.
8. a kind of method based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 6, is characterized in that, in described step (2), pH value in reaction controls between 3 and 6.
9. a kind of method based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 6, is characterized in that, in described step (4), oxidation pond dissolved oxygen DO value controls at 3-5mg/L.
10. a kind of method based on magnetic type Fenton resin advanced treatment antibiotics pharmacy waste water according to claim 6, is characterized in that, in described step (5), pH value in reaction controls between 6-7.
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