CN104445812A - Treatment method of waste liquor obtained after alcohol mother liquor purifying in doxycycline hydrochloride production - Google Patents
Treatment method of waste liquor obtained after alcohol mother liquor purifying in doxycycline hydrochloride production Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
Abstract
The invention discloses a treatment method of waste liquor obtained after alcohol mother liquor purifying in doxycycline hydrochloride production. The treatment method comprises the following steps: (1) cooling: stirring and cooling the waste liquor to 40-45 DEG C in a regulating reservoir; (2) performing primary flocculation and sedimentation: adding a flocculating agent into cooled wastewater, and adding alkaline to neutralize after performing the flocculation and sedimentation, and mud-water separation; (3) performing secondary flocculation and sedimentation: performing filter-pressing on the liquid neutralized in the step (2) by virtue of a filter press, performing flocculation and sedimentation on filtrate again, and separating mud from water; (4) performing biochemical treatment: performing biochemical reaction on liquid supernatant obtained by mud-water separation through an ozone oxidation decoloration unit, an anaerobic treatment unit and an aerobic biochemical unit; (5) filtering and performing membrane separation: treating the liquid treated in the step (4) through a membrane bioreactor, a nanofiltration membrane and a reverse osmosis membrane. Compared with the prior art, the treatment method has the beneficial effects of high treatment efficiency, stable operation and capacity of eliminating the pollution of wastewater on the environment.
Description
Technical field
The present invention relates to the treatment process of waste liquid in chemical process, be specifically related to the treatment process of waste liquid after ethanol mother liquor purification in a kind of sour doxycycline production.
Background technology
Vibramycin hydrochloride is take terramycin as raw material after chloro, dehydration, hydrogenation salify, the reaction of displacement multi-step chemical, then through purification, decolouring, filtration, crystallization, drying and a kind of Broad spectrum antibiotics of making.Its raw materials for production are wide in variety, complex process, and ethanol is a kind of important source material of this product, can give off a large amount of waste water containing ethanol in process of production.After ethanol carries out creating a large amount of purification in the process of Distillation recovery in waste water, waste liquid cannot process.This waste liquid chemical oxygen demand (COD) (COD) is up to hundreds of thousands of milligrams per liter, and biodegradability is poor, and colourity is large, and outward appearance is Vandyke brown, and acidity is large, and inorganic salt content is high.In waste liquid, main component is terramycin degradation product, and tosic acid and sulfosalicylic acid and fluorochemical, hydrochloric acid also has the degradation product of doxycycline and the residue etc. of Acetanilide.Due to this kind of waste liquid, intractability is very large, and the achievement in research published at present is also few, does not also have a kind of applicable treatment process that it can be made to process rear qualified discharge.
Summary of the invention
For problems of the prior art, the object of this invention is to provide a kind for the treatment of process of rear waste liquid of purifying to ethanol mother liquor in high density, the production of difficult Vibramycin hydrochloride, the method has the features such as process is thorough, efficiency is high, stable.
For achieving the above object, the present invention is by the following technical solutions:
In Vibramycin hydrochloride production, a treatment process for the rear waste liquid of ethanol mother liquor purification, comprises the following steps: (1) cools: stirred in equalizing tank by waste liquid, naturally cool to 40-45 DEG C; (2) flocculation sediments: add flocculation agent in waste water, add alkali again and neutralize after flocculation sediment mud-water separation; (3) secondary flocculation sediment: by the liquid after in step (2) through pressure filter press filtration, filtrate flocculation sediment by mud-water separation again; (4) biochemical treatment: step (3) mud-water separation gained supernatant liquor is carried out biochemical reaction through ozone oxidation decolouring, anaerobism, aerobic biochemical unit successively; (5) filtration and membrane sepn: the liquid after step (4) being processed is successively through membrane bioreactor, nanofiltration and reverse osmosis membrane processing.
The flocculation agent added in described step (2) is polymerize aluminum chloride, and dosage is 1000-3000mg/L.
The alkali added in described step (2) is unslaked lime, and unslaked lime dosage is 8g/L; Unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, makes the pH value of waste water be adjusted to 6.5-7.5.
The flocculation agent added during secondary flocculation sediment in described step (3) is polymerize aluminum chloride, and dosage is 500-1000mg/L.
In described step (4), the dosage of ozone is 100-200g/h, and the ozone contact reaction time is 1.5-3 hour.
Adopt complete hybrid anaerobic digester to carry out anaerobic biochemical reaction to the waste water after ozone decolorization in described step (4), waste water is 6 hours in the anaerobic digester residence time.
Adopt biological contact oxidation pond to carry out aerobic biochemical reaction to the waste water after anaerobic biochemical reaction in described step (4), waste water is 10 hours in the biological contact oxidation pond residence time.
Adopt elastic biological filler in described biological contact oxidation pond, described packed height is 2 meters, and filler filament length is 200mm.
Described biological contact oxidation pond is divided into four lattice, installs elastic biological filler in first three lattice pond, installs Nets impregnated in the 4th lattice pond; Described Nets impregnated adopts curtain ultra-filtration membrane, membrane flux be 4-7 liter/square metre. hour.
Double-stage reverse osmosis technique is adopted to filter and membrane sepn the waste water after biochemical treatment in described step (5); The described membrane sepn first step adopts nanofiltration membrane, and the second stage adopts reverse osmosis membrane.
Compared with prior art, beneficial effect of the present invention is: the present invention have process thoroughly, processing efficiency is high, the feature such as stable, by Vibramycin hydrochloride factory effluent can be made after method process of the present invention to discharge the primary standard reached in wastewater discharge standard GB8978-1996, eliminate waste water pollution on the environment simultaneously.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
In conjunction with Figure of description, the specific embodiment of the present invention is as follows:
embodiment 1
Vibramycin hydrochloride produce in ethanol mother liquor purify after the treatment process of waste liquid, comprise the following steps: (1) cools: waste liquid is carried out in equalizing tank water quality, water yield homogenizing stirring, make water temperature naturally cool to 40 DEG C by 90 DEG C, (2) flocculation sediments: by the waste liquid in step (1) by pump delivery to flocculation tank, in waste water, flocculant poly aluminum chloride is added by volume pump, dosage is 1000mg/L, add unslaked lime in supernatant liquor after flocculation sediment mud-water separation again to neutralize, unslaked lime dosage is 8g/L, unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, the pH value of waste water is made to be adjusted to 6.5 by 0.5, the salts substances dissolved in waste water is separated out, the preliminary suspended substance removed in waste liquid, (3) secondary flocculation sediment: the waste liquid after step (2) being neutralized carries out press filtration solid-liquid separation by pump delivery to plate-and-frame filter press again, gained solid matter can be used for brick producing material, leach liquid flow automatically again enter second time flocculation sediment, flocculant poly aluminum chloride is again added in filtrate, dosage is 500mg/L, through flocculation sediment again and by mud-water separation, remove the suspended substance in waste liquid further, (4) ozone oxidation, anaerobic and aerobic biochemical treatment: second time flocculation sedimentation tank water outlet gravity flow in step (3) is entered ozone oxidation pond, ozone is produced by ozonizer, be diffused in waste water by microporous aeration device again, the dosage of ozone is 100g/h, the ozone contact reaction time is 2 hours, waste water after ozone oxidation again by pump delivery to anaerobic digester, anaerobic pond adopts complete mixing pit type, by the effect of anaerobion, larger molecular organics in waste water is degraded, the residence time is 6 hours, anaerobic digester water outlet gravity flow enters biological contact oxidation pond, aerobic biochemical reaction is carried out to the waste water after anaerobic biochemical reaction, waste water is 10 hours in the biological contact oxidation pond residence time, and oxygenic aeration, by the effect of aerobic microbiological, the organism in waste water is thoroughly decomposed, (5) activated carbon filtration and membrane sepn: the liquid after step (4) being processed is through ultrafiltration membrane bioreactor, ultrafiltration membrane bioreactor water outlet removes colourity and organic pollutant further through activated carbon filtration again, and then be delivered to double-stage reverse osmosis system by high-pressure pump, the first step adopts nanofiltration membrane, the second stage adopts reverse osmosis membrane, the discharge of process standard water discharge.
The present embodiment biological contact oxidation pond is divided into four lattice, in first three lattice pond, elastic biological filler is installed, packed height is 2 meters, filler filament length is 200mm, in 4th lattice pond, submerged ultrafiltration bio-reactor is installed, submerged ultrafiltration bio-reactor adopts curtain ultra-filtration membrane, and membrane flux is 4 liters/square metre. hour.
The present embodiment Chinese effluent value: indices value when water inlet, the indices value of water outlet is after treatment in table 1:
Table 1
| COD（mg/L） | BOD5（mg/L） | SS（mg/L） | Colourity (doubly) | pH | |
| Water inlet | 340000 | 22000 | 9000 | 10000 | 1.0 |
| Water outlet | 95 | 20 | 5.0 | － | 6.6 |
| Emission standard | ≤100 | ≤30 | ≤70 | 50 | 6.0－9.0 |
embodiment 2
Vibramycin hydrochloride produce in ethanol mother liquor purify after the treatment process of waste liquid, comprise the following steps: (1) cools: waste liquid is carried out in equalizing tank water quality, water yield homogenizing stirring, make water temperature naturally cool to 42 DEG C by 90 DEG C, (2) flocculation sediments: by the waste liquid in step (1) by pump delivery to flocculation tank, in waste water, flocculant poly aluminum chloride is added by volume pump, dosage is 2500mg/L, add unslaked lime in supernatant liquor after flocculation sediment mud-water separation again to neutralize, unslaked lime dosage is 8g/L, unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, the pH value of waste water is made to be adjusted to 6.9 by 0.7, the salts substances dissolved in waste water is separated out, the preliminary suspended substance removed in waste liquid, (3) secondary flocculation sediment: the waste liquid after step (2) being neutralized carries out press filtration solid-liquid separation by pump delivery to plate-and-frame filter press again, gained solid matter can be used for brick producing material, leach liquid flow automatically again enter second time flocculation sediment, flocculant poly aluminum chloride is again added in filtrate, dosage is 800mg/L, through flocculation sediment again and by mud-water separation, remove the suspended substance in waste liquid further, (4) ozone oxidation, anaerobic and aerobic biochemical treatment: second time flocculation sedimentation tank water outlet gravity flow in step (3) is entered ozone oxidation pond, ozone is produced by ozonizer, be diffused in waste water by microporous aeration device again, the dosage of ozone is 150g/h, the ozone contact reaction time is 2.5 hours, waste water after ozone oxidation again by pump delivery to anaerobic digester, anaerobic pond adopts complete mixing pit type, by the effect of anaerobion, larger molecular organics in waste water is degraded, the residence time is 6 hours, anaerobic digester water outlet gravity flow enters biological contact oxidation pond, aerobic biochemical reaction is carried out to the waste water after anaerobic biochemical reaction, waste water is 10 hours in the biological contact oxidation pond residence time, and oxygenic aeration, by the effect of aerobic microbiological, the organism in waste water is thoroughly decomposed, (5) activated carbon filtration and membrane sepn: the liquid after step (4) being processed is through ultrafiltration membrane bioreactor, ultrafiltration membrane bioreactor water outlet removes colourity and organic pollutant further through activated carbon filtration again, and then be delivered to double-stage reverse osmosis system by high-pressure pump, the first step adopts nanofiltration membrane, the second stage adopts reverse osmosis membrane, the discharge of process standard water discharge.
The present embodiment biological contact oxidation pond is divided into four lattice, in first three lattice pond, elastic biological filler is installed, packed height is 2 meters, filler filament length is 200mm, in 4th lattice pond, submerged ultrafiltration bio-reactor is installed, submerged ultrafiltration bio-reactor adopts curtain ultra-filtration membrane, and membrane flux is 5 liters/square metre. hour.
The present embodiment Chinese effluent value: indices value when water inlet, the indices value of water outlet is after treatment in table 2:
Table 2
| COD（mg/L） | BOD5（mg/L） | SS（mg/L） | Colourity (doubly) | pH | |
| Water inlet | 340000 | 22000 | 9000 | 10000 | 1.0 |
| Water outlet | 83 | 22 | 7.0 | － | 6.5 |
| Emission standard | ≤100 | ≤30 | ≤70 | 50 | 6.0－9.0 |
embodiment 3
Vibramycin hydrochloride produce in ethanol mother liquor purify after the treatment process of waste liquid, comprise the following steps: (1) cools: waste liquid is carried out in equalizing tank water quality, water yield homogenizing stirring, make water temperature naturally cool to 44 DEG C by 90 DEG C, (2) flocculation sediments: by the waste liquid in step (1) by pump delivery to flocculation tank, in waste water, flocculant poly aluminum chloride is added by volume pump, dosage is 1500mg/L, add unslaked lime in supernatant liquor after flocculation sediment mud-water separation again to neutralize, unslaked lime dosage is 8g/L, unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, the pH value of waste water is made to be adjusted to 7.0 by 0.8, the salts substances dissolved in waste water is separated out, the preliminary suspended substance removed in waste liquid, (3) secondary flocculation sediment: the waste liquid after step (2) being neutralized carries out press filtration solid-liquid separation by pump delivery to plate-and-frame filter press again, gained solid matter can be used for brick producing material, leach liquid flow automatically again enter second time flocculation sediment, flocculant poly aluminum chloride is again added in filtrate, dosage is 1000mg/L, through flocculation sediment again and by mud-water separation, remove the suspended substance in waste liquid further, (4) ozone oxidation, anaerobic and aerobic biochemical treatment: second time flocculation sedimentation tank water outlet gravity flow in step (3) is entered ozone oxidation pond, ozone is produced by ozonizer, be diffused in waste water by microporous aeration device again, the dosage of ozone is 200g/h, the ozone contact reaction time is 3 hours, waste water after ozone oxidation again by pump delivery to anaerobic digester, anaerobic pond adopts complete mixing pit type, by the effect of anaerobion, larger molecular organics in waste water is degraded, the residence time is 6 hours, anaerobic digester water outlet gravity flow enters biological contact oxidation pond, aerobic biochemical reaction is carried out to the waste water after anaerobic biochemical reaction, waste water is 10 hours in the biological contact oxidation pond residence time, and oxygenic aeration, by the effect of aerobic microbiological, the organism in waste water is thoroughly decomposed, (5) activated carbon filtration and membrane sepn: the liquid after step (4) being processed is through ultrafiltration membrane bioreactor, ultrafiltration membrane bioreactor water outlet removes colourity and organic pollutant further through activated carbon filtration again, and then be delivered to double-stage reverse osmosis system by high-pressure pump, the first step adopts nanofiltration membrane, the second stage adopts reverse osmosis membrane, the discharge of process standard water discharge.
The present embodiment biological contact oxidation pond is divided into four lattice, in first three lattice pond, elastic biological filler is installed, packed height is 2 meters, filler filament length is 200mm, in 4th lattice pond, submerged ultrafiltration bio-reactor is installed, submerged ultrafiltration bio-reactor adopts curtain ultra-filtration membrane, and membrane flux is 5 liters/square metre. hour.
The present embodiment Chinese effluent value: indices value when water inlet, the indices value of water outlet is after treatment in table 3:
Table 3
| COD（mg/L） | BOD5（mg/L） | SS（mg/L） | Colourity (doubly) | pH | |
| Water inlet | 340000 | 22000 | 9000 | 10000 | 1.0 |
| Water outlet | 75 | 18 | 8.0 | － | 6.8 |
| Emission standard | ≤100 | ≤30 | ≤70 | 50 | 6.0－9.0 |
embodiment 4
Vibramycin hydrochloride produce in ethanol mother liquor purify after the treatment process of waste liquid, comprise the following steps: (1) cools: waste liquid is carried out in equalizing tank water quality, water yield homogenizing stirring, make water temperature naturally cool to 45 DEG C by 90 DEG C, (2) flocculation sediments: by the waste liquid in step (1) by pump delivery to flocculation tank, in waste water, flocculant poly aluminum chloride is added by volume pump, dosage is 3000mg/L, add unslaked lime in supernatant liquor after flocculation sediment mud-water separation again to neutralize, unslaked lime dosage is 8g/L, unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, the pH value of waste water is made to be adjusted to 7.5 by 1, the salts substances dissolved in waste water is separated out, the preliminary suspended substance removed in waste liquid, (3) secondary flocculation sediment: the waste liquid after step (2) being neutralized carries out press filtration solid-liquid separation by pump delivery to plate-and-frame filter press again, gained solid matter can be used for brick producing material, leach liquid flow automatically again enter second time flocculation sediment, flocculant poly aluminum chloride is again added in filtrate, dosage is 1000mg/L, through flocculation sediment again and by mud-water separation, remove the suspended substance in waste liquid further, (4) ozone oxidation, anaerobic and aerobic biochemical treatment: second time flocculation sedimentation tank water outlet gravity flow in step (3) is entered ozone oxidation pond, ozone is produced by ozonizer, be diffused in waste water by microporous aeration device again, the dosage of ozone is 200g/h, the ozone contact reaction time is 3 hours, waste water after ozone oxidation again by pump delivery to anaerobic digester, anaerobic pond adopts complete mixing pit type, by the effect of anaerobion, larger molecular organics in waste water is degraded, the residence time is 6 hours, anaerobic digester water outlet gravity flow enters biological contact oxidation pond, aerobic biochemical reaction is carried out to the waste water after anaerobic biochemical reaction, waste water is 10 hours in the biological contact oxidation pond residence time, and oxygenic aeration, by the effect of aerobic microbiological, the organism in waste water is thoroughly decomposed, (5) activated carbon filtration and membrane sepn: the liquid after step (4) being processed is through ultrafiltration membrane bioreactor, ultrafiltration membrane bioreactor water outlet removes colourity and organic pollutant further through activated carbon filtration again, and then be delivered to double-stage reverse osmosis system by high-pressure pump, the first step adopts nanofiltration membrane, the second stage adopts reverse osmosis membrane, the discharge of process standard water discharge.
The present embodiment biological contact oxidation pond is divided into four lattice, in first three lattice pond, elastic biological filler is installed, packed height is 2 meters, filler filament length is 200mm, in 4th lattice pond, submerged ultrafiltration bio-reactor is installed, submerged ultrafiltration bio-reactor adopts curtain ultra-filtration membrane, and membrane flux is 7 liters/square metre. hour.
The present embodiment Chinese effluent value: indices value when water inlet, the indices value of water outlet is after treatment in table 4:
Table 4
| COD（mg/L） | BOD5（mg/L） | SS（mg/L） | Colourity (doubly) | pH | |
| Water inlet | 340000 | 22000 | 9000 | 10000 | 1.0 |
| Water outlet | 78 | 12 | 9.6 | － | 6.8 |
| Emission standard | ≤100 | ≤30 | ≤70 | 50 | 6.0－9.0 |
embodiment 5
Vibramycin hydrochloride produce in ethanol mother liquor purify after the treatment process of waste liquid, comprise the following steps: (1) cools: waste liquid is carried out in equalizing tank water quality, water yield homogenizing stirring, make water temperature naturally cool to 40-45 DEG C by 90 DEG C, (2) flocculation sediments: by the waste liquid in step (1) by pump delivery to flocculation tank, in waste water, flocculant poly aluminum chloride is added by volume pump, dosage is 2800mg/L, add unslaked lime in supernatant liquor after flocculation sediment mud-water separation again to neutralize, unslaked lime dosage is 8g/L, unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, the pH value of waste water is made to be adjusted to 7.5 by 0.8, the salts substances dissolved in waste water is separated out, the preliminary suspended substance removed in waste liquid, (3) secondary flocculation sediment: the waste liquid after step (2) being neutralized carries out press filtration solid-liquid separation by pump delivery to plate-and-frame filter press again, gained solid matter can be used for brick producing material, leach liquid flow automatically again enter second time flocculation sediment, flocculant poly aluminum chloride is again added in filtrate, dosage is 1000mg/L, through flocculation sediment again and by mud-water separation, remove the suspended substance in waste liquid further, (4) ozone oxidation, anaerobic and aerobic biochemical treatment: second time flocculation sedimentation tank water outlet gravity flow in step (3) is entered ozone oxidation pond, ozone is produced by ozonizer, be diffused in waste water by microporous aeration device again, the dosage of ozone is 180g/h, the ozone contact reaction time is 1.8 hours, waste water after ozone oxidation again by pump delivery to anaerobic digester, anaerobic pond adopts complete mixing pit type, by the effect of anaerobion, larger molecular organics in waste water is degraded, the residence time is 6 hours, anaerobic digester water outlet gravity flow enters biological contact oxidation pond, aerobic biochemical reaction is carried out to the waste water after anaerobic biochemical reaction, waste water is 10 hours in the biological contact oxidation pond residence time, and oxygenic aeration, by the effect of aerobic microbiological, the organism in waste water is thoroughly decomposed, (5) activated carbon filtration and membrane sepn: the liquid after step (4) being processed is through ultrafiltration membrane bioreactor, ultrafiltration membrane bioreactor water outlet removes colourity and organic pollutant further through activated carbon filtration again, and then be delivered to double-stage reverse osmosis system by high-pressure pump, the first step adopts nanofiltration membrane, the second stage adopts reverse osmosis membrane, the discharge of process standard water discharge.
The present embodiment biological contact oxidation pond is divided into four lattice, in first three lattice pond, elastic biological filler is installed, packed height is 2 meters, filler filament length is 200mm, in 4th lattice pond, submerged ultrafiltration bio-reactor is installed, submerged ultrafiltration bio-reactor adopts curtain ultra-filtration membrane, and membrane flux is 6 liters/square metre. hour.
The present embodiment Chinese effluent value: indices value when water inlet, the indices value of water outlet is after treatment in table 5:
Table 5
| COD（mg/L） | BOD5（mg/L） | SS（mg/L） | Colourity (doubly) | pH | |
| Water inlet | 340000 | 22000 | 9000 | 10000 | 1.0 |
| Water outlet | 86 | 10 | 11 | － | 7.1 |
| Emission standard | ≤100 | ≤30 | ≤70 | 50 | 6.0－9.0 |
embodiment 6
Vibramycin hydrochloride produce in ethanol mother liquor purify after the treatment process of waste liquid, comprise the following steps: (1) cools: waste liquid is carried out in equalizing tank water quality, water yield homogenizing stirring, make water temperature naturally cool to 42 DEG C by 90 DEG C, (2) flocculation sediments: by the waste liquid in step (1) by pump delivery to flocculation tank, in waste water, flocculant poly aluminum chloride is added by volume pump, dosage is 2800mg/L, add unslaked lime in supernatant liquor after flocculation sediment mud-water separation again to neutralize, unslaked lime dosage is 8g/L, unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, the pH value of waste water is made to be adjusted to 6.8 by 0.5, the salts substances dissolved in waste water is separated out, the preliminary suspended substance removed in waste liquid, (3) secondary flocculation sediment: the waste liquid after step (2) being neutralized carries out press filtration solid-liquid separation by pump delivery to plate-and-frame filter press again, gained solid matter can be used for brick producing material, leach liquid flow automatically again enter second time flocculation sediment, flocculant poly aluminum chloride is again added in filtrate, dosage is 500mg/L, through flocculation sediment again and by mud-water separation, remove the suspended substance in waste liquid further, (4) ozone oxidation, anaerobic and aerobic biochemical treatment: second time flocculation sedimentation tank water outlet gravity flow in step (3) is entered ozone oxidation pond, ozone is produced by ozonizer, be diffused in waste water by microporous aeration device again, the dosage of ozone is 100g/h, the ozone contact reaction time is 1.5 hours, waste water after ozone oxidation again by pump delivery to anaerobic digester, anaerobic pond adopts complete mixing pit type, by the effect of anaerobion, larger molecular organics in waste water is degraded, the residence time is 6 hours, anaerobic digester water outlet gravity flow enters biological contact oxidation pond, aerobic biochemical reaction is carried out to the waste water after anaerobic biochemical reaction, waste water is 10 hours in the biological contact oxidation pond residence time, and oxygenic aeration, by the effect of aerobic microbiological, the organism in waste water is thoroughly decomposed, (5) activated carbon filtration and membrane sepn: the liquid after step (4) being processed is through ultrafiltration membrane bioreactor, ultrafiltration membrane bioreactor water outlet removes colourity and organic pollutant further through activated carbon filtration again, and then be delivered to double-stage reverse osmosis system by high-pressure pump, the first step adopts nanofiltration membrane, the second stage adopts reverse osmosis membrane, the discharge of process standard water discharge.
The present embodiment biological contact oxidation pond is divided into four lattice, in first three lattice pond, elastic biological filler is installed, packed height is 2 meters, filler filament length is 200mm, in 4th lattice pond, submerged ultrafiltration bio-reactor is installed, submerged ultrafiltration bio-reactor adopts curtain ultra-filtration membrane, and membrane flux is 6 liters/square metre. hour.
The present embodiment Chinese effluent value: indices value when water inlet, the indices value of water outlet is after treatment in table 6:
Table 6
| COD（mg/L） | BOD5（mg/L） | SS（mg/L） | Colourity (doubly) | pH | |
| Water inlet | 340000 | 22000 | 9000 | 10000 | 1.0 |
| Water outlet | 72 | 11 | 4.5 | － | 6.5 |
| Emission standard | ≤100 | ≤30 | ≤70 | 50 | 6.0－9.0 |
Claims (10)
1. Vibramycin hydrochloride produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that comprising the following steps: (1) cools: waste liquid is carried out in equalizing tank stirring and be cooled to 40-45 DEG C; (2) flocculation sediments: add flocculation agent in cooled waste water, add alkali again and neutralize after flocculation sediment and mud-water separation; (3) secondary flocculation sediment: the liquid after step (2) is neutralized through pressure filter press filtration, filtrate flocculation sediment by mud-water separation again; (4) biochemical treatment: step (3) mud-water separation gained supernatant liquor is carried out biochemical reaction through ozone oxidation decolouring, anaerobic treatment, aerobic biochemical unit successively; (5) filtration and membrane sepn: the liquid after step (4) being processed is successively through membrane bioreactor, nanofiltration and reverse osmosis membrane processing.
2. Vibramycin hydrochloride according to claim 1 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: the flocculation agent added in described step (2) is polymerize aluminum chloride, dosage is 1000-3000mg/L.
3. Vibramycin hydrochloride according to claim 1 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: the alkali added in described step (2) is unslaked lime, unslaked lime dosage is 8g/L; Unslaked lime neutralizes with first time flocculation sediment gained supernatant liquor, makes the pH value of waste water be adjusted to 6.5-7.5.
4. Vibramycin hydrochloride according to claim 1 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: the flocculation agent added during secondary flocculation sediment in described step (3) is polymerize aluminum chloride, and dosage is 500-1000mg/L.
5. Vibramycin hydrochloride according to claim 1 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: in described step (4), the dosage of ozone is 100-200g/h, and the ozone contact reaction time is 1.5-3 hour.
6. Vibramycin hydrochloride according to claim 1 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: adopt complete hybrid anaerobic digester to carry out anaerobic biochemical reaction to the waste water after ozone decolorization in described step (4), waste water is 6 hours in the anaerobic digester residence time.
7. Vibramycin hydrochloride according to claim 1 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: adopt biological contact oxidation pond to carry out aerobic biochemical reaction to the waste water after anaerobic biochemical reaction in described step (4), waste water is 10 hours in the biological contact oxidation pond residence time.
8. Vibramycin hydrochloride according to claim 7 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: adopt elastic biological filler in described biological contact oxidation pond, described packed height is 2 meters, and filler filament length is 200mm.
9. Vibramycin hydrochloride according to claim 8 produce in ethanol mother liquor purify after the treatment process of waste liquid, it is characterized in that: described biological contact oxidation pond is divided into four lattice, in first three lattice pond, elastic biological filler is installed, in the 4th lattice pond, Nets impregnated is installed; Described Nets impregnated adopts curtain ultra-filtration membrane, membrane flux be 4-7 liter/square metre. hour.
10. in producing according to the arbitrary described Vibramycin hydrochloride of claim 1-9, the treatment process of the rear waste liquid of ethanol mother liquor purification, is characterized in that: adopt double-stage reverse osmosis technique to filter and membrane sepn the waste water after biochemical treatment in described step (5); The described membrane sepn first step adopts nanofiltration membrane, and the second stage adopts reverse osmosis membrane.
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