CN106746184A - A kind of method for processing epoxychloropropane waste water - Google Patents
A kind of method for processing epoxychloropropane waste water Download PDFInfo
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- CN106746184A CN106746184A CN201611093059.5A CN201611093059A CN106746184A CN 106746184 A CN106746184 A CN 106746184A CN 201611093059 A CN201611093059 A CN 201611093059A CN 106746184 A CN106746184 A CN 106746184A
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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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- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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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
- C02F1/72—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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- 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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- C—CHEMISTRY; METALLURGY
- 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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- 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
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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
- C02F3/284—Anaerobic digestion processes using anaerobic baffled reactors
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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
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
Abstract
The invention discloses a kind of method for processing epoxychloropropane waste water, using ABR anaerobism/BAC it is aerobic/MBR aerobic degradation organic pollutions, MBR water outlets are combined treatment residual organic substances using oxidant deep oxidation and charcoal absorption, deep oxidation water outlet is using electrodialysis concentration, electrodialysis dope is concentrated by evaporation using MVR, MVR condensate liquids do dilution water, and MVR concentrates reach ion film caustic soda reuse;The light liquid of electrodialysis uses reverse osmosis desalination, the light liquid of counter-infiltration to do dilution Water circulation, and counter-infiltration dope returns deep oxidization technique;The clear water of whole technique output of the invention is entirely used for dilution water, inorganic salts complete-reclaiming in epoxychloropropane waste water is in film caustic soda process, reach water, the purpose of the recycling of salt, whole set process is effective, flexible and convenient operation, the recycling of water, salt is reached for epoxychloropropane waste water energy, without outer row, will not be had a negative impact to environment.
Description
Technical field
The invention belongs to sewage water treatment method field, specifically a kind of method for processing epoxychloropropane waste water.
Background technology
Epoxychloropropane is a kind of important Organic Chemicals and fine chemical product, and current industrialized preparing process has
Four kinds:Propylene high-temperature chloridising, acetate propylene ester process, acryladehyde method and glycerin chlorination method.
Wherein, glycerin chlorination method in using the glycerine of renewable resource for raw material, its production process due to by no longer making
With chlorine and sodium hypochlorite, mitigate the pollution to environment, reaction condition is gentle, 1,3- dichlorohydrin high incomes the advantages of increasingly
It is taken seriously.Glycerin chlorination method main process route is reaction generation dichlorohydrin in the presence of glycerine, hydrogen chloride, catalyst;
Dichlorohydrin cyclization saponification in alkaline solution obtains epoxychloropropane product.Alkaline solution is usually calcium hydroxide or hydroxide
Sodium.Therefore, the technique waste water index for being produced under the production technology is as follows, COD20000 ~ 40000mg/L, TDS:250000~
300000mg/L, pH:8~10;The waste water of such high target cannot be excluded directly, it is necessary to such industrial wastewater
Posterior circle is discharged or processed after being processed to use.
Traditional epoxychloropropane waste water is using concentration, evaporation desalination, the group technology of evaporation condensate biochemical treatment.This
The shortcoming of technique is that the salt that is costly, being concentrated by evaporation for concentrating-evaporating belongs to dangerous solid waste, separately needs extra process.
Have in disclosed technology using ammonium hydrogen carbonate and calcium chloride reaction, generation calcium bicarbonate in waste water, heat resolve is produced
Raw precipitation of calcium carbonate and water, carbon dioxide, reclaim the calcium carbonate of high-purity.But the method is only applicable to cyclization saponification, and section is used
The production technology of aqua calcis, and the first step reaction generation ammonium chloride stay in water body, by reverse osmosis concentration reclaim
Ammonium chloride in contain organic matter.Therefore the water for being obtained by the processing method still can influence recycled.
In the method that the salt and recycling of water resource in epoxychloropropane waste water are utilized in the prior art, exist processing cost it is high,
Handling process it is cumbersome and exist the waste water after potential safety hazard or treatment cannot the effectively deficiency such as recycling, because
This, a kind of easy to operate, safety coefficient of design is high and processing cost is low, while enabling to processed waste water to be utilized effectively
Method be always those skilled in the art's technical barrier to be solved.
The content of the invention
The present invention is directed to problems of the prior art, it is proposed that a kind of method for the treatment of epoxychloropropane waste water, leads to
The clear water for crossing the method output is entirely used for dilution water, and the inorganic salts complete-reclaiming in epoxychloropropane waste water is in ion film caustic soda
Technique, reaches water, the purpose of the recycling of salt, does not have a negative impact to environment.
The present invention is achieved in that a kind of method for processing epoxychloropropane waste water, comprises the following steps that:
1)Add in dilution water to epoxychloropropane waste water, control water inlet salinity is less than 5wt%, and regulation pH is to 7 ~ 9;
2)25~35 DEG C of water temperature of control, and to salt tolerant compound bacteria is added in water body, carry out anaerobic biochemical reaction 24 ~ 48 hours;
3)Water body is passed through aerobic reaction tank, pH to 7 ~ 9 is adjusted, 25~35 DEG C of water temperature is controlled, salt tolerant compound bacteria is added, is exposed
Gas one-level aerobic reaction 24 ~ 48 hours, it is 2 ~ 4mg/L to control the dissolved oxygen in Aerobic Pond;Initial breakdown organic pollution;
4)Water body is continued to be passed through MBR aerobic reaction tanks, pH to 7 ~ 9 is adjusted, 25~35 DEG C of water temperature is controlled, adds salt tolerant to be combined
Bacterium, carries out two grades of aerobic reactions 24 ~ 48 hours, and it is 2 ~ 4mg/L to control the dissolved oxygen in Aerobic Pond;Further degrade organic contamination
Thing;
5)By membrane filtration in MBR Aerobic Ponds, clear liquid is collected;Further degradable organic pollutant;
By using ABR anaerobism/BAC it is aerobic/MBR aerobic three biochemical treatment steps, it is most in biochemical degradation waste water
COD;
6)Clear liquid is passed through deep oxidation-activated carbon adsorption tank, is aoxidized using cleaning oxidizer, chemical oxidation residual organic substances;
Treatment residual organic substances are combined using oxidant deep oxidation and charcoal absorption, play a part of further to clean waste water, cut down
Remaining refractory organic in waste water;
7)By step(6)Water is passed through electrodialysis after treatment(ED);The light liquid of electrodialysis and electrodialysis dope are obtained after electrodialysis;Instead
Permeate light liquid and can be used as dilution supplement water or process water;
8)By step(7)Electrodialysis dope is passed through MVR evaporation and concentration;The light liquid of electrodialysis is passed through counter-infiltration(RO);MVR condensate liquids
Biochemical dilution water is done in collection, and MVR concentrates are collected and do ion film caustic soda raw material;The light liquid of counter-infiltration is collected and does biochemical dilution water or life
Production. art water, counter-infiltration dope returns biochemical system treatment;Whole waste water is by that after the treatment of above-mentioned steps, can cause waste water
Maximum resource utilize.
Further, employed in described MBR techniques be hollow-fibre membrane, Flat Membrane MBR devices.
Further, described step(6)In oxidant include ozone, hydrogen peroxide.
Further, described step(6)In activated carbon be cylindrical particle, particle size is 20mm-30mm.
Further, described step(7)Evaporating and concentrating process is not limited to MVR, can also be multi-effect evaporator.
Further, described step(7)Electrodialysis dope can also be without being concentrated by evaporation by MVR, directly use;Gained is dense
Liquid can do ion film caustic soda raw material and use with additional industrial grade sodium chloride configuration saturated brine.
Further, the acid reagent is hydrochloric acid or sulfuric acid, and alkaline reagent is NaOH.
The present invention is relative to beneficial effect of the prior art:
(1)The biochemical system that the present invention is used is the aerobic-MBR aerobic combinations systems of ABR anaerobism-BAC, is joined by salt tolerant compound bacteria
The COD in removal waste water is closed, amount of dilution is reduced;
(2)Two grades of aerobic use MBR techniques in the present invention, reduce precipitation pool process and the maximum amount of retention microorganism and are easy to match somebody with somebody
Set subsequent concentration technique;
(3)The present invention is using deep oxidation-active carbon absorption technology in biochemical end, and it is difficult or not biodegradable in waste water to be directed to
Organic matter carry out the removal of physico-chemical process;
(4)It is, using electrodialytic principle, to make in the effect of electric field using electrodialysis as first concentration technology in the present invention
Inorganic zwitterion reaches concentrated water area by amberplex, and concentrated water area is practically free of organic thing.Its concentrated water area concentration can reach
More than 15wt%;
(5)Except first time water distribution dilutes in the present invention, using extra washing water lower clearly.Remaining is steamed using the light liquid of RO and MVR
Lime set of feeling cold dilutes;
(6)Whole set process is effective, flexible and convenient operation, and the resource profit of water, salt is reached for epoxychloropropane waste water energy
With without outer row.
Brief description of the drawings
Fig. 1 is a kind of process chart of the method for processing epoxychloropropane waste water of the present invention.
Specific implementation portion mode
The present invention provides a kind of method for processing epoxychloropropane waste water, to make the purpose of the present invention, technical scheme and effect more
Plus it is clear, clearly, and referring to the drawings and give an actual example that the present invention is described in more detail.It should be understood that tool described herein
Body is implemented only to be used to explain the present invention, is not intended to limit the present invention.
Wherein, anaerobic biological of the invention and salt-durable microbe bacterium used by aerobic biochemical, can be by being similar to Chinese patent
CN101477105 methods describeds, screen in high-salt wastewater, tame acquisition salt tolerant bacteria strain, it is also possible to obtained by buying.It is existing
Have Facultative Halophiles including but not limited to this, can also be:Gluconobacter oxydans (Gluconobacter oxydans), acidified milk bar
Bacterium (Lactobacillus fermentum), Lactobacillus brevis (Lactobacillus brevis), micrococcus luteus
(Micrococcus leutus), halo micrococcus luteus(Also referred to as Micrococcus halobius, Micrococcus halobius), to produce alkali false single
Born of the same parents bacterium (Pseudomonas alcaligenes), the golden pseudomonad (Pseudomonas aureofaciens) of cause, greenery are false single
Born of the same parents bacterium (Pseudomonas chlororaphis), nitrate reductase pseudomonad (Pseudomonas nitroreducens), core
Flavine pseudomonad (Pseudomonas riboflavina), pseudomonas putida (Pseudomonas putida) and agility
Pseudomonad (Pseudomonas facilis).
Embodiment 1
As shown in the process chart of Fig. 1, epoxychloropropane waste water is pumped into biochemical distribution reservoir first, 4-6 times is added for the first time
It is 5 wt% that clear water is diluted to waste water salt content, and second and subsequent dilution water produce water and MVR condensations using RO in this technique
Liquid, hydrogenation sodium hydroxide solution adjusts PH to 7 ~ 9;Control 25~35 DEG C of water temperature and to salt tolerant compound bacteria is added in water body, carry out anaerobism
Biochemical reaction 36 hours, the structure of the useless Organic substance in water of destruction, partial organic substances of degrading;Water body is continued to be passed through reaction tank, is adjusted
Section pH to 7 ~ 9,25~35 DEG C of addition salt tolerant compound bacterias of control water temperature, carries out one-level aerobic reaction 36 hours, in control Aerobic Pond
Dissolved oxygen be 2 ~ 4mg/L;Aerobic biochemical reacts 24 hours, the organic matter in biodegradable waste water;Water body is continued to be passed through instead
Ying Chi, adjusts pH to 7 ~ 9, control 25 DEG C of water temperature addition salt tolerant compound bacterias, carries out two grades of aerobic reactions 24 hours, controls Aerobic Pond
Interior dissolved oxygen is 2 ~ 4mg/L;Biochemical tail end wastewater and mud mixed liquid realize mud-water separation by MBR, and clear liquid is collected, sludge
Backflow biochemical reaction tank.Clear liquid is passed through deep oxidation-activated carbon adsorption tank, and Plus acidic reagent hydrochloric acid or sulfuric acid adjust pH to 5, institute
Add in waste water concentration for 1 ~ 2% hydrogen peroxide or hydrogen peroxide, during mixed water body then pumped into deep oxidation pond, waste water
With hydrogen peroxide by contacting mixing with fixed activated carbon, there is catalysis oxidation, the reaction time is 2h;Deep oxidation water outlet is received
Collection.
Above-mentioned deep oxidation water outlet is passed through into electrodialysis plant to be concentrated, the wt% of gained concentrated water saliferous 15, light liquid saliferous
0.2 wt%.Light liquid is passed through RO again(Counter-infiltration)Peace and quiet water is obtained(Light liquid), do dilution water use.RO concentrated waters return electrodialysis process;This
While RO techniques are not limited to, also can UF-RO group technologies.
MVR condensate liquids are collected and do biochemical dilution water;Above-mentioned electrodialysis concentrated water is passed through into MVR to be further concentrated by evaporation to saliferous
Amount 28wt%, does ion film caustic soda raw material use;Here evaporating and concentrating process is not limited to MVR, can also be multi-effect evaporator.
Embodiment 2
The present embodiment except electrodialysis concentration after dope without be passed through MVR be concentrated by evaporation, but directly electrodialysis is concentrated after
Dope gained dope can do ion film caustic soda raw material use, other steps and implementation with additional industrial grade sodium chloride configuration saturated brine
Example 1 is identical.
Claims (7)
1. it is a kind of process epoxychloropropane waste water method, it is characterised in that comprise the following steps that:
1)Add in dilution water to epoxychloropropane waste water, control water inlet salinity is less than 5wt%, adjusts pH to 7 ~ 9;
2)25~35 DEG C of water temperature of control, and to salt tolerant compound bacteria is added in water body, carry out anaerobic biochemical reaction 24 ~ 48 hours;
3)Water body is passed through aerobic reaction tank, pH to 7 ~ 9 is adjusted, 25~35 DEG C of water temperature is controlled, salt tolerant compound bacteria is added, one is carried out
Level aerobic reaction 24 ~ 48 hours, it is 2 ~ 4mg/L to control the dissolved oxygen in Aerobic Pond;
4)Water body is continued to be passed through MBR aerobic reaction tanks, pH to 7 ~ 9 is adjusted, 25~35 DEG C of water temperature is controlled, adds salt tolerant to be combined
Bacterium, carries out two grades of aerobic reactions 24 ~ 48 hours, and it is 2 ~ 4mg/L to control the dissolved oxygen in Aerobic Pond;
5)By membrane filtration in MBR Aerobic Ponds, clear liquid is collected;
6)Clear liquid is passed through deep oxidation-activated carbon adsorption tank, is aoxidized using cleaning oxidizer, chemical oxidation residual organic substances;
7)By step(6)Water is passed through electrodialysis after treatment;The light liquid of electrodialysis and electrodialysis dope are obtained after electrodialysis;
8)By step(7)Electrodialysis dope is passed through MVR evaporation and concentration;The light liquid of electrodialysis is passed through counter-infiltration;
9)By step(8)Middle MVR is concentrated by evaporation and obtains concentrate and condensate liquid;The light liquid of counter-infiltration and anti-is obtained after counter-infiltration
Infiltration dope.
2. it is according to claim 1 it is a kind of process epoxychloropropane waste water method, it is characterised in that described MBR works
Employed in skill be hollow-fibre membrane, Flat Membrane MBR devices.
3. it is according to claim 1 it is a kind of process epoxychloropropane waste water method, it is characterised in that described step
(6)In oxidant include ozone, hydrogen peroxide.
4. it is according to claim 1 it is a kind of process epoxychloropropane waste water method, it is characterised in that described step
(6)In activated carbon be cylindrical particle, particle size is 20mm-30mm.
5. it is according to claim 1 it is a kind of process epoxychloropropane waste water method, it is characterised in that described step
(7)Evaporating and concentrating process is not limited to MVR, can also be multi-effect evaporator.
6. it is according to claim 1 it is a kind of process epoxychloropropane waste water method, it is characterised in that described step
(7)Electrodialysis dope can also be without being concentrated by evaporation by MVR, directly use.
7. it is according to claim 1 treatment epoxychloropropane waste water method, it is characterised in that what the regulation PH was used
Acid reagent is hydrochloric acid or sulfuric acid, and alkaline reagent is NaOH.
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CN108609804A (en) * | 2018-05-04 | 2018-10-02 | 山东默锐环境产业股份有限公司 | A kind of BDP wastewater treatment methods |
CN109912118A (en) * | 2018-12-31 | 2019-06-21 | 浙江蓝湖环保有限公司 | Waste water reclaiming Zero discharging system and method are spun in a kind of color separation with high salt |
CN111253007A (en) * | 2020-02-24 | 2020-06-09 | 江苏扬农化工集团有限公司 | Method for treating epichlorohydrin wastewater |
CN113321339A (en) * | 2021-05-06 | 2021-08-31 | 江南大学 | Method for producing fuel ethanol by recycling evaporated condensed water and reusing evaporated condensed water |
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CN108609804B (en) * | 2018-05-04 | 2021-12-03 | 山东默锐环境产业股份有限公司 | BDP wastewater treatment method |
CN109912118A (en) * | 2018-12-31 | 2019-06-21 | 浙江蓝湖环保有限公司 | Waste water reclaiming Zero discharging system and method are spun in a kind of color separation with high salt |
CN111253007A (en) * | 2020-02-24 | 2020-06-09 | 江苏扬农化工集团有限公司 | Method for treating epichlorohydrin wastewater |
CN113321339A (en) * | 2021-05-06 | 2021-08-31 | 江南大学 | Method for producing fuel ethanol by recycling evaporated condensed water and reusing evaporated condensed water |
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Application publication date: 20170531 |