CN108203209A - The processing method of acid-bearing wastewater a kind of generated in acidification oil production process - Google Patents

The processing method of acid-bearing wastewater a kind of generated in acidification oil production process Download PDF

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Publication number
CN108203209A
CN108203209A CN201810137724.9A CN201810137724A CN108203209A CN 108203209 A CN108203209 A CN 108203209A CN 201810137724 A CN201810137724 A CN 201810137724A CN 108203209 A CN108203209 A CN 108203209A
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acid
processing method
waste water
oil
present
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CN108203209B (en
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程娟
张宝玉
马献力
陈刘杨
高峰
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TIELING JINDUO TECHNOLOGY Co Ltd
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TIELING JINDUO TECHNOLOGY Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • C02F1/04Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56Macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/101Sulfur compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/105Phosphorus compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Removal Of Specific Substances (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)

Abstract

The present invention provides a kind of processing methods of acid-bearing wastewater for being acidified and being generated in oil production process, belong to technical field of sewage, and the waste water for producing acidification oil generation is imported oil separator separation oil-yielding stratum and obtains the waste water after oil removal by the present invention;The pH value of waste water carries out neutralizing the waste water after flocculation treatment obtains neutralization flocculation treatment to 8~10 after adjusting oil removal with calcium oxide suspension;Waste water concentrating after neutralization flocculation treatment is evaporated to obtain distillate;Distillate progress Aerobic Process for Treatment must be reached to the liquid of discharge standard.The present invention makes to be substantially reduced into the organic matter in the waste water of forced-circulation evaporator and salt, so the concentrate after concentration significantly reduces when more untreated due to employing before the evaporation in calcium oxide suspension and flocculation treatment process.

Description

The processing method of acid-bearing wastewater a kind of generated in acidification oil production process
Technical field
The present invention relates to technical field of sewage, more particularly to a kind of to produce the waste water generated in acidification oil production process Processing method.
Background technology
Acidification oil refer to the byproduct soap stock produced to oil refining plant carry out acidification obtained oil.Acid Carburetion is substantially aliphatic acid, wherein containing pigment and unacidified triglycerides, diglyceride, monoglyceride (neutral oil) etc. Multiple components.
The acid-bearing wastewater generated in acidification oil production process has with high salt, peracid, high COD (chemical oxygen consumption (COC)), high color and luster " four is high " feature, therefore currently without ripe treatment process, most enterprise can not be handled, only small part enterprise It attempts the method for MVR concentration and evaporations and the method for culture Facultative Halophiles is handled on a small quantity.The technique of wherein MVR concentration and evaporations is deposited Main problem it is more for concentrate, and concentrate liquid belongs to saturated salt solution, and is carnallite, very difficult.
Invention content
In view of this, present invention aims at provide a kind of effective place of acid-bearing wastewater for being acidified and being generated in oil production process Reason method, the present invention employs before the evaporation in calcium oxide suspension and flocculation treatment process, makes the concentrate after concentration more not It is significantly reduced during processing, can continue back to and neutralize flocculation step and gather and handled
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
The present invention provides a kind of processing method of acid-bearing wastewater for being acidified and being generated in oil production process, including following step Suddenly:
1) the acid-bearing wastewater importing oil separator separation oil reservoir generated in oil production process will be acidified, obtained useless after oil removal Water;
2) pH value of waste water to 8~10, is neutralized after the oil removal obtained with the calcium oxide suspension adjusting step 1) It flocculates, separating liquid is obtained after separation of solid and liquid;
3) separating liquid for obtaining the step 2) is concentrated by evaporation, and obtains distillate;
4) distillate for obtaining the step 3) carries out Aerobic Process for Treatment;
The acid-bearing wastewater include dialycerides, triglycerides, aliphatic acid, sodium soap, phosphatide, glycerine, protein, Sterol and pigment, sodium sulphate, sulfuric acid, phosphoric acid, sodium phosphate and water;
Total sulfate radical content is 40000~60000mg/L in the acid-bearing wastewater, and total phosphorus content is 5000~8000mg/ L, chemical oxygen consumption (COC) are 40000~80000mg/L.
Preferably, it is 20~35 DEG C that flocculated temperature is neutralized in the step 2).
Preferably, it is 0.5~3h that the flocculated time is neutralized in the step 2).
Preferably, the mass concentration of calcium oxide suspension is 10~20% in the step 2).
Preferably, it is neutralized in flocculation in the step 2) and further includes addition flocculant.
Preferably, the flocculant is aluminium polychloride and cationic polyacrylamide.
Preferably, the aluminium polychloride dosage is 0.05~0.5% of the wastewater quality after oil removal, and the cation is poly- The dosage of acrylamide is 0.001~0.006% of the wastewater quality after oil removal.
Preferably, the temperature being concentrated by evaporation in the step 3) is 70~80 DEG C;The vacuum degree of evaporation and concentration for 20~ 30kPa。
Preferably, it is concentrated by evaporation in the step 3) and also obtains concentrate, pH value >=10 of the concentrate.
Preferably, the time of Aerobic Process for Treatment is 2~4 days in the step 4)..
Advantageous effects:The present invention provides a kind of processing sides of acid-bearing wastewater for being acidified and being generated in oil production process Method due to employing before the evaporation in calcium oxide suspension and flocculation treatment process, makes separating liquid after neutralization flocculation, separation of solid and liquid In organic matter and salt be substantially reduced, so concentration after concentrate it is more untreated when significantly reduce, be easy to post-process.
Description of the drawings
Fig. 1 is the flow chart of acid-bearing wastewater processing method generated in acidification oil production process in the embodiment of the present invention.
Specific embodiment
The present invention provides a kind of processing method of acid-bearing wastewater for being acidified and being generated in oil production process, including following step Suddenly:
1) the acid-bearing wastewater importing oil separator separation oil reservoir generated in oil production process will be acidified, obtained useless after oil removal Water;
2) pH value of waste water to 8~10, is neutralized after the oil removal obtained with the calcium oxide suspension adjusting step 1) It flocculates, separating liquid is obtained after separation of solid and liquid;
3) separating liquid for obtaining the step 2) is concentrated by evaporation, and obtains distillate;
4) distillate for obtaining the step 3) carries out Aerobic Process for Treatment;
The acid-bearing wastewater include dialycerides, triglycerides, aliphatic acid, sodium soap, phosphatide, glycerine, protein, Sterol and pigment, sodium sulphate, sulfuric acid, phosphoric acid, sodium phosphate and water;
Total sulfate radical content is 40000~60000mg/L in the acid-bearing wastewater, and total phosphorus content is 5000~8000mg/ L, chemical oxygen consumption (COC) are 40000~80000mg/L.
The present invention will be acidified the acid-bearing wastewater importing oil separator separation oil reservoir generated in oil production process, after obtaining oil removal Waste water;The present invention is not particularly limited the source of the acid-bearing wastewater, selects acidification oil production technology familiar in the field of competence The acid-bearing wastewater of generation.In the present invention, the acid-bearing wastewater includes dialycerides, triglycerides, aliphatic acid, fat Sour sodium, phosphatide, glycerine, protein, sterol and pigment, sodium sulphate, sulfuric acid, phosphoric acid, sodium phosphate and water;In the acid-bearing wastewater Total sulfate radical content is 40000~60000mg/L, and total phosphorus content is 5000~8000mg/L, chemical oxygen consumption (COC) for 40000~ 80000mg/L。
In the present invention, scraper plate is preferably provided in the oil separator, after being detached to the oil reservoir on acid-bearing wastewater upper strata Waste water to after lower floor's oil removal.
In the present invention, the upper strata oil reservoir includes diglyceride, triglycerides and aliphatic acid.
After obtaining the waste water after oil removal, the pH value of waste water is to 8 after the oil removal that the present invention is adjusted with calcium oxide suspension ~10, neutralization flocculation is carried out, separating liquid is obtained after separation of solid and liquid.
The pH value of waste water carries out neutralization flocculation, obtains to 8~10 after the oil removal that the present invention is adjusted with calcium oxide suspension To the waste water neutralized after flocculating.
In the present invention, the mass concentration of the calcium oxide suspension is preferably 10~20%, and more preferably 12~15%. In the present invention, the dosage of the calcium oxide suspension can be such that the pH value of waste water after oil removal adjusts to 8~10.In this hair In bright, calcium oxide and water reaction generation calcium hydroxide are reconciled the acid-base value of waste water using hydroxyl in calcium hydroxide, utilized simultaneously Calcium ion and sulfate radical, phosphate radical combine and effectively remove salts substances therein, and utilize the flocculation of calcium hydroxide itself, Will generation precipitation and larger molecular organics therein flocculate, the larger molecular organics include dialycerides, triglycerides, Protein and phosphatide.
In the present invention, the flocculated temperature of neutralization is preferably 20~35 DEG C, more preferably 25~30 DEG C;The neutralization The flocculated time is preferably 0.5~3h, more preferably 1~2h.
In the present invention, if flocculating effect is poor after adding in calcium oxide suspension, there is the unseparated situation of grease, it is also excellent Flocculant is added as the flocculated supplement of calcium hydroxide and auxiliary after being selected in neutralization flocculation.
In the present invention, the flocculant is preferably aluminium polychloride and cationic polyacrylamide.
In the present invention, the aluminium polychloride dosage is preferably 0.05~0.5% of the wastewater quality after oil removal, more excellent It is selected as 0.1~0.4%;The dosage of the cationic polyacrylamide be preferably the wastewater quality after oil removal 0.001~ 0.006%, more preferably 0.002~0.004%.
It obtains after neutralizing the waste water after flocculating, the present invention will neutralize the waste water solid after flocculating and detach, and obtain separating liquid.
In the present invention, the separation of solid and liquid preferably carries out separation of solid and liquid using filter-pressing device, and the filter cake after press filtration is through rubbish It is filled after rubbish treatment plant professional treatment.The present invention is not particularly limited filter-pressing device, selects those skilled in the art ripe The filter-pressing device known, such as filter press.In the present invention, the pressure of the filter press is preferably 2.8MPa, and time of filter pressing is excellent It is selected as 3 hours.
After obtaining separating liquid, the separating liquid concentration and evaporation of the invention that will be obtained obtains distillate and concentrate.
In the present invention, the equipment of the concentration and evaporation is preferably concentration evaporator.
In the present invention, the temperature of the concentration and evaporation is preferably 70~80 DEG C, more preferably 72~75 DEG C;The concentration The vacuum degree of evaporation is preferably 20~30kPa, more preferably 25kPa.
In the present invention, the chemical oxygen consumption (COC) of the distillate is preferably 700~770mg/L, more preferably 720~ 7500mg/L。
In the present invention, when the pH value of the concentrate after the concentration and evaporation >=10, the concentrate is saturated solution, Stop concentration and evaporation, obtained concentrate is subjected to separation of solid and liquid successively, obtains crystal salt and liquid.
In the present invention, the device of the concentration and evaporation is preferably concentration evaporator.
In the present invention, place's water of the concentration evaporator is preferably 6.5m3/ h, the pressure of the concentration evaporator follow Ring pump electric current is preferably 133~135A, and the days running of the concentration evaporator is preferably 45 days.
The present invention is not particularly limited the method for separation of solid and liquid, and the method for selecting the centrifugation of this field routine is It can.
In the present invention, liquid of the concentrate after separation of solid and liquid may return to neutralize flocculation step in after oil removal Waste water carry out neutralization flocculation reaction.
In the present invention, the concentration and evaporation is preferably carried out in concentration evaporator.
After obtaining distillate, obtained distillate is carried out Aerobic Process for Treatment by the present invention, reaches discharge standard.
In the present invention, the time of the Aerobic Process for Treatment is preferably 2~4 days, more preferably 3 days.
Aerobic Process for Treatment is carried out in the present invention, it is preferred to which obtained distillate is imported in biochemistry pool.The present invention is to biochemistry pool It is not particularly limited with the method for Aerobic Process for Treatment, selects biochemistry pool well known to those skilled in the art and Aerobic treatment method i.e. It can.
In the present invention, it is described reach discharge standard waste water be preferably:Total sulfate radical content is 12~20mg/L, total phosphorus Content is 0.1~0.3mg/L, and chemical oxygen consumption (COC) is 20~30mg/L, more preferably 15~18mg/L, total phosphorus content for 0.1~ 0.2mg/L, chemical oxygen consumption (COC) are 22~25mg/L.
With reference to embodiment the processing method of acid-bearing wastewater generated in oil production process is acidified to provided by the invention It is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The acid-bearing wastewater that generates in oil production process will be acidified and carry out the waste water after oil removal handles to obtain oil removal;After oil removal The temperature of waste water is adjusted to 26 DEG C, for 10% calcium oxide suspension neutralize 1 hour by mass concentration, adjusts dirty after neutralizing Water pH is 9, and using plate and frame filter press press filtration, concentrating filter liquor evaporator after press filtration is run 45 days, and processing water is 6.5m3/ (treating capacity that not carrying out pre-treatment is is 6m to h3/ h), forced circulation pump electric current is maintained at 133~135A, distillate after evaporation COD is 700~770mg/L.Distillate after concentration and evaporation enters aerobic tank and carries out Aerobic Process for Treatment, reaches row after two days after testing Standard is put, COD is 25~30mg/L, and total phosphorus (TP) is 0.3mg/L, SO4-For 12~20mg/L, color and luster is fully transparent, meets mark It is accurate;The discharge capacity of concentrate is reduced to 3-4t/ days, by not carrying out 13-15t/ days of pre-treatment into biochemistry pool and other sewage Processing is carried out at the same time, index is same as above after processing.
Embodiment 2
The acid-bearing wastewater that generates in oil production process will be acidified and carry out the waste water after oil removal handles to obtain oil removal;After oil removal The temperature of waste water is adjusted to 30 DEG C, and it is 8.5 to adjust pH by 10% calcium oxide suspension, stirs half an hour, adds in 10% polymerization Liquor alumini chloridi, additive amount are the 5% of sewage, half an hour are mixed slowly, through plate and frame filter press press filtration, concentrating filter liquor evaporator Processing is evaporated, the COD of distillate is 700~750mg/L after evaporation, is run 50 days, it is 6.5m to handle water per hour3, Forced circulation pump electric current is 132~133A.Distillate after concentration and evaporation enter aerobic tank carry out Aerobic Process for Treatment, two days after testing After reach discharge standard, COD is 25~30mg/L, and total phosphorus (TP) is 0.1~0.3mg/L, SO4-For 10~15mg/L, color and luster is complete All-transparent complies with standard, and the discharge capacity of concentrate is 2.5-3.5t/ days, and into biochemistry pool processing, final outflow water index is same as above.
Embodiment 3
The acid-bearing wastewater that generates in oil production process will be acidified and carry out the waste water after oil removal handles to obtain oil removal;After oil removal The temperature of waste water is adjusted to 22 DEG C, and it is 8.2~8.8 to adjust pH by 12% calcium oxide suspension, stirs half an hour, adds in quality A concentration of 5% polymeric aluminum chlorides solution, additive amount are the 5% of sewage quality, mix slowly half an hour, adding mass concentration is 2 ‰ PAM solution, additive amount are the 1% of sewage quality, continue to mix slowly 20min, through plate and frame filter press press filtration, filtrate warp Concentration evaporator is evaporated processing, and the COD of distillate is 680~750mg/L after evaporation, runs 50 days, handles water per hour It measures as 6.6m3, forced circulation pump electric current is 132~133A.Distillate after concentration and evaporation enters aerobic tank and carries out Aerobic Process for Treatment, Reach discharge standard, COD 20-25mg/L after two days after testing, total phosphorus (TP) is 0.1-0.2mg/L, SO4-For 10-15mg/L, Color and luster is fully transparent, complies with standard, and the discharge capacity of concentrate is 2.5-3.4t/ days, into biochemistry pool processing, final outflow water index Ibid.
The above of the invention is only the preferred embodiment of the present invention, it is noted that for the common of the art For technical staff, various improvements and modifications may be made without departing from the principle of the present invention, these are improved and profit Decorations also should be regarded as protection scope of the present invention.

Claims (10)

1. a kind of be acidified the processing method of acid-bearing wastewater generated in oil production process, include the following steps:
1) acid-bearing wastewater is imported into oil separator separation oil reservoir, obtains the waste water after oil removal;
2) pH value of waste water carries out neutralization flocculation to 8~10 after adjusting the oil removal that the step 1) obtains with calcium oxide suspension, Separating liquid is obtained after separation of solid and liquid;
3) separating liquid for obtaining the step 2) is concentrated by evaporation, and obtains distillate;
4) distillate for obtaining the step 3) carries out Aerobic Process for Treatment;
The acid-bearing wastewater includes dialycerides, triglycerides, aliphatic acid, sodium soap, phosphatide, glycerine, protein, sterol With pigment, sodium sulphate, sulfuric acid, phosphoric acid, sodium phosphate and water;
Total sulfate radical content is 40000~60000mg/L in the acid-bearing wastewater, and total phosphorus content is 5000~8000mg/L, is changed Oxygen demand is 40000~80000mg/L.
2. processing method according to claim 1, which is characterized in that neutralize in the step 2) flocculated temperature for 20~ 35℃。
3. processing method according to claim 1 or 2, which is characterized in that the neutralization flocculated time is in the step 2) 0.5~3h.
4. processing method according to claim 1, which is characterized in that the quality of calcium oxide suspension is dense in the step 2) Spend is 10~20%.
5. processing method according to claim 1, which is characterized in that flocculation is neutralized in the step 2) and further includes addition wadding Solidifying agent.
6. processing method according to claim 5, which is characterized in that the flocculant gathers for aluminium polychloride and cation Acrylamide.
7. processing method according to claim 6, which is characterized in that the aluminium polychloride dosage is the waste water after oil removal The 0.05~0.5% of quality, the dosage of the cationic polyacrylamide for the wastewater quality after oil removal 0.001~ 0.006%.
8. processing method according to claim 1, which is characterized in that the temperature being concentrated by evaporation in the step 3) for 70~ 80℃;The vacuum degree of evaporation and concentration is 20~30kPa.
9. processing method according to claim 1, which is characterized in that be concentrated by evaporation in the step 3) and also concentrated Liquid, pH value >=10 of the concentrate.
10. processing method according to claim 1, which is characterized in that in the step 4) time of Aerobic Process for Treatment for 2~ 4 days.
CN201810137724.9A 2018-02-10 2018-02-10 Method for treating acid-containing wastewater generated in production process of acidified oil Active CN108203209B (en)

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CN114477611A (en) * 2021-09-29 2022-05-13 福州市聚泰环境科技有限公司 Method for preparing biological organic nutrient solution and cement grinding aid base material by using acidified oil production wastewater

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CN109942150A (en) * 2019-03-22 2019-06-28 南京大学盐城环保技术与工程研究院 A kind of waste vegetable oil utilizes the processing method of production waste water
CN109942150B (en) * 2019-03-22 2021-11-19 南京大学盐城环保技术与工程研究院 Treatment method of waste water produced by utilizing waste vegetable oil
CN114477611A (en) * 2021-09-29 2022-05-13 福州市聚泰环境科技有限公司 Method for preparing biological organic nutrient solution and cement grinding aid base material by using acidified oil production wastewater
CN114394693A (en) * 2022-01-22 2022-04-26 安徽科技学院 Clarification treatment method for industrial oily wastewater

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