CN107082526A - A kind of preprocess method of waste emulsified mixture - Google Patents

A kind of preprocess method of waste emulsified mixture Download PDF

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Publication number
CN107082526A
CN107082526A CN201710205207.6A CN201710205207A CN107082526A CN 107082526 A CN107082526 A CN 107082526A CN 201710205207 A CN201710205207 A CN 201710205207A CN 107082526 A CN107082526 A CN 107082526A
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solid
fenton
separation
emulsified mixture
water
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CN201710205207.6A
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CN107082526B (en
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孙黎
马瑶
徐跃武
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ANHUI HUIZETONG ENVIRONMENTAL TECHNOLOGY Co Ltd
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ANHUI HUIZETONG ENVIRONMENTAL TECHNOLOGY Co Ltd
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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
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • 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
    • C02F1/52—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
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • 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
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent
    • 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

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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)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Activated Sludge Processes (AREA)

Abstract

The invention discloses a kind of method for being machined oily waste liquor pretreatment, machining oily waste liquor is passed through into grid first, bulky grain pollutant is removed；Then, tank is adjusted by homogeneous, realizes oil, water, sand three phase separation；The aqueous phase isolated is demulsified by two-stage and destroys stable opaque system, and carries out separation of solid and liquid；The supernatant that will be isolated after demulsification, adjusts pH value, carries out Fenton oxidation；After the completion of Fenton's reaction, regulation pH is precipitated, and water outlet enters biochemical system.The method of processing machining oily waste liquor disclosed in this invention, high COD machining oily waste water is set to be directly over simple two grades of demulsifications and Fenton oxidation process, COD contents are greatly reduced, turbidity is substantially reduced, B/C ratios are significantly improved, and are that biochemical treatment creates conditions, and method processing cost of the invention is very low, it is simple to operate, do not produce secondary pollution.

Description

A kind of preprocess method of waste emulsified mixture
Technical field
It is pre- to machining oily waste liquor using two grades of demulsifications and Fenton oxidation combined treatment process the present invention relates to one kind The method of processing, belongs to field of industrial waste water treatment.
Background technology
In the process of mechanical devices, the surface temperature of processing device rises quickly, therefore by several functions The cutting fluid that the materials such as auxiliary agent, mineral oil are formulated is used to cool down and lubricate cutter and workpiece.In process, Cutting fluid temperature rises always, and temperature typically can all reach 45~90 DEG C, now the material quilt such as unsaturated lipid in cutting fluid Oxidation Decomposition, biodegradable organic components increase, microorganism will largely increase under suitable environmental condition, so Just change the composition composition in cutting fluid so that cutting fluid function fails.Therefore, in mechanical processing process, cutting Liquid is typically required for more renewing liquid in use for some time, and the cutting fluid of failure needs outwardly to discharge, and thus also just produces Waste emulsified mixture.
In recent years, with the development of technology, usage amount of the cutting fluid in mechanical processing industry increases year by year, due to cutting Liquid easily occurs to go bad, and usage cycles are again relatively short, and discharge is often accomplished by use for some time, causes waste emulsified mixture Discharge capacity it is also increasing.
The composition such as oily substance, chemical addition agent containing many bio-refractories in waste emulsified mixture, if without processing Natural water is directly discharged into, after the oily substance content in water body is gathered to a certain degree, aqueous bio, ecological environment can be produced Raw serious influence.
Waste emulsified mixture is different from general oily waste water, wherein include various oily substances (oil slick, oil emulsion etc.), Also biodegradable additive (rust-inhibiting additive and EP agent), the soluble metal of part remaining are difficult to comprising various (Fe2+), therefore traditional biochemical processing method and single breaking method (acid-precipitation method, salting out method etc.) are difficult to obtain expected place Manage effect.
Therefore, a kind of high efficiency method for being suitable to processing waste emulsified mixture is urgently excavated.
The content of the invention
It is contemplated that avoiding the weak point present in prior art, propose a kind of using two grades of demulsifications and Fenton oxidation The method that combined treatment process is pre-processed to waste emulsified mixture, to waste emulsified mixture be made effectively to be administered, alleviates useless emulsification The problem of environmental pollution that liquid band is come.
The present invention solves technical problem, adopts the following technical scheme that：
A kind of method pre-processed using two grades of demulsifications and Fenton oxidation combined treatment process to waste emulsified mixture, first will be useless Emulsion passes through grid, removes bulky grain pollutant；Then, tank is adjusted by homogeneous, realizes oil, water, sand three phase separation；Separation The aqueous phase gone out is demulsified by two-stage and destroys stable opaque system, and carries out separation of solid and liquid；The supernatant that will be isolated after demulsification, PH value is adjusted, Fenton oxidation is carried out；After the completion of Fenton's reaction, regulation pH is precipitated, and water outlet enters biochemical system.
Specifically comprise the steps of：
(1) by waste emulsified mixture by grid, bulky grain pollutant is removed；
(2) waste emulsified mixture is then introduced into homogeneous regulation tank, oil, water, sand three phase separation is carried out to waste emulsified mixture；
(3) aqueous phase after separation is introduced into mixing regulating reservoir 1, adds CaCl2One-level demulsification is carried out with PFS；
(4) waste water after demulsification is introduced into equipment for separating liquid from solid and carries out separation of solid and liquid, separate the solid precipitation thing of generation Go out；
(5) supernatant liquor that separation of solid and liquid is obtained is re-introduced into mixing regulating reservoir 2, adds composite demulsifying agent and PAM enters Two grades of demulsifications of row；
(6) waste water after demulsification is introduced into equipment for separating liquid from solid and carries out separation of solid and liquid, separate the solid precipitation thing of generation Go out；
(7) supernatant for obtaining separation of solid and liquid introduces Fenton's reaction pond, is adjusted solution to pH to 2 using pH regulation tanks ~4 (preferably adjusting to pH to 3 or so), while adding Fenton reagent, 1~5 hour of mechanical agitation (is preferably from about 2 small When)；
(8) solution after Fenton's reaction is adjusted into pH to 8~10 (preferably adjusting pH to 9 or so), carries out flocculation sediment, Water outlet introduces biochemical system and carries out subsequent treatment.
CaCl described in step (3)2Dosage with PFS is respectively 1~2g/L and 1~2g/L, the shape of wiring solution-forming Formula is added.It is preferred that, described CaCl2Dosage with PFS is respectively 1.5g/L and 1.5g/L.
Composite demulsifying agent described in step (5) is 1 by mass ratio:2 PAC and PFS is mixed；The composite demulsification Agent and PAM dosage are respectively 1~3g/L and 40~60mg/L, and the form of wiring solution-forming is added.It is preferred that, it is described compound broken Emulsion and PAM dosage are respectively 2g/L and 50mg/L.
Added Fenton reagent is ferrous sulfate solid powder and 30% (w/w) H in step (7)2O2The combination of solution.It is excellent Choosing, COD should with the mass ratio of the ferrous sulfate solid powder in Fenton reagent added in step (7) in the waste emulsified mixture For：100~1000mg:1~2g.Ferrous sulfate solid powder and 30%H in step (7) in added Fenton reagent2O2Solution Mass volume ratio should be：1.5~3g:3~6ml.
Grid described in step (1) is middle grid or is big grid, and purpose is the large particulate matter in water removal, is prevented Only subsequent step is disturbed.
In homogeneous regulation tank described in step (2) separator and floating circulation oil recovery apptss pair are combined comprising waterpower spinning liquid Waste emulsified mixture carries out oil, and water, sand is separated.
Equipment for separating liquid from solid described in step (4) and (6) is inclined-plate clarifying basin.
Add sulphur acid for adjusting pH value in step (7), it is necessary to accurately adjust pH value, it is too low that iron cement can be caused to be difficult to precipitate, it is too high The removal effect to COD can be reduced.
Due to containing high COD in waste emulsified mixture, it, which is once demulsified, can not receive good effect, and significantly The processing load of the follow-up structures of increase, increases operating cost.Moreover, waste emulsified mixture high COD, low BOD, waste water is given birth to The property changed is very low, and the B/C ratios in water need to be improved by Fenton process, increase the biodegradability of waste water.Therefore should in Practical Project The handling process combined using two grades of demulsifications and Fenton.
The present invention not only significantly reduces COD by using two grades of demulsifications and Fenton oxidation combined treatment process, and And improve the biodegradability of waste water.By two grades of demulsifications, the emulsification state oil in the suspension and water in water is fully eliminated, useless The COD of emulsion drops to 20000mg/L or so from 62832mg/L, after Fenton oxidation process, the biodegradability of waste emulsified mixture Greatly improve.
Beneficial effects of the present invention：
(1) method of processing waste emulsified mixture disclosed in this invention, makes high COD waste emulsified mixture be directly over simple two grades Demulsification and Fenton oxidation process, are that biochemical treatment creates conditions；
(2) present invention is, by verification experimental verification, to be treated in the demulsification of waste emulsified mixture using the proportioning of composite demulsifying agent Cheng Zhong, have received good effect；
(3) in the method for the invention, handled by Fenton, the supernatant C OD contents after separation of solid and liquid are greatly reduced, Turbidity is substantially reduced, and B/C ratios are significantly improved, and can substantially reduce the load of subsequent biochemical device；
(4) method processing cost of the invention is very low, simple to operate, does not produce secondary pollution.
Brief description of the drawings
Fig. 1 is the process chart of the inventive method.
Embodiment
Waste emulsified mixture used in the present embodiment comes from Xi'an scrap concrete center, and waste liquid is separately stored in No. 1 holding vessel With No. 2 holding vessels.Wherein No. 1 tank is after mixing water-oil separating, oil phase：Oil content about 83643.38mg/L.Aqueous phase：Oil-containing 908.28mg/L is measured, COD concentration is 62832mg/L or so, and turbidity is 6500NTU or so, and pH is 7.0 or so.No. 2 tanks are through overmulling Close after water-oil separating, oil phase：Oil content about 69966.9mg/L.Aqueous phase：Oil content 1741mg/L, COD concentration are 78336mg/ L or so, turbidity is 7100NTU or so, and pH is 7.0 or so.
Embodiment 1
The present embodiment handles No. 1 tank waste emulsified mixture as follows：
(1) by No. 1 tank waste emulsified mixture by middle grid, the large particulate matter gone in water removal；
(2) waste emulsified mixture is then introduced into homogeneous regulation tank, oil, water, sand three phase separation is carried out to waste emulsified mixture；
(3) aqueous phase after separation is introduced into mixing regulating reservoir 1, is separately added into 1.5g/L CaCl2With 1.5g/L polymerised sulphurs Sour iron (PFS) carries out one-level demulsification；CaCl2Added with the form of bodied ferric sulfate (PFS) wiring solution-forming.
(4) waste water after being demulsified introduces equipment for separating liquid from solid and carries out separation of solid and liquid, isolates the solid precipitation thing of generation Go；
(5) supernatant liquor is introduced back into mixing regulating reservoir 2, adds composite demulsifying agent and PAM carries out two grades of demulsifications；It is multiple It is to enter 1 by PAC (aluminium polychloride) and PFS to close demulsifier:2 ratio is mixed, composite demulsifying agent and PAM (polypropylene Acid amides) dosage be 2g/L and 50mg/L, the form of wiring solution-forming adds.
(6) waste water after demulsification is subjected to separation of solid and liquid, separates the solid precipitation thing of generation；
(7) supernatant is introduced into Fenton's reaction pond, adjusting tank using pH adjusts solution to pH to 3 or so, adds simultaneously Fenton reagent, about 2 hours of mechanical agitation；Added Fenton reagent is ferrous sulfate solid powder and 30%H2O2The group of solution Close.COD and ferrous sulfate solid powder mass ratio should be in waste emulsified mixture：800mg:1.5g；Ferrous sulfate solid powder with 30%H2O2The mass volume ratio of solution is：2g:5ml.
(8) solution after Fenton's reaction is adjusted into pH to 9 or so, carries out flocculation sediment, water outlet introduces biochemical system and carried out Subsequent treatment.
After being handled by the method for the present embodiment No. 1 tank machining oily waste liquor, water outlet COD is down to 20000mg/ L, turbidity is down to 200NTU, while biodegradability is greatly improved, B/C can bring up to 0.37 from 0.16.
Embodiment 2
The present embodiment handles No. 2 tank waste emulsified mixtures as follows：
(1) by No. 2 tank waste emulsified mixtures by middle grid, the large particulate matter gone in water removal；
(2) waste emulsified mixture is then introduced into homogeneous regulation tank, oil, water, sand three phase separation is carried out to waste emulsified mixture；
(3) aqueous phase after separation is introduced into mixing regulating reservoir 1, is separately added into 1.5g/L CaCl2With 1.5g/L polymerised sulphurs Sour iron (PFS) carries out one-level demulsification；CaCl2Added with the form of bodied ferric sulfate (PFS) wiring solution-forming.
(4) waste water after being demulsified introduces equipment for separating liquid from solid and carries out separation of solid and liquid, isolates the solid precipitation thing of generation Go；
(5) supernatant liquor is introduced back into mixing regulating reservoir 2, adds composite demulsifying agent and PAM carries out two grades of demulsifications；It is multiple It is to enter 1 by PAC (aluminium polychloride) and PFS to close demulsifier:2 ratio is mixed, composite demulsifying agent and PAM (polypropylene Acid amides) dosage be 3g/L and 60mg/L, the form of wiring solution-forming adds.
(6) waste water after demulsification is subjected to separation of solid and liquid, separates the solid precipitation thing of generation；
(7) supernatant is introduced into Fenton's reaction pond, adjusting tank using pH adjusts solution to pH to 3 or so, adds simultaneously Fenton reagent, about 3 hours of mechanical agitation；Added Fenton reagent is ferrous sulfate solid powder and 30%H2O2The group of solution Close.COD and ferrous sulfate solid powder mass ratio should be in waste emulsified mixture：1000mg:2g；Ferrous sulfate solid powder with 30%H2O2The mass volume ratio of solution is：3g:6ml.
(8) solution after Fenton's reaction is adjusted into pH to 9 or so, carries out flocculation sediment, water outlet introduces biochemical system and carried out Subsequent treatment.
After being handled by the method for the present embodiment No. 2 tank machining oily waste liquors, water outlet COD is down to 20000mg/ L, turbidity is down to 210NTU, while biodegradability is greatly improved, B/C can bring up to 0.37 from 0.13.

Claims (9)

1. a kind of method pre-processed using two grades of demulsifications and Fenton oxidation combined treatment process to waste emulsified mixture, its feature is existed In：Waste emulsified mixture is passed through into grid first, bulky grain pollutant is removed；Then, tank is adjusted by homogeneous, realizes oil, water, sand three It is separated；The aqueous phase isolated is demulsified by two-stage and destroys stable opaque system, and carries out separation of solid and liquid；It will be separated after demulsification The supernatant gone out, adjusts pH value, carries out Fenton oxidation；After the completion of Fenton's reaction, regulation pH is precipitated, and water outlet enters department of biochemistry System.
2. according to the method described in claim 1, it is characterised in that comprise the steps of：
(1) by waste emulsified mixture by grid, bulky grain pollutant is removed；
(2) waste emulsified mixture is then introduced into homogeneous regulation tank, oil, water, sand three phase separation is carried out to waste emulsified mixture；
(3) aqueous phase after separation is introduced into mixing regulating reservoir 1, adds CaCl2One-level demulsification is carried out with PFS；
(4) waste water after demulsification is subjected to separation of solid and liquid, separates the solid precipitation thing of generation；
(5) supernatant liquor that separation of solid and liquid is obtained is re-introduced into mixing regulating reservoir 2, adds composite demulsifying agent and PAM carries out two Level demulsification；
(6) waste water after demulsification is subjected to separation of solid and liquid, separates the solid precipitation thing of generation；
(7) supernatant for obtaining separation of solid and liquid introduces Fenton's reaction pond, is adjusted solution to pH to 2~4 using pH regulation tanks, Fenton reagent, 1~5 hour of mechanical agitation are added simultaneously；
(8) solution after Fenton's reaction is adjusted into pH to 8~10, carries out flocculation sediment, water outlet introduces biochemical system and carried out subsequently Processing.
3. method according to claim 2, it is characterised in that：CaCl described in step (3)2Distinguish with PFS dosage For 1~2g/L and 1~2g/L, the form of wiring solution-forming is added.
4. method according to claim 3, it is characterised in that：Described CaCl2Dosage with PFS is respectively 1.5g/L And 1.5g/L.
5. method according to claim 2, it is characterised in that：Composite demulsifying agent described in step (5) is by mass ratio 1:2 PAC and PFS is mixed；The dosage of the composite demulsifying agent and PAM is respectively 1~3g/L and 40~60mg/L, is matched somebody with somebody Form into solution is added.
6. method according to claim 5, it is characterised in that：The dosage of the composite demulsifying agent and PAM is respectively 2g/ L and 50mg/L.
7. method according to claim 2, it is characterised in that：Added Fenton reagent is solid for ferrous sulfate in step (7) Body powder and 30%H2O2The combination of solution.
8. method according to claim 7, it is characterised in that：COD and sweet smell added in step (7) in the waste emulsified mixture The mass ratio of ferrous sulfate solid powder in reagent should be：100~1000mg:1~2g.
9. the method according to claim 2 or 7, it is characterised in that：Sulfuric acid in step (7) in added Fenton reagent is sub- Iron solid powder and 30%H2O2The mass volume ratio of solution should be：1.5~3g:3~6ml.
CN201710205207.6A 2017-03-31 2017-03-31 Pretreatment method of waste emulsion Expired - Fee Related CN107082526B (en)

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Cited By (11)

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CN108793497A (en) * 2018-06-27 2018-11-13 泰山玻璃纤维邹城有限公司 A kind of method that chemical method reduces glass fiber infiltration agent waste liquid COD value
CN109111032A (en) * 2018-08-29 2019-01-01 洛阳昊海工贸有限公司 A kind of process of waste emulsified mixture disposal of resources
CN109231722A (en) * 2018-11-16 2019-01-18 郑州轻工业学院 A kind of processing method being machined emulsifiable oil waste water
CN110451682A (en) * 2019-07-31 2019-11-15 天津大学 A kind of method that advanced oxidation handles high COD emulsification preparation waste water
CN110526494A (en) * 2019-08-07 2019-12-03 四川绿艺华福石化科技有限公司 A kind of processing method of waste emulsified mixture
CN110540315A (en) * 2018-05-28 2019-12-06 宝山钢铁股份有限公司 Method and system for pretreating waste emulsion
CN111892233A (en) * 2019-12-27 2020-11-06 深圳市宝安东江环保技术有限公司 Method for treating waste emulsion
US20210078883A1 (en) * 2019-09-17 2021-03-18 Kun Shan University Oil-containing wastewater treatment method and equipment with creating and saving energy efficiency
CN112759199A (en) * 2021-01-13 2021-05-07 湖北爱国环保技术开发有限公司 Treatment process of waste cutting fluid
CN113697993A (en) * 2021-08-30 2021-11-26 衢州华友钴新材料有限公司 Method for removing oil and reducing COD (chemical oxygen demand) of hydrometallurgy sodium sulfate wastewater
CN114477527A (en) * 2022-01-14 2022-05-13 广东闻扬环境科技有限公司 Workshop cleaning wastewater treatment method and system

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Cited By (12)

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CN110540315A (en) * 2018-05-28 2019-12-06 宝山钢铁股份有限公司 Method and system for pretreating waste emulsion
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