CN105461121A - Electrocoagulation treatment method of wastewater from oil-field work - Google Patents

Electrocoagulation treatment method of wastewater from oil-field work Download PDF

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Publication number
CN105461121A
CN105461121A CN201510826820.0A CN201510826820A CN105461121A CN 105461121 A CN105461121 A CN 105461121A CN 201510826820 A CN201510826820 A CN 201510826820A CN 105461121 A CN105461121 A CN 105461121A
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oil
wastewater
treatment
water
field
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CN201510826820.0A
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Chinese (zh)
Inventor
马超
王澄滨
王益军
黄连华
贾宝贵
马兰
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KARAMAY SANDA NEW TECHNOLOGY Co Ltd
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KARAMAY SANDA NEW TECHNOLOGY Co Ltd
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Priority to CN201510826820.0A priority Critical patent/CN105461121A/en
Publication of CN105461121A publication Critical patent/CN105461121A/en
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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
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/38Treatment of water, waste water, or sewage by centrifugal separation
    • 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
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • 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
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/463Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
    • 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
    • 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
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104Devices therefor; Their operating or servicing
    • C02F1/46109Electrodes
    • C02F2001/46133Electrodes characterised by the material
    • 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
    • C02F2101/32Hydrocarbons, e.g. oil
    • 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
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The invention belongs to the technical field of oil-field wastewater treatment and specifically relates to an electrocoagulation treatment method of wastewater from oil-field work. The method comprises the following steps: (1) carrying out oil separation and settlement treatment on wastewater from oil-field work by an oil removal device; (2) carrying out static settling, and pumping an intermediate-layer clear liquid in the wastewater through a lift pump into an electrocoagulation treatment device to react and carry out low-pressure pulse electrocoagulation treatment, wherein DC power control output current density is 1-50 mA/cm<2>, polar plate spacing is 0.5-4 cm, and electrolysis time is 1-15 min; (3) adjusting pH to 6-7 by adding NaOH, and entering a swirl-flow oil-water separator with three separator outlets for respectively outputting effluent, dross and sump oil; and (4) filtering the effluent by an active sand filter such that the effluent finally reaches the standard. The method is simple to operate and is economic and efficient.

Description

A kind of electric coagulating/flocculating method for processing of oil field operation waste liquid
Technical field
The invention belongs to disposing polluted water in oil technical field, be specifically related to a kind of electricity flocculation water treatment method of operation wastewater in oil field.
Background technology
Oil well operation waste water main source is acidizing waste fluid, fracturing waste liquor, well cementation waste liquid, petroleum drilling waste liquid, well-flushing waste liquid.
Wherein the feature of waste liquid of drilling is: pollutent composition complicated, solid phase particles granularity is tiny, grating is poor, outward appearance is viscous fluid or semi-fluid shape, colourity is large, water ratio height not easily dewaters (water ratio is about 30%-90%), solid content is higher, and viscosity is large, oil-containing (part oil drilling waste oleaginousness reaches more than 10%) etc.
Unspent acid solution when wherein acidizing waste fluid mainly refers to return from Oil/gas Well remaining acid solution and the construction of discharge after acidizing treatment, composition mainly comprises acid solution and residual acid solution, containing viscosifying agent, hydrochloric acid, hydrofluoric acid, organic additive (fluid loss agent, anti-clayswelling agent, cleanup additive, corrosion inhibitors for acidic media etc.), soluble trace elements etc.
Wherein fracturing waste liquor feature: organic content is very high, pH lower (generally lower than 3), corrodibility is strong, and chloride ion content is very high, and suspended substance is many, and colourity is large, frowziness, the features such as high volence metal ion content is high, and intractability is larger.
Because acidizing waste fluid acidity is stronger, chloride ion content is high, and containing a large amount of high volence metal ions, therefore untreated or process acidizing waste fluid entered environment not up to standard, by serious harm farm crop, the acid-basicity of serious change soil property is simultaneously owing to there is a large amount of chlorions, very large to harm such as water body, crop, fish.
Electricity flocculation process is a kind of common method of wastewater treatment, its reaction principle take metal as anode, under galvanic effect, anode is dissoluted, produce metal ion, again through a series of hydrolysis, polymerization and oxidising process, develop into various hydroxo complex, multinuclear hydroxo complex so that oxyhydroxide, make the colloidal state impurity in waste water, suspended impurity coagulative precipitation and being separated; Simultaneously charged contaminant particle swimming in the electric field, its Partial charge is neutralized by electrode and impels its de-steady coagulation.But simple electric flocculation process also exists the shortcoming of traditional electrical solution technique, because it adopts open reaction compartment, water oxygen level is not enough, and cause the redox reaction in electrolysis not thorough, effluent quality is difficult to reach desirable quality.
The removal of low voltage pulsed electric flocculation technology to composition each in oil well operation waste water contains several step:
(1) polyacrylamide type organic, oil in water emulsion, the contour zeta-potential of colloid, stable colloidal particle is under electrochemical action, there is charge neutrality, electric compressive action, because under electric throwing out, its zeta-potential reduces, electrostatic double layer is breakdown of emulsion by compressing, oil, the absorption each other of solid suspension thing, emulsifying effect reduce, and become de-steady suspended substance.
(2) Fe 2+, sulfide is reduced into simple substance Fe, elemental sulfur on negative electrode, separate from water.
(3) oil after de-steady, suspended substance, sulfide are agglomerated into flco, thus are able to remove from water by sedimentation, filteration under coagulating agent, flocculation agent effect.
Specifically there is following chemical action process at electrode surface:
Organism adsorbs C+ organic pollutant (R) → C (R) ADSORPTION STATE on electrode.
Water and muriate generate hydroxyl radical free radical, chlorine in anodic oxidation:
H 2O→·OH+H ++e
2Cl -→Cl 2+2e
Water and other reducible things are at the minimizing of negative electrode: 2H 2o+2e --→ H 2+ 2OH -
The electrochemistry disproportionation reaction of chlorine molecule generates oxidisability hypochlorous acid
Cl 2+H 2O→HOCl+H ++Cl (pH≤7.5)
HOCl→H ++OCl (pH>7.5)
Oxidation operation reaction becomes carbonic acid gas:
R+·OH+(Cl 2/H 2O)→CO 2+H 2O
Desulfurization principle:
Negative electrode: RSH+2H ++ 2e ?→ RH+H 2s
Anode: H 2s → 2H ++ S+2e ?
Ferrous ion removes principle:
Negative electrode: Fe 2++ 2e ?→ Fe
Ferrous ions reacts: Fe 2++ OH+H +→ Fe+H 2o
Suspended substance removal principle:
Aluminum anode Al-3e → Al 3+al in the basic conditions 3++ 3OH -→ Al (OH) 3al in acid condition 3++ 3H 2o → Al (OH) 3+ 3H +iron anode Fe-2e → Fe 2+fe in the basic conditions 2++ 2OH -→ Fe (OH) 2
(oil well operation pH value of sewage water=4-6, is mainly the reaction under this acidic conditions): 4Fe in acid condition 2++ O 2+ 2H 2o → 4Fe 3++ 4OH -
In addition, the electrolysis of water also has oxygen to release 2H 2o-4e → O 2+ 4H +;
Occur to react 2H as follows at negative electrode 2o+2e → H 2+ 2OH -.
The metal ion that above-mentioned electrode reaction produces, in the oxidising process through a series of hydrolysis, polymerization and ferrous iron, develops into various hydroxo complex, multinuclear hydroxo complex so that oxyhydroxide, makes the colloidal state impurity in waste water, suspended impurity coagulative precipitation and being separated.Electricity flocculence is removed water pollutant process and is seen Fig. 1.
Current well workover liquid waste disposal adopts physico-chemical process process mostly, in waste water, add chemical agent, and useless impurities in water forms flco, is removed by precipitation forms.This method Shortcomings mainly contain following some: it is large that (1) adds chemical drugs dosage.(2) chemical agent working cost is high.(3) medicament addition device is increased.(4) manual operation is complicated, loaded down with trivial details.(5) maintenance of the equipment is complicated.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of easy and simple to handle, the treatment process of the operation wastewater in oil field of economical and efficient.
The electric coagulating/flocculating method for processing of oil well operation waste liquid of the present invention, comprises the steps:
(1) be 2 ~ 6 to pH value, specific conductivity is that 300 ~ 2000 μ s/cm operation wastewater in oil field carry out oil removal, settlement treatment in oil removal plant;
(2) quiet heavy rear upper strata is oil slick, and next time is mud, and middle level is clear liquid, and the middle level clear liquid getting waste water enters in electric flocculation treatment device through lift pump and reacts, and carry out action of low-voltage pulse electricity flocculation treatment, DC power control outward current density is 1 ~ 50mA/cm 2, polar plate spacing is 0.5 ~ 4cm, and electrolysis time is 1 ~ 15min;
(3) add after NaOH adjusts pH6-7 and add 7mg/LPAM again, then enter aerating oil-water separator, separator outlet has three, water outlet respectively, scum silica frost and sump oil;
(4) water outlet of aerating oil-water separator enters active husky strainer and carries out filtration treatment, and last water outlet reaches oil-field flooding standard.
The pulse electro-flocculation treatment process of above-mentioned operation wastewater in oil field, step once changes positive and negative electrode by per hour in (2), slows down pole plate passivation, reduces waste of energy.
The pulse electro-flocculation treatment process of above-mentioned operation wastewater in oil field and device, battery lead plate all selects iron or aluminium to make pole plate.Of the present invention is electric flocculation process, produces a large amount of ironic hydroxide (aluminium) flcos, is caught that volume is swept, adsorption bridging is used for absorb polluted matter by the absorption flco energy more efficient that produces in electric flocculation process by exclusive absorption, net; Its negative electrode can produce the hydroxyl radical free radical of strong oxidizing property on the other hand, and hydroxyl radical free radical has high oxidisability, the complicated organic molecule of energy oxidize majority, degradation polymer.To reach the effect destroying group, decolouring.
Accompanying drawing explanation
Fig. 1 electricity flocculence removes water pollutant process.
Fig. 2 is the present invention's electricity flocculation water treatment method schema.
Embodiment
Embodiment 1
1, certain oil field operation waste liquid complete water quality analysis.
Table 1 complete water quality analysis data sheet unit: mg/l
2, above-mentioned sewage is through process, finally will reach following standard;
Table 2 water quality reaching standard data sheet unit: mg/l
Project SS Oil Fe 2+ S 2-
Well workover waste liquid ≤10 ≤10 ≤1.0 ≤2.0
3, conventional treatment method:
Present stage mainly adopts technical process to be: operation wastewater in oil field → gravity oil-removing → coagulant precipitation → filtration → re-injection.
Key step: the first step, a kind of operation wastewater in oil field are separated oil slick and wait until mixed solution in oil removal plant.Mixed solution in second step, oil removal plant enters retort dosing reaction through lift pump.Mixed solution is coagulation, settlement separate under coagulating agent A/B/C/D/E tetra-kinds effect.(chemical feeding quantity: A is oxygenant: 650mg/l, B are pH adjusting agent PAM:400mg/l, C is coagulating agent: 1500mg/l, D are settling agent: 400mg/l, E are coagulant aids: 10mg/l).
Conventional chemical agent-feeding treatment, final process water-quality guideline up to standard is: oil≤10mg/l, ss≤10mg/l, and adding chemical drugs dosage is 2310mg/l, and processing cost is 13 yuan/side.
4, treatment process of the present invention:
Key step:
The first step, operation wastewater in oil field are separated oil slick and wait until mixed solution in oil removal plant.
Mixed solution in second step, oil removal plant enters in action of low-voltage pulse electricity flocculation treatment device through lift pump and reacts.There is oxidizing reaction in mixed solution, polymkeric substance a large amount of in degraded operation wastewater in oil field, the difficult de-steady material of oxidation under the effect of battery lead plate;
3rd step, de-steady under pole plate Action of Metal Ions through the mixed solution of pole plate preoxidation.
4th step, add the lower coagulation of coagulating agent B/E two kinds effect, settlement separate.(chemical feeding quantity: B is pH adjusting agent: 200mg/l, E are coagulant aids PAM:7mg/l).
5th step, electric flocculation plant water outlet enter active husky metre filter.
Significant parameter:
Polar plate spacing is from being 0.5 ~ 4cm, and polar period is 1 time/hour, and pole plate adopts iron or aluminium to make pole plate, and electrolysis time is 1 ~ 15min, and electric current can pass through water water quality regulation (10-100A).
After the technical process in the inventive method, device processes, final process water-quality guideline up to standard is: oil≤10mg/l, ss≤10mg/l, and adding chemical drugs dosage is 210mg/l, and processing cost is 3.5 yuan/side.

Claims (3)

1. an electric coagulating/flocculating method for processing for oil field operation waste liquid, comprises the steps:
(1) be 2 ~ 6 to pH value, specific conductivity is that 300 ~ 2000 μ s/cm operation wastewater in oil field carry out oil removal, settlement treatment in oil removal plant;
(2) quiet heavy rear upper strata is oil slick, and next time is mud, and middle level is clear liquid, and the middle level clear liquid getting waste water enters in electric flocculation treatment device through lift pump and reacts, and carry out action of low-voltage pulse electricity flocculation treatment, DC power control outward current density is 1 ~ 50mA/cm 2, polar plate spacing is 0.5 ~ 4cm, and electrolysis time is 1 ~ 15min;
(3) add after NaOH adjusts pH6-7 and add 7mg/LPAM again, then enter aerating oil-water separator, separator outlet has three, water outlet respectively, scum silica frost and sump oil;
(4) water outlet of aerating oil-water separator enters active husky strainer and carries out filtration treatment, and last water outlet reaches oil-field flooding standard.
2. electric coagulating/flocculating method for processing according to claim 1, is characterized in that, periodic replacement positive and negative electrode in step (2).
3. electric coagulating/flocculating method for processing according to claim 1, is characterized in that, electric flocculation treatment device, and battery lead plate all selects iron or aluminium to make pole plate.
CN201510826820.0A 2015-11-25 2015-11-25 Electrocoagulation treatment method of wastewater from oil-field work Pending CN105461121A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106746048A (en) * 2016-12-15 2017-05-31 西安思坦环境科技有限公司 A kind of efficient oil-contained waste water treatment device and method
CN107010755A (en) * 2017-04-18 2017-08-04 中国石油大学(华东) Tank fire reveals Oil Recovery and fire-fighting water circulation utilization system
CN108911292A (en) * 2018-09-13 2018-11-30 苏州特曼清环保科技有限公司 A kind of industrial wastewater efficient process equipment and treatment process
CN109095698A (en) * 2018-09-13 2018-12-28 苏州特曼清环保科技有限公司 One kind filtering industrial waste water high-efficiency processing equipment based on electrochemistry and film
CN109437452A (en) * 2018-12-21 2019-03-08 中国石油大学(北京) A kind for the treatment of method and apparatus of acid fracturing backflow waste liquid
CN109485185A (en) * 2017-09-13 2019-03-19 中国石油天然气集团公司 A kind of pulse electrochemical processing method and processing device of oil field operation waste liquid
CN112759040A (en) * 2020-12-02 2021-05-07 北京中科圣泰环境科技有限公司 Composite electric flocculant and method for treating cold-rolling emulsion wastewater through electric flocculation

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106746048A (en) * 2016-12-15 2017-05-31 西安思坦环境科技有限公司 A kind of efficient oil-contained waste water treatment device and method
CN107010755A (en) * 2017-04-18 2017-08-04 中国石油大学(华东) Tank fire reveals Oil Recovery and fire-fighting water circulation utilization system
CN109485185A (en) * 2017-09-13 2019-03-19 中国石油天然气集团公司 A kind of pulse electrochemical processing method and processing device of oil field operation waste liquid
CN109485185B (en) * 2017-09-13 2022-03-01 中国石油天然气集团公司 Pulse electrochemical treatment method and device for waste liquid of oil field operation
CN108911292A (en) * 2018-09-13 2018-11-30 苏州特曼清环保科技有限公司 A kind of industrial wastewater efficient process equipment and treatment process
CN109095698A (en) * 2018-09-13 2018-12-28 苏州特曼清环保科技有限公司 One kind filtering industrial waste water high-efficiency processing equipment based on electrochemistry and film
CN109437452A (en) * 2018-12-21 2019-03-08 中国石油大学(北京) A kind for the treatment of method and apparatus of acid fracturing backflow waste liquid
CN112759040A (en) * 2020-12-02 2021-05-07 北京中科圣泰环境科技有限公司 Composite electric flocculant and method for treating cold-rolling emulsion wastewater through electric flocculation

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Application publication date: 20160406