CN110467301A - A kind of shale gas fracturing outlet liquid processing method and system and device - Google Patents
A kind of shale gas fracturing outlet liquid processing method and system and device Download PDFInfo
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- CN110467301A CN110467301A CN201910711767.8A CN201910711767A CN110467301A CN 110467301 A CN110467301 A CN 110467301A CN 201910711767 A CN201910711767 A CN 201910711767A CN 110467301 A CN110467301 A CN 110467301A
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—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
- C02F1/44—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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- 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
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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
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The present invention discloses a kind of shale gas fracturing outlet liquid processing method and processing system device, including returning drain standing, coagulating sedimentation, clarification, filtering, electrodialysis process, reverse osmosis membrane apparatus component concentration step recycling fresh water, concentrated water after concentration enters evaporation concentrator, generates crystal salt and condensate liquid fresh water through being concentrated by evaporation.The present invention realizes that resource utmostly recycles, reaches the near-zero release of sewage, system apparatus arrangements are simple, strong operability for salt and high organic content, this difficult problem during the reuse of shale gas fracturing outlet liquid or outlet.
Description
Technical field
The invention belongs to environmentally friendly water treatment fields more particularly to a kind of shale gas fracturing outlet liquid processing method and system to fill
It sets.
Background technique
Shale gas industrial development in recent years is rapid, and shale gas resource China proven reserve reaches the first in the world, and yield reaches
To the world first three.Hydrofracturing method is a kind of technology for being widely used in shale gas exploitation, it is opened by hydraulic pressurization drilling well
To allow shale gas to flow to drilling well mouth, fracturing outlet liquid is the mixing that initial stage row of returning from well is completed in hydraulic fracturing in small gap
Liquid.Its water quality characteristics difference due to geological conditions difference, is generally speaking complicated components, high COD, high TSS, high TDS,
Processing difficulty is big, becomes gas industries face one big technical problem.If direct emission, ecological environment can be seriously endangered.
Therefore, development fracturing returns drain near-zero release technique and realizes the problem of resource recycling is at urgent need to resolve instantly.
Organic pollutant mainly includes macromolecule hydrocarbon, polyacrylamide, polyacrylamide in shale gas fracturing outlet liquid
In fracturing process by broken glue oxidation after by-product and other small organic molecules, inorganic pollution be mainly metal ion,
Landwaste, clay, wherein metal ion specifically includes that sodium, potassium, calcium, magnesium, barium etc., and the total salinity of shale gas fracturing outlet liquid can
Up to 20000mg/L~140000mg/L, the content of solid suspension is about 100~2000mgL up to 80~1000mg/L, COD.
Salt content in shale gas fracturing outlet liquid wants much higher compared to other industry waste water, and organic matter molecular mass is also larger, adheres to
Ability is stronger, is the difficulty in treatment place of gas industries waste water.
The concentration technique of shale gas fracturing outlet liquid is softening+ultrafiltration+reverse osmosis concentration at present, i.e., quiet by dosing
It sets to reduce the hardness of waste water, then carries out ultrafiltration again, solvent and small molecule solute is made to pass through ultrafiltration membrane, and macromolecular solute
It cannot penetrate, then to ultra filtration filtrate by the water outlet after being purified after reverse osmosis concentration.The method that dosing stands softening can only
The hardness of water quality is reduced, effluent quality is bad；Ultrafiltration membrane also easily generates serious film in the case where influent quality is bad
Pollution can be such that outlet effect weakens significantly if cleaning is infrequently not thorough, and the salt content after the concentration of single-stage reverse osmosis unit
Ideal concentrated effect, poor processing effect are also not achieved with organic matter.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of shale gas fracturing outlet liquid processing method and processing system
Device is reached for salt during the reuse of shale gas fracturing outlet liquid or outlet and high organic content, this difficult problem
The resource reclaim for handling and generating to near-zero release, structure is simple, strong operability.
Solve a kind of shale gas fracturing outlet liquid processing method of the above technical problem, it is characterised in that: including following step
It is rapid:
(1) shale gas fracturing outlet liquid is added foul water tank and is stood；
(2) shale gas fracturing outlet liquid enters coagulating sedimentation device progress coagulating sedimentation；
(3) coagulating sedimentation supernatant enters Clear liquid tank clarification；
(4) clarified solution enters filter device and is filtered；
(5) for ceramic membrane filter device concentrate recirculation to foul water tank, the ratio between concentrate recirculation amount and inflow are 1:3~5；Filtering
Clear water enters electrodialysis process device, and the circular treatment time is 120~160min；
(6) electrodialysis concentrated water enters reverse osmosis membrane apparatus I and carries out concentration decrement treatment, and electrodialysis fresh water enters reverse osmosis membrane
Device II carries out deep purifying processing；The fresh water and electrodialysis fresh water that reverse osmosis membrane apparatus I generates enter reverse osmosis membrane dress together
The processing of II deep purifying is set, the concentrated water that reverse osmosis membrane apparatus I generates enters evaporation concentrator；It is generated in reverse osmosis membrane apparatus II
Concentrated water and electrodialysis concentrated water enter reverse osmosis membrane apparatus I together and decrement treatment, the fresh water generated in reverse osmosis membrane apparatus II are concentrated
For the final outflow water for the treatment of process；
(7) crystal salt and condensate liquid are generated through being concentrated by evaporation into the concentrated water of evaporation concentrator.
The processing system device of one of present invention shale gas fracturing outlet liquid, it is characterised in that: described device includes
It is set equipped with foul water tank, pretreatment unit, electrodialysis process device, reverse osmosis membrane assembly and evaporation concentrator, reverse osmosis membrane assembly
There are reverse osmosis membrane apparatus I and reverse osmosis membrane apparatus II；Foul water tank is connect with pretreatment unit, pretreatment unit and electrodialysis process
Device connection, the outlet of electrodialysis concentrated water room are connect with I water inlet of reverse osmosis membrane apparatus, the outlet of electrodialysis fresh water room and reverse osmosis membrane
The connection of II water inlet of device, the outlet of I concentrated water of reverse osmosis membrane apparatus are connect with evaporation concentrator, I water outlet of reverse osmosis membrane apparatus
It is connect with II water inlet of reverse osmosis membrane apparatus, the outlet of II concentrated water of reverse osmosis membrane apparatus is connect with I water inlet of reverse osmosis membrane apparatus, instead
The fresh water generated in permeable membrane device II is the final outflow water for the treatment of process.
The pretreatment unit is equipped with coagulating sedimentation device and ceramic membrane filter device, coagulating sedimentation device water inlet end and foul water tank
Connection, coagulating sedimentation device water outlet are connect with ceramic membrane filter device water inlet end, and ceramic membrane filter device concentrate recirculation end passes through
Pipeline is connected in foul water tank, and the ratio between reflux concentrated water and water inlet are 1:3~5.
The ceramic membrane filter device is tubular type inorganic ceramic film filter, is equipped with internal circulation apparatus in filter device.
The pretreatment unit is additionally provided with Clear liquid tank, and Clear liquid tank is between coagulating sedimentation device and ceramic membrane.
I film type of reverse osmosis membrane apparatus selects rolling high-pressure membrane, and operating pressure is 3.0~4.0Mpa, reverse osmosis membrane
II film type of device selects rolling low-pressure membrane, and operating pressure is 0.5~0.8Mpa.
Technical characterstic
It is asked for salt during the reuse of shale gas fracturing outlet liquid or outlet and high organic content, difficult this
Topic, for the resource reclaim for reaching near-zero release processing and generating, the present invention passes through to processing method and processing system device
Optimization realizes the advantages that method is simple and easy to operate, and apparatus structure is simple, strong operability, and method and processing system in the present invention
System has good effect.Difficult point of the invention is:
(1) shale gas fracturing outlet liquid groups of contaminants is at complex, comprising suspended solid, complicated organic matter, salinity and
Other chemical components are needed for its features of pollution, design treatment method and processing system device；
(2) treatment process does not answer too complex, to be conducive to the practical application of engineering；
(3) method is easy to operate, rapidly and efficiently, should not generate secondary pollution and should realize reasonable resource reclaim；
(4) it is eager to excel for the adaptability of shale gas fracturing outlet liquid variation water quality, and realizes near-zero release as far as possible.
Aforementioned techniques problem is solved, for shale gas fracturing outlet liquid processing method and processing system device in the present invention
Preferably so that treatment process is simple and easy to operate, apparatus structure is simple, and realizes reasonable resource recycling, and it is final go out
Water almost realizes that near-zero release is significant innovation of the invention.
In the present invention, it is added in coagulating sedimentation device in step (2) and is clarified, coagulant PAC dosage is 500~
2000mg/L, flocculation aid CPAM1200Dosage be 40~130mg/L, dosage according to the water quality of handled fracturing outlet liquid come
It determines, the colloidal substance in coagulant and water occurs strong charge neutrality effect and has good suction to the product after hydrolyzing in water
Attached bridging action, the colloidal organic matter in shale gas fracturing outlet liquid are adsorbed, and are formed settling of floccus and are got off, reduce COD value；
When dosage of PAC is too small, particle surface current potential is higher, and electrostatic repulsion is larger between particle, it is difficult to formed biggish wadding body and
Sinking speed is slow, when PAC dosage is too big, taken off steady colloidal grain surface can be again positively charged and be again at stable shape
, wadding body leakiness and there is rising phenomenon in state, and coagulation effect is gradually deteriorated, and preferred coagulant PAC handles shale gas pressure break
500~2000mg/L of drain dosage is returned with good coagulation effect.Flocculation aid is added to promote the removal effect of COD in positive
Into effect, PAM molecule makes to build bridge between particle or makes particle condensation by charge neutrality by the suspended solid ion in absorption water
At big flocculate, accelerate the settling of floccus in solution, more bigger and more than the wadding body that PAC makes only is added, the sedimentation time is shorter,
For fracturing outlet liquid water quality, the cationic PAM dosage of preferred 12,000,000 molecular weight is 40~130mg/L.
Supernatant in step (3) after coagulating sedimentation enters Clear liquid tank and is further clarified, and the residence time is 1~2h.
Filter device is ceramic film device, i.e. tubular type inorganic ceramic film filter in step (4), uses membrane aperture for 20
~2000nm, transmembrane pressure be 0.1~0.2MPa, the ratio between internal circulating load and inflow are 10:1~60:1；It is ceramic in prioritization scheme
Film membrane aperture is 200nm, the ratio between transmembrane pressure 0.16MPa, internal circulating load and inflow are 30:1.
Ceramic membrane filter aperture significantly affects process operation efficiency, for main contamination characteristics in shale gas fracturing outlet liquid
Analysis shows wherein the pollutant of suspended state specifically includes that master in clay, landwaste powder, especially shale gas fracturing outlet liquid
Wanting organic pollutant is polyacrylamide, and molecular weight is larger, and when filtering mutually winds between each molecule of ceramic membrane surface, rolls into a ball
It is poly-, form supermolecule unity structure, while the reticular structure that is formed of poly- propionyl amine molecule can net catch inorganic particulate matter and form complicated dirt
Dye group, particle diameter distribution is about 200~500nm, and has certain viscosity, therefore ceramic membrane aperture optimization aspect, is needed
Under the premise of improving permeation flux as far as possible, the blocking of fenestra is prevented.Aperture is too greatly for clay, rock in shale gas fracturing outlet liquid
The rejection effect of the suspended matters such as crumbs powder and small organic molecule is bad, causes ceramic membrane filter outlet effect bad, simultaneously
Have sticking complicated pollution group and be likely to enter ceramic membrane duct, leads to the irreversible membrane fouling of film；The too small ceramic membrane in aperture,
It is smaller that it crosses permeation flux, is easy blocking and results in the need for continually being cleaned, unfavorable continuous operation in practical application
Operation.The film of preferred 200nm is that processing fracturing outlet liquid ensure that good treatment effect and contamination resistance in the present invention.
It is preferred that transmembrane pressure is in 0.1~0.2MPa, it is smaller that lesser transmembrane pressure crosses permeation flux, while in filter process
The cake layer that organic macromolecule and suspended matter cover film surface generation is not easy to be washed, and causes ceramic membrane contaminated, filtering
Low efficiency；Biggish transmembrane pressure then can make organic macromolecule and suspended matter be squeezed into fenestra, cause Pore Blocking, so that
The speed of fouling membrane is accelerated, and but will aggravate irreversible membrane fouling, and currently preferred transmembrane pressure 0.16MPa, is both guaranteeing
While water efficiency, pollutant is decreased in the deposition of film surface.It is followed in setting in heretofore described purpose ceramic-film filter
Loop device, the ratio between feed liquid circulation flow and shale gas fracturing outlet liquid inflow are 30:1 in purpose ceramic-film filter, preferred to expect
Liquid recycle stream amount makes its lateral shearing force play preferable souring to ceramic membrane film surface pollutant is attached to, and is not easy it
It is deposited in film surface, while strengthening the effect of mass transmitting of film, so that film is not easy to block, ceramic membrane concentrate recirculation end passes through
Pipeline is connected in foul water tank, and in conjunction with pollutant characteristic in shale gas fracturing outlet liquid, the ratio between optimization reflux concentrated water and water inlet are
1:3~5, regurgitant volume is excessive, causes the operational efficiency of filter lower, and too low regurgitant volume causes pollutant in filter device negative
Lotus is excessively high, and ceramic membrane blocking is more serious, is unfavorable for the normal operation of filter.
Ceramic membrane is backwashed with acid & alkali liquid after its flux depression 70%, film is avoided to block.
Electrodialysis process device operation voltage is 10~30V in step (5), flow of inlet water is 500~700L/h.m2, pole
Water concentration is 0.5%~1.0%, and pole water is the aqueous solution of NaCl；Partial organic substances in shale gas fracturing outlet liquid pass through electricity
Dialysis, which is powered, occurs charged effect or hydrolysis, realizes synchronous except COD and salt；Electrodialysis operation voltage 20V in prioritization scheme,
Flow of inlet water 600L/h.m2, pole water NaCl concentration 0.75%.
The speed of zwitterion migration velocity depends on the size of membrane stack two sides institute add operation voltage, behaviour in electrodialysis membrane stack
Make voltage and largely determine that the deep or light phase of electrodialysis is carrying out shale gas fracturing outlet liquid the effect with desalination is concentrated,
Due in shale gas fracturing outlet liquid total salinity up to 20000mg/L~140000mg/L, low electrodialysis operation voltage pair
Shale gas fracturing outlet liquid salt rejection rate with high salt is low, and the too high fuel factor that will cause Ion transfer generation of voltage increases, and causes
The relative drop of current efficiency causes energy loss bigger.For shale gas fracturing outlet liquid water quality characteristics, preferred operation electricity
Pressure 20V more can carry out desalination and concentration to stability and high efficiency.It is bigger in the front half section time electroendosmosis analysis flow of inlet water that processing carries out
Treatment effeciency improves faster, but to the latter half of processing when can make since the inorganic scale that traffic load is too big and generates pollutes
It obtains treatment effeciency to be deteriorated, since the metal ion contents such as calcium, magnesium, barium are higher in shale gas fracturing outlet liquid, generates inorganic scale
Possibility is bigger, simultaneously because water flow is too fast, the time that liquid to be treated rests on amberplex is shorter, and shale gas pressure break returns row
Liquid saliferous index is high, rest on amberplex time it is short in the case where treatment effect can be deteriorated, under comprehensively considering, the present invention
Preferred flow of inlet water 600L/h.m2It is best to desalination and concentrated effect.
Electrodialysis pole water is sodium-chloride water solution, when the concentration of pole water ion is in very low state, pole room electric conductivity
Can significantly it weaken, it is possible to cause polarization phenomena；And in the excessively high situation of pole water concentration, when concentrated phase concentration is also higher, from
Son will be unable to permeate, and can may inhibit to a certain extent migration due to concentration polarization；So improving in a certain range extremely water-soluble
The concentration of liquid can promote and reinforce the ability of the ionic conduction of solution to improve electrodialysis desalination and concentrated effect, this hair
Bright preferred 0.75% pole water NaCl then ensure that the satisfactory electrical conductivity and electrodialytic treatment effect of pole water.
I water outlet of reverse osmosis membrane apparatus is connect with II water inlet of reverse osmosis membrane apparatus in step (6), reverse osmosis membrane apparatus
The outlet of II concentrated water is connect with I water inlet of reverse osmosis membrane apparatus.Reverse osmosis membrane apparatus I is concentrated the fresh water that electrodialysis concentrated water generates and enters
Reverse osmosis membrane apparatus II and electrodialysis fresh water carry out deep purifying processing together；The concentrated water that reverse osmosis membrane apparatus II generates enters anti-
Permeable membrane device I and electrodialysis concentrated water carry out concentration decrement treatment together.Since the process object of reverse osmosis membrane apparatus II is electric osmose
Fresh water is analysed, concentrated water water quality that treated is compared to the water inlet of reverse osmosis membrane apparatus I, i.e., for electrodialysis concentrated water, though COD value
So it is not much different, but TDS concentration is far smaller than electrodialysis concentrated water TDS concentration (about its 0.5% or so), reverse osmosis membrane apparatus II
Concentrated water enter reverse osmosis membrane apparatus I can to electrodialysis concentrated water carry out water quality adjustment effect, reduce reverse osmosis membrane apparatus I salt
Load, avoid reverse osmosis membrane apparatus I because caused by the TDS load of electrodialysis concentrated water water quality is excessively high the rate of output water it is excessively slow,
And it can reduce and lead to calcium, magnesium, barium since the TDS of electrodialysis concentrated water water quality is excessively high etc. Hydrolysis Reactions of Metal-ions product reaches ion
A possibility that excessive inorganic scale generates fouling membrane is precipitated in saturation degree, so that reverse osmosis membrane apparatus I is when being concentrated electrodialysis concentrated water
For the more adaptable of variation water quality, it is smaller to generate a possibility that inorganic scale pollutes；And the presence of reverse osmosis membrane apparatus I,
Be the further concentration decrement treatment to electrodialysis concentrated water, electrodialysis concentrated water can be reduced 80% or so again, thus improve into
Enter the salt content and content of organics of vapo(u)rization system concentrate so that vapo(u)rization system handled under same temperature parameter it is less
Water but obtains more crystal salts, reduces the energy consumption of vapo(u)rization system.The light of electrodialysis concentrated water generation is concentrated in reverse osmosis membrane apparatus I
Water enters reverse osmosis membrane apparatus II and electrodialysis fresh water and continues deep purifying processing together, due to electrodialysis concentrated water COD value
Excessively high, reverse osmosis membrane apparatus I is concentrated the fresh water COD value that electrodialysis concentrated water generates and is greater than 30mg/L, by by reverse osmosis membrane apparatus I
The fresh water of generation enters reverse osmosis membrane apparatus II and is further processed, so that final outflow water water quality almost realizes near-zero release, improves
Water quality is to the friendly of environment after processing, and the presence of reverse osmosis membrane apparatus II, is the further depth to electrodialysis fresh water
Purified treatment needs to carry out advanced treating and is just able to achieve discharge since the COD value of electrodialysis fresh water is greater than 30mg/L.It is reverse osmosis
By the reasonable circular treatment to feed liquid between film device I and reverse osmosis membrane apparatus II, so that for shale gas fracturing outlet liquid
Variation water quality it is more adaptable, a possibility that membranous system generates inorganic scale pollution, is smaller, and final outflow water almost realizes nearly zero
Discharge, makes membranous system give full play to effectiveness, obtains ideal treatment effect.Through reverse osmosis membrane apparatus I to electrodialysis concentrated water into one
Step, which carries out the concentrate after concentration decrement treatment, to be sent to evaporation and crystallization system and is evaporated crystallization；Into the concentration of vapo(u)rization system
Liquid, which is concentrated by evaporation, will generate crystal salt and condensate liquid, and crystal salt can be used as Nacl sale, and condensate liquid can be used as shale
The make-up water of gas fracturing outlet liquid.
Reverse osmosis membrane apparatus I and reverse osmosis membrane apparatus II in step (6), the preferred rolling of I film type of reverse osmosis membrane apparatus are high
Press mold, operating pressure are 3.0~4.0Mpa, and the operating pressure of high pressure reverse osmosis membrane is high, and salt rejection rate is high, and water yield is small, is suitable for
Highly concentrated water quality, and compared to mesolow film more resistant to pollution, since the water inlet of reverse osmosis membrane apparatus I is electrodialysis concentrated water,
Middle salt content and organic matter are all very high, and organic matter such as polyacrylamide containing larger molecular organics in shale gas fracturing outlet liquid
Deng, it is easy to fouling membrane is caused, preferably high-pressure membrane enables reverse osmosis membrane apparatus I to electrodialysis concentrated water treatment effect and antipollution
Power is all optimal；The preferred rolling low-pressure membrane of II film type of reverse osmosis membrane apparatus, operating pressure are 0.5~0.8Mpa, low-pressure membrane
Treatment effect when influent quality condition is preferable for salt in fracturing outlet liquid and organic matter is better than medium and high pressure film, water outlet
Water quality is more preferable, while energy consumption is also lower, and since the water inlet of reverse osmosis membrane apparatus II is electrodialysis fresh water, salt content and organic matter are all
Not high, the preferred low-pressure membrane of reverse osmosis membrane apparatus II is suitable for the process object of reverse osmosis membrane apparatus II.
Processing system device process is simple in the present invention, and strong operability can effectively remove shale gas fracturing outlet liquid
Middle suspended solid, complicated organic matter, salinity and other chemical components；Electrodialysis concentrated water after reverse osmosis concentrated reduction by obtaining
Reverse osmosis concentrated water the salt of waste liquid can be extracted by being concentrated by evaporation, realize resource recycling, electrodialysis fresh water warp
Cross the reverse osmosis freshwater that reverse osmosis further deep purifying is handled may be implemented near-zero release substantially；Solves shale air pressure
It splits and returns that drain process flow is complicated, the environment caused by salinity and organic matter and other chemical components are exceeded when reuse or discharge
Pollution problem, with good economic efficiency and social benefit.
Detailed description of the invention
With reference to the accompanying drawing and specific embodiment does more detailed description to the present invention:
Fig. 1 is the structural schematic diagram of processing system device in the present invention；
Fig. 2 is processing method process flow chart in the present invention；
It is specifically identified in figure are as follows:
1. foul water tank, 2. water inlet control valves, 3. coagulating sedimentation devices, 4. water inlet control valves, 5. Clear liquid tanks, 6. water inlet controls
Valve, 7. intake pumps, 8. ceramic film devices, 9. circulating pumps, 10. return flow control valves, 11. intake pumps, 12. water inlet control valves,
13. water inlet control valve, 14. electrodialysis process devices, 15. intake pumps, 16. electrodialysis fresh water rooms, 17. intake pumps, 18. electrodialysis
Concentrated water room, 19. water inlet control valves, 20. reverse osmosis membrane apparatus I, 21. water inlet control valves, 22. reverse osmosis membrane apparatus II, 23. water inlets
Pump, 24. evaporation concentrators, 25. outlet water control valves, 101. foul water tanks, 201. coagulating sedimentation devices, 202. Clear liquid tanks, 203. tubular types
Inorganic ceramic film filter, 301. electrodialysis process devices, 401. reverse osmosis membrane apparatus I, 402. reverse osmosis membrane apparatus II
Specific embodiment
Invention is further explained With reference to embodiment:
Embodiment 1
A kind of shale gas fracturing outlet liquid processing method, comprising the following steps:
(1) shale gas fracturing outlet liquid is added foul water tank and is stood；
(2) shale gas fracturing outlet liquid enters coagulating sedimentation device progress coagulating sedimentation；It is carried out in addition coagulating sedimentation device clear
Clearly, coagulant PAC dosage is 500mg/L, flocculation aid CPAM1200Dosage is 40mg/L；
(3) coagulating sedimentation supernatant enters Clear liquid tank clarification；Supernatant after coagulating sedimentation, which enters Clear liquid tank, to carry out into one
Step clarification, residence time 1h；
(4) clarified solution enters filter device and is filtered: filter device can be ceramic film device, i.e. tubular type inorganic ceramic membrane
Filter device, using membrane aperture for the ratio between 200nm, transmembrane pressure 0.16MPa, internal circulating load and inflow is 30:1, and to pottery
Porcelain film is backwashed after its membrane flux is decreased obviously 70% with acid & alkali liquid；
(5) filtered fluid enters electrodialysis process device, and the circular treatment time is 120min；Electrodialysis process device operation electricity
Press 20V, flow of inlet water 600L/h.m2, concentrated water flow 500L/h.m2, pole water NaCl concentration 0.75%, flow 200L/h.m2；
(6) electrodialysis concentrated water enters reverse osmosis membrane apparatus I and carries out concentration decrement treatment, and electrodialysis fresh water enters reverse osmosis membrane
Device II carries out deep purifying processing；The fresh water and electrodialysis fresh water that reverse osmosis membrane apparatus I generates enter reverse osmosis membrane dress together
The processing of II deep purifying is set, the concentrated water that reverse osmosis membrane apparatus I generates enters evaporation concentrator；It is generated in reverse osmosis membrane apparatus II
Concentrated water and electrodialysis concentrated water enter reverse osmosis membrane apparatus I together and decrement treatment, the fresh water generated in reverse osmosis membrane apparatus II are concentrated
For the final outflow water for the treatment of process；
I film type of reverse osmosis membrane apparatus selects rolling high-pressure membrane, operating pressure 3.0Mpa, II film class of reverse osmosis membrane apparatus
Type selects rolling low-pressure membrane, operating pressure 0.5Mpa；
(7) crystal salt and condensate liquid are generated through being concentrated by evaporation into the concentrated water of evaporation concentrator.
Embodiment 2
A kind of shale gas fracturing outlet liquid processing method, comprising the following steps:
(1) shale gas fracturing outlet liquid is added foul water tank and is stood；
(2) shale gas fracturing outlet liquid enters coagulating sedimentation device progress coagulating sedimentation；It is carried out in addition coagulating sedimentation device clear
Clearly, coagulant PAC dosage is 1200mg/L, flocculation aid CPAM1200Dosage is 80mg/L；
(3) coagulating sedimentation supernatant enters Clear liquid tank clarification；Supernatant after coagulating sedimentation, which enters Clear liquid tank, to carry out into one
Step clarification, residence time 1.5h；
(4) clarified solution enters filter device and is filtered: filter device can be ceramic film device, i.e. tubular type inorganic ceramic membrane
Filter device, using membrane aperture for the ratio between 200nm, transmembrane pressure 0.16MPa, internal circulating load and inflow is 30:1, and to pottery
Porcelain film is backwashed after its membrane flux is decreased obviously 70% with acid & alkali liquid；
(5) filtered fluid enters electrodialysis process device, and the circular treatment time is 140min；Electrodialysis process device operation electricity
Press 20V, flow of inlet water 600L/h.m2, concentrated water flow 500L/h.m2, pole water NaCl concentration 0.75%, flow 200L/h.m2；
(6) electrodialysis concentrated water enters reverse osmosis membrane apparatus I and carries out concentration decrement treatment, and electrodialysis fresh water enters reverse osmosis membrane
Device II carries out deep purifying processing；The fresh water and electrodialysis fresh water that reverse osmosis membrane apparatus I generates enter reverse osmosis membrane dress together
The processing of II deep purifying is set, the concentrated water that reverse osmosis membrane apparatus I generates enters evaporation concentrator；It is generated in reverse osmosis membrane apparatus II
Concentrated water and electrodialysis concentrated water enter reverse osmosis membrane apparatus I together and decrement treatment, the fresh water generated in reverse osmosis membrane apparatus II are concentrated
For the final outflow water for the treatment of process；
I film type of reverse osmosis membrane apparatus selects rolling high-pressure membrane, operating pressure 3.5Mpa, II film class of reverse osmosis membrane apparatus
Type selects rolling low-pressure membrane, operating pressure 0.65Mpa；
(7) crystal salt and condensate liquid are generated through being concentrated by evaporation into the concentrated water of evaporation concentrator.
Embodiment 3
A kind of shale gas fracturing outlet liquid processing method, comprising the following steps:
(1) shale gas fracturing outlet liquid is added foul water tank and is stood；
(2) shale gas fracturing outlet liquid enters coagulating sedimentation device progress coagulating sedimentation；It is carried out in addition coagulating sedimentation device clear
Clearly, coagulant PAC dosage is 2000mg/L, flocculation aid CPAM1200Dosage is 130mg/L；
(3) coagulating sedimentation supernatant enters Clear liquid tank clarification；Supernatant after coagulating sedimentation, which enters Clear liquid tank, to carry out into one
Step clarification, residence time 2h；
(4) clarified solution enters filter device and is filtered: filter device can be ceramic film device, i.e. tubular type inorganic ceramic membrane
Filter device, using membrane aperture for the ratio between 200nm, transmembrane pressure 0.16MPa, internal circulating load and inflow is 30:1, and to pottery
Porcelain film is backwashed after its membrane flux is decreased obviously 70% with acid & alkali liquid；
(5) filtered fluid enters electrodialysis process device, and the circular treatment time is 160min；Electrodialysis process device operation electricity
Press 20V, flow of inlet water 600L/h.m2, concentrated water flow 500L/h.m2, pole water NaCl concentration 0.75%, flow 200L/h.m2；
(6) electrodialysis concentrated water enters reverse osmosis membrane apparatus I and carries out concentration decrement treatment, and electrodialysis fresh water enters reverse osmosis membrane
Device II carries out deep purifying processing；The fresh water and electrodialysis fresh water that reverse osmosis membrane apparatus I generates enter reverse osmosis membrane dress together
The processing of II deep purifying is set, the concentrated water that reverse osmosis membrane apparatus I generates enters evaporation concentrator；It is generated in reverse osmosis membrane apparatus II
Concentrated water and electrodialysis concentrated water enter reverse osmosis membrane apparatus I together and decrement treatment, the fresh water generated in reverse osmosis membrane apparatus II are concentrated
For the final outflow water for the treatment of process；
I film type of reverse osmosis membrane apparatus selects rolling high-pressure membrane, operating pressure 4.0Mpa, II film class of reverse osmosis membrane apparatus
Type selects rolling low-pressure membrane, operating pressure 0.8Mpa；
(7) crystal salt and condensate liquid are generated through being concentrated by evaporation into the concentrated water of evaporation concentrator.
Embodiment 4
A kind of processing system device of shale gas fracturing outlet liquid is equipped with foul water tank, pretreatment unit, electrodialysis process dress
It sets, reverse osmosis membrane assembly and evaporation concentrator, reverse osmosis membrane assembly are equipped with reverse osmosis membrane apparatus I and reverse osmosis membrane apparatus II；It is dirty
Water tank is connect with pretreatment unit, and pretreatment unit is connect with electrodialysis process device, electrodialysis concentrated water room outlet with it is reverse osmosis
Film device I connects, and the outlet of electrodialysis fresh water room is connect with reverse osmosis membrane apparatus II, and reverse osmosis membrane apparatus I and evaporation concentrator connect
It connects.
Wherein pretreatment unit is equipped with coagulating sedimentation device and ceramic membrane, and coagulating sedimentation device water inlet end is connect with foul water tank, mixes
Solidifying settling vessel water outlet is connect with ceramic membrane water inlet end, and ceramic membrane concentrate recirculation end is connected in foul water tank by pipeline.
Foul water tank is for storing shale gas fracturing outlet liquid, and pretreatment unit is for mixing shale gas fracturing outlet liquid
Retrogradation is formed sediment and filtering pretreatment, coagulative precipitation tank are organic for removing large particulate matter and part colloid in fracturing outlet liquid
Object；Clarifying basin is used to retain the impurity particle that separation suspends, and tubular type inorganic ceramic film filter is returned for filtering retention pressure break
Remaining suspended solid material in drain.Electrodialysis process device be used to synchronize shale gas fracturing outlet liquid except COD and
Salt, reverse osmosis membrane apparatus I are used to that decrement treatment to be concentrated to electrodialysis concentrated water further progress, and reverse osmosis membrane apparatus II is to electrodialysis
The processing of fresh water further progress deep purifying.Reverse osmosis membrane apparatus II is concentrated the fresh water that electrodialysis concentrated water generates and enters reverse osmosis membrane
Device I and electrodialysis fresh water carry out deep purifying processing together；The concentrated water that reverse osmosis membrane apparatus I generates enters reverse osmosis membrane apparatus
II and electrodialysis concentrated water carry out concentration decrement treatment together, while water quality adjustment effect has been played to electrodialysis concentrated water.
The above device is connected by pipeline；Electrodialysis concentrated water further progress is concentrated through reverse osmosis membrane apparatus II
Concentrate after decrement treatment send to evaporation and crystallization system and is evaporated crystallization.
Embodiment 5
A kind of processing system device of shale gas fracturing outlet liquid is equipped with foul water tank, pretreatment unit, electrodialysis process dress
It sets, reverse osmosis membrane assembly and evaporation concentrator, pretreatment unit are equipped with coagulating sedimentation device, Clear liquid tank and ceramic membrane, coagulating sedimentation
Device water inlet end is connect with foul water tank, and coagulating sedimentation device water outlet is connect with ceramic membrane water inlet end, and ceramic membrane concentrate recirculation end passes through
Pipeline is connected in foul water tank, and between coagulating sedimentation device and ceramic membrane, electrodialysis process device goes out Clear liquid tank with ceramic membrane
Water end (W.E.) connection；
Reverse osmosis membrane apparatus is equipped with reverse osmosis membrane apparatus I and reverse osmosis membrane apparatus II；Foul water tank is connect with pretreatment unit,
Pretreatment unit is connect with electrodialysis process device, and the outlet of electrodialysis concentrated water room is connect with reverse osmosis membrane apparatus I, electrodialysis fresh water
Room outlet is connect with reverse osmosis membrane apparatus II, and reverse osmosis membrane apparatus I is connect with evaporation concentrator.
Ceramic membrane is tubular type inorganic ceramic film filter, and the above device is sequentially connected by pipeline；Through reverse osmosis
Permeable membrane device I, which send to evaporation and crystallization system the concentrate after electrodialysis concentrated water further progress concentration decrement treatment, to be steamed
Hair crystallization.
System and device device therefor is conventional equipment in the present invention, and specific operating procedure is exemplified below:
Gas well is returned to the 15L fracturing outlet liquid addition foul water tank ejected to store, coagulant PAC in coagulating sedimentation device
Dosage is 2000mg/L, flocculation aid CPAM1200Dosage is 130mg/L, the supernatant after coagulating sedimentation enter Clear liquid tank into
Row further clarification, residence time of the fracturing outlet liquid in Clear liquid tank are 1h.Later, clarified solution enters tubular type inorganic ceramic membrane
Filter device, wherein ceramic membrane membrane aperture is 200nm, the ratio between transmembrane pressure 0.16MPa, internal circulating load and inflow are 30:1,
And ceramic membrane is backwashed after flux depression 70% with acid & alkali liquid.Later, ceramic membrane water outlet enters electrodialysis process
Device, electrodialysis operation voltage 20V, flow of inlet water 600L/h.m2, concentrated water flow 500L/h.m2, pole water NaCl concentration 0.75%,
Flow 200L/h.m2, the circular treatment time is 140min.
Electrodialysis concentrated water enters I further progress of reverse osmosis membrane apparatus concentration decrement treatment later, and water inlet volume is
5.43L, pressure 3.5Mpa, the fresh water of generation enters reverse osmosis membrane apparatus II and electrodialysis fresh water to carry out at deep purifying together
Reason, the concentrated water of generation enter evaporation concentrator；Reverse osmosis membrane apparatus II handles electrodialysis fresh water further progress deep purifying,
Water inlet volume is 4L, and the concentrated water of pressure 1.5Mpa, generation enter mentioned-above reverse osmosis membrane apparatus I and electrodialysis concentrated water one
It rises and carries out concentration decrement treatment, while water quality adjustment effect has been played to electrodialysis concentrated water, reverse osmosis membrane apparatus II generates light
Water near-zero release.The concentrate that reverse osmosis membrane apparatus I enters vapo(u)rization system, which is concentrated by evaporation, will generate crystal salt and condensate liquid, knot
Brilliant salt can be used as Nacl sale, and condensate liquid can be used as the make-up water of shale gas fracturing outlet liquid, and evaporating temperature is 65 degree.
Each equipment effluent quality of the small testing device of citing is as shown in table 1.
Each equipment effluent quality of table 1
From the above, it can be seen that reverse osmosis 401 fresh water outlet water-quality COD value is 61.57mg/L, removal rate up to 81.22%,
TDS is 490mg/L, removal rate 96.43%.Concentrated water be concentrated reduced training it is obvious, have in 5.43L electrodialysis concentrated water 1.04L into
Enter vaporising device, so that into vaporising device treating capacity decrement 80.85%.
In reverse osmosis 402 fresh water outlet water quality COD value be 11.56mg/L, removal rate up to 83.08%, TDS value be 4mg/L,
Removal rate is up to 83.67%.
Method and processing system have the effect of in the present invention:
(1) it carries out coupling synergistic effect with two reverse osmosis treatment devices by electrodialysis, reverse osmosis membrane apparatus I is to electric osmose
Analysis concentrated water carries out concentration decrement treatment, and reverse osmosis membrane apparatus II carries out deep purifying processing to electrodialysis fresh water, so that concentration effect
Fruit and final outflow water water quality are attained by optimal；
(2) by the reasonable circular treatment to feed liquid between reverse osmosis membrane apparatus I and reverse osmosis membrane apparatus II, so that for
Shale gas fracturing outlet liquid variation water quality it is more adaptable, a possibility that generating inorganic scale pollution, is smaller, and final outflow water is several
It realizes near-zero release, so that membranous system is given full play to effectiveness, obtain ideal treatment effect；
(3) processing system process is simple, strong operability；
(4) can effectively remove suspended solid in shale gas fracturing outlet liquid, complicated organic matter, salinity and other chemistry at
Point, near-zero release may be implemented in fresh water substantially, and concentrated water can extract the salt of waste liquid, realizes resource recycling；
(5) it is complicated to solve shale gas fracturing outlet liquid process flow, when reuse or discharge salinity and organic matter and its
Problem of environmental pollution caused by its chemical component, with good economic efficiency and social benefit.
Above-mentioned specific embodiment is used to illustrate the present invention, is merely a preferred embodiment of the present invention, rather than
Limit the invention, within the spirit of the invention and the scope of protection of the claims, to the present invention make any modification,
Equivalent replacement, improvement etc., both fall within protection scope of the present invention.
Claims (9)
1. a kind of shale gas fracturing outlet liquid processing method, it is characterised in that: the following steps are included:
(1) shale gas fracturing outlet liquid is added foul water tank and is stood；
(2) shale gas fracturing outlet liquid enters coagulating sedimentation device progress coagulating sedimentation；
(3) coagulating sedimentation supernatant enters Clear liquid tank clarification；
(4) clarified solution enters filter device and is filtered；
(5) filtered fluid enters electrodialysis process device, and the circular treatment time is 120~160min；
(6) electrodialysis concentrated water enters reverse osmosis membrane apparatus I and carries out concentration decrement treatment, and electrodialysis fresh water enters reverse osmosis membrane apparatus
II carries out deep purifying processing；The fresh water and electrodialysis fresh water that reverse osmosis membrane apparatus I generates enter reverse osmosis membrane apparatus II together
Deep purifying processing, the concentrated water that reverse osmosis membrane apparatus I generates enter evaporation concentrator；The concentrated water generated in reverse osmosis membrane apparatus II
Enter reverse osmosis membrane apparatus I together with electrodialysis concentrated water and decrement treatment is concentrated, the fresh water generated in reverse osmosis membrane apparatus II is place
The final outflow water of science and engineering skill；
(7) crystal salt and condensate liquid are generated through being concentrated by evaporation into the concentrated water of evaporation concentrator.
2. a kind of shale gas fracturing outlet liquid processing method according to claim 1, it is characterised in that: the step (2)
The middle coagulating sedimentation device that enters carries out coagulating sedimentation, and coagulant includes PB1 gene, poly-ferric chloride PFC and polyaluminium
One of ferro-aluminum PAFC or more than one, in preferred embodiment be PAC, dosage be 500~2000mg/L, flocculation aid include sun
One of cationic polyacrylamide CPAM, non-ionic polyacrylamide NPAM and anionic polyacrylamide APAM or a kind of
More than, it is CPAM in preferred embodiment1200, dosage is 40~130mg/L.
3. a kind of shale gas fracturing outlet liquid processing method according to claim 1, it is characterised in that: the step (3)
Supernatant after middle coagulating sedimentation enters Clear liquid tank and is further clarified.
4. a kind of shale gas fracturing outlet liquid processing method according to claim 1, it is characterised in that: the step (4)
Middle filter device is ceramic film device, is further tubular type inorganic ceramic film filter, use membrane aperture for 20~2000nm,
Transmembrane pressure is 0.1~0.2MPa, has internal circulation apparatus in ceramic membrane filter device, the ratio between concentrated water internal circulating load and inflow are
10:1~60:1, ceramic membrane are backwashed after its flux depression 70% with acid & alkali liquid；Ceramic membrane fenestra in prioritization scheme
Diameter is 200nm, the ratio between transmembrane pressure 0.16MPa, internal circulating load and inflow are 30:1.
5. a kind of shale gas fracturing outlet liquid processing method according to claim 1, it is characterised in that: the step (5)
Middle electrodialysis process device operation voltage is 10~30V, flow of inlet water is 500~700L/h.m2, pole water concentration be 0.5%~
1.0%, pole water is the aqueous solution of NaCl；Electrodialysis operation voltage 20V, flow of inlet water 600L/h.m in prioritization scheme2, pole water
NaCl concentration 0.75%.
6. a kind of processing system device of shale gas fracturing outlet liquid, it is characterised in that: described device includes equipped with foul water tank, in advance
Processing unit, electrodialysis process device, reverse osmosis membrane assembly and evaporation concentrator, reverse osmosis membrane assembly are equipped with reverse osmosis membrane apparatus
I and reverse osmosis membrane apparatus II；Foul water tank is connect with pretreatment unit, and pretreatment unit is connect with electrodialysis process device, electric osmose
The outlet of analysis concentrated water room is connect with I water inlet of reverse osmosis membrane apparatus, the outlet of electrodialysis fresh water room and II water inlet of reverse osmosis membrane apparatus
Connection, the outlet of I concentrated water of reverse osmosis membrane apparatus are connect with evaporation concentrator, and I water outlet of reverse osmosis membrane apparatus and reverse osmosis membrane fill
The connection of II water inlet is set, the outlet of II concentrated water of reverse osmosis membrane apparatus is connect with I water inlet of reverse osmosis membrane apparatus, reverse osmosis membrane apparatus II
The fresh water of middle generation is the final outflow water for the treatment of process.
7. a kind of processing system device of shale gas fracturing outlet liquid according to claim 6, it is characterised in that: described pre-
Processing unit is equipped with coagulating sedimentation device and ceramic membrane filter device, and coagulating sedimentation device water inlet end is connect with foul water tank, coagulating sedimentation
Device water outlet is connect with ceramic membrane filter device water inlet end, and ceramic membrane filter device concentrate recirculation end is connected to sewage by pipeline
On case, the ratio between reflux concentrated water and water inlet are 1:3~5.
8. a kind of processing system device of shale gas fracturing outlet liquid according to claim 6, it is characterised in that: described pre-
Processing unit is additionally provided with Clear liquid tank, and Clear liquid tank is between coagulating sedimentation device and ceramic membrane.
9. a kind of processing system device of shale gas fracturing outlet liquid according to claim 7, it is characterised in that: described anti-
I film type of permeable membrane device selects rolling high-pressure membrane, and operating pressure is 3.0~4.0Mpa, the choosing of II film type of reverse osmosis membrane apparatus
With rolling low-pressure membrane, operating pressure is 0.5~0.8Mpa.
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