CN109851104A - A kind of oil gas field high slat-containing wastewater processing method and equipment - Google Patents
A kind of oil gas field high slat-containing wastewater processing method and equipment Download PDFInfo
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- 238000003672 processing method Methods 0.000 title claims abstract description 19
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 36
- 238000012545 processing Methods 0.000 claims abstract description 32
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- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 29
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- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000001223 reverse osmosis Methods 0.000 claims description 11
- 238000004065 wastewater treatment Methods 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001424 calcium ion Inorganic materials 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
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- 239000007789 gas Substances 0.000 description 73
- 238000012360 testing method Methods 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
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- 239000005416 organic matter Substances 0.000 description 8
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of oil gas field high slat-containing wastewater processing method and equipment, this method comprises: (S1) flocculation sedimentation；(S2) light electrolysis ozone oxidation: light electrolysis ozone Oxidation Treatment will be carried out to 5.0~8.0, then by waste water by the pH value adjustment of the waste water of step (S1) flocculation sedimentation processing, and will remove the COD in waste water；(S3) aeration softening: sodium hydroxide and sodium carbonate will be added in the waste water Jing Guo step (S2) light electrolysis ozone Oxidation Treatment, will then be aerated, and react sodium hydroxide and sodium carbonate with the precipitable metal ion in waste water and generate sediment；(S4) it is separated by solid-liquid separation: the sediment obtained by step (S3) aeration sofening treatment is separated from waste water；(S5) bipolar membrane electrodialysis: the waste water Jing Guo step (S4) solid-liquid separation treatment is subjected to bipolar membrane electrodialysis treatment, obtains acid solution, aqueous slkali and initial demineralized water.This method simple process, save the cost can effectively remove COD and salt in waste water, and purification of waste water effect is good.
Description
Technical field
The present invention relates to a kind of methods of the high slat-containing wastewater generated in field of waste water treatment more particularly to oil gas field processing
And equipment.
Background technique
Petroleum, natural gas are the most common energy of modern society.It needs that many kinds of substance is added in oilfield development process, generates
The high waste water of complicated component, salt content.These wastewater sources are extensive, production quantity is big, a large amount of salinity will cause environment in water
Very big influence, processing and transport have very big difficulty, therefore how to be effectively treated to these high slat-containing wastewaters, are one
A urgent problem to be solved.
The target of high slat-containing wastewater processing technique is to reach the zero-emission of waste water, it is desirable that the salt in waste water is with solid or liquid
The form of body is recycled or is utilized.Therefore, organic matter and salinity in high slat-containing wastewater are effectively treated using suitable technology,
To guarantee subsequent film device stable operation, generate can reuse soda acid guarantee.
Micro-electrolysis method is to constitute primary battery system using waste water, Zero-valent Iron and active carbon three, by iron and activated carbon it
Between 1.2eV potential difference removal waste water in pollutant, be widely used in the processing of organic wastewater with difficult degradation thereby in recent years, answer
With needing to carry out in the lower situation of pH value during micro-electrolysis treatment waste water, therefore, using being needed before this method to useless
The pH value of water is adjusted, and the cost of wastewater treatment is greatly improved.
Ozonation is the organic matter in the strong oxidizing property degradation water using its own.The degradation of Pre-Ozonation on Organic Matter has
There is certain selectivity, and the speed of oxidation reaction is slower.A certain amount of H is usually added in alkaline environment2O2, metal ion,
Active carbon, metal oxide etc. generate that oxidisability is stronger and the hydroxyl radical free radical of non-selectivity improves oxidation efficiency.
Light electrolysis Ozonation can overcome to a certain extent ozone to consume hydroxide ion in use, reduce
The problem of waste water pH value；Overcome when carrying out wastewater treatment using micro-electrolysis stuffing merely, oxidation dissolution zeroth order during the reaction
Iron consumes H in water+, improve waste water pH value the drawbacks of.Therefore, combining both can not only control in reaction process
PH value more can be improved waste water treatment efficiency.
Salinity is the Main way of modern high slat-containing wastewater treatment research in membrane separation process removal waste water, passes through variety classes
The combination of film can be handled for different waste water.Membrane separating method is a kind of physical method, can be effectively concentrated
Organic matter and metal ion solution in waste water etc., but cannot effectively degrade, precipitate organic matter and metal ion in water, it cannot
Reach the target that zero-emission is realized in high slat-containing wastewater treatment process.
Therefore, how easy, economically carry out the target that high slat-containing wastewater processing reaches wastewater zero discharge, be one
Technical problem urgently to be resolved.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of processing of oil gas field high slat-containing wastewater
Method and apparatus.This method simple process, save the cost can remove (the Chemical Oxygen of COD in waste water
Demand, COD) and salt, the effect of purification of waste water it is good.
To achieve the above object, the technical solution of oil gas field high slat-containing wastewater processing method of the present invention is as follows:
A kind of oil gas field high slat-containing wastewater processing method, comprising:
(S1) flocculation sedimentation: carrying out homogeneity processing for the waste water, flocculant be added, suspended matter in the waste water and
Part larger molecular organics are converted into sediment；
(S2) light electrolysis ozone oxidation: will treated that waste water pH value adjustment arrives by the step (S1) flocculation sedimentation
5.0~8.0, then the waste water is subjected to light electrolysis ozone Oxidation Treatment, remove the COD in the waste water；
(S3) aeration softening: hydroxide will be added in the waste water after the step (S2) light electrolysis ozone Oxidation Treatment
Then sodium and sodium carbonate are aerated with adjusting the pH value of the waste water, make the sodium hydroxide and the sodium carbonate with it is described
Precipitable metal ion reaction in waste water generates sediment；
(S4) it is separated by solid-liquid separation: will be by the step (S3) obtained described sediment of aeration sofening treatment from the waste water
In separate；
(S5) waste water Jing Guo the step (S4) solid-liquid separation treatment bipolar membrane electrodialysis: is subjected to bipolar membrane electrodialysis
Processing, obtains acid solution, aqueous slkali and initial demineralized water.
Further, further includes: it is reverse osmosis, the initial demineralized water is concentrated, a concentrated water and a desalination are obtained
Water.
Further, further includes: concentrated water processing, by a concentrated water with subsequent by the step (S4) separation of solid and liquid
The waste water of reason mixes, and carries out the step (S5) bipolar membrane electrodialysis treatment, and obtained demineralized water carries out the reverse osmosis treatment,
Secondary concentrated water is obtained, then the secondary concentrated water is mixed with the subsequent waste water Jing Guo the step (S4) solid-liquid separation treatment, then
The step (S5) bipolar membrane electrodialysis treatment is carried out, the concentrated water treatment process is continued, up to the amount in the concentrated water is pre-
If amount is following.
Further, the sediment separated in the step (S4) separation of solid and liquid is dehydrated, by abjection
Water carries out all steps of the oil gas field high slat-containing wastewater processing method in addition to the step (S1) flocculation sedimentation.
Further, described (S1) before the flocculant being added in the step (S1) flocculation sedimentation further include: according to
The work pH value of the flocculant carries out pH value adjustment to the waste water.
Further, the step of described (S3) aeration softening are as follows: a certain amount of sodium hydroxide and sodium carbonate is added, makes described useless
The pH value of water is 9.0~11.0, is aerated, and makes the concentration of calcium ion in the waste water lower than 45mg/L, the concentration of magnesium ion
Lower than 30mg/L.
Further, before sodium hydroxide, sodium carbonate is added, the concentration and magnesium ion of the calcium ion in the waste water are detected
Concentration.
Further, by the tail gas of the ozone gas in the step (S2) light electrolysis ozone oxidation after drying,
It is continued to use for the step (S2) light electrolysis ozone oxidation.
Further, the Adding Way of flocculant described in step (S1) flocculation sedimentation are as follows: bodied ferric sulfate is added, makes
After it is sufficiently mixed with the waste water, polyacrylamide (Polyacrylamide, PAM) aqueous solution is added.
Further, the acid solution and the aqueous slkali generated in step (S5) bipolar membrane electrodialysis is for described
Step (S1), the step (S2), the pH value adjustment of waste water in the step (S3) at least one step.
Oil gas field high slat-containing wastewater processing method of the invention compared with prior art, has the advantage that
The present invention makes the suspended matter of waste water using flocculation sedimentation in the technical process that the high slat-containing wastewater of oil gas field is handled
It is converted into precipitating；Using the pollutant in light electrolysis ozone oxidation waste water, achieve the purpose that remove COD；Soften work by aeration
Skill removes precipitable metal ion such as calcium ion, magnesium ion in waste water, prevents the solid-liquid separation step and Bipolar Membrane later
In electrodialysis step, because the presence of calcium ion, magnesium ion makes film generate fouling on film, separation of solid and liquid and bipolar membrane electrodialysis are influenced
Technological effect；Salt content in waste water is greatly reduced using bipolar membrane electrodialysis, and generates the acid solution of recoverable
And aqueous slkali.The technical process of above-mentioned processing waste water does not generate the waste liquid of outlet, and can be carried out continuously the processing of waste water.
To sum up, by above-mentioned processing step, make oil gas field high slat-containing wastewater processing method simple process of the invention, save
Cost, can effectively remove COD and salt in waste water, and the effect of purification of waste water is good.
The present invention also provides a kind of equipment using above method processing oil gas field high slat-containing wastewater:
A kind of oil gas field high slat-containing wastewater processing equipment, comprising: light electrolysis ozone reaction integrated apparatus, the light electrolysis
Ozone reaction integrated apparatus includes: the light electrolysis ozone reactor of can-like, is provided with iron in the light electrolysis ozone reactor
Carbon micro-electrolysis filler layer；The iron-carbon micro-electrolysis filler layer includes several strings hung above the light electrolysis ozone reactor
Filler string；Every string filler is several filler units connected one by one by flexible material.
Further, there is the interval flowed through for waste water between the adjacent filler unit.
Further, the filler unit accounts for the 70%~80% of the light electrolysis ozone reactor volume.
Further, the light electrolysis ozone reactor further includes the aeration dress below the iron-carbon micro-electrolysis filler layer
It sets, the aerator is connect by air inlet pipe with ozone generator.
Further, the gas outlet positioned at light electrolysis ozone reactor upper end passes through the one of escape pipe and gas-drying apparatus
End connection, the other end of the gas-drying apparatus connect to form gas return path by muffler with the air inlet pipe；The air inlet
Pipe is the first connecting pin with the connecting pin of the muffler, between first connecting pin and the ozone generator it is described into
First check valve is intratracheally installed, opening direction is to flow to first connecting pin from the ozone generator；Described time
Second one-way valve is intratracheally installed, opening direction is to flow to first connecting pin from the gas-drying apparatus.
Further, the light electrolysis ozone reaction integrated apparatus further includes first gas flowmeter, the first gas
Flowmeter is mounted in the air inlet pipe between first connecting pin and first check valve.
Further, the light electrolysis ozone reaction integrated apparatus further includes second gas flowmeter, the second gas
Flowmeter is mounted on the muffler between the gas-drying apparatus and the second one-way valve.
Further, the air inlet pipe is connected to by first testing tube with ozone concentration analyzer, first test
The connecting pin of pipe and the air inlet pipe is second connection end, and the second connection end is sent out in first check valve and the ozone
Between raw device；The first valve is installed on first testing tube.
Further, the ozone concentration analyzer is connected to by the second testing tube with the muffler, the muffler and
The connecting pin of second testing tube is third connecting pin, and the third connecting pin is in the gas-drying apparatus and second list
To between valve；The second valve is installed on second testing tube.
Further, the bottom end of the light electrolysis ozone reactor is additionally provided with sewage draining exit, the row of being equipped on the sewage draining exit
Dirty valve.
Oil gas field high slat-containing wastewater processing equipment of the invention compared with prior art, has the advantage that
1. light electrolysis is smelly in the light electrolysis ozone reaction integrated apparatus of oil gas field high slat-containing wastewater processing equipment of the present invention
Iron-carbon micro-electrolysis filler layer inside oxygen reactor includes several string filler strings to gather in radial direction；By the way that several strings are filled out
Material string is hung up, and be come into full contact with each filler unit on every a string of fillers can with waste water and is reacted, improves micro- electricity
Solve filler utilization rate, avoid previous iron-carbon micro-electrolysis filler put together and generate passivation, hardened phenomenon, Yi Jipin
Numerous the problems such as supplementing iron simple substance into filler and discharging stirring frequently is carried out to iron-carbon micro-electrolysis filler.
2. in currently preferred technical solution, between the adjacent filler unit of every string filler and adjacent string filler it
Between have the interval flowed through for waste water.
3. ozone gas is passed through light electrolysis ozone reaction in aerator in the further preferred technical solution of the present invention
After device, under the action of air-flow, several string filler strings of iron-carbon micro-electrolysis filler layer will do it swing, promotes filler unit and gives up
The progress of water come into full contact with to promote micro-electrolysis reaction, meanwhile, metal ion that micro-electrolysis reaction generates and from the micro- electricity of iron carbon
The active carbon split away off on solution filler can be as the catalyst of ozone oxidation reaction, therefore, in light electrolysis ozone reactor
Ozone oxidation reaction do not have to additional addition catalyst, ozone gas can be passed directly in light electrolysis ozone reactor, give up
The oxidation effectiveness of water is good.
4. in the further preferred technical solution of the present invention, the unreacted ozone that is passed into light electrolysis ozone reactor
Gas, by muffler, can be passed into light electrolysis ozone reactor again and be reacted, no into after crossing the drying of gas-drying apparatus
The reclaimer for needing to be arranged ozone gas improves the utilization rate of ozone gas.
Detailed description of the invention
Fig. 1 is high slat-containing wastewater processing method flow chart of the present invention；
Fig. 2 is the schematic diagram of light electrolysis ozone reaction integrated apparatus in high slat-containing wastewater processing equipment of the present invention.
The structural schematic diagram that Fig. 3 is in Fig. 29；
A kind of structural schematic diagram in connecting pin that Fig. 4 is in Fig. 2 11 and 10；
Another structural schematic diagram in connecting pin that Fig. 5 is in Fig. 2 11 and 10；
In figure: 1-light electrolysis ozone reactor；2-ozone generators；3-gas-drying apparatus；4-centrifugal pumps；5-into
Water pipe；6-iron-carbon micro-electrolysis filler layers；7-flexible materials；8-inner ears；9-micro-electrolysis stuffing appending disks；10-aeration plates；
11-air inlet pipe；12-first gas flowmeters；13-the first check valve；14. the first valve；15-ozone concentration analyzers；
16-escape pipes；17-second gas flowmeters；18-the second valve；19-outlet pipes；20-sewage draining exits；21-blowdown valves；
22-mufflers；23-the first testing tube；24-the second testing tube；25-second one-way valves；
61-filler strings；
91-grid sections；
The first connecting pin a-；B-second connection end；C-third connecting pin；The 4th connecting pin d-.
Specific embodiment
To clearly demonstrate design philosophy of the invention, with reference to the accompanying drawing to oil gas field high slat-containing wastewater of the invention at
Reason method overall process is described in detail, and the present invention is not limited to following embodiments in protection scope.The reference present invention,
Those skilled in the art can obtain the optimization processing work of different quality according to the different corresponding technological parameters of water quality survey
Skill makes the water quality that water is discharged meet technique requirement and environmental requirement.
Embodiment 1
It is as shown in Figure 1 the first embodiment of oil gas field high slat-containing wastewater processing method of the present invention, in the present embodiment,
The pH value of oil gas field high slat-containing wastewater is 7~10, and average COD concentration is 1800mg/L, and conductivity is 5000~6000 μ S/cm.
Oil gas field high slat-containing wastewater processing method, comprising:
(S1) flocculation sedimentation: carrying out homogeneity processing for waste water, and flocculant is added, big point of suspended matter and part in waste water
Sub- organic matter is converted into sediment；
After mixing by oil gas field high slat-containing wastewater, the addition for carrying out flocculant is added into uniformly mixed waste water
The bodied ferric sulfate of 150mg/L adjusts pH value, and then the PAM aqueous solution of 15mg/L is added in stirring, after staticly settling, in waste water
Suspended matter and part larger molecular organics are converted into sediment and remove from waste water.
(S2) light electrolysis ozone oxidation: will by the waste water pH value adjustment after step (S1) flocculation sedimentation to 5.0~8.0,
Above-mentioned waste water is passed through in light electrolysis ozone reaction tank again, while being passed through ozone gas into reactor tank, passes through micro-electrolysis stuffing
Waste water is handled jointly with ozone gas, removes the COD in waste water.
In the step, ozone gas flow 4L/min, the tail gas of ozone gas continues to be passed through micro- after being dried
In electrolysis ozone reactor tank, circulation continues to handle to subsequent sewage, this can be improved the utilization rate of ozone gas, in figure
Arrow direction is the flow direction of ozone gas.
(S3) aeration softening: sodium hydroxide and carbon will be added in the waste water Jing Guo step (S2) light electrolysis ozone Oxidation Treatment
Then sour sodium is aerated with adjusting its pH value, react sodium hydroxide and sodium carbonate with the precipitable metal ion in waste water
Generate sediment.
A certain amount of sodium hydroxide is added in the step and sodium carbonate adjusts pH value 9.0~11.0, sodium hydroxide and carbonic acid
The specific additional amount of sodium by the waste water pH value before the step process by determining.Calcium ion in waste water after the step process
Concentration is lower than 45mg/L, and magnesium ion concentration is lower than 30mg/L.
(S4) it is separated by solid-liquid separation: the sediment obtained by step (S3) aeration sofening treatment is separated from waste water；
The sediment isolated to sediment obtained in step (S1) and step (S4) is dehydrated, dewatered precipitating
Mud cake is made in object, can be used for other purposes.It is smelly by light electrolysis from the device that the water deviate from sediment is passed through light electrolysis ozone oxidation
Oxygen aoxidize so that abjection water in organic matter effectively degraded, this part abjection water can also carry out step (S2)~(S5) or
(S2) processing of~(S6) method avoids the harmful substance in the part water from polluting environment.
(S5) bipolar membrane electrodialysis: being passed through bipolar membrane electrodialysis device for the waste water after step (S4) filtration treatment,
By the bipolar membrane electrodialysis treatment of device, acid solution, aqueous slkali and initial demineralized water, acid solution and aqueous slkali therein are obtained
It can be used for step (S1) flocculation sedimentation, step (S2) light electrolysis ozone oxidation and step (S3) and be aerated at least one step in softening
In waste water PH adjusting.
(S6) reverse osmosis: the initial demineralized water obtained after step (S5) bipolar membrane electrodialysis treatment is concentrated,
The operating pressure of reverse osmosis membrane is 2MPa, and the high-pressure side of reverse osmosis membrane obtains a concentrated water, and low-pressure side obtains a demineralized water.
The a concentrated water also needed processing that the step obtains: a concentrated water is passed through bipolar membrane electrodialysis device
In, step (S5) bipolar membrane electrodialysis is carried out together with the waste water that step in subsequent wastewater treatment (S4) separation of solid and liquid obtains, is obtained
To acid solution, aqueous slkali and demineralized water, acid solution and aqueous slkali therein can be used for step (S1) flocculation sedimentation, step
(S2) light electrolysis ozone oxidation and step (S3) are aerated the adjusting of the waste water PH in softening at least one step.Desalination therein
Water, then be passed through in reverse osmosis equipment and be concentrated, obtain secondary concentrated water and secondary demineralized water.It similarly, can also be by secondary concentrated water
It is passed through in bipolar membrane electrodialysis device, processes together with being separated by solid-liquid separation obtained waste water with step in subsequent wastewater treatment (S4)
Journey is same as the treatment process of a concentrated water, and circulation executes above-mentioned treatment process, until obtain the amount of concentrated water no more than predetermined amount or
Until person no longer generates concentrated water, stop the process.The predetermined amount of concentrated water amount is carried out according to the case where waste water with related process requirement
It determines.
In other embodiments of the invention can be reverse osmosis without containing step (S6), it will be by step (S5) Bipolar Membrane electricity
The primary demineralized water of dialysis processing is detected, can be direct by primary demineralized water if water quality meets the requirement of technique and environment
Discharge, no longer needs to the reverse osmosis treatment by step (S6), if water quality is unsatisfactory for requiring, it is also necessary to it is reverse osmosis to carry out step (S6)
Processing.
Embodiment 2
The step of second of embodiment of oil gas field high slat-containing wastewater processing method of the present invention, is same as the step of embodiment 1
Suddenly, difference from example 1 is that:
In the present embodiment, the pH value of oil gas field high slat-containing wastewater is 5~9, and average COD concentration is 1000mg/L, conductance
Rate is 7000~10000 μ S/cm.
In step (S1) flocculation sedimentation, the adition process of flocculant are as follows: 100mg/L is added into uniformly mixed waste water
Bodied ferric sulfate, adjust pH value, then the PAM of 10mg/L is added in stirring, and after staticly settling, suspended matter and part are big in waste water
Molecular organic is converted into sediment and removes from waste water.
In step (S2) light electrolysis ozone oxidation, ozone gas flow 3L/min.
It is separated by solid-liquid separation in step (S4), is separated by solid-liquid separation using the method for inclined plate sedimentation.
It should be noted that step (S1) flocculation sedimentation, step (S2) light electrolysis ozone oxidation and step (S3) aeration are soft
Contain pH value detection device in the discharging device of the technique of change, also contains hardness determination in the device of step (S3) aeration softening
Device, these devices are all conventional equipments in the prior art.These are all that those skilled in the art are understanding inventive concept
On the basis of can be made based on its basic skills, therefore will not enumerate herein.
Embodiment 3
In example as shown in Figure 2, the light electrolysis ozone reaction one of oil gas field high slat-containing wastewater processing equipment of the present invention
Makeup is set, comprising: can-like light electrolysis ozone reactor 1 is provided with iron-carbon micro-electrolysis filler layer 6 in light electrolysis ozone reactor 1；
Iron-carbon micro-electrolysis filler layer 6 includes several string filler strings 61 of 1 top of hanging light electrolysis ozone reactor；Every string filler string 61 is
Several filler units connected one by one by flexible material 7.In this example, filler unit is the burning that diameter is 1.5~2.0cm
Ball filler is tied, flexible material 7 is cord, after the punching of each ball filler, a string of filler strings 61 are connected into using cord,
The densely covered several string filler strings 61 of cross-wise direction constitute the iron-carbon micro-electrolysis filler layer 6 in this example, are existed by cord hanging
The upper end of light electrolysis ozone reactor 1, in this example, there are four above inside for the upper end setting of light electrolysis ozone reactor 1
The inner ear 8 of protrusion, is supported by micro-electrolysis stuffing appending disk 9 on inner ear 8, as shown in figure 3, more grid sections 91 are provided with,
Every string filler string 61 ties up to grid section 91 by cord and is hung, and several string filler strings 61 are equably hung anti-in light electrolysis ozone
It answers in device 1, makes filling rate 70%~80% of the ball filler in light electrolysis ozone reactor 1, i.e. ball filler Zhan Wei electricity
The 70%~80% of 1 volume of ozone reactor is solved, iron-carbon micro-electrolysis filler layer 6 fills too closely to be unfavorable for the activity to fall off
The flowing of powdered carbon and the wadding body of generation, it is excessively loose to will lead to iron-carbon micro-electrolysis filler layer 6 and the contact area of waste water is small, thus
Reduce its contact probability and the extent of reaction with useless Organic substance in water.
By the filler string 61 for conspiring to create ball filler, comes into full contact with every string filler string 61 with waste water and react, improve
The utilization rate of micro-electrolysis stuffing avoids hardened, the problem of passivation of traditional iron-carbon micro-electrolysis filler.Disappear during micro-electrolysis reaction
Consumption iron and active carbon can fall on the bottom of light electrolysis ozone reactor 1, will not influence subsequent micro-electrolysis reaction, avoid and passing
Unite micro-electrolysis reaction in, need frequently to supplement iron and frequent progress discharging stirring the problem of.
When needing to increase or replacing filler string, the filler needed replacing is taken off from grid section 91, is filled out what is gone here and there
Material ties up on grid section 91.
Have between adjacent ball filler on every string filler string 61 and between adjacent filler string 61 and is flowed through for waste water
Interval.On every string filler string 61, it is spaced apart between adjacent ball filler by the way that cord knots, keeps every ball filler equal
It can be come into full contact with waste water, come into full contact with the organic matter in waste water with iron-carbon micro-electrolysis filler layer 6 and react, further increase
The utilization rate of iron-carbon micro-electrolysis filler；Further, it is possible to the wadding generated in the active powdered carbon and water that fall off after preventing micro-electrolysis reaction
Filler blocking occurs for body, hinders correlative.
Above-mentioned 7 material of flexible material for connecting ball filler can be polyvinyl chloride (Polyvinyl chloride,
PVC), thin zinc-coated wire and thin copper wire etc.；The material of micro-electrolysis stuffing appending disk 9 can be 316 stainless steels or galvanized steel etc..
The material that flexible material 7 and micro-electrolysis stuffing appending disk 9 are corroded using above-mentioned resistance to ozone oxidation and resistance to waste water, can prevent waste water
The loss of iron-carbon micro-electrolysis filler layer 6 and the corruption of micro-electrolysis stuffing appending disk 9 caused by being broken in treatment process because of flexible material 7
Erosion, makes them have longer service life.
The upper end of iron-carbon micro-electrolysis filler layer 6 is provided with outlet pipe 19, and micro- electricity will be passed through in light electrolysis ozone reactor 1
Water discharge after solving ozone reaction.
As shown in Fig. 2, light electrolysis ozone reactor 1 further includes aerator, aerator is located at iron-carbon micro-electrolysis filler
The lower section of layer 6, ozone generator 2 is connect with aerator by air inlet pipe 11, for providing into light electrolysis ozone reactor 1
Ozone gas carries out oxidation processes to waste water, and the aerator in this example is the multiple aeration plates uniformly connecting with air inlet pipe 11
10, as shown in figure 4, the air inlet pipe 11 connecting in light electrolysis ozone reactor 1 with aeration plate 10 is multiple concentric loop pipe, this
Sample can install more aeration plate 10, come into full contact with ozone gas with waste water, complete the ozone oxidation reaction of waste water.
In other examples of the invention, the air inlet pipe 11 connecting in light electrolysis ozone reactor 1 with aeration plate 10 can also
To be spiral tube structure as shown in Figure 5.
Waste water carries out ozone oxidation reaction and micro-electrolysis reaction simultaneously in light electrolysis ozone reactor 1, eliminates point
Not She Zhi reaction unit cost.
While carrying out micro-electrolysis reaction, aeration plate 10 is aerated, and under the action of air-flow, filler string 61 be will do it
It swings, promotes the progress of ball filler and waste water come into full contact with to promote micro-electrolysis reaction, meanwhile, what micro-electrolysis reaction generated
Metal ion and the active carbon split away off from iron-carbon micro-electrolysis filler can be as the catalyst of ozone oxidation reaction, can
Promote the generation of OH, improves the degradation rate of COD in water.Therefore, the ozone oxidation reaction in light electrolysis ozone reactor 1 is not
With additional addition catalyst, ozone gas can be passed directly in light electrolysis ozone reactor 1.
As shown in Fig. 2, one end of gas-drying apparatus 3 is by escape pipe 16 and is located at 1 upper end of light electrolysis ozone reactor
Gas outlet connection, for the ozone gas for having neither part nor lot in reaction to be dried.It is had neither part nor lot in since gas-drying apparatus 3 is only used for removal
Moisture in the ozone gas of reaction, so the desiccant in gas-drying apparatus 3 is using the neutral desiccant such as calcium chloride or silica gel
?.The other end of gas-drying apparatus 3 connect to form gas return path by muffler 22 with air inlet pipe 11；Air inlet pipe 11 and return-air
The connecting pin of pipe 22 is the first connecting pin a, is equipped with first in the air inlet pipe 11 between the first connecting pin a and ozone generator 2
Check valve 13, opening direction are to flow to the first connecting pin a from ozone generator 2, prevent ozone gas from flowing back into ozone
In device 2；Second one-way valve 25 is installed in muffler 22, opening direction is to flow to the first connecting pin a from gas-drying apparatus 3,
It prevents that ozone gas being accidentally passed into muffler 22 when ozone generator 2 is passed through ozone gas to air inlet pipe 11.It has neither part nor lot in
The ozone gas of reaction flows through second one-way valve 25 and the first connecting pin a, by air inlet pipe after gas-drying apparatus 3 is dry
It is flowed into light electrolysis ozone reactor 1 after 11, continues to participate in ozone oxidation reaction, do not had to setting ozone recyclable device in this way, mention
The high utilization rate of ozone gas.
It is also equipped with first gas flowmeter 12 in air inlet pipe 11 between the first connecting pin a and the first check valve 13,
For monitoring the gas flow for being passed through light electrolysis ozone reactor 1 by the ozone gas that ozone generator 2 generates.
Second gas flowmeter is also equipped on the muffler 22 between gas-drying apparatus 3 and second one-way valve 25
17, for monitoring the flow for having neither part nor lot in the ozone gas of reaction.
In the example, ozone concentration analyzer 15 is connected to by first testing tube 23 with air inlet pipe 11, the first test
The connecting pin of pipe 23 and air inlet pipe 11 is second connection end b, second connection end b the first check valve 13 and ozone generator 2 it
Between.First valve 14 is mounted on the first testing tube, when the first valve 14 is opened, the ozone gas of the generation of ozone generator 2
It can flow into ozone concentration analyzer 15 by the first testing tube 23, can be obtained by ozone concentration analyzer 15 by ozone
The concentration for the ozone gas that generator 2 generates plays the role of the working condition for monitoring ozone generator 2.
Ozone concentration analyzer 15 is connected to by the second testing tube 24 with muffler 22, muffler 22 and the second testing tube
Connecting pin is third connecting pin c, third of the third connecting pin between gas-drying apparatus 3 and second one-way valve 25, in this example
Connecting pin is also between gas-drying apparatus 3 and second gas flowmeter 17；The company of first testing tube 23 and the second testing tube 24
Connecing end is the 4th connecting pin d, and the 4th connecting pin d is between the first valve 13 and ozone concentration analyzer 15；Second valve 18 peace
On the second testing tube 24 between third connecting pin c and the 4th connecting pin d.When the closing of the first valve 14, the second valve 18
When unlatching, the ozone gas for having neither part nor lot in reaction after drying can flow into ozone concentration analyzer by the second testing tube 24
In 15, at this point, ozone concentration analyzer 15 can measure the concentration for having neither part nor lot in the ozone gas of reaction.
The bottom end of light electrolysis ozone reactor 1 is additionally provided with sewage draining exit 20, and blowdown valve 21 is equipped on sewage draining exit 20.By
The sludge that light electrolysis ozone reaction generates is discharged by opening blowdown valve 21 through sewage draining exit 20.
The course of work of light electrolysis ozone reaction integrated apparatus in this example are as follows: passing through water inlet pipe 5 by centrifugal pump 4 will
Waste water is pumped into light electrolysis ozone reactor 1, while ozone generator 2 being opened, by 11 delivery of ozone gas of air inlet pipe,
Aeration plate 10 starts to expose into light electrolysis ozone reactor 1 into ozone gas.Waste water is filled out by aeration plate 10 and iron-carbon micro-electrolysis
The bed of material 6 to water outlet 19 is discharged.
For ozone oxidation reaction, the ozone gas amount being passed through is higher than real reaction requirement, to having in waste water
The removal of machine object could more thoroughly after the ozone gas by that will have neither part nor lot in reaction carries out the drying of gas-drying apparatus 3, be passed through
Muffler 22, which backs within, participates in reaction in light electrolysis ozone reactor 1, do not need the reclaimer of setting ozone gas,
After handling a certain amount of waste water, the bottom end of light electrolysis ozone reactor 1 has the accumulation of sludge, needs to open at sewage draining exit 20
Blowdown valve 21 sludge is discharged.
During carrying out wastewater treatment, the first valve 14 and the second valve 18 may each be the state of closing, or
One of them is the state opened, and when the first valve 14 is opened, and the second valve 18 is closed, ozone concentration analyzer 15 can be surveyed
Obtain the concentration of ozone gas that ozone generator 2 generates；When the first valve 14 is closed, and the second valve 18 is opened, ozone concentration is surveyed
The concentration of ozone gas for having neither part nor lot in reaction can be measured by determining instrument 15.
It should be noted that some of which structure can have different selections other than the above-mentioned specific example provided.
Such as, the structure for hanging filler string 61 can also be using other structures, for example, the top of light electrolysis ozone reactor 1 is uniformly set
Hook is set, the hanging of filler string 61 is tied up on small ring on these hooks, or by filler string 61, small ring string is filled out in light electrolysis
On the grid section 91 for expecting appending disk 9；Filler unit can also be other three-dimensional shapes in addition to ball filler, for example, cube or circle
Cylinder；The production of filler string 61 can not also punch in ball filler, be fixed ball filler one by one using netted cord；The
One testing tube 23 and the second testing tube 24 can also be connected with ozone concentration analyzer 15 respectively；Etc., and these are all abilities
What field technique personnel can be made on the basis of understanding inventive concept based on its basic skills, therefore no longer an example herein
It lifts.
Finally, it will be appreciated that the principle that embodiment of above is intended to be merely illustrative of the present and the example that uses
Property embodiment, however the present invention is not limited thereto.For those of ordinary skills, do not depart from it is of the invention
In the case where principle and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection model of the invention
It encloses.
Claims (10)
1. a kind of oil gas field high slat-containing wastewater processing method characterized by comprising
(S1) flocculation sedimentation: carrying out homogeneity processing for the waste water, and flocculant, suspended matter and part in the waste water is added
Larger molecular organics are converted into sediment；
(S2) light electrolysis ozone oxidation: will by the pH value adjustment of the waste water of the step (S1) flocculation sedimentation processing to 5.0~
8.0, then the waste water is subjected to light electrolysis ozone Oxidation Treatment, remove the COD in the waste water；
(S3) aeration softening: sodium hydroxide and carbon will be added in the waste water Jing Guo the step (S2) light electrolysis ozone Oxidation Treatment
Then sour sodium is aerated with adjusting the pH value of the waste water, make in the sodium hydroxide and the sodium carbonate and the waste water
Precipitable metal ion reaction generate sediment；
(S4) it is separated by solid-liquid separation: the sediment obtained by the step (S3) aeration sofening treatment is divided from the waste water
It separates out and；
(S5) bipolar membrane electrodialysis: the waste water Jing Guo the step (S4) solid-liquid separation treatment is carried out at bipolar membrane electrodialysis
Reason, obtains acid solution, aqueous slkali and initial demineralized water.
2. oil gas field high slat-containing wastewater processing method according to claim 1, which is characterized in that further include: it is reverse osmosis, it will
The initial demineralized water is concentrated, and a concentrated water and a demineralized water are obtained.
3. oil gas field high slat-containing wastewater processing method according to claim 2, which is characterized in that further include: concentrated water processing,
Concentrated water is mixed with the subsequent waste water Jing Guo the step (S4) solid-liquid separation treatment, it is double to carry out the step (S5)
The processing of pole membrane electrodialysis, obtained demineralized water carry out the reverse osmosis treatment, obtain secondary concentrated water, then will the secondary concentrated water and
The subsequent waste water mixing Jing Guo the step (S4) solid-liquid separation treatment, then carry out at the step (S5) bipolar membrane electrodialysis
Reason continues the concentrated water treatment process, up to the amount in the concentrated water is below predetermined amount.
4. oil gas field high slat-containing wastewater processing method according to claim 1-3, which is characterized in that by the step
Suddenly the sediment separated in (S4) separation of solid and liquid is dehydrated, and the water of abjection flocculate except the step (S1)
All steps of the wastewater treatment method of the high saliferous of the oil gas field other than precipitating.
5. oil gas field high slat-containing wastewater processing method according to claim 1-3, which is characterized in that (S3)
It is aerated bating step are as follows: a certain amount of sodium hydroxide and sodium carbonate is added, makes the pH value 9.0~11.0 of the waste water, carries out
Aeration, makes the concentration of calcium ion in the waste water lower than 45mg/L, and the concentration of magnesium ion is lower than 30mg/L.
6. oil gas field high slat-containing wastewater processing method according to claim 1-3, which is characterized in that by the step
Suddenly the tail gas of the ozone gas in (S2) light electrolysis ozone oxidation is after drying, for the step (S2) light electrolysis ozone
Oxidation continues to use.
7. oil gas field high slat-containing wastewater processing method according to claim 1-3, which is characterized in that the step
(S5) acid solution and the aqueous slkali generated in bipolar membrane electrodialysis is for the step (S1), (S2), described
The pH value adjustment of waste water in step (S3) at least one step.
8. a kind of oil gas field high slat-containing wastewater processing equipment characterized by comprising light electrolysis ozone reaction integrated apparatus,
The light electrolysis ozone oxidation integrated apparatus includes: the light electrolysis ozone reactor of can-like, the light electrolysis ozone reactor
In be provided with iron-carbon micro-electrolysis filler layer；The iron-carbon micro-electrolysis filler layer includes hanging on the light electrolysis ozone reactor
Several string filler strings of side；Every string filler is several filler units connected one by one by flexible material.
9. oil gas field high slat-containing wastewater processing equipment according to claim 8, which is characterized in that the filler unit accounts for institute
State the 70%~80% of light electrolysis ozone reactor volume.
10. oil gas field high slat-containing wastewater processing equipment according to claim 8, which is characterized in that be located at the light electrolysis
The gas outlet of ozone reactor upper end is connected by one end of escape pipe and gas-drying apparatus, the other end of the gas-drying apparatus
It connect to form gas return path with the air inlet pipe by muffler；The connecting pin of the air inlet pipe and the muffler is the first company
End is connect, the first check valve is installed in the air inlet pipe between first connecting pin and the ozone generator, is opened
Direction is to flow to first connecting pin from the ozone generator；Second one-way valve is installed in the muffler, is opened
Direction is to flow to first connecting pin from the gas-drying apparatus.
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