CN112960815A - Recycling treatment method and device for fracturing flowback fluid - Google Patents
Recycling treatment method and device for fracturing flowback fluid Download PDFInfo
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Abstract
The invention provides a method and a device for recycling fracturing flow-back fluid. The method comprises the following steps: sequentially carrying out electric flocculation treatment, electric floatation treatment, electrocatalysis treatment and electric adsorption treatment on the fracturing flow-back fluid to obtain desalted fresh water and electric adsorption concentrated water; adding alkali into the electro-adsorbed concentrated water for hardness removal and filtering, and performing bipolar membrane electrodialysis treatment on the filtered water to obtain acid, alkali and desalted fresh water. The method can effectively remove petroleum, suspended matters, organic matters, total iron, total mineralization, bacteria, total hardness and the like in the fracturing flow-back fluid through the treatment processes of electric flocculation, electric floatation, electric catalysis, electric adsorption and the like, and the treated water quality meets the requirement of the reuse water quality; and simultaneously, further carrying out hardness removal, filtration and bipolar membrane electrodialysis treatment on the electro-adsorbed concentrated water, wherein the generated acid can be reused in the production processes of acidification, acid fracturing and the like of an oil field, and the generated alkali can be reused in an alkali-adding hardness removal treatment process, so that zero emission of the fracturing flow-back fluid is really realized.
Description
Technical Field
The invention belongs to the technical field of oilfield wastewater treatment, and relates to a method and a device for recycling fracturing flow-back fluid.
Background
Fracturing is one of the main measures for increasing the yield of an oil-gas well, a high-viscosity fracturing fluid is pressed into a stratum by a high-pressure pump set in the fracturing construction process, a seam is formed, a propping agent is carried into the fracture, the fracturing fluid needs to be drained back after fracturing is finished, and the amount of the drained-back fluid generally accounts for 70% of the amount of the injected fracturing fluid. Because the fracturing flowback fluid contains pollutants such as petroleum hydrocarbons, broken and uncracked guar gum/jelly, high molecular polymers, high-concentration salt, heavy metals, various chemical additives and the like, if the treatment is not up to the standard, the pollutants are directly discharged, so that the environmental influence is caused. The fracturing flow-back fluid water quality parameters are as follows: 10-300 mg/L of oil, 60-1200 mg/L of suspended matters, 5-10 mPa.s of viscosity, 10-50 mg/L of total iron, 1500-80000 mg/L of mineralization degree, 120-7900 mg/L, SRB 2.5.5-60 pieces/mL of total hardness and 800-1500 mg/L of COD.
At present, the main treatment modes of the fracturing flowback fluid are as follows: the first is direct reuse without treatment. This is the simplest and least expensive treatment that is often used in the united states, but continued reuse can lead to problems such as residual chemicals, sediment, and debris that can cause the fracturing fluid to fail or the fracturing process to plug; the second is deep well injection. The flowback fluid is injected and stored by simply drilling some other well. This treatment mode may contaminate drinking water underground, which has been banned in some countries; the third is in-situ treatment and reuse. The treatment method is to remove most suspended substances in the sewage and scaling substances such as barium, calcium, iron, magnesium, strontium and the like which can block a gas well, and then mix the substances with fresh water for fracturing again; the limit is less, and the safety and the efficiency are high.
Publication No. CN106865835A discloses a method and a device for treating shale gas fracturing flowback waste liquid, the method comprises the steps of carrying out water quality mixing adjustment, aeration/electric coagulation coupling iron removal, ion precipitation descaling and electrooxidation sterilization on the fracturing flowback waste liquid separated from a shale gas well field separator, and obtaining treated effluent water quality indexes: pH7.91, total iron 0.22mg/L, total suspended matter 9mg/L, total hardness 22mg/L, petroleum 0.8mg/L, COD34mg/L, ammonia nitrogen 12.4mg/L, and meets the requirements of recycling and reinjection. The method is an effective treatment method for the flowback liquid with low total mineralization, but complex fracturing flowback liquids with high salt content, high COD content and the like are difficult to recycle, and the total mineralization, the organic matter content and the like of water are strictly required by preparing fresh fracturing liquid, thick oil steam injection boiler feed water and the like.
Disclosure of Invention
Based on the technical problems existing in the recycling of the fracturing flow-back fluid in the prior art, the invention aims to provide a recycling treatment method of the fracturing flow-back fluid, which has the characteristics of high efficiency, environmental protection, simple process and reliable operation and can realize the resource recycling of the fracturing flow-back fluid; the invention also aims to provide a recycling treatment device for the fracturing flow-back fluid.
The purpose of the invention is realized by the following technical means:
in one aspect, the invention provides a method for recycling a fracturing flow-back fluid, which comprises the following steps:
sequentially carrying out electric flocculation treatment, electric floatation treatment, electrocatalysis treatment and electric adsorption treatment on the fracturing flow-back fluid to obtain desalted fresh water and electric adsorption concentrated water;
adding alkali into the electro-adsorbed concentrated water for hardness removal and filtering, and performing bipolar membrane electrodialysis treatment on the filtered water to obtain acid, alkali and desalted fresh water.
In the invention, through electric flocculation treatment, the produced flocculant can aggregate and remove part of pollutants in the fracturing flow-back fluid; then, performing electro-flotation treatment, and removing suspended matters, petroleum and excessive electroflocculation flocs, colloids and the like in the fracturing flow-back fluid by utilizing bubbles formed by oxygen separated out from the anode and hydrogen separated out from the cathode in the electro-flotation treatment process; then electrocatalysis treatment is carried out, hydroxyl free radicals and other strong oxidants generated in the electrocatalysis treatment process are utilized to realize the degradation of residual polymers (guar gum) and various chemical additives in the fracturing flowback fluid, and finally, the oxidative decomposition is carried out to obtain CO2And H2O, reducing COD; performing electric adsorption treatment, wherein in the electric adsorption treatment process, anions and cations in the solution move to the electrode under the action of an electric field and are adsorbed on an electric double layer formed between the electrode and the solution interface through capacitance desalination and under the condition of external voltage, so that salt is removed, and the obtained fresh water is recycled; the concentrated water adsorbed in the electro-adsorption process is subjected to alkali-adding hardness removal and Gole membrane filtration to remove substances such as calcium ions and magnesium ions in the water, which cause membrane stack blockage; and then performing electrodialysis treatment by using a bipolar membrane, wherein anions and cations respectively pass through an anion exchange membrane and a cation exchange membrane and are respectively combined with hydrogen ions and hydroxide ions generated by water electrolysis of the bipolar membrane to generate acid and alkali, the generated acid is reused in an acidification or acid fracturing process of an oil field, the produced alkali is reused in an alkali-adding and hardness-removing section of the treatment process, and the generated desalted water is reused. The treatment process can really realize zero emission of the fracturing flow-back fluid, and the obtained desalted water can reach the standard of resource recycling.
In the method, preferably, the cathode plate and the anode plate adopted in the electrocoagulation treatment are all soluble electrode plates, the cathode plate and the anode plate both comprise aluminum electrode plates or iron electrode plates, and the distance between the cathode plate and the anode plate is 20-60 mm; the electric flocculation current density is 5-15 mA/cm2The reaction time of the electric flocculation is 20-50 min.
In the electric flocculation process, pollutants in the fracturing flow-back fluid are gathered and removed by the generated polyaluminium or polyferric flocculant through a soluble electrode plate (such as an aluminium electrode plate, an iron electrode plate and the like).
In the method, preferably, the anode plate used in the electro-flotation treatment is a titanium-coated ruthenium oxide plate, the cathode plate is a stainless steel plate, the cathode plate is positioned above the anode plate, the distance between the cathode plate and the anode plate is 1-2 cm, and the cathode plate is provided with a plurality of holes (determined according to the size of the anode plate) with the aperture of 6 mm; the current density of the electro-flotation is 5-10 mA/cm2(ii) a The reaction time of the electro-flotation is 5-20 min.
In the above method, preferably, the method for preparing the titanium-coated ruthenium oxide electrode plate comprises:
ruthenium trichloride hydrate, ethylene glycol and acetic acid are mixed according to the weight ratio of (200-400) mg: (10-15) mL: (1-2) mixing and dissolving in a ratio of mL to obtain a solution A;
after a titanium plate is polished by sand paper and degreased (conventional operation in the field), hydrofluoric acid and nitric acid are adopted according to the volume ratio of (1-2): 3, etching the mixed solution to obtain a treated titanium plate;
and coating the solution A on the surface of the treated titanium plate, drying, treating at 350-400 ℃ for 8-15 min, repeating for 3-5 times, and roasting at 450-500 ℃ for 1.5-3 h to obtain the titanium-coated ruthenium oxide polar plate.
In the electro-flotation process, the special titanium-coated ruthenium oxide polar plate (anode plate) and the perforated stainless steel polar plate (cathode plate) are subjected to electro-flotation treatment, the polar plate has good conductivity and long service life, and flocs which are not removed in the electro-flocculation process and colloids, fine suspended matters, dispersed oil drops and the like which are difficult to remove in the electro-flocculation process are taken out of the water surface by 10-30 mu m oxygen bubbles and hydrogen bubbles which are separated out from the anode plate and the cathode plate respectively, and are scraped by a slag scraping system carried by the electro-flotation process.
The electric flocculation and the electric floatation in the invention can be an integral structural unit or can be divided into two units, and the upper part of the electric floatation device is provided with a scum scraping system and a scum collecting system.
In the above method, preferably, the anode plate used for the electrocatalytic treatment is a surface-modified titanium plate or cathodeThe polar plate is a graphite plate, and the distance between the cathode plate and the anode plate is 30-70 mm; the bottom of the electro-catalytic treatment device is provided with an activated carbon porous material, and is uniformly provided with an air distribution device (provided with an air blowing device), the air supply amount is 0.5-2.5L/min, water flows in from the bottom, and flows out from the top; the current density of the electrocatalytic reaction is 5-20 mA/cm2The reaction time of the electrocatalytic reaction is 60-120 min.
In the above method, preferably, the method for preparing the surface-modified titanium plate comprises:
tin dichloride, iridium trichloride and ruthenium trichloride are mixed according to a molar ratio of (4-6): (2-4): (0.5-2) mixing and dissolving in a hydrochloric acid solution of ethylene glycol to obtain a mixed solution; and coating the mixed solution on the surface of the titanium plate, drying, treating at 450-500 ℃ for 8-15 min, repeating for 5-8 times, and finally roasting at 500-600 ℃ for 1-2 h to obtain the surface-modified titanium plate.
In the electrocatalysis process, electrocatalysis treatment is carried out through a special surface-modified titanium plate (anode plate) and a graphite plate (cathode plate), and degradation of residual polymer (guar gum) and various chemical additives in fracturing flowback fluid is realized through strong oxidants such as hydroxyl free radicals generated by electrodes, and finally, the degradation is carried out through oxidation decomposition to CO2And H2O, reducing COD; the oil content of the effluent water after electrocatalysis treatment is less than 3mg/L, the suspended matter is less than 5mg/L, and the COD is less than 80 mg/L.
In the method, preferably, the cathode plate and the anode plate used for the electro-adsorption treatment are all carbon material-conductive polymer composite electrode plates, and the distance between the cathode plate and the anode plate is 1-3 mm; the voltage of the electro-adsorption is 1.0-1.8V, and the reaction time of the electro-adsorption is 15-30 min.
In the above method, preferably, the method for manufacturing the carbon material-conductive polymer composite electrode plate includes:
dissolving a carbon material in water, performing ultrasonic dispersion, adding a polymer monomer and ammonium persulfate, performing ice-bath reaction for 4-6 hours, collecting a precipitation product, and performing vacuum drying (wherein the dosage proportion of the carbon material, the polymer monomer and the ammonium persulfate is reasonably selected according to actual operation); and then mixing the vacuum-dried product with polyvinylidene fluoride and graphite powder according to the mass ratio of (5-8): (1-2): and (2) uniformly mixing, and performing pressure forming to obtain the carbon material-conductive polymer composite electrode plate.
In the above method, preferably, the carbon material includes one or more of activated carbon, carbon nanotubes, and graphene.
In the above method, preferably, the polymer monomer includes pyrrole and/or aniline.
In the electric adsorption process, the special carbon material-conductive polymer composite electrode plate is used for electric adsorption treatment, under the condition of externally adding 1.0-1.8V voltage, anions and cations in the solution move towards the electrode under the action of an electric field and are adsorbed on an electric double layer formed between the electrode and a solution interface, so that salt-containing components are removed, the TDS (total dissolved solids) of treated effluent is less than 1000mg/L, and desalted fresh water is recycled.
In the above method, preferably, the process of removing hardness and filtering the concentrated water by adding alkali to the concentrated water by electro-adsorption comprises:
adding alkali liquor into the concentrated water obtained by electro-adsorption to adjust the pH value to be more than 12, introducing carbon dioxide to precipitate scaling ions, and filtering by a Gole membrane to remove the precipitation of the scaling ions.
In the above method, the pore diameter of the Goll membrane is preferably 0.5 to 10 μm.
According to the invention, the precipitation of scaling ions such as calcium ions and magnesium ions in the electro-adsorption concentrated water can be effectively removed by adding alkali for hardness removal and Gole membrane filtration, and the content of the scaling ions such as calcium ions and magnesium ions in effluent filtered by the Gole membrane can be reduced to below 10 mg/L.
In the above method, preferably, the bipolar membrane electrodialysis treatment has a current density of 30 to 60mA/cm2。
According to the invention, through bipolar membrane electrodialysis treatment, anions and cations respectively pass through an anion exchange membrane and a cation exchange membrane and are respectively combined with hydrogen ions and hydroxide ions generated by bipolar membrane electrolysis water to generate acid and alkali, the concentration of the generated acid is more than 1.5mol/L, the concentration of the generated alkali is more than 2.0mol/L, the generated acid is reused in an oil field acidification or acid pressure process, the produced alkali is reused in an alkali-adding and hardness-removing section of a treatment process, and the generated desalted water is reused. The treatment process can really realize zero emission of the fracturing flow-back fluid, and the obtained desalted water can reach the standard of resource recycling.
In another aspect, the present invention further provides a recycling treatment apparatus for a fracturing flow-back fluid, comprising:
the electric flocculation unit is used for flocculating and removing part of pollutants in the fracturing flow-back fluid;
the electric floating unit is used for removing suspended matters and petroleum in the fracturing flow-back fluid and excessive floccules and colloids in electric flocculation;
the electro-catalytic unit is used for oxidizing and degrading residual polymers and chemical additives in the fracturing flow-back fluid;
the electro-adsorption unit is used for generating desalted fresh water and electro-adsorption concentrated water through capacitive desalination;
the hard removing unit is used for adding alkali to realize the precipitation of scale ions in the electric adsorption concentrated water;
a filtering unit for filtering out the precipitate of scaling ions;
the bipolar membrane electrodialysis unit is used for electrolyzing the filtered water to obtain acid, alkali and desalted fresh water;
the electric flocculation unit, the electric air flotation unit, the electric catalysis unit, the electric adsorption unit, the hardness removal unit, the filtering unit and the bipolar membrane electrodialysis unit are sequentially communicated; the bipolar membrane electrodialysis unit is communicated with the hardness removal unit.
The invention has the beneficial effects that:
the method can effectively remove petroleum, suspended matters, organic matters, total iron, total mineralization degree, bacteria, total hardness and the like in the fracturing flow-back fluid through the treatment processes of electric flocculation, electric floatation, electric catalysis, electric adsorption and the like, and the treated water quality meets the requirements of preparing fresh fracturing fluid, feeding water of a thick oil thermal recovery steam injection boiler and other recycling water quality; and simultaneously, further carrying out hardness removal, filtration and bipolar membrane electrodialysis treatment on the electro-adsorbed concentrated water, wherein the generated acid can be reused in the production processes of acidification, acid fracturing and the like of an oil field, and the generated alkali can be reused in an alkali-adding hardness removal treatment process, so that zero emission of the fracturing flow-back fluid is really realized. All treatment sections in the method are based on an electrically driven treatment method, no chemical agent is additionally added, and secondary pollution is eliminated. According to the invention, each processing unit is modularly combined and can be combined and switched according to the requirement, and meanwhile, the electro-adsorption unit can also adjust the desalination rate according to the water requirement, so that the processing unit combination and the unit process parameter adjustment are realized according to the recycling requirement.
Drawings
Fig. 1 is a schematic view of a fracturing flow-back fluid recycling device used in the embodiment of the present invention.
Description of the symbols of the drawings:
1. an electrocoagulation unit; 2. an electrically floating unit; 3. an electrocatalytic unit; 4. an electro-adsorption unit; 5. a hard removal unit; 6. a filtration unit; 7. a bipolar membrane electrodialysis unit.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example (b):
the present embodiment provides a reuse treatment apparatus for a fracturing flowback fluid, as shown in fig. 1, the apparatus includes:
the electric flocculation unit 1 is used for removing part of pollutants in the fracturing flow-back fluid through flocculation;
the electric floating unit 2 is used for removing suspended matters and petroleum in the fracturing flow-back fluid and excessive floccules and colloids in electric flocculation;
the electro-catalytic unit 3 is used for oxidizing and degrading residual polymers and chemical additives in the fracturing flow-back fluid;
the electro-adsorption unit 4 is used for generating desalted fresh water and electro-adsorption concentrated water through capacitive desalination;
the hard removing unit 5 is used for adding alkali to realize the precipitation of scale ions in the electric adsorption concentrated water;
a filtering unit 6 for filtering out the precipitate of scaling ions;
a bipolar membrane electrodialysis unit 7 for electrolyzing the filtered water to obtain acid, alkali and desalted fresh water;
the electric flocculation unit 1, the electric floatation unit 2, the electric catalysis unit 3, the electric adsorption unit 4, the hardness removal unit 5, the filtering unit 6 and the bipolar membrane electrodialysis unit 7 are communicated in sequence; the bipolar membrane electrodialysis unit 7 is communicated with the hardness removing unit 5.
The embodiment also provides a method for recycling the fracturing flow-back fluid by using the recycling treatment device for the fracturing flow-back fluid, which comprises the following steps:
the fracturing flow-back fluid obtained in the oil extraction process of a certain oil field is selected, and the water quality parameters of the fracturing flow-back fluid are as follows: 20.8mg/L of oil, 201mg/L of suspended matters, 5.3mPa.s of viscosity, 8mg/L of total iron, 5086mg/L of degree of mineralization, 128mg/L, SRB 2.5 of total hardness, 2.5/mL of total hardness and 980 COD, 980mg/L of COD. The fracturing flowback fluid is recycled as follows:
(1) electric flocculation and electric floatation treatment:
and (3) introducing the pressure backflow liquid into an electric flocculation unit 1 (an electric flocculation device), wherein the cathode plate and the anode plate in the electric flocculation device are both soluble electrode plates, the cathode plate and the anode plate are both aluminum electrode plates, and the distance between the cathode plate and the anode plate is 30 mm. The current density of the electric flocculation is 7.5mA/cm2The reaction time of the electric flocculation is 20 min; and the polyaluminium generated by the electric flocculation removes the pollutant accumulation in the fracturing flow-back fluid.
The effluent of the electric flocculation is introduced into an electric floatation unit 2 (electric floatation device), wherein an anode plate in the electric floatation device is a titanium-coated ruthenium oxide polar plate, a cathode plate is a stainless steel polar plate, the cathode plate is positioned above the anode plate, the anode plate is positioned at the bottom in the electric floatation device, the distance between a cathode plate and an anode plate is 1.5cm, and a plurality of holes (determined according to the size of the polar plate) with the aperture of 6mm are arranged on the cathode plate.
The preparation method of the titanium-coated ruthenium oxide polar plate comprises the following steps:
ruthenium trichloride hydrate, ethylene glycol and acetic acid were mixed according to a ratio of 300 mg: 10mL of: 1.5mL to obtain a solution A; polishing and degreasing an industrial titanium plate by using sand paper, and etching by using a mixed solution (volume ratio is 1:3) of hydrofluoric acid and nitric acid to obtain a treated titanium plate; and coating the solution A on the surface of the treated titanium plate, drying at 60 ℃ for 10min, treating at 370 ℃ for 10min, repeating for 5 times, and roasting at 470 ℃ for 2h to obtain the titanium-coated ruthenium oxide polar plate.
The current density of the electro-flotation treatment is 7.5mA/cm2And the time of the electro-flotation treatment is 10min, flocs which are not removed in the electro-flocculation process, colloids, fine suspended matters, dispersed petroleum oil drops and the like which are difficult to remove in the electro-flocculation process are taken out of the water surface through 10-30 mu m oxygen bubbles and hydrogen bubbles which are respectively separated out of an anode plate and a cathode plate of the electro-flotation device, and the flocs, the fine suspended matters, the dispersed petroleum oil drops and the like are scraped by a slag scraping system carried by the electro-flotation device.
The effluent quality after the electric flocculation and electric floatation treatment is shown in the following table 1:
table 1:
| analysis item | Numerical value | Analysis item | Numerical value |
| Oil content mg/L | 1.8 | Suspended substance mg/L | 10.1 |
| Viscosity mPa.s | 1.9 | Total iron mg/L | /(means nothing) |
| Degree of mineralization (TDS) mg/L | 4998 | Total hardness mg/L | 109 |
| SRB number/mL | / | COD mg/L | 850 |
(2) Electrocatalytic treatment:
introducing effluent subjected to flocculation and electro-flotation treatment in the step (1) into an electro-catalysis unit 3 (electro-catalysis device), wherein an anode plate adopted by the electro-catalysis device is a surface-modified titanium plate, a cathode plate is a graphite plate, and the distance between a cathode plate and an anode plate is 40 mm; the preparation method of the surface-modified titanium plate comprises the following steps:
mixing and dissolving tin dichloride, iridium trichloride and ruthenium trichloride in a molar ratio of 5:3:1 in a hydrochloric acid solution of ethylene glycol to obtain a mixed solution; and (3) coating the mixed solution on the surface of a titanium plate, drying at 100 ℃ for 10min, treating at 500 ℃ for 10min, repeating for 8 times, and finally roasting at 550 ℃ for 1.5h to obtain the surface-modified titanium plate.
The electro-catalytic treatment device is of a vertical cylindrical structure, the bottom of the device is distributed with an activated carbon porous material, and is uniformly provided with an air supply device, the air supply amount is 2L/min, water flows in from the bottom, and flows out from the top; the current density of the electrocatalytic treatment is 10mA/cm2The reaction time is 100 min. The degradation of residual polymer (guar gum) and various chemical additives in the fracturing flowback fluid is realized through strong oxidants such as hydroxyl free radicals generated by the electrode, and the degradation is finally oxidized and decomposed into CO2And H2O, and reduces COD.
The quality of the effluent after electrocatalysis treatment is shown in the following table 2:
table 2:
| analysis item | Numerical value | Analysis item | Numerical value |
| Oil content mg/L | Not detected out | Suspended substance mg/L | 3.3 |
| Viscosity mPa.s | 1.5 | Total iron mg/L | / |
| Degree of mineralization mg/L | 4907 | Total hardness mg/L | 102 |
| SRB number/mL | / | COD mg/L | 78 |
Through electrocatalysis treatment, the COD value in the effluent quality is greatly reduced, and the water quality of the effluent after electrocatalysis can reach the first-level standard of Integrated wastewater discharge Standard (GB 8978-1996).
(3) Electro-adsorption treatment:
introducing the effluent subjected to the electrocatalysis treatment in the step (2) into an electric adsorption unit 4 (an electric adsorption device), wherein cathode plates and anode plates adopted by the electric adsorption device are carbon material-conductive polymer composite electrode plates, and the distance between the cathode plates and the anode plates is 1.5 mm; the preparation method of the carbon material-conductive polymer composite electrode plate comprises the following steps:
dissolving graphene in water, performing ultrasonic dispersion, adding polymer monomer pyrrole and ammonium persulfate (the dosage is conventional operation in the field), performing ice-bath reaction for 5 hours, collecting a precipitation product, and performing vacuum drying; and then uniformly mixing the vacuum-dried product with polyvinylidene fluoride and graphite powder according to the mass ratio of 6:1:2, and carrying out pressure molding to obtain the carbon material-conductive polymer composite electrode plate.
The voltage of the electro-adsorption is 1.6V, the reaction time of the electro-adsorption is 20min, so that the anions and cations in the solution move to the electrode under the action of the electric field and are adsorbed on an electric double layer formed between the electrode and the solution interface, thereby removing salt-containing components and obtaining desalted fresh water and electro-adsorbed concentrated water.
The water quality of the desalted fresh water after the electro-adsorption treatment is shown in the following table 3:
table 3:
| analysis item | Numerical value | Analysis item | Numerical value |
| Oil content mg/L | / | Suspended substance mg/L | / |
| Viscosity mPa.s | / | Total iron mg/L | / |
| TDSmg/L | 785 | Total hardness mg/L | 58 |
| SRB number/mL | / | COD mg/L | 67 |
After electric adsorption treatment, the quality of the outlet fresh water meets the water quality requirements of water used in oil field production processes such as preparation of fracturing fluid, feeding of thick oil injection steam boilers and the like. The water quality of the concentrated water after the electro-adsorption treatment has the TSD of 10221mg/L, the total hardness of 240mg/L and the COD of 75 mg/L.
(4) And (3) hardness removal and filtration treatment:
adding alkali liquor into the residual concentrated water after the electro-adsorption treatment to adjust the pH value to 12, then introducing carbon dioxide to precipitate the scale formation ions such as calcium ions, magnesium ions and the like in the electro-adsorption concentrated water, filtering and removing the scale formation ions by a 1 mu m Gole membrane, and reducing the content of the scale formation ions such as calcium ions, magnesium ions and the like in the filtered water to below 10 mg/L.
(5) Bipolar membrane electrodialysis treatment:
the filtered effluent is subjected to bipolar membrane electrodialysis treatment, the bipolar membrane electrodialysis adopts a three-compartment configuration and is conventionally arranged in the field and is formed by compounding a cation exchange layer (N-type membrane), an interface hydrophilic layer (catalyst layer) and an anion exchange layer (P-type membrane), and H between the catalyst layers is catalyzed under the action of a direct current electric field2Dissociation of O into H+And OH-And pass through the yin and yang membranes, respectively, as H+And OH-By virtue of this feature, salts in aqueous solution can be converted into the corresponding acids and bases without introducing new components, collected by membrane separation, and the current density of bipolar membrane electrodialysis is 40mA/cm2The acid and base produced are concentratedThe degrees are respectively 1.7mol/L and 2.2mol/L, acid is recycled in the acidification or acid fracturing process of the oil field, alkali is recycled in the alkali-adding and hardness-removing unit of the treatment process, and desalted water generated by bipolar membrane electrodialysis is recycled.
Claims (10)
1. A recycling treatment method of fracturing flowback fluid comprises the following steps:
sequentially carrying out electric flocculation treatment, electric floatation treatment, electrocatalysis treatment and electric adsorption treatment on the fracturing flow-back fluid to obtain desalted fresh water and electric adsorption concentrated water;
adding alkali into the electro-adsorbed concentrated water for hardness removal and filtering, and performing bipolar membrane electrodialysis treatment on the filtered water to obtain acid, alkali and desalted fresh water.
2. The method according to claim 1, wherein the cathode plate and the anode plate adopted in the electrocoagulation treatment are both soluble electrode plates, the cathode plate and the anode plate both comprise aluminum electrode plates or iron electrode plates, and the spacing between the cathode plate and the anode plate is 20-60 mm; the electric flocculation current density is 5-15 mA/cm2The reaction time of the electric flocculation is 20-50 min.
3. The method according to claim 1, wherein the electro-flotation treatment adopts titanium-coated ruthenium oxide plates as anode plates, stainless steel plates as cathode plates, the cathode plates are positioned above the anode plates, the distance between the cathode plates and the anode plates is 1-2 cm, and a plurality of holes with the diameter of 6mm are formed in the cathode plates; the current density of the electro-flotation is 5-10 mA/cm2(ii) a The reaction time of the electro-flotation is 5-20 min;
preferably, the preparation method of the titanium-coated ruthenium oxide polar plate comprises the following steps:
ruthenium trichloride hydrate, ethylene glycol and acetic acid are mixed according to the weight ratio of (200-400) mg: (10-15) mL: (1-2) mixing and dissolving in a ratio of mL to obtain a solution A;
after a titanium plate is polished and degreased by sand paper, hydrofluoric acid and nitric acid are adopted according to the volume ratio of (1-2): 3, etching the mixed solution to obtain a treated titanium plate;
and coating the solution A on the surface of the treated titanium plate, drying, treating at 350-400 ℃ for 8-15 min, repeating for 3-5 times, and roasting at 450-500 ℃ for 1.5-3 h to obtain the titanium-coated ruthenium oxide polar plate.
4. The method according to claim 1, wherein the anode plate used for the electrocatalytic treatment is a surface-modified titanium plate, the cathode plate is a graphite plate, and the distance between the cathode plate and the anode plate is 30-70 mm; the bottom of the electro-catalytic treatment device is provided with an activated carbon porous material, and is uniformly provided with an air distribution device, the air supply amount is 0.5-2.5L/min, water flows in from the bottom, and flows out from the top; the current density of the electrocatalytic reaction is 5-20 mA/cm2The reaction time of the electrocatalytic reaction is 60-120 min.
5. The method of claim 4, wherein the surface modified titanium plate is prepared by a method comprising:
tin dichloride, iridium trichloride and ruthenium trichloride are mixed according to a molar ratio of (4-6): (2-4): (0.5-2) mixing and dissolving in a hydrochloric acid solution of ethylene glycol to obtain a mixed solution; and coating the mixed solution on the surface of the titanium plate, drying, treating at 450-500 ℃ for 8-15 min, repeating for 5-8 times, and finally roasting at 500-600 ℃ for 1-2 h to obtain the surface-modified titanium plate.
6. The method according to claim 1, wherein the cathode and anode plates used in the electro-adsorption treatment are carbon material-conductive polymer composite electrode plates, and the spacing between the cathode and anode plates is 1-3 mm; the voltage of the electro-adsorption is 1.0-1.8V, and the reaction time of the electro-adsorption is 15-30 min.
7. The method of claim 6, wherein the carbon material-conductive polymer composite electrode plate preparation method comprises:
dissolving a carbon material in water, performing ultrasonic dispersion, adding a polymer monomer and ammonium persulfate, performing ice-bath reaction for 4-6 hours, collecting a precipitation product, and performing vacuum drying; and then mixing the vacuum-dried product with polyvinylidene fluoride and graphite powder according to the mass ratio of (5-8): (1-2): (2-4) uniformly mixing, and performing pressure forming to obtain a carbon material-conductive polymer composite electrode plate;
preferably, the carbon material comprises one or more of activated carbon, carbon nanotubes and graphene;
preferably, the polymer monomer comprises pyrrole and/or aniline.
8. The method of claim 1, wherein the process of de-hardening and filtering the electro-adsorbed concentrated water with an alkali comprises:
adding alkali liquor into the concentrated water obtained by electro-adsorption to adjust the pH value to be more than 12, introducing carbon dioxide to precipitate scaling ions, and filtering by a Gole membrane to remove the precipitation of the scaling ions;
preferably, the pore diameter of the Goll membrane is 0.5-10 μm.
9. The method of claim 1, wherein the bipolar membrane electrodialysis treatment has a current density of 30-60 mA/cm2。
10. A fracturing flow-back fluid recycling treatment device, comprising:
the electric flocculation unit is used for flocculating and removing part of pollutants in the fracturing flow-back fluid;
the electric floating unit is used for removing suspended matters and petroleum in the fracturing flow-back fluid and excessive floccules and colloids in electric flocculation;
the electro-catalytic unit is used for oxidizing and degrading residual polymers and chemical additives in the fracturing flow-back fluid;
the electro-adsorption unit is used for generating desalted fresh water and electro-adsorption concentrated water through capacitive desalination;
the hard removing unit is used for adding alkali to realize the precipitation of scale ions in the electric adsorption concentrated water;
a filtering unit for filtering out the precipitate of scaling ions;
the bipolar membrane electrodialysis unit is used for electrolyzing the filtered water to obtain acid, alkali and desalted fresh water;
the electric flocculation unit, the electric air flotation unit, the electric catalysis unit, the electric adsorption unit, the hardness removal unit, the filtering unit and the bipolar membrane electrodialysis unit are sequentially communicated; the bipolar membrane electrodialysis unit is communicated with the hardness removal unit.
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