WO2017096569A1 - 一种采用陶瓷膜处理油气田压裂返排液的方法及装置 - Google Patents

一种采用陶瓷膜处理油气田压裂返排液的方法及装置 Download PDF

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WO2017096569A1
WO2017096569A1 PCT/CN2015/096873 CN2015096873W WO2017096569A1 WO 2017096569 A1 WO2017096569 A1 WO 2017096569A1 CN 2015096873 W CN2015096873 W CN 2015096873W WO 2017096569 A1 WO2017096569 A1 WO 2017096569A1
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ceramic membrane
gas field
treating oil
membrane according
field fracturing
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English (en)
French (fr)
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张春
张斯凡
刘飞
邓唯
彭文博
张宏
范克银
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江苏久吾高科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • 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
    • 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
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281—Installations for water purification using chemical agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Definitions

  • the invention relates to a method and a device for treating oil and gas field fracturing and returning liquid by using a ceramic membrane, and belongs to the technical field of water treatment.
  • Fracturing operation is an important measure to increase oil and gas production. It can also improve the conductivity of oil and gas layers. Therefore, it is widely used in major oil and gas fields. After the operation, a large amount of waste liquid returns to the ground, becoming the main source of pollution in current oil and gas fields. one.
  • the fracturing fluids currently developed have water-based, oil-based, foam and other fracturing fluids. Because water-based fracturing fluids have low cost, low fluid loss, little damage to the oil layer, and good temperature suitability, they are widely used in various oil and gas fields. Its market share is as high as 95%.
  • the composition of water-based fracturing fluid is very complicated, including more than ten kinds of additives, mainly including cementing agents, fungicides, thickeners, clay stabilizers, pH regulators, drainage aids, etc., so the fracturing waste liquid often shows High acidity, high COD, high salinity, high viscosity, high stability, etc., it is difficult to handle.
  • the main methods for treating fracturing and returning liquid are flocculation sedimentation, adsorption, filtration, oxidation, biological methods, etc., and the actual production process is mostly the comprehensive application of several methods.
  • Zhang Hong studied the characteristics of the anti-discharge of fracturing fluid in Henan Oilfield, and studied the harmless treatment method: coagulation-oxidation-Te/C micro-electrolysis-Fenton oxidation-activated carbon adsorption five-step treatment process. It is not difficult to see that the core of the process is an oxidized part, the purpose of which is to oxidize and decompose as much as possible of the organic matter in the fracturing and returning liquid, so that the process will consume a large amount of oxidant and the treatment cost is high.
  • the current fracturing and returning fluid treatment technology is still based on oxidation as the core technology, the oxidant consumption is large, the oxidation time process, and can only meet the national secondary emission standards; under the increasingly strict national environmental protection policy , a process flow segment, cost-effective, high-standard process technology has been put on the agenda.
  • the invention provides a method and a device for treating oil and gas field fracturing and returning liquid by using a ceramic membrane.
  • the method firstly performs a gelation flocculation treatment of a colloidal backflow liquid containing colloid, and then reduces the viscosity of the returning liquid by ozone treatment.
  • the ceramic membrane filtration technology is used for fine filtration; this method can not only improve the flux and operation stability of the ceramic membrane, but also shorten the processing time and process flow, and reduce the processing cost of the fracturing fluid; the treated water It can reach the re-injection water index of the ultra-low permeability oilfield or the national first-level emission standard.
  • a method for treating oil and gas field fracturing fluids by using a ceramic membrane comprising the following steps:
  • a gel breaker and a flocculant are added to the fracturing backflow liquid to perform gel breaking and flocculation treatment;
  • the viscosity of the liquid is lowered after the treatment in the first step
  • the liquid obtained in the second step is subjected to filtration treatment using a ceramic membrane.
  • the ceramic membrane has an average pore diameter in the range of 5 to 800 nm, and more preferably in the range of 20 to 200 nm.
  • the flow rate of the membrane surface is 1 to 8 m/s.
  • the breaker is selected from one or a mixture of persulfate, hypochlorite, perchlorate, hydrogen peroxide or permanganate.
  • the flocculating agent is selected from one or a mixture of a polymer flocculant or an inorganic flocculant.
  • a flocculating agent is also added when the flocculating agent is added.
  • the flocculating agent is selected from one or a mixture of several of CaO, MgO, Ca(OH) 2 , Na 2 CO 3 , NaHCO 3 .
  • the viscosity of the feed liquid is lowered by O 3 treatment.
  • the utility model relates to a device for treating oil and gas field fracturing and returning liquid by using a ceramic membrane, comprising a flocculation sedimentation tank, a gelling agent and a flocculating agent adding device are arranged on the flocculation sedimentation tank, the flocculation sedimentation tank is connected with the viscosity reducing reaction kettle, and the viscosity reducing reaction is carried out.
  • An ozone inlet is provided on the kettle, and the viscosity reduction reactor is connected to the inlet of the trap side of the ceramic membrane.
  • the breaker and flocculant adding device comprises a flocculating agent inlet and a breaker inlet; and a flocculation and returning tank inlet is arranged on the flocculation tank.
  • the ceramic membrane has an average pore diameter in the range of 5 to 800 nm, and more preferably in the range of 20 to 200 nm.
  • the permeate side of the ceramic membrane is connected to a desalination apparatus, and the desalination apparatus may be selected from one or a combination of an electrodialysis apparatus, an ion exchange resin bed, a nanofiltration membrane, or a reverse osmosis membrane.
  • the invention provides a method for treating oil and gas field fracturing and returning liquid by using ceramic membrane, and the remarkable advantages thereof are as follows: (1) through the coupling of gel breaking and flocculation, the precipitation efficiency is improved, the filtration flux and purification effect of the ceramic membrane are significantly improved, and the effect is improved.
  • the effluent water quality has made the effluent completely reach the “5-1-1” standard for re-injection water in ultra-low permeability oilfields (ie oil mass concentration ⁇ 5mg/L, solid grain mass concentration ⁇ 1mg/L, median particle size ⁇ 1 ⁇ m) and National level emission standards.
  • Figure 1 is a flow chart showing the process of the present invention.
  • FIG. 2 is a schematic view showing the structure of an apparatus in an embodiment of the present invention.
  • the treatment process provided by the invention is mainly applied to the treatment of the fracturing and returning liquid in the oil field and the gas field, and firstly, by flocculation and gel breaking treatment, the larger impurities, organic substances and the like therein can be first removed.
  • Flocculation precipitation is the process of flocculation and precipitation of particulate matter in water. After the coagulant is added in water, the colloid and dispersed particles of the suspended matter form floccules under the interaction of molecular forces, and they collide and collide with each other during the sedimentation process, and their size and quality are continuously increased, and the rate of constant growth is constant. increase. After the gelled liquid, the load of the ceramic membrane to filter can be reduced.
  • the fracturing backflow liquid contains some incomplete jelly, its main component is a compound formed by hydroxypropyl guar gum and borax, resulting in a large viscosity, generally about 10 Mps, still causing ceramics.
  • the process of membrane operation is low in sustainability, membrane fouling, and low membrane flux. Therefore, in the fracturing backflow treatment, a breaker such as (NH 4 ) 2 S 2 O 8 , Na 2 S 2 O 8 , K 2 S 2 O 8 , FeCl 3 , H 2 O 2 may be used . NaClO, KMnO 4 , NaClO 4 and the like.
  • flocculants which can be exemplified by high molecular flocculants and inorganic flocculants.
  • the polymer flocculant include a cationic type, an anionic type, and an amphoteric type, and examples thereof include an oxime flocculating agent, an acrylamide flocculating agent, and an acrylic flocculating agent.
  • the inorganic flocculant examples include iron-based flocculating aids such as polyferric sulfate (iron concentration: 5 to 15%) and ferric chloride; aluminum flocculating aids such as aluminum sulfate and PAC; and polyaluminum ferric chloride; Ferrous chloride, aluminum chloride, polyacrylamide, etc. are commonly used flocculants, but O 3 and some flocculating agents with reducing action will form an oxidative-flocculation effect, which can improve the effect of gelation flocculation. Further improving the operating flux of the subsequent ceramic membrane; therefore, the flocculating agent may select some flocculating agent having reducing properties such as ferrous chloride and ferrous sulfate.
  • iron-based flocculating aids such as polyferric sulfate (iron concentration: 5 to 15%) and ferric chloride
  • aluminum flocculating aids such as aluminum sulfate and PAC
  • polyaluminum ferric chloride Ferrous chloride, aluminum chlor
  • coagulant Considering the sedimentation rate, it is also necessary to add some coagulant during the sedimentation process to accelerate the sedimentation rate and sedimentation effect.
  • Conventional coagulants generally have CaO, MgO, Ca(OH) 2 , Na 2 CO 3 and NaHCO 3 . It is known that the fracturing fluid is generally acidic, and therefore, in addition to the above effects, the coagulant has a function of adjusting the pH.
  • Another difficulty in the treatment of fracturing and returning liquid is high viscosity and viscosity up to 10Mps. Its main components are oil, methanol, and artificially added organic additives. Among them, hydroxypropyl guar is the main factor of viscosity generation. It is easy to cause the flux of the ceramic membrane to decrease rapidly during the operation, so how to reduce the viscosity of the sewage is also an important part of the invention; and the invention adopts the method of ozone viscosity reduction, and can be part of organic molecules such as hydroxypropyl guar gum.
  • the bond breaks, and the cross-linking between the colloids can be broken, thereby reducing the viscosity, and the operating flux of the subsequent ceramic membrane and the water quality of the membrane can be effectively improved.
  • the dosage of ozone can be 20-500 mg/L, and the reaction temperature can be It can be 10 to 90 ° C, and the reaction time can be 10 to 200 minutes.
  • the effluent After the reduced viscosity, the effluent enters the ceramic membrane treatment system, and the clean water on the permeate side can be re-injected or discharged, and the reflux liquid returns to flocculation and sedimentation for reprocessing.
  • the ceramic film used in the present invention is preferably a ceramic ultrafiltration membrane.
  • the material of the porous film constituting the ceramic separation membrane can be appropriately selected from conventionally known ceramic materials.
  • an oxide material such as alumina, zirconia, magnesia, silica, titania, cerium oxide, cerium oxide or barium titanate; cordierite, mullite, forsterite, talc, silicon may be used.
  • a composite oxide material such as aluminous oxynitride ceramic, zircon or ferrite; a nitride material such as silicon nitride or aluminum nitride; a carbide material such as silicon carbide; and a hydroxide material such as hydroxyapatite; Elemental materials such as carbon or silicon; or two or more inorganic composite materials containing them.
  • Natural minerals (clay, clay minerals, ceramsite, silica sand, pottery, feldspar, white sand) or blast furnace slag, fly ash, etc. can also be used.
  • alumina, zirconia, titania, magnesia, and silica are preferable, and ceramic powder mainly composed of alumina, zirconia, or titania is more preferable.
  • the term "main body” as used herein means that 50% by mass or more (preferably 75% by mass or more, more preferably 80% by mass to 100% by mass) of the total ceramic powder is alumina or silica.
  • alumina is relatively inexpensive and excellent in handleability.
  • a porous structure having a pore diameter suitable for liquid separation can be easily formed, a ceramic separation membrane having excellent liquid permeability can be easily produced.
  • ⁇ -alumina is particularly preferably used.
  • the ⁇ -alumina has a property of being chemically stable and having a high melting point and high mechanical strength. Therefore, by using ⁇ -alumina, it is possible to manufacture a ceramic separation membrane which can be utilized in a wide range of applications such as industrial fields.
  • the membrane adopts a cross-flow filtration mode, the membrane surface flow rate is 1-8 m/s, and the transmembrane pressure difference is 0.1-1 MPa.
  • the membrane separation process is a fluid separation process in the form of "cross-flow filtration”: the raw material liquid flows at a high speed in the membrane tube, and the clarified permeate containing the small molecular component is driven through the membrane in a direction perpendicular to the pressure driven by the pressure, including The turbid pollutants of the macromolecular components are trapped by the membrane, so that the fluid can be separated, concentrated, and purified.
  • the ceramic membrane has an average pore diameter in the range of 5 to 800 nm, and more preferably in the range of 20 to 200 nm.
  • the structure of the device which can be used in the present invention is as shown in FIG. 2, and the pressure is connected to the flocculation sedimentation tank 1.
  • the cracking and returning liquid inlet 8 the function of the flocculation and sedimentation tank 1 is to make the liquid through the gel breaking, flocculation treatment, and at the same time to cause the floc to settle, and the flocculation sedimentation tank 1 is also connected with the gelling agent and the flocculating agent adding device 9
  • the device is used for adding a breaker and a flocculating agent to the flocculation settling tank 1, and the breaker and flocculating agent adding device 9 may be integrated, that is, the breaker and the flocculating agent are simultaneously added thereto.
  • the breaker and flocculating agent adding device 9 includes a flocculating agent inlet port 5 and a breaker inlet port 6, that is, a split structure is adopted, and two inlets are adopted. Add gel breaker and flocculant separately.
  • the flocculation sedimentation tank 1 is further provided with a pipeline connected to the viscosity reduction reactor 2, and the viscosity reduction reactor 2 is used to make the effluent after the gelation flocculation and then subjected to ozone viscosity reduction treatment, and further on the viscosity reduction reactor 2
  • An ozone inlet port 7 is provided, the function of which is to add ozone thereto, and the outlet of the viscosity reduction reactor 2 is also connected to the inlet of the trap side of the ceramic membrane 3.
  • the main material and specifications of the ceramic membrane 3 are as described above;
  • the cut-off side outlet of the membrane 3 can also be reconnected to the flocculation settling tank 1 to allow the retentate to be reused again;
  • the permeate side of the ceramic membrane 3 can be connected to the desalination unit 4 for deep desalination, and the desalination apparatus can be selected from One or a combination of electrodialysis devices, ion exchange resin beds, nanofiltration membranes or reverse osmosis membranes.
  • the fracturing backflow fluid used in the present invention is provided for Daqing Oilfield.
  • the table below shows the water quality analysis data.
  • Viscosity (mps) COD (mg/l) SS (mg/l) Turbidity 11 10283 432 82
  • the average flux of the separation membrane was calculated based on the total water production/total time.
  • Step 1 Debonding and flocculation precipitation of the fracturing fluid; firstly, the agent used for the gelling flocculant is a composite formulation of Na 2 S 2 O 8 /FeCl 2 /CaO, wherein Na 2 S 2 O 8 and FeCl The concentrations of 2 were 132 mg/l and 258 mg/l, respectively, and the dosage of CaO was determined according to the pH of the water; the reaction time was 30 min.
  • the agent used for the gelling flocculant is a composite formulation of Na 2 S 2 O 8 /FeCl 2 /CaO, wherein Na 2 S 2 O 8 and FeCl
  • concentrations of 2 were 132 mg/l and 258 mg/l, respectively, and the dosage of CaO was determined according to the pH of the water; the reaction time was 30 min.
  • Step 2 The effluent after the gelation and flocculation precipitation was subjected to viscosity reduction treatment, wherein the dosage of O 3 was 112 mg/l, and the reaction time was 15 min.
  • the properties of the treated liquid are as follows:
  • Step 3 The wastewater is treated by a membrane device.
  • the average pore diameter of the ceramic membrane is 50 nm, and the membrane pressure is 0.3 MPa, and the sewage temperature is 35 °C.
  • the sewage is cross-flow filtered in the membrane equipment, and the permeate is directly used for reinjection.
  • the non-permeable membrane circulating liquid is mixed with the incoming water and then enters the membrane equipment for filtration again.
  • the sewage is circulated and filtered by the circulation pump. When the filtration flux drops to 10% of the original flux, the filtration is stopped and the average flux is calculated.
  • the table below shows the water quality analysis data.
  • Example 1 The difference from Example 1 is that the breaker Na 2 S 2 O 8 is not added.
  • Step 1 Breaking and flocculation and sedimentation of the fracturing fluid; firstly, the agent used for the gelling flocculant is a composite formula of FeCl 2 /CaO, wherein the concentration of FeCl 2 is 258 mg/l, and the dosage of CaO is based on The pH of the incoming water was determined; the reaction time was 30 min.
  • the agent used for the gelling flocculant is a composite formula of FeCl 2 /CaO, wherein the concentration of FeCl 2 is 258 mg/l, and the dosage of CaO is based on The pH of the incoming water was determined; the reaction time was 30 min.
  • Step 2 The effluent after flocculation and sedimentation is subjected to viscosity reduction treatment, wherein the dosage of O 3 is 112 mg/l, and the reaction time is 15 min.
  • the properties of the treated liquid are as follows:
  • Step 3 The wastewater is treated by a membrane device.
  • the average pore diameter of the ceramic membrane is 50 nm, and the membrane pressure is 0.3 MPa, and the sewage temperature is 35 °C.
  • the sewage is cross-flow filtered in the membrane equipment, and the permeate is directly used for reinjection.
  • the non-permeable membrane circulating liquid is mixed with the incoming water and then enters the membrane equipment for filtration again.
  • the sewage is circulated and filtered by the circulation pump. When the filtration flux drops to 10% of the original flux, the filtration is stopped and the average flux is calculated.
  • the table below shows the water quality analysis data.
  • Example 1 The difference from Example 1 is that the O 3 viscosity reduction treatment of the second step is not performed.
  • Step 1 Debonding and flocculation precipitation of the fracturing fluid; firstly, the agent used for the gelling flocculant is a composite formulation of Na 2 S 2 O 8 /FeCl 2 /CaO, wherein Na 2 S 2 O 8 and FeCl The concentrations of 2 were 132 mg/l and 258 mg/l, respectively, and the dosage of CaO was determined according to the pH of the water; the reaction time was 30 min.
  • the agent used for the gelling flocculant is a composite formulation of Na 2 S 2 O 8 /FeCl 2 /CaO, wherein Na 2 S 2 O 8 and FeCl
  • concentrations of 2 were 132 mg/l and 258 mg/l, respectively, and the dosage of CaO was determined according to the pH of the water; the reaction time was 30 min.
  • the properties of the treated liquid are as follows:
  • Step 2 The sewage treatment was carried out by using a membrane device.
  • the average pore diameter of the ceramic membrane used was 50 nm, and the membrane pressure was operated at different membrane surface flow rates, the transmembrane pressure difference was 0.3 MPa, and the sewage temperature was 35 °C.
  • the sewage is cross-flow filtered in the membrane equipment, and the permeate is directly used for reinjection.
  • the non-permeable membrane circulating liquid is mixed with the incoming water and then enters the membrane equipment for filtration again.
  • the sewage is circulated and filtered by the circulation pump. When the filtration flux drops to 10% of the original flux, the filtration is stopped and the average flux is calculated.
  • the table below shows the water quality analysis data.
  • Step 1 Debonding and flocculation precipitation of the fracturing fluid; firstly, the agent used for the gelling flocculant is a compound formula of (NH 4 ) 2 S 2 O 8 /FeCl 2 /Na 2 CO 3 , wherein (NH 4 ) The concentrations of 2 S 2 O 8 and FeCl 2 were 166 mg/l and 289 mg/l, respectively, and the dosage of Na 2 CO 3 was determined according to the pH of the water; the reaction time was 40 min.
  • the agent used for the gelling flocculant is a compound formula of (NH 4 ) 2 S 2 O 8 /FeCl 2 /Na 2 CO 3 , wherein (NH 4 )
  • the concentrations of 2 S 2 O 8 and FeCl 2 were 166 mg/l and 289 mg/l, respectively, and the dosage of Na 2 CO 3 was determined according to the pH of the water; the reaction time was 40 min.
  • Step 2 The effluent after the gelation and flocculation precipitation was subjected to viscosity reduction treatment, wherein the dosage of O 3 was 136 mg/l, and the reaction time was 20 min.
  • the properties of the treated liquid are as follows:
  • Viscosity COD (mg/l) SS (mg/l) Turbidity (NTU)
  • Step 3 The sewage treatment was carried out by using membrane equipment, and the ceramic membrane filters with different average pore diameters were used, the membrane surface flow rate was 4 m/s, the transmembrane pressure difference was 0.3 MPa, and the sewage temperature was 35 °C.
  • the sewage is cross-flow filtered in the membrane equipment, and the permeate is directly used for reinjection.
  • the non-permeable membrane circulating liquid is mixed with the incoming water and then enters the membrane equipment for filtration again.
  • the sewage is circulated and filtered by the circulation pump. When the filtration flux drops to 10% of the original flux, the filtration is stopped and the average flux is calculated.
  • the table below shows the water quality analysis data.
  • Step 1 Debonding and flocculation precipitation of the fracturing fluid;
  • the agent used for the gelling flocculant is a composite formulation of K 2 S 2 O 8 /polyferric sulfate/Na 2 CO 3 , wherein K 2 S 2
  • concentrations of O 8 and polyferric sulfate were 200 mg/l and 300 mg/l, respectively, and the dosage of Na 2 CO 3 was determined according to the pH of the water; the reaction time was 40 min.
  • Step 2 The effluent after the gelation and flocculation precipitation is subjected to viscosity reduction treatment, wherein the dosage of O 3 is 350 mg/l, and the reaction time is 30 min.
  • the properties of the treated liquid are as follows:
  • Step 3 The sewage treatment was carried out by using a membrane device, and a ceramic membrane filter having an average pore diameter of 50 nm was used, and the membrane surface flow rate was 3 m/s, and filtered under different conditions of transmembrane pressure difference, and the sewage temperature was 40 °C. Sewage is cross-flow filtered in membrane equipment The liquid is directly used for reinjection. The circulating fluid that has not passed through the membrane is mixed with the incoming water and then enters the membrane equipment for filtration. The sewage is circulated and filtered by the circulation pump, and the filtration flux is reduced to 10 of the original flux. When %, stop filtering and calculate the average flux. The table below shows the water quality analysis data.
  • This example examines the effect of different gel breaking and flocculating agent combinations on the treatment effect.
  • Step 1 Debonding and flocculation and sedimentation of the fracturing and returning liquid; firstly, different flocculating agents and different gelling agents are arranged and combined, the breaker is Na 2 S 2 O 8 , and the flocculating agent is CaO, wherein The concentrations of Na 2 S 2 O 8 and the flocculant were 162 mg/l and 235 mg/l, respectively (some nucleating agents may also be added), and the dosage of CaO was determined according to the pH of the water; the reaction time was 40 min.
  • Step 2 The effluent after the gelation and flocculation precipitation was subjected to viscosity reduction treatment, wherein the dosage of O 3 was 135 mg/l, and the reaction time was 20 min.
  • Step 3 The sewage treatment was carried out by using a membrane device.
  • the average pore diameter of the ceramic membrane used was 50 nm, the membrane surface velocity was 4 m/s, the transmembrane pressure difference was 0.4 MPa, and the sewage temperature was 40 °C.
  • the sewage is cross-flow filtered in the membrane equipment, and the permeate is directly used for reinjection.
  • the non-permeable membrane circulating liquid is mixed with the incoming water and then enters the membrane equipment for filtration again.
  • the sewage is circulated and filtered by the circulation pump. When the filtration flux drops to 10% of the original flux, the filtration is stopped and the average flux is calculated.
  • the table below shows the water quality analysis data.

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Abstract

一种采用陶瓷膜处理油气田压裂返排液的方法及装置，属于水处理技术领域。该方法首先将含有胶体的压裂返排液进行破胶絮凝处理，然后通过臭氧处理降低返排液的黏度，最后采用陶瓷膜过滤技术进行精过滤；这种方法不仅可以提高陶瓷膜的通量和运行稳定性，而且缩短了处理时间和工艺流程，降低压裂返排液的处理成本。该装置包括有絮凝沉降槽(1)，其特征在于，絮凝沉降槽(1)与降黏反应釜(2)连接，降黏反应釜(2)上设置有臭氧加入口(7)，降黏反应釜(2)与陶瓷膜(3)的截留侧的入口连接。

Description

一种采用陶瓷膜处理油气田压裂返排液的方法及装置 技术领域
本发明涉及一种采用陶瓷膜处理油气田压裂返排液的方法及装置，属于水处理技术领域。
背景技术
压裂作业是油气增产的一项重要举措，同时也可以改善油气层的导流能力，因此被各大油气田广泛采用，作业结束后，大量的废液返回至地面，成为当前油气田水体的主要污染源之一。
目前开发的压裂液有水基、油基、泡沫等压裂液，由于水基压裂液具有成本低，滤失低，对油层伤害小，温度适宜能力较好，被各个油气田广泛采用，其所占市场份额高达95％。水基压裂液的成分非常复杂，包含十多种助剂，主要有胶联剂，杀菌剂，稠化剂，粘土稳定剂，PH调节剂，助排剂等，因此压裂废液常表现出高酸度，高COD，高矿化度，高粘度，高稳定性等特点，处理难度较大。目前处理压裂返排液的主要方法有絮凝沉降、吸附、过滤、氧化、生物等方法，实际生产过程中多为几种方法的综合应用。
张宏针对河南油田压裂液反排液的特点，研究了与之相适应的无害化处理方法：混凝-氧化-Te/C微电解-Fenton氧化-活性炭吸附五步处理工艺，从此工艺不难看出，该工艺的核心为氧化部分，其目的是将压裂返排液中的有机物尽可能多的氧化分解，因此该工艺将会消耗大量的氧化剂，处理成本较高。
综上所述，目前的压裂返排液处理技术仍然是以氧化为核心技术，氧化剂消耗量大，氧化时间过程，且只能达到国家二级排放标准；在国家环保政策日趋严格的状况下，一种工艺流程段，经济高效，高标准的工艺技术已经提上日程。
发明内容
本发明提供了一种采用陶瓷膜处理油气田压裂返排液的方法及装置，该方法首先将含有胶体的压裂返排液进行破胶絮凝处理，然后通过臭氧处理降低返排液的黏度，最后采用陶瓷膜过滤技术进行精过滤；这种方法不仅可以提高陶瓷膜的通量和运行稳定性，而且缩短了处理时间和工艺流程，降低压裂返排液的处理成本；经处理后的水可达到特低渗透油田回注水指标或者国家一级排放标准。
根据本发明的第一个方面：
一种采用陶瓷膜处理油气田压裂返排液的方法，包括如下步骤：
第1步，对压裂返排液中加入破胶剂和絮凝剂，进行破胶和絮凝处理；
第2步，再使第1步处理后料液的黏度降低；
第3步，对第2步中得到的料液用陶瓷膜进行过滤处理。
陶瓷膜的平均孔径范围是5～800nm，更优选范围是20～200nm。
陶瓷膜进行过滤时，采用的是错流过滤模式；膜面流速1～8m/s。
所述的第1步中，破胶剂选自过硫酸盐、次氯酸盐、高氯酸盐、过氧化氢或高锰酸盐中的一种或者几种的混合物。
所述的第1步中，絮凝剂选自高分子絮凝剂或者无机絮凝剂一种或者几种的混合物。
所述的第1步中，在加入絮凝剂时，还加入助絮凝剂。
所述的助絮凝剂选自CaO、MgO、Ca(OH)2、Na2CO3、NaHCO3中的一种或者几种的混合物。
所述的第2步中，使料液黏度降低是采用O3处理。
根据本发明的第二个方面：
一种采用陶瓷膜处理油气田压裂返排液的装置，包括有絮凝沉降槽，在絮凝沉降槽上设置有破胶剂和絮凝剂加入装置，絮凝沉降槽与降黏反应釜连接，降黏反应釜上设置有臭氧加入口，降黏反应釜与陶瓷膜的截留侧的入口连接。
破胶剂和絮凝剂加入装置上包括有絮凝剂加入口和破胶剂加入口；絮凝沉降槽上设置压裂返排液入口。
所述陶瓷膜平均孔径范围是5～800nm，更优选范围是20～200nm。
陶瓷膜的渗透侧与除盐装置连接，脱盐装置可以选自电渗析装置、离子交换树脂床、纳滤膜或者反渗透膜中的一种或者几种的组合。
有益效果
本发明提供的一种采用陶瓷膜处理油气田压裂返排液的方法，其显著优点在于：①通过破胶和絮凝耦合作用，提高了沉淀效率，显著提高陶瓷膜过滤通量和净化效果，提高了出水水质，使出水完全达到了特低渗透油田回注水“5-1-1”标准(即油质量浓度≤5mg/L，固粒质量浓度≤1mg/L，粒径中值≤1μm)和国家一级排放标准。
附图说明
图1是本发明的处理工艺流程图。
图2是本发明的一个实施方式中的装置结构示意图。
其中，1、絮凝沉降槽；2、降黏反应釜；3、陶瓷膜；4、除盐装置；5、絮凝剂加入口；6、破胶剂加入口；7、臭氧加入口；8、压裂返排液入口；9、破胶剂和絮凝剂加入装置。
具体实施方式
下面通过具体实施方式对本发明作进一步详细说明。但本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件(例如参考徐南平等著的《无机膜分离技术与应用》，化学工业出版社，2003)或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
本文使用的近似语在整个说明书和权利要求书中可用于修饰任何数量表述，其可在不导致其相关的基本功能发生变化的条件下准许进行改变。因此，由诸如“约”的术语修饰的值并不局限于所指定的精确值。在至少一些情况下，近似语可与用于测量该值的仪器的精度相对应。除非上下文或语句中另有指出，否则范围界限可以进行组合和/或互换，并且这种范围被确定为且包括本文中所包括的所有子范围。除了在操作实施例中或其他地方中指明之外，说明书和权利要求书中所使用的所有表示成分的量、反应条件等等的数字或表达在所有情况下都应被理解为受到词语“约”的修饰。
以范围形式表达的值应当以灵活的方式理解为不仅包括明确列举出的作为范围限值的数值，而且还包括涵盖在该范围内的所有单个数值或子区间，犹如每个数值和子区间被明确列举出。例如，“大约0.1％至约5％”的浓度范围应当理解为不仅包括明确列举出的约0.1％至约5％的浓度，还包括有所指范围内的单个浓度(如，1％、2％、3％和4％)和子区间(例如，0.1％至0.5％、1％至2.2％、3.3％至4.4％)。
本说明书中的“去除”，不仅包括完全去除目标物质的情况，还包括部分去除(减少该物质的量)的情况。本说明书中的“提纯”，包括去除任意的或特定的杂质。
本发明中所述的“多个”、“几个”等类似用语在无特别说明的情况下，是指2个以上。
本文使用的词语“包括”、“包含”、“具有”或其任何其他变体意欲涵盖非排它性的包括。例如，包括列出要素的工艺、方法、物品或设备不必受限于那些要素，而是可以包括其他没有明确列出或属于这种工艺、方法、物品或设备固有的要素。当一个元件被提及与另一个元件“连接”时，它可以与其他元件直接相连或者与其他元件间接相连，而它们之间插入有元件。
本发明提供的处理工艺主要是应用于油田、气田中的压裂返排液的处理，首先是通过絮凝、破胶处理，可以使其中的较大的杂质、有机物等首先被去除。絮凝沉淀是颗粒物在水中絮凝沉淀的过程。在水中投加混凝剂后，其中悬浮物的胶体及分散颗粒在分子力的相互作用下生成絮状体，且在沉降过程中它们互相碰撞凝聚，其尺寸和质量不断变大，沉速不断增加。经过破胶后的料液，可以降低陶瓷膜进行过滤的负荷。
但是，但是由于压裂返排液中含有一些不完全的冻胶，其主要成分为羟丙基瓜胶和硼砂形成的化合物，导致其黏度较大，一般情况下约为10Mps，仍然会造成陶瓷膜的运行过程的可持续性低、膜污染严重以及膜通量较低的问题。因此，在压裂返排液处理中，可以采用的破胶剂例如(NH4)2S2O8，Na2S2O8，K2S2O8，FeCl3，H2O2，NaClO，KMnO4，NaClO4等。
为了进一步提高破胶和絮凝沉淀的效果，我们也对絮凝剂进行了筛选，可以例举的是：高分子絮凝剂、无机絮凝剂。作为高分子絮凝剂，作为高分子絮凝剂，可列举出阳离子系、阴离子系、两性系等，例如可列举出脒系絮凝剂、丙烯酰胺系絮凝剂、丙烯酸系絮凝剂等；。作为无机絮凝剂，例如可列举出聚合硫酸铁(铁浓度为5～15％)、氯化铁等铁系絮凝助剂；硫酸铝、PAC等铝系絮凝助剂等；聚合氯化铝铁、氯化亚铁、氯化铝、聚丙烯酰胺等是常用的絮凝剂，但是由于O3和一些具有还原作用的絮凝剂会形成氧化-絮凝效应，这种效应可以提高破胶絮凝的效果，能够进一步地提高后续的陶瓷膜的运行通量；因此絮凝剂可以选择氯化亚铁，硫酸亚铁等一些具有还原性质的絮凝剂。
考虑到沉降速率，还需要在沉降过程中增加一些助凝剂，加快沉降速率和沉降效果，常规助凝剂一般有CaO、MgO、Ca(OH)2、Na2CO3、NaHCO3。我们知道，压裂返排液一般为酸性，因此，助凝剂除了具有上述作用之外，还兼具调节pH值的作用。
压裂返排液处理的另外一个难点就是黏度高，黏度甚至高达10Mps，其主要成分为油、甲醇，以及人工添加的有机助剂，其中羟丙基瓜胶是黏度产生的主要因素，因此，容易导致陶瓷膜在运行过程中通量下降迅速，因此如何降低污水黏度也是本发明的一个重要组成部分；而本发明采用臭氧降黏的手段，能够将羟丙基瓜胶等有机分子中的部分键发生断裂，并且可以破坏胶体之间的交联，从而降低其黏度，可以有效地提高后续的陶瓷膜的运行通量以及膜出水水质，臭氧投加量可以为20～500mg/L，反应温度可以为10～90℃，反应时间可以是10～200min。
通过破胶，助凝，絮凝，臭氧降黏的协同作用，压裂返排液中的部分悬浮固体，有机小分子和矿化度将会大大降低，而且部分大分子也会被破坏，减轻了后续处理工艺的压力，同时也为保证最终出水水质打下了良好的基础。
经过降黏后的出水进入陶瓷膜处理系统，渗透侧的清水可进行回注或者外排，回流液回到絮凝沉淀，进行再处理。
本发明中所采用的陶瓷膜，优选为陶瓷超滤膜。作为构成陶瓷分离膜的多孔膜的材料，能够从现有公知的陶瓷材料中适当选择。例如，可以使用氧化铝、氧化锆、氧化镁、氧化硅、氧化钛、氧化铈、氧化钇，钛酸钡等氧化物类材料；堇青石、多铝红柱石、镁橄榄石、块滑石、硅铝氧氮陶瓷、锆石、铁酸盐等复合氧化物类材料；氮化硅，氮化铝等氮化物类材料；碳化硅等碳化物类材料；羟基磷灰石等氢氧化物类材料；碳、硅等元素类材料；或者含有它们的两种以上的无机复合材料等。还可以使用天然矿物(粘土、粘土矿物、陶渣、硅砂、陶石、长石、白砂)或高炉炉渣、飞灰等。其中，优选选自氧化铝、二氧化锆、氧化钛、氧化镁、氧化硅中的1种或2种以上，更优选以氧化铝、二氧化锆或者氧化钛作为主体构成的陶瓷粉末。其中，这里所说的“作为主体”表示陶瓷粉末总体的50质量％以上(优选75质量％以上、更优选80质量％～100质量％)为氧化铝或二氧化硅。例如，在多孔材料中，氧化铝较为廉价且操作性优异。并且，能够容易地形成具有适合于液体分离的孔径的多孔结构，因此能够容易地制造具有优异的液体透过性的陶瓷分离膜。并且，在上述氧化铝中，特别优选使用α-氧化铝。α-氧化铝具有在化学方面稳定、且熔点和机械强度高的特性。因此，通过使用α-氧化铝，能够制造可以在宽泛用途(例如工业领域)中利用的陶瓷分离膜。
膜采用错流过滤模式，膜面流速为1～8m/s，跨膜压差为0.1～1MPa。膜分离工艺是一种“错流过滤”形式的流体分离过程：原料液在膜管内高速流动，在压力驱动下含小分子组分的澄清渗透液沿与之垂直方向向外透过膜，含大分子组分的混浊污染物被膜截留，从而使流体达到分离、浓缩、纯化的目的。由于油滴和有机小分子的可压缩性，当跨膜压差增大，污水中的油滴和小分子有机物会逐步吸附、累积在膜表面，并在压差的作用下，使得油滴和小分子有机物受挤压变形透过膜孔进入渗透侧，导致滤后水中COD增加，当跨膜压差小于0.1MPa时，滤后水中悬浮物含量基本小于1mg/L，COD含量小于80mg/L，可达到低渗透油田注水水质标准和国家一级排放标准，但是跨膜压差过小，会导致通量过小，浓缩倍数低，不能满足工程实际所需以及会导致处理量很小；当跨膜压差大于1MPa时，原先吸附在膜表面、膜孔道中的悬浮物和有机小分子被挤压到膜的另一侧，导致滤后水中悬浮物和COD含量大于增加，不符合低渗透油田注水水质标准和排放要求。在膜面流速为1m/s时增大流速可提高膜通量，但流速增大到8m/s时，能耗较高，不利于工程应用。陶瓷膜的平均孔径范围是5～800nm，更优选范围是20～200nm。
根据上述的方法，本发明可以采用的装置结构如图2所示，在絮凝沉降槽1上连接有压 裂返排液入口8，絮凝沉降槽1的作用是使料液经过破胶、絮凝处理，并同时使絮凝物沉降，而在絮凝沉降槽1上还连接有破胶剂和絮凝剂加入装置9，这一装置是用于向絮凝沉降槽1中加入破胶剂和絮凝剂，破胶剂和絮凝剂加入装置9可以是一体式的，也就是说将破胶剂和絮凝剂同时加入其中，并同时投加；在另外的一个实施方式中，破胶剂和絮凝剂加入装置9上包括有絮凝剂加入口5和破胶剂加入口6，也就是采用了分体式结构，由两个入口分别投加破胶剂和絮凝剂。在絮凝沉降槽1上还设置有管路连接于降黏反应釜2，降黏反应釜2的作用是使经过破胶絮凝后的出水再经过臭氧降黏处理，在降黏反应釜2上还设置有臭氧加入口7，其作用是向其中加入臭氧，在降黏反应釜2的出口还与陶瓷膜3的截留侧的入口相连接，陶瓷膜3的主要材质及规格如上所述；在陶瓷膜3的截留侧的出口还可以与絮凝沉降槽1再连接，使截留液再次回用处理；陶瓷膜3的渗透侧可以与除盐装置4相连接以进行深度除盐，脱盐装置可以选自电渗析装置、离子交换树脂床、纳滤膜或者反渗透膜中的一种或者几种的组合。
本发明所使用的压裂返排液为大庆油田提供。下表为水质分析数据。
黏度(mps) COD(mg/l) SS(mg/l) 浊度
11 10283 432 82
以下实施例中，分离膜的平均通量是按照总产水量/总时间进行计算得到的。
实施例1
步骤1：对压裂返排液进行破胶和絮凝沉淀；首先将破胶絮凝剂所用的药剂为Na2S2O8/FeCl2/CaO的复合配方，其中Na2S2O8和FeCl2的浓度分别为132mg/l和258mg/l，CaO的投加量根据来水的pH而定；反应时间为30min。
步骤2：对破胶和絮凝沉淀后的出水进行降黏处理，其中O3的投加量为112mg/l，反应时间为15min。处理后的料液性质如下：
项目 黏度(mps) COD(mg/l) SS(mg/l) 浊度(NTU)
降黏后 1.5 8074 184 42
步骤3：采用膜设备对污水进行处理，采用的陶瓷膜的平均孔径为50nm，在不同的膜面流速下运行，跨膜压差为0.3MPa，污水温度为35℃。污水在膜设备内进行错流过滤，透过液直接用于回注，未透过膜的循环液与来水进行混合后进入膜设备再次进行过滤，污水在循环泵的作用下进行循环过滤，当过滤通量下降为原始通量的10％时，停止过滤，计算平均通量。下表为水质分析数据。
膜面流速(m/s) 0 1 4 7
黏度(mps) 0.2 0.2 0.2 0.2
COD(mg/l) 76 81 76 75
SS(mg/l) 0.67 0.65 0.67 0.64
浊度(NTU) 0.55 0.61 0.58 0.59
平均通量(L/m2·h) 21 71 137 145
运行周期(h) 1.2 78 189 201
对照例1
与实施例1的区别在于：未加入破胶剂Na2S2O8。
步骤1：对压裂返排液进行破胶和絮凝沉淀；首先将破胶絮凝剂所用的药剂为FeCl2/CaO的复合配方，其中FeCl2的浓度为258mg/l，CaO的投加量根据来水的pH而定；反应时间为30min。
步骤2：对絮凝沉淀后的出水进行降黏处理，其中O3的投加量为112mg/l，反应时间为15min。处理后的料液性质如下：
项目 黏度(mps) COD(mg/l) SS(mg/l) 浊度(NTU)
降黏后 5.9 9069 224 68
步骤3：采用膜设备对污水进行处理，采用的陶瓷膜的平均孔径为50nm，在不同的膜面流速下运行，跨膜压差为0.3MPa，污水温度为35℃。污水在膜设备内进行错流过滤，透过液直接用于回注，未透过膜的循环液与来水进行混合后进入膜设备再次进行过滤，污水在循环泵的作用下进行循环过滤，当过滤通量下降为原始通量的10％时，停止过滤，计算平均通量。下表为水质分析数据。
膜面流速(m/s) 0 1 4 7
黏度(mps) 0.3 0.3 0.3 0.3
COD(mg/l) 89 87 85 83
SS(mg/l) 0.86 0.82 0.83 0.86
浊度(NTU) 0.85 0.86 0.83 0.83
平均通量(L/m2·h) 22 31 58 72
运行周期(h) 1.1 10 13 21
可以看出，通过加入破胶剂处理之后，可以有效地提高分离膜的运行通量和运行周期。
对照例2
与实施例1的区别在于：未进行第2步的O3降黏处理。
步骤1：对压裂返排液进行破胶和絮凝沉淀；首先将破胶絮凝剂所用的药剂为Na2S2O8/FeCl2/CaO的复合配方，其中Na2S2O8和FeCl2的浓度分别为132mg/l和258mg/l，CaO的投加量根据来水的pH而定；反应时间为30min。
处理后的料液性质如下：
项目 黏度(mps) COD(mg/l) SS(mg/l) 浊度(NTU)
降黏后 5.5 9337 177 39
步骤2：采用膜设备对污水进行处理，采用的陶瓷膜的平均孔径为50nm，在不同的膜面流速下运行，跨膜压差为0.3MPa，污水温度为35℃。污水在膜设备内进行错流过滤，透过液直接用于回注，未透过膜的循环液与来水进行混合后进入膜设备再次进行过滤，污水在循环泵的作用下进行循环过滤，当过滤通量下降为原始通量的10％时，停止过滤，计算平均通量。下表为水质分析数据。
膜面流速(m/s) 0 1 4 7
黏度(mps) 0.3 0.3 0.3 0.3
COD(mg/l) 93 94 91 91
SS(mg/l) 0.83 0.86 0.85 0.88
浊度(NTU) 0.92 0.98 0.96 0.97
平均通量(L/m2·h) 23 35 63 75
运行周期(h) 1.0 14 14 23
可以看出，通过加入O3降黏处理之后，可以有效地提高分离膜的运行通量和运行周期。
实施例2
本实施例中考察在不同的膜孔径条件下采用该工艺对于压裂返排液的处理效果。
步骤1：对压裂返排液进行破胶和絮凝沉淀；首先将破胶絮凝剂所用的药剂为(NH4)2S2O8/FeCl2/Na2CO3的复合配方，其中(NH4)2S2O8和FeCl2的浓度分别为166mg/l和289mg/l，Na2CO3的投加量根据来水的pH而定；反应时间为40min。
步骤2：对破胶和絮凝沉淀后的出水进行降黏处理，其中O3的投加量为136mg/l，反应时间为20min。处理后的料液性质如下：
项目 黏度(mps) COD(mg/l) SS(mg/l) 浊度(NTU)
降黏后 1.4 7876 178 39
步骤3：采用膜设备对污水进行处理，采用的不同平均孔径的陶瓷膜过滤器，膜面流速4m/s，跨膜压差为0.3MPa，污水温度为35℃。污水在膜设备内进行错流过滤，透过液直接用于回注，未透过膜的循环液与来水进行混合后进入膜设备再次进行过滤，污水在循环泵的作用下进行循环过滤，当过滤通量下降为原始通量的10％时，停止过滤，计算平均通量。下表为水质分析数据。
Figure PCTCN2015096873-appb-000001
实施例3
本实施例中考察在不同的陶瓷膜过滤压力条件下采用该工艺对于压裂返排液的处理效果。
步骤1：对压裂返排液进行破胶和絮凝沉淀；首先将破胶絮凝剂所用的药剂为K2S2O8/聚合硫酸铁/Na2CO3的复合配方，其中K2S2O8和聚合硫酸铁的浓度分别为200mg/l和300mg/l，Na2CO3的投加量根据来水的pH而定；反应时间为40min。
步骤2：对破胶和絮凝沉淀后的出水进行降黏处理，其中O3的投加量为350mg/l，反应时间为30min。处理后的料液性质如下：
项目 黏度(mps) COD(mg/l) SS(mg/l) 浊度(NTU)
降黏后 1.3 7233 169 41
步骤3：采用膜设备对污水进行处理，采用的平均孔径50nm的陶瓷膜过滤器，膜面流速3m/s，在不同的跨膜压差条件下过滤，污水温度为40℃。污水在膜设备内进行错流过滤，透 过液直接用于回注，未透过膜的循环液与来水进行混合后进入膜设备再次进行过滤，污水在循环泵的作用下进行循环过滤，当过滤通量下降为原始通量的10％时，停止过滤，计算平均通量。下表为水质分析数据。
跨膜压差MPa 0.1 0.2 0.3 0.4 0.5
黏度(mps) 0.2 0.2 0.2 0.5 0.7
COD(mg/l) 51 52 74 94 139
SS(mg/l) 0.33 0.38 0.41 0.43 0.41
浊度(NTU) 0.47 0.49 0.53 0.43 0.56
平均通量(L/m2·h) 63 83 137 145 128
运行周期(h) 192 190 164 105 84
实施例4
本实施例考察了不同的破胶、絮凝剂组合对处理效果的影响。
步骤1：对压裂返排液进行破胶和絮凝沉淀；首先将不同的絮凝剂和不同的破胶剂进行排列组合，破胶剂采用Na2S2O8，助絮凝剂是CaO，其中Na2S2O8和絮凝剂的浓度分别为162mg/l和235mg/l(另外也可以加入一些成核剂)，CaO的投加量根据来水的pH而定；反应时间为40min。
步骤2：对破胶和絮凝沉淀后的出水进行降黏处理，其中O3的投加量为135mg/l，反应时间为20min。
步骤3：采用膜设备对污水进行处理，采用的陶瓷膜的平均孔径为50nm，膜面流速4m/s，跨膜压差为0.4MPa，污水温度为40℃。污水在膜设备内进行错流过滤，透过液直接用于回注，未透过膜的循环液与来水进行混合后进入膜设备再次进行过滤，污水在循环泵的作用下进行循环过滤，当过滤通量下降为原始通量的10％时，停止过滤，计算平均通量。下表为水质分析数据。
Figure PCTCN2015096873-appb-000002
Figure PCTCN2015096873-appb-000003

Claims (22)

  1. 一种采用陶瓷膜处理油气田压裂返排液的方法，其特征在于，包括如下步骤：
    第1步，对压裂返排液中加入破胶剂和絮凝剂，进行破胶和絮凝处理；
    第2步，再使第1步处理后料液的黏度降低；
    第3步，对第2步中得到的料液用陶瓷膜进行过滤处理。
  2. 根据权利要求1所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的第3步中，陶瓷膜的平均孔径范围是5～800nm。
  3. 根据权利要求2所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：陶瓷膜的平均孔径范围是20～200nm。
  4. 根据权利要求1所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：陶瓷膜进行过滤时，采用的是错流过滤模式。
  5. 根据权利要求4所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：膜面流速1～8m/s。
  6. 根据权利要求1所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的第1步中，破胶剂选自过硫酸盐、次氯酸盐、高氯酸盐、过氧化氢或者高锰酸盐中的一种或者几种的混合物。
  7. 根据权利要求1所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的第1步中，絮凝剂选自高分子絮凝剂或者无机絮凝剂一种或者几种的混合物。
  8. 根据权利要求7所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的絮凝剂高分子絮凝剂选自脒系絮凝剂、丙烯酰胺系絮凝剂或者丙烯酸系絮凝剂。
  9. 根据权利要求7所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：无机絮凝剂选自聚合硫酸铁、氯化铁、硫酸铝、PAC、聚合氯化铝铁、氯化亚铁或者硫酸亚铁中的一种或者几种的混合物。
  10. 根据权利要求9所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：无机絮凝剂选自氯化亚铁或者硫酸亚铁中的一种或者两种的混合物。
  11. 根据权利要求1所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的第1步中，在加入絮凝剂时，还加入助絮凝剂。
  12. 根据权利要求11所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的助絮凝剂选自CaO、MgO、Ca(OH)2、Na2CO3或者NaHCO3中的一种或者几种的混合物。
  13. 根据权利要求1所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的第2步中，使料液黏度降低是采用O3处理。
  14. 根据权利要求1所述的采用陶瓷膜处理油气田压裂返排液的方法，其特征在于：所述的第11步中，还加入成核剂；所述的成核剂是玻化微珠。
  15. 一种采用陶瓷膜处理油气田压裂返排液的装置，包括有絮凝沉降槽(1)，其特征在于，絮凝沉降槽(1)与降黏反应釜(2)连接，降黏反应釜(2)上设置有臭氧加入口(7)，降黏反应釜(2)与陶瓷膜(3)的截留侧的入口连接。
  16. 根据权利要求15所述的采用陶瓷膜处理油气田压裂返排液的装置，其特征在于：在絮凝沉降槽(1)上设置有破胶剂和絮凝剂加入装置(9)。
  17. 根据权利要求16所述的采用陶瓷膜处理油气田压裂返排液的装置，其特征在于：破胶剂和絮凝剂加入装置(9)上包括有絮凝剂加入口(5)和破胶剂加入口(6)。
  18. 根据权利要求15所述的采用陶瓷膜处理油气田压裂返排液的装置，其特征在于：絮凝沉降槽(1)上设置压裂返排液入口(8)。
  19. 根据权利要求15所述的采用陶瓷膜处理油气田压裂返排液的装置，其特征在于：所述陶瓷膜(3)平均孔径范围是5～800nm。
  20. 根据权利要求19所述的采用陶瓷膜处理油气田压裂返排液的装置，其特征在于：陶瓷膜(3)平均孔径范围是20～200nm。
  21. 根据权利要求15所述的采用陶瓷膜处理油气田压裂返排液的装置，其特征在于：陶瓷膜(3)的渗透侧与除盐装置(4)连接。
  22. 根据权利要求21所述的采用陶瓷膜处理油气田压裂返排液的装置，其特征在于：脱盐装置(4)可以选自电渗析装置、离子交换树脂床、纳滤膜或者反渗透膜中的一种或者几种的组合。
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