WO2017067161A1 - 一种采油废水的处理装置和方法 - Google Patents

一种采油废水的处理装置和方法 Download PDF

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WO2017067161A1
WO2017067161A1 PCT/CN2016/082665 CN2016082665W WO2017067161A1 WO 2017067161 A1 WO2017067161 A1 WO 2017067161A1 CN 2016082665 W CN2016082665 W CN 2016082665W WO 2017067161 A1 WO2017067161 A1 WO 2017067161A1
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wastewater
tank
treatment
oil
electrolysis
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PCT/CN2016/082665
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English (en)
French (fr)
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张世文
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波鹰(厦门)科技有限公司
张世文
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Publication of WO2017067161A1 publication Critical patent/WO2017067161A1/zh

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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
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening

Definitions

  • the invention relates to a device and a method for treating oil production wastewater, in particular to a device for treating oil production wastewater by a combination of pH demulsification, gravity sedimentation separation, centrifugal separation or air flotation separation, micro electrolysis, anaerobic and aerobic processes.
  • the method belongs to the field of water pollution control of environmental engineering.
  • Oilfield oil-derived wastewater also known as 'produced water'
  • oil production wastewater has the following characteristics:
  • High oil content oil production wastewater usually contains 1000-2000mg/L of petroleum, and some even up to 5000mg/L, including oil slick, dispersing oil, emulsified oil and dissolved oil;
  • the diameter of the particles is generally 1 ⁇ 100 ⁇ m, mainly including: 1 mud sand; 2 various minerals; 3 bacteria: sulfate reducing bacteria (SRB) 5 ⁇ 10 ⁇ m, saprophytic bacteria (TGB) 10 ⁇ 30 ⁇ m ; 4 organic matter: heavy oil such as colloidal asphaltenes and paraffin.
  • SRB sulfate reducing bacteria
  • TGB saprophytic bacteria
  • the salt content is high.
  • the oil content of oilfield wastewater is generally high. From thousands to tens of thousands, even hundreds of thousands of milligrams per liter, each oilfield, even each block and oil layer is different; mainly includes: 1 dissolution Inorganic salts in water. It is basically in the form of an anion or a cation, and its particle diameter is below 1 ⁇ 10 -3 ⁇ m, mainly including Ca 2+ , Mg 2+ , K + , Na + , Fe 3+ , Cl ⁇ , HCO 3 ⁇ CO 3 2-, etc.;
  • Containing bacteria mainly saprophytic and sulfate-reducing bacteria
  • the water temperature of the wastewater is mostly 40-80 ° C, and the pH of the wastewater is 6.5-9.5;
  • oil recovery wastewater also contains surfactants and polymers.
  • the domestic treatment technology for oil production wastewater is mainly designed for sewage reinjection.
  • the purpose of oilfield wastewater treatment is to remove oil, suspended solids and other unfavorable components that impede water injection, corrosion of the water injection system and structure. Due to the large difference in physical and chemical properties of oilseed wastewater in various oilfields, the process flow of various oilfield wastewater treatment processes is also different. Due to the characteristics of oil well reservoirs, the physical properties of produced fluids and the distribution of oilfield blocks, and the continuous improvement of oilfield wastewater treatment by environmental protection, the requirements for oilfield wastewater treatment are increasing, and oilfield wastewater treatment and reinjection are not easy.
  • the existing oil recovery wastewater treatment technologies mainly include: sloping plate degreasing, air flotation deoiling, anaerobic (hydrolysis acidification), aerobic, sedimentation and disinfection treatment steps.
  • Chen Zhian et al. used anaerobic or hydrolyzed acidification-aerobic activated sludge process to treat alkaline oily sewage.
  • the results of the study indicated that biological (hydrolysis) acidification of the first and second aeration precipitates is a suitable biochemical treatment process for refinery alkali-containing sewage.
  • Liu Huiqing et al. used flocculation-biological contact oxidation to treat oily wastewater. The results showed that the COD removal rate could reach 68%.
  • Chinese patent CN104445792A introduces that the oil field sewage is cooled by forced drying open spray tower, then treated by A/O biochemical system, then added with Ca(ClO) 2 for oxidation treatment, and finally treated by multi-media filtration filled with activated carbon.
  • the method requires that the influent water requirement of the sewage is 350-600 mg/L, and the effluent is 50-150 mg/L.
  • Chinese patent CN1047100354A introduces an advanced treatment method for oilfield produced water, which includes the following steps: the oil produced water is subjected to pretreatment, then subjected to cooling treatment, a coagulating agent is added, and uniform mixing treatment is performed; and an immersion ultrafiltration device is introduced. Ultrafiltration method.
  • the recovered petroleum contains a large amount of impurities, which makes the processing of the subsequent utilization of recovered petroleum difficult;
  • the object of the present invention is to provide a treatment device and method for oil recovery wastewater in view of the deficiencies of the existing oil recovery wastewater treatment technology.
  • a processing device for oil production wastewater is composed of the following units:
  • the petroleum recovery unit consists of a wastewater regulating tank, an accident tank, a demulsification tank, an acid storage tank, a gravity degreasing device, a centrifuge or an air flotation degreasing device, a petroleum storage tank, and a wastewater pool;
  • the water outlet of the pool or accident pool is connected to the water inlet of the demulsifier pool through the tee, the acid inlet of the demulsifier pool is connected with the outlet of the acid storage tank, the waste water outlet of the demulsifier pool and the gravity degreasing device, the centrifuge or the air flotation
  • the water inlet of the degreasing device is connected, the water outlet of the gravity degreasing device, the centrifuge or the air flotation device is connected with the water inlet of the wastewater pool, and the oil outlet of the gravity degreasing device, the centrifuge or the air flotation device is Import connection of petroleum storage tanks;
  • the micro-electrolysis unit is composed of a micro-electrolysis cell body or a tank body, a filler support, an iron-carbon micro-electrolysis filler, an aeration device, a waste water collection cover, and an absorption tower;
  • the filler support is installed in a micro-electrolysis cell or micro-electrolysis
  • the iron-carbon micro-electrolytic filler is placed on the filler support
  • the waste water collection cover is installed on the top of the micro-electrolysis cell or the tank to collect the exhaust gas generated during the operation of the micro-electrolysis unit
  • the absorption tower constitutes an activated carbon containing the exhaust gas. Or resin;
  • the biochemical treatment unit is composed of an anaerobic treatment tank, an aerobic treatment tank and a sedimentation tank; the inlet of the anaerobic treatment tank is connected with the outlet of the micro-electrolysis unit, and the outlet of the anaerobic treatment tank is good.
  • the water inlet of the oxygen pool is connected, the water outlet of the aerobic tank is connected with the water inlet of the sedimentation tank, and the water outlet of the sedimentation tank is connected with the water inlet of the electrolysis unit;
  • the electrolytic unit is a kind of ordinary electrolysis equipment or nano-catalytic electrolysis equipment, which is used for eliminating residual COD which is difficult to remove by biochemicals and disinfecting waste water to kill microorganisms in waste water;
  • the sludge treatment unit includes a sludge collection tank, a gravity concentration tank, a dehydrator, a harmless treatment device; a sludge outlet of an anaerobic tank, an aerobic tank and a sedimentation tank in the biochemical treatment unit
  • the inlet of the sludge collection tank is connected, the outlet of the sludge collection tank is connected with the inlet of the gravity concentration tank, the outlet of the gravity concentration tank is connected with the inlet of the sludge dewatering machine, the sludge outlet of the sludge dewatering machine and the sludge deoiling device
  • the inlet connection, the sewage outlet of the sludge dewatering machine is connected with the inlet of the anaerobic tank; the outlet of the sludge deoiling device is connected with the inlet of the harmless treatment device; the petroleum recovery unit, the micro-electrolysis unit, the biochemical treatment unit, and the electrolysis The unit and the sludge treatment unit
  • the gravity degreasing device is one of a natural sedimentation separation tank, a swash plate deoiling device or a hydrocyclone deoiling device.
  • a filtering device or a centrifuge is further disposed between the sedimentation tank of the biochemical treatment unit and the electrolysis unit;
  • the filtering device is one of an MBR device, a column ultrafiltration device, and a tubular ultrafiltration device;
  • the membrane material of the filtration device is A type of ceramic film, metal film or organic film.
  • the method for treating the above-mentioned oil recovery wastewater treatment device comprises the following steps:
  • Demulsification adding oily wastewater with oil content of 50-6100mg/L, COD of 300 ⁇ 7000mg/L, SS of 50 ⁇ 500mg/L, salt content of 1000 ⁇ 20000mg/L and pH of 6.5 ⁇ 9.5
  • the acid adjusts the pH to 2-6 to break the milk, and the oil and wax are precipitated;
  • Micro-electrolysis The deoiling or dewaxing wastewater after the step (2) petroleum recovery is subjected to micro-electrolysis through a micro-electrolysis device to further remove 30-70% of COD and improve its biodegradability, and the COD of the wastewater drops to 300mg/L or less;
  • Aerobic the wastewater obtained by the step (4) anaerobic treatment is introduced into the aerobic tank, and the organic matter in the wastewater is further oxidized by aerobic treatment to deeply remove COD and BOD, and the COD of the wastewater drops below 150 mg/L. ;
  • Electrolytic treatment the clear liquid obtained by the aerobic treatment in step (5) is treated into an electrolytic treatment equipment to further degrade the COD, and at the same time kill the microorganisms in the water, and the effluent fully reaches the Technical Specification for the Engineering of Oil Production Wastewater Treatment (HJ2041-2014) Emission standards.
  • Step (1) Demulsification
  • the acid is one of sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid.
  • Step (1) Demulsification of the acid
  • the most preferred acid is sulfuric acid.
  • Step (1) The optimal demulsification condition for demulsification is to add waste water to the acid to adjust its pH to 2.5 to 3.
  • the oil recovery in the step (2) is that the oil recovery wastewater after gravity sedimentation and degreasing is added to the acid to adjust the pH to 2-6, and then pumped into the gravity sedimentation tank, and separated into the upper layer of oil and the lower layer by gravity sedimentation. Waste water, the upper layer of oil is recovered through a recovery pipe.
  • the petroleum separation in step (2) is carried out by adding the oil-removing wastewater after gravity sedimentation to the acid to adjust the pH to 2-6, pumping it into the centrifuge, and separating it into the lower layer of oil and the upper layer of deoiling.
  • the waste water and the lower layer of oil are recovered through a recovery pipe; the centrifugal force of the centrifugal separation is 2200 to 4000.
  • step (3) is iron/carbon microelectrolysis, and the residence time is 60-150 min.
  • Table 1 shows the removal effect of main pollution indicators in each step of Table 1.
  • Project pH Oily (mg/L) COD (mg/L) SS (mg/L) Contaminant removal rate (%) Raw water 6.5-9.5 50-500 300-7000 50-500 Demulsification 2-6 50-500 300-7000 50-500 Oil recovery 2-6 1-5 ⁇ 900 10-60 COD30-87%
  • the present invention has the following outstanding advantages:
  • FIG. 1 is a schematic view showing the structure of an oil recovery wastewater treatment device of the present invention
  • FIG. 2 is a schematic structural view of a petroleum recovery unit in an oil recovery wastewater treatment device of the present invention
  • FIG. 3 is a schematic structural view of a biochemical treatment unit in an oil recovery wastewater treatment device of the present invention.
  • FIG. 4 is a schematic structural view of a sludge treatment unit in an oil recovery wastewater treatment device of the present invention
  • FIG. 5 is a schematic view showing the process flow of a method for treating oil production wastewater according to the present invention.
  • the invention designs a treatment device for oil production wastewater based on the composition, properties and existing treatment scheme of the oil production wastewater.
  • a treatment device for oil production wastewater based on the composition, properties and existing treatment scheme of the oil production wastewater.
  • it is composed of a petroleum recovery unit 10, a micro-electrolysis unit 20, a biochemical treatment unit 30, and electrolysis.
  • Unit 40 is combined with sludge treatment unit 50 and the like to form a device that can efficiently treat oil recovery wastewater.
  • the oil recovery unit consists of wastewater regulating tank 1-1, accident tank 1-2, demulsification tank 1-3, acid storage tank 1-4, gravity sedimentation tank/centrifuge or air flotation device 1-5, petroleum storage tank 1- 6.
  • the wastewater collection tank 1-7 is constructed;
  • the micro-electrolysis device unit is composed of a micro-electrolysis reaction cell 2;
  • the biochemical treatment unit is composed of an anaerobic tank 3-1, an aerobic tank 3-2, and a sedimentation tank 3-3;
  • the sludge treatment unit is composed of a sludge collection tank 5-1, a gravity concentration tank 5-2, a dehydrator 5-3, a sludge deoiling device 5-4, and a harmless treatment device 5-5.
  • the oil production wastewater is collected through the pipeline and sent to the wastewater regulating tank 1-1 or the accident tank 1-2 through the three-way connection, the wastewater regulating tank 1-1 or the accident pool 1-2 through the pipeline and the valve and the demulsifier 1-3
  • the water inlet is connected, the acid inlet of the p-breaking tank 1-3 is connected with the outlet of the acid storage tank 1-4, and the outlet of the demulsifier 1-3 is connected with the inlet of the gravity sedimentation tank, the centrifuge or the air flotation device 1-5.
  • the petroleum outlet of the gravity sedimentation tank, the centrifuge or the air flotation device 1-5 is connected with the inlet of the petroleum storage tank 1-6, the wastewater outlet of the gravity sedimentation tank, the centrifuge or the air flotation device 1-5, and the wastewater collection tank 1-7
  • the inlet connection, the outlet of the wastewater collection tank 1-7 is connected to the inlet of the micro-electrolysis unit 20, the waste water outlet of the micro-electrolysis unit 20 is connected to the inlet of the anaerobic tank 3-1, and the wastewater outlet of the anaerobic tank 3-1 is
  • the aerobic tank 3-2 is connected to the inlet, the wastewater outlet of the aerobic tank 3-2 is connected to the inlet of the sedimentation tank 3-3, and the waste water outlet of the sedimentation tank 3-3 is connected to the inlet of the electrolysis unit 40, and the outlet of the electrolysis unit 40 Connect the drain.
  • the sludge outlets of the anaerobic tank 3-1, the aerobic tank 3-2 and the sedimentation tank 3-3 are connected to the inlet of the sludge collection tank 5-1, and the outlet of the sludge collection tank 5-1 and the gravity concentration tank 5-
  • the inlet connection of 2 is connected with the inlet of the sludge dewatering machine 5-3, and the sludge outlet of the sludge dewatering machine 5-3 is connected with the inlet of the harmless treatment device 5-4, and the sewage is connected.
  • the sewage outlet of the mud dewatering machine 5-3 is connected to the water inlet of the anaerobic tank 3-1.
  • the oil production wastewater is collected in the wastewater regulating tank 1-1 through a pipeline and uniformly mixed in the wastewater regulating tank 1-1 to adjust the amount of wastewater, and the oil content is 50 mg/L and the COD is 300 mg/L.
  • the SS was 50 mg/L, the salt content was 1000 mg/L, and the pH was 6.5.
  • the oil production wastewater passing through the wastewater regulating tank 1 is pumped into the demulsification tank 1-3, sulfuric acid is added to adjust the pH to 6 demulsification, and PAM is added at 5 g/m 3 .
  • the oil recovery wastewater obtained by the step (1) demulsification is pumped into the gravity sedimentation tank 1-5, and the oil is discharged after gravity separation and recovery of 49 g/m 3 and deoiled oil.
  • the petroleum is stored in petroleum storage.
  • the deoiled oil wastewater is stored in the wastewater collection tanks 1-7, and the COD of the wastewater is reduced from 300 mg/L to 256 mg/L.
  • the gravity sedimentation separation is to put the oil production wastewater into the gravity sedimentation tank 1-5, and separate into the upper layer of oil and the lower layer of deoiling wastewater by gravity sedimentation, and the upper layer of oil is recovered through the recovery pipe.
  • Micro-electrolysis The deoiled wastewater recovered by the step (2) oil was subjected to micro-electrolysis for 90 min through the iron-carbon microelectrolysis cell 20, and the COD of the wastewater was decreased from 256 mg/L to 156 mg/L.
  • the wastewater obtained by the micro-electrolysis in step (3) is introduced into the anaerobic tank 3-1, and the B/C value of the wastewater is improved by anaerobic treatment to improve the biodegradability of the wastewater.
  • the COD of the wastewater is from 156 mg/L. Dropped to 82mg/L.
  • Aerobic the wastewater obtained by the step (4) anaerobic treatment is introduced into the aerobic tank 3-2, and the organic matter in the wastewater is further oxidized by aerobic treatment to deeply remove COD and BOD, and the COD of the wastewater is from 82 mg/ L drops to 32 mg/L.
  • Electrolysis The clear liquid obtained by the aerobic treatment in the step (5) is electrolyzed into the electrolysis machine 40, and the electrolyzed water fully meets the discharge standard of the Technical Specification for Oil Production Wastewater Treatment Engineering (HJ2041-2014).
  • the electrolysis machine has an operating voltage of 1 to 36 V, a voltage between the two electrodes of 1 to 2 V, a current density of 5 to 320 mA/cm 2 , and a residence time of the aerobic cell effluent in the electrolysis machine in step (5) of 30 s. 1min.
  • the electrolyzer is provided with a power source and an electrolysis cell, and the electrodes in the electrolysis cell are one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, an alloy, and a nano catalytic inert electrode.
  • the surface layer of the nano catalytic inert electrode is coated with a noble metal oxide inert catalytic coating having a crystal grain of 10 to 35 nm, and the substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.
  • the oil production wastewater is collected in the regulating tank 1-1 through the pipeline and mixed uniformly in the regulating tank 1-1 to adjust the amount of wastewater, and the oil content is 6100 mg/L, the COD is 7000 mg/L, and the SS is 500 mg/L, a salt content of 200,000 mg/L, and a pH of 9.5.
  • the oil recovery wastewater passing through the conditioning tank is pumped into the pH adjusting tank (demulsifier) 1-3, sulfuric acid is added to adjust the pH to 2 demulsification, and PAM is added at 10 g/m 3 .
  • the oil production wastewater obtained by the step (1) demulsification is separated and recovered by centrifuge to obtain 5998g/m 3 of petroleum and deoiled oil wastewater.
  • the petroleum is stored in storage tank 1-6, and the deoiled oil wastewater is stored in wastewater.
  • the COD of the wastewater dropped from 7000 mg/L to 892 mg/L.
  • the centrifugal separation is to pump the oil wastewater after demulsification into the centrifuge 1-5, and the centrifugal force of the centrifugal separation is 2200-4000; after centrifugation, it is separated into the lower layer of petroleum and the upper deoiling wastewater, and the lower layer of oil is passed through the recovery pipe. Recycling.
  • Micro-electrolysis The deoiled wastewater recovered by the step (2) oil is subjected to micro-electrolysis through the iron-carbon micro-electrolysis cell 20, and the COD of the wastewater is decreased from 298 mg/L to 291 mg/L.
  • the wastewater obtained by the micro-electrolysis in step (4) is introduced into the anaerobic tank 3-1, and the B/C value of the wastewater is improved by anaerobic treatment to improve the biodegradability of the wastewater.
  • the COD of the wastewater is from 291 mg/L. Dropped to 192mg/L.
  • Aerobic the wastewater obtained by the step (5) anaerobic treatment is introduced into the aerobic tank 3-2, and the organic matter in the wastewater is further oxidized by aerobic treatment to deeply remove COD and BOD, and the COD of the wastewater is from 192 mg/ L drops to 129 mg/L.
  • Electrolysis The clear liquid obtained by the aerobic treatment in the step (5) is electrolyzed into the electrolysis machine 40, and the electrolyzed water fully meets the discharge standard of the Technical Specification for Oil Production Wastewater Treatment Engineering (HJ2041-2014).
  • the electrolysis machine has an operating voltage of 1 to 36 V, a voltage between the two electrodes of 1 to 3 V, a current density of 5 to 320 mA/cm 2 , and a residence time of the aerobic cell effluent in the electrolysis machine in step (5) of 8 to 8 10min.
  • the electrolyzer is provided with a power source and an electrolysis cell, and the electrodes in the electrolysis cell are one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, an alloy, and a nano catalytic inert electrode.
  • the surface layer of the nano catalytic inert electrode is coated with a noble metal oxide inert catalytic coating having a crystal grain of 10 to 35 nm, and the substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.
  • the oil production wastewater is collected in the wastewater regulating tank 1-1 through a pipeline and uniformly mixed in the wastewater regulating tank 1-1 to adjust the amount of wastewater, and the oil content is 450 mg/L, and the COD is 610 mg/L.
  • the SS was 200 mg/L, the salt content was 3200 mg/L, and the pH was 7.2.
  • the oil production wastewater passing through the wastewater regulating tank 1 is pumped into the demulsification tank 1-3, hydrochloric acid is added to adjust the pH to 4 demulsification, and PAM is added at 1 g/m 3 .
  • the centrifugal separation is to pump the oil wastewater after the demulsification into the centrifuge 1-5, and then centrifuge to separate the lower layer of petroleum and the upper deoiling wastewater, and the lower layer of oil is recovered through the recovery pipe; the centrifugal force of the centrifugal separation is 3300. ⁇ 3500.
  • Aerobic The wastewater obtained after the anaerobic treatment in step (6) is introduced into the aerobic tank 3-2, and the organic matter in the wastewater is further oxidized by aerobic treatment to deeply remove COD and BOD.
  • Electrolysis The clear liquid obtained by the aerobic treatment in the step (5) is electrolyzed into the electrolysis machine 40, and the electrolyzed water fully meets the discharge standard of the Technical Specification for Oil Production Wastewater Treatment Engineering (HJ2041-2014).
  • the working voltage of the electrolyzer is 1 to 36 V
  • the voltage between the two electrodes is 1 to 3 V
  • the current density is 5 to 320 mA/cm 2
  • the residence time of the aerobic tank effluent in the electrolysis machine 40 is 5 in the step (5). ⁇ 9min.
  • the electrolyzer is provided with a power source and an electrolysis cell, and the electrodes in the electrolysis cell are one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, an alloy, and a nano catalytic inert electrode.
  • the surface layer of the nano catalytic inert electrode is coated with a noble metal oxide inert catalytic coating having a crystal grain of 10 to 35 nm, and the substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.
  • the oil production wastewater is collected in the wastewater regulating tank 1-1 through the pipeline, and uniformly mixed in the wastewater regulating tank 1-1 to adjust the amount of wastewater, and the oil content is 4320 mg/L, and the COD is 5200 mg/L.
  • the SS was 200 mg/L, the salt content was 15,200 mg/L, and the pH was 9.5.
  • the oil production wastewater passing through the wastewater regulating tank is pumped into the demulsification tank 1-3, nitric acid is added to adjust the pH to 4 demulsification, and PAM is added at 8 g/m 3 .
  • the oil recovery wastewater obtained by the step (1) demulsification is separated and recovered by the centrifuge to obtain 4316 g/m 3 of petroleum and deoiled wastewater.
  • the petroleum is stored in the petroleum storage tank 1-6, and the deoiled oil wastewater is stored in the wastewater.
  • the COD of the wastewater dropped from 5400 mg/L to 859 mg/L.
  • Aerobic The wastewater obtained by the step (4) anaerobic treatment is introduced into the aerobic tank 3-2, and the organic matter in the wastewater is further oxidized by aerobic treatment to deeply remove COD and BOD, and the COD of the wastewater is from 163 mg/ L drops to 123 mg/L.
  • Electrolysis The clear liquid obtained by the aerobic treatment in the step (5) is electrolyzed into the electrolysis machine 40, and the electrolyzed water fully meets the discharge standard of the Technical Specification for Oil Production Wastewater Treatment Engineering (HJ2041-2014).
  • the working voltage of the electrolyzer is 1 to 36V
  • the voltage between the two electrodes is 1 to 3V
  • the current density is 5 to 320 mA/cm 2
  • the residence time of the effluent of the aerobic tank 3-2 in the electrolysis machine in step (5) It is 30s to 5min.
  • the electrolyzer is provided with a power source and an electrolysis cell, and the electrodes in the electrolysis cell are one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, an alloy, and a nano catalytic inert electrode.
  • the surface layer of the nano catalytic inert electrode is coated with a noble metal oxide inert catalytic coating having a crystal grain of 10 to 35 nm, and the substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.
  • the oil production wastewater is collected in the wastewater regulating tank 1-1 through a pipeline and uniformly mixed in the wastewater regulating tank 1-1 to adjust the amount of wastewater, and the oil content is 520 mg/L, and the COD is 650 mg/L.
  • the SS was 200 mg/L, the salt content was 3500 mg/L, and the pH was 7.3.
  • the oil production wastewater passing through the wastewater regulating tank 1-1 is pumped into the demulsification tank 1-3, and sulfuric acid is added to adjust the pH to 4 demulsification.
  • Aerobic The wastewater obtained by the step (4) anaerobic treatment is introduced into the aerobic tank 3-2, and the organic matter in the wastewater is further oxidized by aerobic treatment to deeply remove COD and BOD.
  • Electrolysis The clear liquid obtained by the aerobic treatment in the step (5) is electrolyzed into the electrolysis machine 40, and the electrolyzed water fully meets the discharge standard of the Technical Specification for Oil Production Wastewater Treatment Engineering (HJ2041-2014).
  • the electrolysis machine has an operating voltage of 1 to 36 V, a voltage between the two electrodes of 1 to 3 V, a current density of 5 to 320 mA/cm 2 , and a residence time of the aerobic cell effluent in the electrolysis machine 40 in step (5) of 30 s. ⁇ 10min.
  • the electrolyzer is provided with a power source and an electrolysis cell, and the electrodes in the electrolysis cell are one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, an alloy, and a nano catalytic inert electrode.
  • the surface layer of the nano catalytic inert electrode is coated with a noble metal oxide inert catalytic coating having a crystal grain of 10 to 35 nm, and the substrate of the nano catalytic inert electrode is a titanium plate or a plastic plate.
  • the oil production wastewater is collected in the wastewater regulating tank 1-1 through the pipeline, and uniformly mixed in the wastewater regulating tank 1-1 to adjust the amount of wastewater, and the oil content is 1420 mg/L, and the COD is 2165 mg/L.
  • SS is 90mg / L
  • salt content is 5200mg / L
  • pH is 9.3
  • the oil production wastewater passing through the wastewater conditioning tank 1 is pumped into the demulsifier 1-3
  • sulfuric acid is added to adjust the pH to 2 demulsification, according to 0.1g / m 3 is added to the PAM.
  • the centrifugal separation is to pump the oily wastewater after demulsification into the centrifuge 1-5, and centrifuge to separate the lower layer of petroleum and the upper deoiling wastewater, and the lower layer of oil is recovered by the recovery pipe to obtain 406 g/m 3 of oil;
  • the centrifugal force for separation is 3200 to 4000.
  • Aerobic The wastewater obtained by the step (4) anaerobic treatment is introduced into the aerobic tank 3-2, and the organic matter in the wastewater is further oxidized by aerobic treatment to deeply remove COD and BOD.
  • Electrolysis The clear liquid obtained by the aerobic treatment in the step (5) is electrolyzed into the electrolysis machine 40, and the electrolyzed water fully meets the discharge standard of the Technical Specification for Oil Production Wastewater Treatment Engineering (HJ2041-2014).
  • the electrolysis machine has an operating voltage of 1 to 36 V, a voltage between the two electrodes of 1 to 3 V, a current density of 5 to 320 mA/cm 2 , and a residence time of the aerobic cell effluent in the electrolysis machine 40 in step (5) of 30 s. ⁇ 10min.
  • the electrolyzer is provided with a power source and an electrolysis cell, and the electrodes in the electrolysis cell are one of graphite, titanium, iron, aluminum, zinc, copper, lead, nickel, molybdenum, chromium, an alloy, and a nano catalytic inert electrode.
  • the present invention is easy to implement in the industry and has good industrial applicability.

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Abstract

一种采油废水的处理装置，包括：石油回收单元（10）、微电解单元（20）、生化处理单元（30）、电解单元（40）以及污泥处理单元（50）；一种采油废水的处理方法依次包括以下步骤：破乳→石油回收→微电解→厌氧→好氧→电解处理。在处理采油废水污染的同时，实现了资源的回收利用。

Description

一种采油废水的处理装置和方法 技术领域
本发明涉及一种采油废水的处理装置和方法，特别是涉及采用调节pH破乳、重力沉降分离、离心分离或气浮分离、微电解、厌氧、好氧等过程组合处理采油废水的装置及方法，属于环境工程的水污染治理领域。
背景技术
当前，我国陆上油田基本都采用注水开发方式，即向地层注入高压水驱动原油使其从油井中被开采出来。经过一段时间注水后，注入水将随原油一起被采出，随着开发时间延长，采出原油含水率不断上升。从地层中随原油一起开采出来的、含有原油的油田采油污水(又称'采出水')，是油田开发和生产中产生的最主要的一类废水。由于各油田的地质条件、开发方式、油层改造措施、注水水质、集输工艺等的不同，各油田采油废水的性质差异很大。一般来说，采油废水具有如下特性：
（1）含油量高，采油废水中通常含有1000～2000mg/L的石油，有的甚至高达5000mg/L，包括浮油、分散油、乳化油和溶解油；
（2）含有悬浮固体颗粒，颗粒直径一般为1～100µm，主要包括：①泥砂；②各种矿物质；③细菌：硫酸盐还原菌（SRB）5～10µm，腐生菌（TGB）10～30µm；④有机物：胶质沥青质类和石蜡等重质油类。
（3）含盐量高，油田采油废水一般无机盐含量很高，从几千至几万，甚至于几十万毫克/升，各油田，甚至各区块、油层都不同；主要包括：①溶解在水中的无机盐类。基本上以阴、阳离子的形式存在，其粒径都在1×10-3µm以下，主要包括Ca2+、Mg2+、K+、Na+、Fe3+、Cl-、HCO3-、CO3 2-等；
（4）含细菌，主要是腐生菌和硫酸盐还原菌；
（5）高温和高pH，废水的水温多为40～80℃，废水的pH为6.5～9.5；
此外，部分采油废水还含有表面活性剂和聚合物。
当前，国内的采油污水的处理技术主要是针对污水回注设计的。油田污水处理的目的是去除水中的油、悬浮物以及其它有碍注水、易造成注水系统腐蚀、结构的不利成分。由于各油田采油污水的物理化学性质差异较大，因此各种油田采油污水处理工艺流程也不尽相同。由于油井油藏特性、采出液物性及油田区块分布等的不同，加之环境保护对油田污水处理的不断提高，有油田污水处理的要求日益提高，油田污水处理及回注并非易事。
随着环保要求的提高，水资源日趋紧张，搞好油田采油污水处理是当务之急。由于石油开采的不断深入，注水是一种常用的油田开发技术，许多油田已经进入中后期开采阶段，原油含水率甚至达到90%以上，导致采油污水处理量增加较快，处理难度加大。由于水环境污染越来越严重，采油废水处理摆上了议事日程。近年来，国外油田采油废水治理技术已经得到改善和提高。已由原来的隔油→混凝→过滤技术改变为隔油→混凝气浮→生化→过滤技术。现有的采油废水处理技术主要包括：斜板除油、气浮除油、厌氧（水解酸化）、好氧、沉淀和消毒处理等步骤。陈治安等采用厌氧或水解酸化一好氧活性污泥法处理碱性含油污水，研究结果认为生物(水解)酸化一二级曝气沉淀是炼油含碱污水合适的生化处理流程。刘惠卿等利用絮凝-生物接触氧化法处理含油废水，结果表明COD去除率可达68%。中国专利CN104445792A介绍了油田污水先经强制通风敞开喷淋塔进行冷却、然后通过A/O生化系统处理，再投加Ca(ClO)2进行氧化处理，最后通过填有活性炭的多介质过滤处理的方法，其污水的进水要求COD为350～600mg/L，出水为50～150mg/L。中国专利CN1047100354A介绍了一种油田采出水深度处理方法，包括如下步骤：油田采出水经过预处理后再进行降温处理，投加混凝药剂，并进行均匀混合处理；通入浸没式超滤装置进行超滤的方法。
为指导采油废水处理工作，环境部于2014年出台了《采油废水治理工程技术规范》（HJ2041-2014），规范推荐采用：采油废水→预处理→厌氧生物处理→好氧生物处理→生化后处理→达标排放的处理工艺。综上所述，尽管采油废水的处理技术已有不少，但都具有如下缺点：
1、回收的石油中含有大量的杂质，导致回收石油的后续利用的加工困难；
2、采油废水经重力沉降后直接进行气浮，要消耗大量的絮凝剂和助凝剂，导致运行费用高；
3、会产生大量的含油污泥，污泥的进一步处理会产生较多的费用；
4、经回收石油后的采油废水水质指标通常不能满足《采油废水治理工程技术规范》（HJ2041-2014）中要求的排放标准。
 技术问题
本发明的目的在于针对现有采油废水处理技术的不足，提供一种采油废水的处理装置和方法。
技术解决方案
一种采油废水的处理装置，由以下单元构成：
（1）石油回收单元：石油回收单元由废水调节池、事故池、破乳池、酸储罐、重力除油装置、离心机或气浮除油装置、石油贮罐、废水池构成；废水调节池或事故池的出水口经过三通与破乳池的进水口联接，破乳池的酸进口与酸储罐的出口连接，破乳池的废水出口与重力除油装置、离心机或气浮除油装置的进水口连接，重力除油装置、离心机或气浮除油装置的出水口与废水池的进水口连接，重力除油装置、离心机或气浮除油装置的出油口与石油贮罐的进口连接；
（2）微电解单元：微电解单元由微电解池体或罐体、填料支架、铁碳微电解填料、曝气装置、废水收集罩、吸收塔构成；填料支架安装在微电解池或微电解罐底部，铁碳微电解填料安放在填料支架上，废水收集罩安装在微电解池体或罐体的顶部，用于收集微电解单元工作时产生的废气；吸收塔构成内装有处理废气的活性炭或树脂；
（3）生化处理单元：生化处理单元由厌氧处理池、好氧处理池和沉淀池构成；厌氧处理池的进水口与微电解单元的出水口连接，厌氧处理池的出水口与好氧池的进水口连接，好氧池的出水口与沉淀池的进水口连接，沉淀池的出水口与电解单元的进水口连接；
（4）电解单元：电解单元是普通电解设备或纳米催化电解设备的一种，用于消除生化难以去除的残余COD和对废水进行消毒处理，杀灭废水中的微生物；
（5）污泥处理单元：污泥处理单元包括污泥收集池、重力浓缩池、脱水机、无害化处理装置；生化处理单元中厌氧池、好氧池和沉淀池的污泥出口与污泥收集池的进口联接，污泥收集池的出口与重力浓缩池的进口联接，重力浓缩池的出口与污泥脱水机的进口联接，污泥脱水机的污泥出口与污泥脱油装置的进口联接，污泥脱水机的污水出口与厌氧池的进水口联接；污泥脱油装置的出口与无害化处理装置的进口联接；石油回收单元、微电解单元、生化处理单元、电解单元和污泥处理单元通过管道、泵依次连接。
所述的重力除油装置是自然沉降分离池、斜板除油装置或水力旋流除油装置中的一种。
所述破乳池之前还有一个热交换器。
所述生化处理单元的沉淀池与电解单元之间还设有一个过滤装置或离心机；过滤装置是MBR装置、柱式超滤装置、管式超滤装置的一种；过滤装置的膜材料为陶瓷膜、金属膜或有机膜的一种。
采用上述采油废水处理装置的处理方法，包括如下步骤：
（1）破乳：将含油为50～6100mg/L、COD为300～7000mg/L、SS为50～500mg/L、含盐量为1000～20000mg/L、pH为6.5～9.5的采油废水加入酸调节pH至2～6破乳，使石油和蜡质析出；
（2）石油回收：将经过步骤（1）破乳后的采油废水中加入0.1～10mg/L的PAM使石油和蜡质析出，然后经过重力沉降分离或离心分离，得回收的石油和脱油或脱蜡废水，脱油或脱蜡废水的COD下降到900mg/L以下；
（3）微电解：将经步骤（2）石油回收后的脱油或脱蜡废水经微电解装置进行微电解，进一步去除30～70%的COD并提高其可生化性，废水的COD下降到300mg/L以下；
（4）厌氧：使经步骤（3）微电解处理后所得废水进入厌氧池，经厌氧处理提高废水的B/C值，改善废水的可生化性，废水的COD下降到200mg/L以下；
（5）好氧：使经步骤（4）厌氧处理后所得废水进入好氧池，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD，废水的COD下降到150mg/L以下；
（6）电解处理：使步骤（5）好氧处理所得的清液进入电解处理设备处理，进一步降解COD，同时杀灭水中微生物，出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
步骤（1）破乳所述酸为硫酸、硝酸、磷酸或盐酸的一种。
步骤（1）破乳所述酸最佳酸为硫酸。
步骤（1）破乳的最佳破乳条件是将废水加入酸调节其pH至2.5～3。
步骤（2）所述的石油回收是将经过重力沉降除油后的采油废水加入酸调节pH至2～6破乳后泵入重力沉降池中，经过重力沉降分离为上层的石油和下层的采油废水，上层的石油经回收管回收。
步骤（2）的石油回收所述的离心分离是将经过重力沉降除油后的采油废水加入酸调节pH至2～6后泵入离心机中，经过离心分离为下层的石油和上层的脱油废水，下层的石油经回收管回收；离心分离的离心力为2200～4000。
步骤（2）的石油回收所述离心分离的最佳条件是离心力为3200～4000。
步骤（3）的微电解为铁/碳微电解，停留时间为60-150min。
 有益效果
如上所述，各步骤对采油废水的主要污染物去除效果如表1。
表1各步骤对主要污染指标的去除效果表
项目 pH 含油 (mg/L) COD (mg/L) SS (mg/L) 污染物去除率（%）
原水 6.5-9.5 50-500 300-7000 50-500
破乳 2-6 50-500 300-7000 50-500
石油回收 2-6 1-5 ≤900 10-60 COD30-87%
微电解 7-8 0.5-1 ≤300 10-50 COD15-55%
厌氧 6-7 ≤1 ≤200 5-20 COD75%以上
好氧 7-8 ≤1 ≤150 5-10 COD60%以上
沉淀 7-8 ≤1 ≤50 ≤10
电解 7-8 ≤1 ≤50 3-8 -
本发明与现有技术比较，具有以下突出优点：
（1）在回收石油时，除了加酸作为破乳剂之外，不使用絮凝剂和气浮剂，不仅从废水中回收石油纯度较高，含杂质少，便于加工，而且，大量节省药剂成本，减少污泥量及污泥处理成本；
（2）通过采油废水中的石油回收，在处理采油废水污染的同时，实现了资源的回收利用，与此同时对采油废水进行了污染治理，使废水水质可达《采油废水治理工程技术规范》（HJ2041-2014）中的排放标准；
（3）产生污泥少，大幅度减少了污泥处理成本；
（4）在回收石油的同时，回收的蜡质成份，给后续的废水处理创造了良好条件；
（5）废水处理工艺流程短，废水处理成本低。
 附图说明
图1为本发明一种采油废水处理装置结构组成示意图；
图2为本发明一种采油废水处理装置中石油回收单元的结构组成示意图；
图3为本发明一种采油废水处理装置中生化处理单元的结构组成示意图；
图4为本发明一种采油废水处理装置中污泥处理单元的结构组成示意图；
图5为本发明一种采油废水处理方法的工艺流程示意图。
 本发明的最佳实施方式
本发明基于采油废水的成份、性质和现有处理方案，设计了一种采油废水的处理装置，参照图1至图4，它由石油回收单元10、微电解单元20、生化处理单元30、电解单元40和污泥处理单元50等组合，从而形成一种可高效处理采油废水的装置。
石油回收单元由废水调节池1-1、事故池1-2、破乳池1-3、酸贮罐1-4、重力沉降池/离心机或气浮装置1-5、石油贮存罐1-6、废水收集池1-7构成；
微电解装置单元由微电解反应池2构成；
生化处理单元由厌氧池3-1、好氧池3-2以及沉淀池3-3构成；
污泥处理单元由污泥收集池5-1、重力浓缩池5-2、脱水机5-3、污泥脱油装置5-4、无害化处理装置5-5构成。
采油废水经过管道收集并经过三通联接分别输送至废水调节池1-1或事故池1-2，废水调节池1-1或事故池1-2通过管道和阀门与破乳池1-3的进水口连接，p破乳池1-3的酸进口与酸贮罐1-4的出口连接，破乳池1-3出水口与重力沉降池、离心机或气浮装置1-5的进口连接，重力沉降池、离心机或气浮装置1-5的石油出口与石油贮存罐1-6进口连接，重力沉降池、离心机或气浮装置1-5的废水出口与废水收集池1-7的进口连接，废水收集池1-7的出水口与微电解装置20的进口连接，微电解装置20的废水出口与厌氧池3-1的进口连接，厌氧池3-1的废水出口与好氧池3-2进口连接，好氧池3-2的废水出口与沉淀池3-3的进口连接，沉淀池3-3的废水出口与电解装置40的进口连接，电解装置40的出水口接排放口。
厌氧池3-1、好氧池3-2和沉淀池3-3的污泥出口与污泥收集池5-1的进口联接，污泥收集池5-1的出口与重力浓缩池5-2的进口联接，重力浓缩池5-2的出口与污泥脱水机5-3的进口联接，污泥脱水机5-3的污泥出口与无害化处理装置5-4的进口联接，污泥脱水机5-3的污水出口与厌氧池3-1的进水口联接。
 本发明的实施方式
下面结合图5说明采用本发明采油废水的处理装置的采油废水处理方法。
实施例1
（1）破乳：将采油废水经管道收集于废水调节池1-1中并在废水调节池1-1中混合均匀，调节废水水量，检测其含油为50mg/L、COD为300mg/L、SS为50mg/L、含盐量为1000mg/L、pH为6.5。将经过废水调节池1的采油废水泵入破乳池1-3，加入硫酸调节pH至6破乳，按5g/m3加入PAM。
（2）石油回收：将步骤（1）破乳所得的采油废水泵入重力沉降池1-5，经过重力沉降分离回收得石油49g/m3和脱油后的采油废水,石油贮存于石油贮存罐1-6中，脱油采油废水贮存于废水收集池1-7中，废水的COD从300mg/L下降至256mg/L。
所述重力沉降分离是将采油废水放入重力沉降池1-5中，经过重力沉降分离为上层的石油和下层的脱油废水，上层的石油经回收管回收。
（3）微电解：将经步骤（2）石油回收后的脱油废水经铁碳微电解池20进行微电解90min，废水的COD从256mg/L下降到156mg/L。
（4）厌氧：使经步骤（3）微电解所得废水进入厌氧池3-1，经厌氧处理提高废水的B/C值，改善废水的可生化性，废水的COD从156mg/L下降到82mg/L。
（5）好氧：使经步骤（4）厌氧处理后所得废水进入好氧池3-2，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD，废水的COD从82mg/L下降到32mg/L。
（6）电解：使步骤（5）好氧处理所得的清液进入电解机40中电解，电解出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
所述电解机的工作电压为1～36V，两电极间的电压为1～2V，电流密度为5～320mA/cm2,步骤（5）好氧池出水在电解机中的停留时间为30s～1min。
所述电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种。
所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的贵金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。
实施例2
（1）破乳：将采油废水经管道收集于调节池1-1中并在调节池1-1中混合均匀，调节废水水量，检测其含油为6100mg/L，COD为7000mg/L、SS为500mg/L、含盐量为200000mg/L、pH为9.5。将经过调节池的采油废水泵入pH调节池（破乳池）1-3，加入硫酸调节pH至2破乳，按10g/m3加入PAM。
（2）石油回收：将步骤（1）破乳所得采油废水经过离心机分离回收得石油5998g/m3和脱油采油废水,石油贮存于贮存罐1-6中，脱油采油废水贮存于废水收集池1-7中，废水的COD从7000mg/L下降到892mg/L。
所述离心分离是将破乳后的采油废水泵入离心机1-5中，离心分离的离心力为2200～4000；经过离心分离为下层的石油和上层的脱油废水，下层的石油经回收管回收。
（3）微电解：将经步骤（2）石油回收后的脱油废水经铁碳微电解池20进行微电解，废水的COD从298mg/L下降到291mg/L。
（4）厌氧：使经步骤（4）微电解所得废水进入厌氧池3-1，经厌氧处理提高废水的B/C值，改善废水的可生化性，废水的COD从291mg/L下降到192mg/L。
（5）好氧：使经步骤（5）厌氧处理后所得废水进入好氧池3-2，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD，废水的COD从192mg/L下降到129mg/L。
（6）电解：使步骤（5）好氧处理所得的清液进入电解机40中电解，电解出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
所述电解机的工作电压为1～36V，两电极间的电压为1～3V，电流密度为5～320mA/cm2,步骤（5）好氧池出水在电解机中的停留时间为8～10min。
所述电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种。
所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的贵金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。
实施例3
（1）破乳：将采油废水经管道收集于废水调节池1-1中并在废水调节池1-1中混合均匀，调节废水水量，检测其含油为450mg/L，COD为610mg/L、SS为200mg/L、含盐量为3200mg/L、pH为7.2。将经过废水调节池1的采油废水泵入破乳池1-3，加入盐酸调节pH至4破乳，按1g/m3加入PAM。
（2）石油回收：将步骤（1）破乳所得采油废水经过离心机分离回收得石油448g/m3和脱油废水,石油贮存于石油贮存罐1-6中，脱油采油废水贮存于废水收集池1-7中。
所述离心分离是将经过破乳后的采油废水泵入离心机1-5中，经过离心分离为下层的石油和上层的脱油废水，下层的石油经回收管回收；离心分离的离心力为3300～3500。
（3）微电解：将经步骤（2）石油回收后的脱油废水经铁碳微电解池20进行微电解。
（4）厌氧：使经步骤（5）气浮除油后所得废水进入厌氧池3-1，经厌氧处理提高废水的B/C值，改善废水的可生化性。
（5）好氧：使经步骤（6）厌氧处理后所得废水进入好氧池3-2，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD。
（6）电解：使步骤（5）好氧处理所得的清液进入电解机40中电解，电解出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
所述电解机的工作电压为1～36V，两电极间的电压为1～3V，电流密度为5～320mA/cm2,步骤（5）好氧池出水在电解机40中的停留时间为5～9min。
所述电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种。
所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的贵金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。
实施例4
（1）破乳：将采油废水经管道收集于废水调节池1-1中，并在废水调节池1-1中混合均匀，调节废水水量，检测其含油为4320mg/L，COD为5200mg/L、SS为200mg/L、含盐量为15200mg/L、pH为9.5。将经过废水调节池的采油废水泵入破乳池1-3，加入硝酸调节pH至4破乳，按8g/m3加入PAM。
（2）石油回收：将步骤（1）破乳所得采油废水经过离心机分离回收得石油4316g/m3和脱油废水,石油贮存于石油贮存罐1-6中，脱油采油废水贮存于废水收集池1-7中，废水的COD从5400mg/L下降到859mg/L。
（3）微电解：将经步骤（2）石油回收后的脱油废水经铁碳微电解池20进行微电解，废水的COD从859mg/L下降到283mg/L。
（4）厌氧：使经步骤（3）微电解后所得废水进入厌氧池3-1，经厌氧处理提高废水的B/C值，改善废水的可生化性，废水的COD从283mg/L下降到163mg/L。
（5）好氧：使经步骤（4）厌氧处理后所得废水进入好氧池3-2，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD，废水的COD从163mg/L下降到123mg/L。
（6）电解：使步骤（5）好氧处理所得的清液进入电解机40中电解，电解出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
所述电解机的工作电压为1～36V，两电极间的电压为1～3V，电流密度为5～320mA/cm2,步骤（5）好氧池3-2出水在电解机中的停留时间为30s～5min。
所述电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种。
所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的贵金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。
实施例5
（1）破乳：将采油废水经管道收集于废水调节池1-1中并在废水调节池1-1中混合均匀，调节废水水量，检测其含油为520mg/L，COD为650mg/L、SS为200mg/L、含盐量为3500mg/L、pH为7.3。将经过废水调节池1-1的采油废水泵入破乳池1-3，加入硫酸调节pH至4破乳。
（2）石油回收：将步骤（1）破乳所得废水泵入重力沉降池1-5中，经过重力沉降分离，得回收的石油516g/m3和脱油废水，石油贮存在石油贮存罐1-6中，脱油废水送入废水收集池1-7中。
（3）微电解：将经步骤（2）石油回收后的脱油废水经铁碳微电解池20进行微电解。
（4）厌氧：使经步骤（2）微电解后所得废水进入厌氧池3-1，经厌氧处理提高废水的B/C值，改善废水的可生化性。
（5）好氧：使经步骤（4）厌氧处理后所得废水进入好氧池3-2，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD。
（6）电解：使步骤（5）好氧处理所得的清液进入电解机40中电解，电解出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
所述电解机的工作电压为1～36V，两电极间的电压为1～3V，电流密度为5～320mA/cm2,步骤（5）好氧池出水在电解机40中的停留时间为30s～10min。
所述电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种。
所述纳米催化惰性电极的表层涂覆有晶粒为10～35nm的贵金属氧化物惰性催化涂层，所述纳米催化惰性电极的基板为钛板或塑料板。
实施例6
（1）破乳：将采油废水经管道收集于废水调节池1-1中，并在废水调节池1-1中混合均匀，调节废水水量，检测其含油为1420mg/L，COD为2165mg/L、SS为90mg/L、含盐量为5200mg/L、pH为9.3，将经过废水调节池1的采油废水泵入破乳池1-3，加入硫酸调节pH至2破乳，按0.1g/m3加入PAM。
（2）石油回收：将步骤（1）破乳所得采油废水经过离心机1-5分离回收得石油406g/m3和脱油废水,石油贮存于石油贮存罐1-6中，脱油采油废水贮存于废水收集池1-7中。
所述离心分离是将破乳后的采油废水泵入离心机1-5中，经过离心分离为下层的石油和上层的脱油废水，下层的石油经回收管回收得石油406g/m3；离心分离的离心力为3200～4000。
（3）微电解：将经步骤（2）石油回收后的脱油废水经铁碳微电解池20进行微电解。
（4）厌氧：使经步骤（2）微电解后所得废水进入厌氧池3-1，经厌氧处理提高废水的B/C值，改善废水的可生化性。
（5）好氧：使经步骤（4）厌氧处理后所得废水进入好氧池3-2，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD。
（6）电解：使步骤（5）好氧处理所得的清液进入电解机40中电解，电解出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
所述电解机的工作电压为1～36V，两电极间的电压为1～3V，电流密度为5～320mA/cm2,步骤（5）好氧池出水在电解机40中的停留时间为30s～10min。
所述电解机设有电源和电解槽，所述电解槽内的电极为石墨、钛、铁、铝、锌、铜、铅、镍、钼、铬、合金和纳米催化惰性电极中的一种。
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Claims (11)

  1. 一种采油废水的处理装置，其特征在于，它由以下单元构成：
    （1）石油回收单元：石油回收单元由废水调节池、事故池、破乳池、酸储罐、重力除油装置、离心机或气浮除油装置、石油贮罐、废水池构成；废水调节池或事故池的出水口经过三通与破乳池的进水口联接，破乳池的酸进口与酸储罐的出口连接，破乳池的废水出口与重力除油装置、离心机或气浮除油装置的进水口连接，重力除油装置、离心机或气浮除油装置的出水口与废水池的进水口连接，重力除油装置、离心机或气浮除油装置的出油口与石油贮罐的进口连接；
    （2）微电解单元：微电解单元由微电解池体或罐体、填料支架、铁碳微电解填料、曝气装置、废水收集罩、吸收塔构成；填料支架安装在微电解池或微电解罐底部，铁碳微电解填料安放在填料支架上，废水收集罩安装在微电解池体或罐体的顶部，用于收集微电解单元工作时产生的废气；吸收塔构成内装有处理废气的活性炭或树脂；
    （3）生化处理单元：生化处理单元由厌氧处理池、好氧处理池和沉淀池构成；厌氧处理池的进水口与微电解单元的出水口连接，厌氧处理池的出水口与好氧池的进水口连接，好氧池的出水口与沉淀池的进水口连接，沉淀池的出水口与电解单元的进水口连接；
    （4）电解单元：电解单元是普通电解设备或纳米催化电解设备的一种，用于消除生化难以去除的残余COD和对废水进行消毒处理，杀灭废水中的微生物；
    （5）污泥处理单元：污泥处理单元包括污泥收集池、重力浓缩池、脱水机、污泥脱油装置、无害化处理装置；生化处理单元中厌氧池、好氧池和沉淀池的污泥出口与污泥收集池的进口联接，污泥收集池的出口与重力浓缩池的进口联接，重力浓缩池的出口与污泥脱水机的进口联接，污泥脱水机的污泥出口与污泥脱油装置的进口联接，污泥脱水机的污水出口与厌氧池的进水口联接；污泥脱油装置的出口与无害化处理装置的进口联接；石油回收单元、微电解单元、生化处理单元、电解单元和污泥处理单元通过管道、泵依次连接。
  2. 如权利要求1所述的一种采油废水的处理装置，其特征在于：所述的重力除油装置是自然沉降分离池、斜板除油装置或水力旋流除油装置中的一种。
  3. 如权利要求1所述的一种采油废水的处理装置，其特征在于：所述破乳池之前还有一个热交换器。
  4. 如权利要求1所述的一种采油废水的处理装置，其特征在于：所述生化处理单元的沉淀池与电解单元之间还设有一个过滤装置或离心机；过滤装置是MBR装置、柱式超滤装置、管式超滤装置的一种；过滤装置的膜材料为陶瓷膜、金属膜或有机膜的一种。
  5. 一种采油废水的处理方法，其特征在于，采用权利要求1所述的采油废水处理装置从而实现废水处理，包括如下步骤：
    （1）破乳：将含油为50～6100mg/L、COD为300～7000mg/L、SS为50～500mg/L、含盐量为1000～20000mg/L、pH为6.5～9.5的采油废水加入酸调节pH至2～6破乳，使石油和蜡质析出；
    （2）石油回收：将经过步骤（1）破乳后的采油废水中加入0.1～10mg/L的PAM使石油和蜡质析出，然后经过重力沉降分离或离心分离，得回收的石油和脱油或脱蜡废水，脱油或脱蜡废水的COD下降到900mg/L以下；
    （3）微电解：将经步骤（2）石油回收后的脱油或脱蜡废水经微电解装置进行微电解，进一步去除30～70%的COD并提高其可生化性，废水的COD下降到300mg/L以下；
    （4）厌氧：使经步骤（3）微电解处理后所得废水进入厌氧池，经厌氧处理提高废水的B/C值，改善废水的可生化性，废水的COD下降到200mg/L以下；
    （5）好氧：使经步骤（4）厌氧处理后所得废水进入好氧池，通过好氧处理进一步氧化分解废水中的有机物，深度去除COD和BOD，废水的COD下降到150mg/L以下；
    （6）电解处理：使步骤（5）好氧处理所得的清液进入电解处理设备处理，进一步降解COD，同时杀灭水中微生物，出水即全面达到《采油废水治理工程技术规范》（HJ2041-2014）的排放标准。
  6. 如权利要求5所述的采油废水的处理方法，其特征在于：步骤（1）破乳所述酸为硫酸、硝酸、磷酸或盐酸的一种。
  7. 如权利要求6所述的采油废水的处理方法，其特征在于：步骤（1）破乳所述酸最佳酸为硫酸。
  8. 如权利要求5所述的采油废水的处理方法，其特征在于：步骤（1）破乳的最佳破乳条件是将废水加入酸调节其pH至2.5～3。
  9. 如权利要求5所述的采油废水的处理方法，其特征在于：步骤（2）所述的石油回收是将经过重力沉降除油后的采油废水加入酸调节pH至2～6破乳后泵入重力沉降池中，经过重力沉降分离为上层的石油和下层的采油废水，上层的石油经回收管回收。
  10. 如权利要求5所述的采油废水的处理方法，其特征在于：步骤（2）的石油回收所述的离心分离是将经过重力沉降除油后的采油废水加入酸调节pH至2～6后泵入离心机中，经过离心分离为下层的石油和上层的脱油废水，下层的石油经回收管回收；离心分离的离心力为2200～4000。
  11. 如权利要求10所述的采油废水的处理方法，其特征在于：步骤（2）的石油回收所述离心分离的最佳条件是离心力为3200～4000
    。
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