CN110713236A - Oil field chemical flooding produced water viscosity reduction device and method based on ozone-electrocatalytic oxidation combination - Google Patents
Oil field chemical flooding produced water viscosity reduction device and method based on ozone-electrocatalytic oxidation combination Download PDFInfo
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention discloses an oil field chemical flooding produced water viscosity reduction device and method based on ozone-electrocatalytic oxidation combination, and belongs to the technical field of water treatment methods. The viscosity reduction device provided by the invention combines an ozone oxidation system and an electrocatalytic oxidation system, and oilfield chemical flooding produced water is subjected to primary viscosity reduction treatment in the ozone oxidation system and is subjected to secondary viscosity reduction treatment in the electrocatalytic oxidation system. The viscosity reduction device and the viscosity reduction method provided by the invention can effectively improve the quality of the oilfield chemical flooding produced water, degrade organic matters such as polymers and the like, reduce the viscosity of the produced water, greatly improve the oil, mud and water separation efficiency, improve the treatment efficiency of the established sedimentation and filtration process technology of the oilfield, and meet the requirement of standard treatment of reinjection of the quality of the oilfield chemical flooding produced water.
Description
Technical Field
The invention belongs to the technical field of oilfield chemical flooding produced water treatment in the technical field of water treatment methods, and particularly relates to an oilfield chemical flooding produced water viscosity reduction device and method based on ozone-electrocatalytic oxidation combined use.
Background
The oil displacement of the chemical flooding is based on adding water-soluble polymer into injection liquid, so that the polymer is the basis of the chemical flooding, and the produced water is the chemical flooding produced water, namely the produced water of the oil field produced after the oil displacement by using a chemical flooding method comprises polymer flooding, surfactant-polymer flooding, alkali-surfactant-polymer flooding and alkali-polymer flooding produced water. Along with the injection of the ultra-high molecular weight polymer in the oilfield chemical flooding, the viscosity of the produced water which returns to the ground is higher and higher, and the treatment difficulty is higher and higher. Polymer-based chemical flooding affects produced water treatment primarily by: (1) the polymer increases the viscosity of the produced water. The viscosity of the polymer-containing sewage at 40 ℃ is generally 0.7-1.0 mPa & s, the viscosity of the polymer-containing sewage increases with the increase of the content of the polymer, the polymer concentration is generally 2.0-2.5 mPa & s at the peak time, and the viscosity of the ternary composite flooding produced water can reach 9.0mPa & s at most. The increase of the water viscosity can increase the stability of colloid particles in water and reduce the rising speed of oil droplets and the settling speed of suspended solids; (2) after the viscosity of the produced water is increased, the produced water oil droplets become small, the interface charge is enhanced, and the small oil droplets in the produced water stably exist in a water body, so that the treatment difficulty is increased; (3) the existence of the anionic polymer for oil displacement seriously weakens the use effect of the oilfield produced water treatment agent, and the high-alkaline environment of the ternary produced water (alkali-surfactant-polymer flooding) also makes the use effect of the oilfield produced water treatment agent poor, thereby obviously increasing the use amount of the agent; (4) due to the strong adsorbability of the polymer, more silt suspended solids and tiny particles carried in the sewage are difficult to float or sink, and meanwhile, the filtering efficiency of the ternary produced water is reduced due to the existence of the alkali, the surfactant and the polymer; (5) the emulsion formed by the high-viscosity produced water after polymer gathering is more stable, the viscoelasticity of the emulsion increases the strength of an oil-water interface film, and the difficulty of oil-water separation of the produced water is also increased.
At present, a settlement and filtration treatment process technology is mostly adopted for oilfield chemical flooding produced water treatment, and related monomer equipment mainly comprises a natural settling tank, a coagulation settling tank, an air floatation or aeration settling tank, a dissolved air flotation device, a granular filter material filter tank and the like, and then oilfield chemical agents such as a flotation agent, a flocculating agent and the like are added in a matched mode to realize effective treatment of sewage. The process technology mainly adopts a physical method as a main part, oil, water and mud are separated through the density difference of a medium and the theory of oil drop collision coalescence or shallow air flotation, the water quality of the reinjection water is ensured to reach the standard through the measures of adsorption, interception and the like of a filter material, and the water quality modification, the viscosity reduction of the produced water and the like basically have no effect, so the adaptability of the existing chemical flooding produced water treatment process is increasingly poor, and the main performance is as follows: high cost of the medicament, large slag yield after adding the medicament and lower standard operation load rate.
The advanced oxidation technology for water treatment is a new technology which is started in nearly 20 years, and the advanced oxidation technology is used for directly oxidizing organic pollutants in sewage into inorganic matters or converting the organic matters into low molecular weight organic matters by a chemical or physical-chemical method, and is mainly characterized by short reaction time and quick response. The related advanced oxidation technology mainly comprises an ozone oxidation technology, a photocatalytic oxidation technology, an electrocatalytic oxidation technology, an ultrasonic oxidation technology, a Fenton-like oxidation technology and the like. However, technically, a single advanced oxidation technology generates limited hydroxyl radicals, has limited selectivity to degraded pollutants and insufficient oxidation capacity, and is difficult to achieve ideal effects; from the economic analysis, the single advanced oxidation technology has low efficiency for oxidizing pollutants, high cost and large consumption of oxidant.
Disclosure of Invention
In view of one or more of the problems in the prior art, one aspect of the present invention provides an apparatus for reducing viscosity of oilfield chemical flooding produced water based on ozone-electrocatalytic oxidation, comprising:
an ozone generator (1) for generating ozone;
the gas-liquid powerful mixing cavity (3) is connected with the ozone generator (1);
a first ozone reactor (4) which comprises a first water inlet (41) and a first water outlet (42), wherein the first water inlet (41) is connected with the gas-liquid powerful mixing chamber (3);
the ozone circulating tank (6) comprises a circulating water inlet (61), a circulating water outlet (62), an incoming water inlet (63) and a third water outlet (64), wherein the circulating water inlet (61) is connected with the first water outlet (42), and the incoming water inlet (63) is used for being connected with an external produced water source;
one end of the circulating pump (2) is connected with a circulating water outlet (62) of the ozone circulating tank (6), and the other end of the circulating pump is connected with the gas-liquid powerful mixing cavity (3); and
an electro-catalytic tank (7) comprising a third water inlet (71), said third water inlet (71) being connected to a third water outlet (64) of said ozone recycling tank (6).
Above-mentioned viscosity reduction device still includes:
a second ozone reactor (5) arranged between the first ozone reactor (4) and the ozone circulation tank (6), wherein a second water inlet (51) and a second water outlet (52) are arranged on the second ozone reactor (5), the second water inlet (51) is connected with the first water outlet (42), and the second water outlet (52) is connected with a circulating water inlet (61) of the ozone circulation tank (6);
preferably, the first water inlet (41) is arranged at the bottom of the first ozone reactor (4), and the first water outlet (42) is arranged at the top of the first ozone reactor (4); the second water inlet (51) is arranged at the bottom of the second ozone reactor (5), and the second water outlet (52) is arranged at the top of the second ozone reactor (5);
further preferably, 3-4 layers of cross flow perforated plates are arranged in the first ozone reactor (4) and the second ozone reactor (5), and a water-insoluble metal catalyst is arranged between the cross flow perforated plates; preferably, the metal catalyst is a titania or alumina supported transition metal or transition metal oxide heterogeneous catalyst.
The ozone circulation tank (6) further comprises:
a water inlet central column (611) vertically arranged at the central upper part in the ozone circulating tank (6), wherein the bottom of the water inlet central column (611) is connected with the water inlet (63);
a water distribution system (613) disposed at the top inside the ozone circulation tank (6) and connected to the incoming water center post (611);
a flow guide member (614) disposed below the water distribution system (613) and disposed in the ozone circulation tank (6) around the water center post (611);
the water outlet central column (612) is vertically arranged below the water inlet central column (611), and the bottom of the water outlet central column is respectively connected with the circulating water outlet (62) and the third water outlet (64);
a circulating swirl plate (617) disposed below the flow guide member (614) and disposed in the ozone circulating tank (6) around an upper portion of the effluent center post (612) or around a lower portion of the incoming center post (611); and
and the water collecting system (618) is arranged below the circulating rotational flow plate (617) and is connected with the water outlet central column (612).
The water distribution system (613) comprises a plurality of water distribution bellmouths (6131) and a water distribution conduit (6132) which connects the water distribution bellmouths (6131) with the water inlet central column (611); and/or
The flow guide component (614) comprises a first upper layer flow guide plate (6141), a first inclined plate filler (6142) and a first lower layer flow guide plate (6143) which are fixedly connected; and/or
The water collecting system (618) comprises a plurality of water collecting bellmouths (6181) and a water collecting conduit (6182) for connecting the plurality of water collecting bellmouths (6181) with the water outlet central column (612); and/or
The ozone circulating tank (6) further comprises a tail gas discharge port (619) which is arranged at the top of the ozone circulating tank (6).
The third water inlet (71) is connected with a third water outlet (64) of the ozone circulating tank (6) through an inverted U-shaped pipeline, and a siphon breaking pipe (620) is arranged on the inverted U-shaped pipeline.
The electrocatalysis box body (7) also comprises an electrocatalysis contact zone (711), an electrocatalysis separation zone (713) and a water outlet zone (715); wherein:
the bottom of the electrocatalytic contact zone (711) is connected with the third water inlet (71), and an electrolytic cell (712) is arranged in the electrocatalytic contact zone;
the upper part of the electrocatalytic separation zone (713) is connected with the upper part of the electrocatalytic contact zone (711), and a second inclined plate filler (714), a second upper layer guide plate (7141) and a second lower layer guide plate (7142) are arranged in the electrocatalytic separation zone;
the bottom of said effluent zone (715) is connected to the bottom of said electrocatalytic separation zone (713);
wherein the bottom of the electrocatalytic contact zone (711) is provided with a first sludge accumulation zone (718), and the bottoms of the electrocatalytic separation zone (713) and the water outlet zone (715) are provided with a second sludge accumulation zone (719).
The electrocatalytic tank (7) further comprises:
a skimmer (716) disposed above the electrocatalytic separation zone (713);
a regulating weir (717) disposed above the exit region (715); and
a fourth water outlet (72) for discharging the water treated by the electrocatalytic tank (7).
A plurality of groups of electrode plates (7121) are arranged in the electrolytic cell (712), the plurality of groups of electrode plates (7121) are arranged in parallel, and the arrangement direction is the same as the water flow direction; preferably, the electrode plates (7121) adopt a titanium alloy material as a substrate, precious metal as a coating, and each group of electrode plates (7121) is provided with a pair of anodes and a pair of cathodes, and can be switched at regular time; further preferably, the distance between two adjacent groups of electrode plates (7121) is 10-15 mm.
The invention also provides a method for treating oilfield produced water by using the viscosity reduction device, which comprises the following steps:
1) the viscosity reducing device is installed according to the above steps;
2) and (3) connecting an incoming water inlet (63) on the ozone circulating tank (6) with an oilfield produced water source, starting the viscosity reduction device to treat oilfield produced water, and discharging the treated produced water from a fourth water outlet (72).
When the viscosity reduction device is used for treating the oilfield produced water in the step 2), the hydraulic retention time of the ozone circulating tank (6) is 40min-60min, and the hydraulic downward flow rate is 0.5mm/s-1.0 mm/s; and/or
The hydraulic retention time of the first ozone reactor (4) is 10min-20 min; and/or
The hydraulic retention time of the second ozone reactor (5) is 10min-20 min; and/or
The reflux ratio in the circulating pump (2) is 3:1-6: 1; and/or
The adding concentration of ozone per ton of water is 200mg/L-400 mg/L; and/or
The hydraulic retention time in the electrocatalytic contact zone (711) is 10min-20 min; and/or
The hydraulic retention time in the electrocatalytic separation zone (713) is 60min-100 min; and/or
The volume load of the water passing section of the electrocatalytic separation zone (713) is 1.0m3/m2·h-1.5m3/m2H; and/or
The flow velocity between the electrode plates (7121) is 8m/h-10m/h, and the current density of the electrode plates (7121) is 130A/m2-250 A/m2。
The device and the method for reducing the viscosity of the oilfield chemical flooding produced water based on ozone-electrocatalytic oxidation combination provided by the technical scheme combine two single advanced oxidation technologies to treat target wastewater through scientific combination, wherein the device for reducing the viscosity provided by the invention comprises an ozone oxidation system and an electrocatalytic oxidation system, can continuously carry out twice viscosity reduction treatment on the oilfield chemical flooding produced water, and particularly can prolong the oxidation reaction time and the contact area of the oilfield produced water and ozone through the design of a unique internal structure of an ozone circulating tank arranged in the ozone oxidation system. The device and the method provided by the invention can effectively improve the quality of the chemical-flooding produced water of the oil field, particularly the quality of the ternary complex flooding produced water, degrade organic matters such as polymers and the like, reduce the viscosity of the produced water, greatly improve the separation efficiency of oil, mud and water, improve the treatment efficiency of the established sedimentation and filtration process technology of the oil field, and meet the requirement of standard treatment of the quality of the chemical-flooding produced water of the oil field. The treatment efficiency of the device and the method provided by the invention changes according to the difference of the water quality of the chemical-flooding produced water, taking ternary composite flooding produced water with highest emulsification degree and highest treatment difficulty in the chemical-flooding produced water as an example, after the device and the method are used for treating the ternary composite flooding produced water, the oil removal rate is over 75 percent, the suspended solid removal rate is over 50 percent, and the viscosity reduction rate is over 70 percent, so that the device and the method have obvious and effective treatment efficiency on the chemical-flooding produced water.
Drawings
FIG. 1 is a schematic diagram of the principle of electroflocculation, wherein FIG. 1(A) is a schematic diagram of induced dipolarization of particles as they pass through an electrode; FIG. 1(B) is a schematic view of the polymerization process when the dipolarized particles pass through the electrodes;
FIG. 2 is a schematic structural diagram of an oilfield chemical flooding produced water viscosity reduction device based on ozone-electrocatalytic oxidation combination provided by the invention;
FIG. 3 is a schematic structural view of an ozone recycling tank provided by the present invention;
FIG. 4 is a schematic diagram of a water distribution system provided by the present invention;
FIG. 5 is a schematic structural view of a water collection system provided by the present invention;
FIG. 6 is a schematic structural diagram of an electrocatalytic tank provided by the invention.
Detailed Description
The ozone oxidation technology is one of advanced oxidation technologies for wastewater treatment. Ozone, also known as triatomic oxygen, is an allotrope of oxygen having the molecular formula O3. Ozone degradation of pollutants is mainly carried out through two ways, one is that ozone and organic matters directly react to degrade the pollutants, and the reaction speed is slow. The other is indirect reaction of the generated hydroxyl free radical, and the reaction speed is high. The inventor analyzes and considers that: because ozone in high pH value solution, the autodecomposition aggravates, and the hydroxyl radical that produces promptly takes the leading position, consequently is particularly useful for the oil field chemical flooding produced water oxidation treatment of high basicity, but simultaneously because ozone is very big to the oxidation activity phase difference of different substances, the organic matter is by easy to difficult general oxidation order: alkene > amine > phenol > polycyclic aromatic hydrocarbon > alcohol > aldehyde > alkane, which makes it difficult to completely degrade high molecular organic matters in oilfield chemical flooding produced water.
Based on the oxidation characteristics of the ozone analyzed, the invention provides a comprehensive treatment scheme aiming at the oilfield chemical flooding produced water, which comprises the following steps: firstly, the ozone oxidation is utilized to open and break the ring of the pollutant so that the high molecular substance is changed into the low molecular substance, and then the electrocatalytic oxidation is carried out to thoroughly or further degrade the pollutant, thereby improving the oxidation viscosity reduction efficiency of the oilfield chemical flooding produced water.
The electrocatalytic oxidation is a multi-phase multi-element catalytic electrolytic oxidation, has the functions of electrocoagulation, electroflotation, electrocatalytic oxidation and the like, and integrates several treatment functions into a whole. The electrocatalytic oxidation utilizes the water quality characteristics of high salinity, high conductivity and rich chloride ions of the oilfield chemical flooding produced water, and generates hydroxyl free radicals OH, active chlorine and O through the anode in-situ electrolytic reaction in the low-energy consumption catalysis process2And O3The small molecular strong oxidant has the effects of destroying a hydration layer, causing the hydration layer to be polarized and destabilized for highly stable oilfield chemical flooding produced water, and then utilizes H with the diameter of 10-60 mu m generated in the electrode process2And O2Micro bubbles are attached to the destabilized high polymerThe removal effect is achieved by the electric floating action on substances such as substances, oil, suspended solids and the like. The main principle of electrocatalytic oxidation is as follows:
1. principle of electric flocculation
The existing forms of oil in water mainly comprise oil slick (>100 mu m), dispersed oil (10-100 mu m), emulsified oil (0.1-10 mu m), dissolved oil (<0.1 mu m), oil consolidation complex and suspended solid, the main mechanism of oil removal and suspended solid by an electrochemical coagulation method is that particles are polarized by using the induction of an electric field, as shown in A in figure 1, the particles are charged with positive and negative charges after being polarized by the electric field, which is different from the traditional particles which are charged with only one kind of charge. During the flowing process, as shown in B in FIG. 1, the positive and negative charges attract each other, the two particles approach each other and combine to form a new particle, the new particle is re-polarized in the electric field, and while the particles are continuously polarized and polymerized, the following electrolysis process occurs on the positive and negative electrodes of the electrode:
and (3) anode reaction: 2H2O-4e-→O2↑+4H+
And (3) cathode reaction: 4H2O+4e-→2H2↑+4OH-
The amount and size of hydrogen and oxygen bubbles generated at the electrode depends on the current density at the electrode, and 0.0224Nm can be generated per 1F (26.8 A.h) of electricity according to Faraday's law3Hydrogen and oxygen. When the hydrogen bubbles and the oxygen bubbles rise, a velocity gradient is formed from bottom to top to generate stirring action, so that the opportunity of collision polymerization of the dipole oil particles is greatly increased.
2. Principle of electric levitation
Electrochemical flotation is a unit operation that electrochemically removes impurities such as oil and suspended matter from the liquid phase. The principle of floating is that produced water generates three reactions when passing through an electrolytic cell, and hydrogen, oxygen, chlorine and the like can be generated in situ:
and (3) cathode reaction: 2H++2e→H2↑
And (3) anode reaction: 4OH--4e→2H2O+O2↑
2C1--2e→Cl2↑
The produced water is electrolyzed to generate hydrogen, oxygen and chlorine gas which carry pollution particles in the produced water to accelerate floating, thereby achieving the purposes of separation and purification. The smaller the diameter of the bubble particles generated by the electro-flotation method, the smaller the limiting diameter of the adsorbable particles, and the better the quality of the treated water.
3. Principle of electrocatalytic oxidation
The electrocatalytic oxidation utilizes the characteristic that the content of chloride ions in the oilfield chemical flooding produced water is higher, and the reaction generated on the electrocatalytic oxidation anode mainly comprises the reaction of active chlorine and active oxygen:
(1) by means of active chlorine generated in situ
Upon electrolysis of produced water containing chloride ions, HClO and small amounts of higher chlorate may be produced. The reactions at the electrodes are as follows:
anode: 2Cl--2e→C12
Cl2+H2O→HClO+HCl
OH-Ions diffuse into the liquid layer around the anode to react with hypochlorous acid to generate chloric acid:
12ClO-+6H2O-12e-→4HClO3+8HCl+3H2O
HClO and HClO3Are both strong oxidizers.
(2) By virtue of active oxygen generated at the anode:
one is physically adsorbed active oxygen-hydroxyl radical. OH, fully oxidized:
H2O+MOx＝MOx[·OH]+H++e
MOx[·OH]+R＝MOx+CO2+zH++ze
one is active oxygen MO of chemical adsorptionx+1Partial oxidation:
MOx[·OH]＝MOx+1+H++e
MOx+1+R＝MOx+RO
the invention fully utilizes the water quality characteristics of the oilfield chemical flooding produced water, and combines the principles of ozone oxidation and electrocatalytic oxidation, and provides the oilfield chemical flooding produced water viscosity reduction device and method based on ozone-electrocatalytic oxidation combination, which can improve the water quality of the oilfield chemical flooding produced water, degrade organic matters such as polymers and the like, reduce the viscosity of the produced water, greatly improve the separation efficiency of oil, mud and water, improve the treatment efficiency of the established sedimentation and filtration process technology of the oilfield, and meet the requirement of standard water quality treatment of the oilfield chemical flooding produced water.
The present invention will be described in detail with reference to specific embodiments.
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
The methods used in the following examples are conventional methods unless otherwise specified.
Example 1: oil field chemical flooding produced water viscosity reduction device based on ozone-electrocatalytic oxidation combination
As shown in fig. 2, a schematic structural diagram of an embodiment of a viscosity reduction device for oilfield chemical flooding produced water based on ozone-electrocatalytic oxidation combined use is shown, which mainly includes two parts, one is an ozone oxidation system, and the other is an electrocatalytic oxidation system, where the ozone oxidation system mainly includes: the system comprises an ozone generator 1, a circulating pump 2, a gas-liquid powerful mixing chamber 3, a first ozone reactor 4, a second ozone reactor 5, an ozone circulating tank 6, and auxiliary supporting equipment such as a flowmeter, a pressure gauge and a valve, wherein the auxiliary supporting equipment is matched with the ozone reactor; the electrocatalytic oxidation system mainly comprises an electrocatalytic box body 7, and auxiliary supporting equipment such as a flowmeter, a pressure gauge, a valve and the like is used in a matching way.
As shown in fig. 3, a schematic structural diagram of the ozone recycling tank 6 is shown, which includes an incoming water inlet 63, a third water outlet 64, a recycled water inlet 61, a recycled water outlet 62, an incoming water central column 611, an outgoing water central column 612, a water distribution system 613, a flow guide component 614, a circulating rotational flow plate 617, a water collection system 618 and a tail gas discharge port 619, wherein the incoming water inlet 63 may be disposed on the incoming water central column 611, and may be used to communicate an external oilfield produced water source with the incoming water central column 611 through a pipeline, and convey the external oilfield produced water into the incoming water central column 611; the water inlet central column 611 can be vertically arranged at the upper part of the center in the ozone circulation tank 6, the water outlet central column 612 is arranged at the lower part of the center in the ozone circulation tank 6, the water inlet central column 611 and the water outlet central column 612 can be integrally connected, the interiors of the water inlet central column 611 and the water outlet central column 612 are both hollow structures and are not communicated, for example, the water inlet central column 611 and the water outlet central column 612 can be separated by a partition plate; the water inlet 63 is arranged at the bottom of the water inlet center column 611, the oilfield produced water is introduced from the bottom of the water inlet center column 611, the circulating water outlet 62 and the third water outlet 64 are arranged at the bottom of the water outlet center column 612, and are used for respectively conveying return water to the circulating pump 2 and conveying the oilfield produced water treated by the ozone circulating tank 6 to the electro-catalysis box 7. The water distribution system 613 is arranged at the top of the ozone circulation tank 6 and is connected with the incoming water center post 611, the produced water entering the incoming water center post 611 through the incoming water inlet 63 rises in the incoming water center post 611 and then enters the water distribution system 613, the produced water is dispersed through the uniform water distribution function of the water distribution system 613, and the contact area with ozone in the further treatment is increased. As shown in fig. 4, a schematic diagram of the water distribution system 613 is shown, comprising a plurality of water distribution horns 6131 for uniform distribution and a water distribution conduit 6132 connecting the water distribution horns 6131 to the water center post 611. The flow guide component 614 is arranged below the water distribution system 613 and is arranged around the water inlet central post 611, and can be used for containing produced water falling from the water distribution system 613, the circulating rotational flow plate 617 is arranged below the flow guide component 614 and is arranged around the bottom of the water inlet central post 611 or the upper part of the water outlet central post 612, and the circulating water inlet 61 is arranged above the circulating rotational flow plate 617, so that after backflow water carrying a large amount of ozone in the circulating water inlet pipe flows out of the circulating water inlet 61, a large amount of ozone can be released into the ozone circulating tank 6 under the action of the circulating rotational flow plate 617, and the backflow water moves upwards from bottom to top into the flow guide component 614. The flow guiding component 614 includes a first upper layer flow guiding plate 6141, a first lower layer flow guiding plate 6143 and a first inclined plate filler 6142 arranged between the first upper layer flow guiding plate 6141 and the first lower layer flow guiding plate 6143, so that produced water falling from the water distribution system 613 enters the first inclined plate filler 6142 from top to bottom through the first upper layer flow guiding plate 6141, a large amount of ozone released from the circulating rotational flow plate 617 enters the first inclined plate filler 6142 from bottom to top through the first lower layer flow guiding plate 6143, and the produced water and the ozone carry out a convection reaction in the first inclined plate filler 6142, so that the produced water can be fully oxidized. The water collection system 618 is disposed below the circulating rotational flow plate 617 and connected to the water outlet central column 612, as shown in fig. 5, which shows a schematic structural diagram of the water collection system 618, including a water collection bell-mouth 6181 for collecting water and a water collection conduit 6182 for connecting the water collection bell-mouth 6181 to the water outlet central column 612. Because the projected area of the water collecting system 618 in the ozone circulating tank 6 is larger than the projected area of the circulating rotational flow plate 617 in the ozone circulating tank 6, the fully oxidized produced water and the return water introduced from the circulating water inlet 61 can fall into the water collecting system 618 through the gap between the periphery of the circulating rotational flow plate 617 and the inner tank wall of the ozone circulating tank 6, then enter the water outlet central column 612 through the water collecting system 618, part of the water in the water outlet central column 612 enters the electrocatalysis tank 7 through the third water outlet 64 for further treatment, and the other part of the water enters the circulating water outlet pipe through the circulating water outlet 62 and enters the circulating pump 2 as the return water for internal circulating and returning. The tail gas generated in the working process of the ozone circulating tank 6 is discharged through a tail gas discharge port 619 arranged at the top of the ozone circulating tank, and the tail gas only contains low-content ozone and can be directly discharged through the tail gas discharge port 619 under the condition of reaching the discharge standard; in addition, the tail gas can be introduced into a potassium iodide solution firstly and then discharged; or the tail gas can be discharged into a low-level recovery water tank of the sewage treatment station, and the tail gas is discharged after being further absorbed and decomposed by the sewage in the recovery water tank.
In this embodiment, through the produced water and the backward flow water that contains a large amount of ozone carry out convection collision reaction in ozone circulation jar 6, carry the backward flow water of a large amount of ozone promptly and get into the 6 jar backs of ozone circulation jar through circulation whirl board 617, the ozone of backward flow water release upwards, the produced water is downward, simultaneously through the first swash plate filler 6142 of 6 inside arrangements of ozone circulation jar, increase the cross-sectional wet cycle of water, increase convection collision area to ozone reaction efficiency has been improved.
As shown in fig. 6, there is shown a schematic structural diagram of the electrocatalytic tank 7, which comprises a third water inlet 71, an electrocatalytic contact zone 711, an electrolytic cell 712, an electrocatalytic separation zone 713, a second inclined plate packing 714, a water outlet zone 715, a slag scraper 716, a regulating weir 717 and a fourth water outlet 72. The produced water after ozone oxidation passes through a third water outlet 64 arranged on the ozone circulating tank 6, is conveyed to a third water inlet 71 of the electro-catalysis box body 7 through an inverted U-shaped pipeline, and then is introduced into an electro-catalysis contact zone 711; the liquid level in the ozone circulating tank 6 can be controlled to be at a constant high liquid level by the arranged inverted U-shaped pipeline through hydraulic calculation, and at the moment, a fixed oil receiving tank is adopted for receiving oil, so that power equipment does not need to be additionally arranged at the top of the ozone circulating tank 6 for receiving oil or slag; a siphon 620 is also arranged on the inverted U-shaped pipeline, so that the produced water after ozone oxidation can smoothly enter the electro-catalytic box body 7. The third water inlet 71 is arranged at the bottom of the electrocatalysis contact zone 711, the electrolytic cell 712 is arranged in the electrocatalysis contact zone 711 and is positioned above the third water inlet 71, wherein a plurality of groups of electrode plates 7121 are arranged in the electrolytic cell 712, the spacing between the electrode plates is 10-15 mm, for example, a titanium alloy material is used as a substrate, noble metals (such as platinum, palladium and the like) are used as coatings, and each group of electrode plates 7121 is a pair of cathode and a pair of anode, and can be switched at regular time, so that the service life of the electrode plates is greatly prolonged and can reach more than 6 years; the produced water entering the electrocatalysis contact zone 711 is electrolyzed by the in-situ electrolysis reaction of the electrolytic cell 712 from bottom to top, and sludge contained in the produced water can be deposited in a first sludge accumulation zone 718 arranged at the bottom of the electrocatalysis contact zone 711. The top of the electrocatalysis separation zone 713 is connected with the top of the electrocatalysis contact zone 711, that is, the produced water electrolyzed by the electrolytic cell 712 in the electrocatalysis contact zone 711 flows into the second inclined plate packing 714 arranged in the electrocatalysis separation zone 713 from top to bottom, the upper side and the lower side of the second inclined plate packing 714 are respectively provided with a second upper layer guide plate 7141 and a second lower layer guide plate 7142 which play roles of guiding and fixing the second inclined plate packing 714. In the electrocatalytic separation zone 713, the rapidly rising particles in the electrolyzed produced water float to the water surface, the particles with slower rising speed are separated when passing through the second inclined plate packing 714 in the electrocatalytic separation zone 713, that is, the lighter particles rise in a counter-current manner once contacting the second upper layer flow guide component 7141, and the heavier particles sink into the second sludge accumulation zone 719 arranged at the bottom in the electrocatalytic separation zone 713 through the second inclined plate packing 714. The separated produced water flows out of the second inclined plate packing 714 to reach the bottom of the electrocatalytic separation region 713, and further flows into the bottom of the water outlet region 715 connected with the bottom of the electrocatalytic separation region 713 from the bottom, and because the second sludge deposition region 719 is also arranged at the bottom of the water outlet region 715, a part of heavy particles such as sludge and the like are deposited in the second sludge deposition region 719 in the process that the separated produced water flows from the bottom of the electrocatalytic separation region 713 to the bottom of the water outlet region 715. In addition, still be provided with in the top of electro-catalytic separation region 713 and scrape sediment ware 716, its effect is outside conveying the oily cinder that rises to the liquid level and receiving oil or receiving the interior discharge electro-catalytic box 7 of sediment groove, and this embodiment will set up the sediment ware that scrapes that probably explodes danger in ozone oxidation system and set up in electro-catalytic box 7 upper portion, can effectively avoid the risk of explosion, has improved operating safety factor greatly. In the water outlet zone 715, the produced water flows out of the electrocatalysis tank 7 from the fourth water outlet 72 after passing through the adjusting weir 717 from bottom to top, the adjusting weir 717 plays a role in adjusting the liquid level, the liquid level in the electrocatalysis tank 7 is controlled, and the slag scraper 716 arranged above the electrocatalysis separation zone 713 is convenient to scrape oil or slag on the liquid level smoothly and enter an oil collection or slag collection tank.
The oilfield produced water firstly enters an ozone oxidation system for primary viscosity reduction, then enters an electrocatalytic oxidation system for secondary viscosity reduction, and the viscosity reduction treatment of the oilfield produced water is realized through the two viscosity reduction processes, so that the requirement of standard treatment of the oilfield chemical flooding produced water quality is met. In the ozone oxidation system, an ozone circulating tank 6 is connected with a circulating water outlet 62 and a circulating pump 2 which are arranged on the ozone circulating tank through a circulating water outlet pipe, return water in the ozone circulating tank 6 is conveyed into the circulating pump 2 through the circulating water outlet pipe to be pressurized and lifted, and the return water is pumped into a gas-liquid powerful mixing cavity 3; the ozone generator 1 is used for generating ozone and introducing the generated ozone into the gas-liquid strong mixing cavity 3, and the gas-liquid strong mixing cavity 3 is used for introducing the ozone from the ozone generator 1 and recycling the ozoneThe return water that pump 2 pump was gone into mixes, the play water of the powerful hybrid chamber of gas-liquid 3 loops through first ozone reactor 4 and second ozone reactor 5 afterwards and gets into in the ozone circulation jar 6, wherein the powerful hybrid chamber of gas-liquid 3 is connected with the first water inlet 41 that first ozone reactor 4 bottom set up, the first delivery port 42 that first ozone reactor 4 top set up is connected with the second delivery port 51 that second ozone reactor 5 bottom set up, the second delivery port 52 that second ozone reactor 5 top set up is connected with the circulating water import 61 that sets up in the ozone circulation jar 6 through a circulation inlet tube. 3-4 layers of cross-flow perforated plates can be arranged in the first ozone reactor 4 and the second ozone reactor 5, and a metal catalyst is arranged between the cross-flow perforated plates, is insoluble in water, and is preferably a transition metal oxide heterogeneous catalyst loaded by titanium dioxide or aluminum oxide, such as a transition metal composite oxide (Fe)2O3\Co3O4etc.)/TiO2Such metal catalysts are commercially available or can be prepared by conventional methods, such as for example, Liuhong et al Fe2O3/TiO2Preparation of composite photocatalyst and its characterization (Liuhong, etc., Fe)2O3/TiO2Preparation and characterization of the composite photocatalyst, Wuhan university of science and technology, Vol.35 of 12 months, 2012, No. 6), and photo-assisted heterogeneous TiO of Liyan group2-Co3O4Research on degradation of dye wastewater by PMS activated by composite catalyst (Leyan group, photo-assisted heterogeneous TiO)2-Co3O4The research on the degradation of dye wastewater by PMS activated by the composite catalyst, Daqing university, Master thesis 2014), the catalyst has no consumption or low consumption in the use process, the service life is long, and the annual loss rate is less than or equal to 5 percent, so the cost is greatly saved; in addition, the process of dissolving the ozone in the gas-liquid powerful mixing cavity 3 is a negative pressure air suction process, the backflow water pumped by the circulating pump 2 is utilized to generate larger negative pressure when passing through the gas-liquid powerful mixing cavity 3, the ozone generated by the ozone generator 1 is sucked, the sucked ozone and the backflow water are fully contacted in the gas-liquid powerful mixing cavity 3 to generate vortex, rotate and collide with each other to form a cavitation effect, and the subsequent cavitation effect is realizedThe first ozone reactor 4 and the second ozone reactor 5 prolong the catalytic oxidation reaction time of the return water and the ozone, thereby achieving the best gas dissolving effect. In the process, because the negative pressure air suction is adopted, a compression process of the ozone generated by the ozone generator 1 is not needed, namely the ozone generated by the ozone generator 1 can be released into the gas-liquid powerful mixing cavity 3 under a very low pressure, so that the problem of 'ozone quenching' is not generated. After the primary viscosity reduction treatment of the ozone oxidation system, one part of the produced water subjected to the primary viscosity reduction treatment is introduced into an electrocatalysis box 7 in the electrocatalysis oxidation system by an ozone circulating tank 6 for secondary viscosity reduction treatment, and the other part of the produced water enters a circulating water outlet pipe and is introduced into a circulating pump 2 as backflow water.
The oil field chemical flooding produced water viscosity reduction device based on ozone-electrocatalytic oxidation combined use provided by the embodiment can effectively improve the water quality of oil field chemical flooding produced water, degrade organic matters such as polymers, reduce the viscosity of the produced water, greatly improve the oil, mud and water separation efficiency, improve the treatment efficiency of the established sedimentation and filtration process technology of the oil field, and meet the requirement of standard treatment of the water quality of the oil field chemical flooding produced water.
Example 2: treatment method for reducing viscosity of oilfield produced water by using oilfield chemical flooding produced water viscosity reduction device based on ozone-electrocatalytic oxidation combination
In this embodiment, the viscosity reduction treatment is performed on the oilfield produced water by using the oilfield chemical flooding produced water viscosity reduction device based on ozone-electrocatalytic oxidation coupling provided in embodiment 1, where the oilfield produced water is an ASP flooding produced water, and the method mainly includes the following steps:
1) assembling or installing the viscosity reduction device for oilfield chemical flooding produced water based on ozone-electrocatalytic oxidation combination as described in example 1;
2) an incoming water inlet 63 arranged on an ozone circulating tank 6 in the viscosity reducing device is connected with an oilfield produced water source through an incoming water inlet pipe, and then the viscosity reducing device is started to treat oilfield produced water.
The method specifically comprises the following steps: as shown in fig. 2 and 3, the oilfield produced water first enters the water central column 611 through a water inlet pipe, then enters the water distribution system 613 from bottom to top, and passes through the upper guide plate 6141, the first inclined plate filler 6142 and the lower guide plate 6143 from top to bottom in sequence under the action of the water distribution system 613. In the process that the produced water in the oil field flows from top to bottom, a large amount of ozone carried by a circulating water inlet pipe connected with a circulating water inlet of an ozone circulating tank 6 is released into the ozone circulating tank 6 through a circulating rotational flow plate 617, the released ozone and the produced water from top to bottom carry out convection collision reaction, meanwhile, the wet circumference of a water cross section is increased through a first inclined plate filler 6142 arranged in the ozone circulating tank 6, the convection collision area is increased, the ozone reaction efficiency is improved, the produced water is fully oxidized in the ozone circulating tank 6, the produced water after ozone oxidation enters a central column effluent 612 through a water collecting system 8, a part of the produced water oxidized by ozone in the effluent central column 612 flows out of a third water outlet 64 and enters an electro-catalytic box 7 through an inverted U-shaped pipe to carry out further viscosity reduction treatment; the other part of the produced water after being oxidized by ozone flows into the circulating pump 2 from the circulating water outlet 62 through a circulating water outlet pipe to be used as internal circulating return water.
In the ozone oxidation process, the ozone oxidation parameters are designed as follows:
1. the hydraulic retention time of the ozone circulating tank 6 is 50min, and the hydraulic downward flow rate is 0.7 mm/s.
2. The hydraulic retention time of the first ozone reactor 4 is 10min, 3-4 layers of cross flow perforated plates are arranged in the reactor, and a metal catalyst is arranged between the cross flow perforated plates, in this embodiment, a transition metal composite oxide (Fe)2O3\Co3O4etc.)/TiO2。
3. The force retention time of the water 5 in the second ozone reactor is 10min, 3-4 layers of cross flow perforated plates are arranged in the reactor, and a metal catalyst is arranged between the cross flow perforated plates, in this embodiment, the metal catalyst is transition metal composite oxide (Fe)2O3\Co3O4etc.)/TiO2。
4. The reflux ratio in the circulating pump 2 is 4: 1.
5. The adding concentration of ozone per ton of water is 300 mg/L.
As shown in fig. 4, the produced water after ozone oxidation firstly enters the electrocatalytic contact zone 711 through the third water inlet 64, a part of impurity sludge and the like in the produced water is deposited in the first sludge deposition zone 718, and the water flow is electrolyzed from bottom to top through the in-situ electrolysis reaction of the electrolytic cell 712 arranged in the electrocatalytic contact zone 711. The electrolyzed effluent enters an electrocatalytic separation zone 713 from the top of the electrocatalytic contact zone 711; in the electrocatalysis separation zone 713, the flow state of water flow is from top to bottom, particles which quickly rise in water float to the water surface, particles which slowly rise are separated when passing through the second inclined plate filler 714 in the electrocatalysis separation zone 713 and then are deposited in the second sludge accumulation zone 719, water enters the water outlet zone 715 from the bottom of the electrocatalysis separation zone 713 after passing through the second inclined plate filler 714 of the electrocatalysis separation zone 713 from top to bottom, and water flows out of the electrocatalysis box 7 from the fourth water outlet 718 after passing through the regulating weir 717 from bottom to top, so that secondary viscosity reduction treatment of the oilfield produced water is realized.
In the electrocatalytic oxidation process, the electrocatalytic oxidation parameters are designed as follows:
1. the hydraulic retention time of the electrocatalytic contact zone 711 is 10min, and the hydraulic retention time of the electrocatalytic separation zone 713 is 80 min.
2. The flow velocity of the produced water between the electrode plates 7121 is 9.5m/h, and the current density of the electrode plates 7121 is 150A/m2。
3. The volume load of the cross section of the electrocatalytic separation zone 713 is 1.25m3/m2·h。
After the viscosity reduction device for the oilfield chemical flooding produced water based on ozone-electrocatalytic oxidation combination provided in embodiment 1 is used for treating the ASP flooding produced water according to the method, the oil removal rate of the ASP flooding produced water is over 75%, the suspended solid removal rate is over 50%, and the viscosity reduction rate is over 70%, so that the requirement of standard treatment of the oilfield chemical flooding produced water quality is met.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides an oil field chemical flooding produced water viscosity reduction device based on ozone-electricity catalytic oxidation allies oneself with usefulness which characterized in that includes:
an ozone generator (1) for generating ozone;
the gas-liquid powerful mixing cavity (3) is connected with the ozone generator (1);
a first ozone reactor (4) which comprises a first water inlet (41) and a first water outlet (42), wherein the first water inlet (41) is connected with the gas-liquid powerful mixing chamber (3);
the ozone circulating tank (6) comprises a circulating water inlet (61), a circulating water outlet (62), an incoming water inlet (63) and a third water outlet (64), wherein the circulating water inlet (61) is connected with the first water outlet (42), and the incoming water inlet (63) is used for being connected with an external produced water source;
one end of the circulating pump (2) is connected with a circulating water outlet (62) of the ozone circulating tank (6), and the other end of the circulating pump is connected with the gas-liquid powerful mixing cavity (3); and
an electro-catalytic tank (7) comprising a third water inlet (71), said third water inlet (71) being connected to a third water outlet (64) of said ozone recycling tank (6).
2. The viscosity reduction device of claim 1, further comprising:
a second ozone reactor (5) arranged between the first ozone reactor (4) and the ozone circulation tank (6), wherein a second water inlet (51) and a second water outlet (52) are arranged on the second ozone reactor (5), the second water inlet (51) is connected with the first water outlet (42), and the second water outlet (52) is connected with a circulating water inlet (61) of the ozone circulation tank (6);
preferably, the first water inlet (41) is arranged at the bottom of the first ozone reactor (4), and the first water outlet (42) is arranged at the top of the first ozone reactor (4); the second water inlet (51) is arranged at the bottom of the second ozone reactor (5), and the second water outlet (52) is arranged at the top of the second ozone reactor (5).
3. The viscosity reduction device according to claim 1, wherein 3-4 layers of cross flow perforated plates are arranged in each of the first ozone reactor (4) and the second ozone reactor (5), and a water-insoluble metal catalyst is arranged between the cross flow perforated plates; preferably, the metal catalyst is a titania or alumina supported transition metal or transition metal oxide heterogeneous catalyst.
4. Viscosity reduction device according to claim 1 or 2 or 3, characterized in that the ozone recycling tank (6) further comprises:
a water inlet central column (611) vertically arranged at the central upper part in the ozone circulating tank (6), wherein the bottom of the water inlet central column (611) is connected with the water inlet (63);
a water distribution system (613) disposed at the top inside the ozone circulation tank (6) and connected to the incoming water center post (611);
a flow guide member (614) disposed below the water distribution system (613) and disposed in the ozone circulation tank (6) around the water center post (611);
the water outlet central column (612) is vertically arranged below the water inlet central column (611), and the bottom of the water outlet central column is respectively connected with the circulating water outlet (62) and the third water outlet (64);
a circulating swirl plate (617) disposed below the flow guide member (614) and disposed in the ozone circulating tank (6) around an upper portion of the effluent center post (612) or around a lower portion of the incoming center post (611); and
and the water collecting system (618) is arranged below the circulating rotational flow plate (617) and is connected with the water outlet central column (612).
5. The viscosity reduction device according to claim 4, characterized in that the water distribution system (613) comprises a plurality of water distribution bellmouths (6131) and a water distribution conduit (6132) connecting the plurality of water distribution bellmouths (6131) with the water central column (611); and/or
The flow guide component (614) comprises a first upper layer flow guide plate (6141), a first inclined plate filler (6142) and a first lower layer flow guide plate (6143) which are fixedly connected; and/or
The water collection system (618) comprises a plurality of water collection bellmouths (6181) and a water collection conduit (6182) connecting the plurality of water collection bellmouths (6181) with the water outlet central column (612); and/or
Ozone recycle tank (6) still includes tail gas vent (619), and it sets up the top of ozone recycle tank (6).
6. Viscosity reduction device according to any of claims 1 to 5, characterized in that the third water inlet (71) is connected to the third water outlet (64) of the ozone circulation tank (6) by an inverted U-shaped pipe, on which a broken siphon (620) is arranged.
7. Viscosity reduction device according to any of claims 1 to 6, characterized in that the electrocatalytic tank (7) further comprises an electrocatalytic contact zone (711), an electrocatalytic separation zone (713) and an outlet zone (715); wherein:
the bottom of the electrocatalytic contact zone (711) is connected with the third water inlet (71), and an electrolytic cell (712) is arranged in the electrocatalytic contact zone;
the upper part of the electrocatalytic separation zone (713) is connected with the upper part of the electrocatalytic contact zone (711), and a second inclined plate filler (714), a second upper layer guide plate (7141) and a second lower layer guide plate (7142) are arranged in the electrocatalytic separation zone;
the bottom of the effluent zone (715) is connected to the bottom of the electrocatalytic separation zone (713);
wherein the bottom of the electrocatalytic contact zone (711) is provided with a first sludge accumulation zone (718), and the bottoms of the electrocatalytic separation zone (713) and the water outlet zone (715) are provided with a second sludge accumulation zone (719).
8. Viscosity-reducing device according to claim 7, characterized in that the electrocatalytic tank (7) further comprises:
a skimmer (716) disposed above the electrocatalytic separation zone (713);
a regulating weir (717) disposed above the exit region (715); and
a fourth water outlet (72) for discharging the water treated by the electrocatalytic tank (7);
a plurality of groups of electrode plates (7121) are arranged in the electrolytic cell (712), the plurality of groups of electrode plates (7121) are arranged in parallel, and the direction of the electrode plates is the same as the water flow direction; preferably, the electrode plate (7121) adopts a titanium alloy material as a substrate, a noble metal as a coating, and the cathode and the anode can be switched; further preferably, the distance between two adjacent groups of electrode plates (7121) is 10-15 mm.
9. The method for treating oilfield produced water by using the viscosity reduction device of any one of claims 1-8, which is characterized by comprising the following steps:
1) installing the viscosity reduction device according to any one of claims 1 to 8;
2) and (3) connecting an incoming water inlet (63) on the ozone circulating tank (6) with an oilfield produced water source, starting the viscosity reduction device to treat oilfield produced water, and discharging the treated produced water from a fourth water outlet (72).
10. The method according to claim 9, wherein when the viscosity reduction device is used for treating the oilfield produced water in the step 2), the hydraulic retention time of the ozone circulating tank (6) is 40min-60min, and the hydraulic downward flow rate is 0.5mm/s-1.0 mm/s; and/or
The hydraulic retention time of the first ozone reactor (4) is 10min-20 min; and/or
The hydraulic retention time of the second ozone reactor (5) is 10min-20 min; and/or
The reflux ratio in the circulating pump (2) is 3:1-6: 1; and/or
The adding concentration of ozone per ton of water is 200mg/L-400 mg/L; and/or
The hydraulic retention time in the electrocatalytic contact zone (711) is 10min-20 min; and/or
The hydraulic retention time in the electrocatalytic separation zone (713) is 60min-100 min; and/or
The volume load of the water passing section of the electrocatalytic separation zone (713) is 1.0m3/m2·h-1.5m3/m2H; and/or
The flow velocity between the electrode plates (7121) is 8m/h-10m/h, and the current density of the electrode plates (7121) is 130A/m2-250A/m2。
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Application publication date: 20200121 |