CN111056650A - Method for treating carbon dioxide flooding oilfield produced water - Google Patents

Method for treating carbon dioxide flooding oilfield produced water Download PDF

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Publication number
CN111056650A
CN111056650A CN201811207144.9A CN201811207144A CN111056650A CN 111056650 A CN111056650 A CN 111056650A CN 201811207144 A CN201811207144 A CN 201811207144A CN 111056650 A CN111056650 A CN 111056650A
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water
produced water
carbon dioxide
content
effluent
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魏玉梅
栾金义
张新妙
侯秀华
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to CN201811207144.9A priority Critical patent/CN111056650A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/24Treatment of water, waste water, or sewage by flotation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/20Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/10Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physical Water Treatments (AREA)

Abstract

The invention discloses a treatment method of carbon dioxide flooding oilfield produced water, which comprises the following steps: s1, carrying out dissolved air flotation treatment on the oilfield produced water to remove oil and solid suspended matters in the oilfield produced water to obtain air flotation effluent; s2, degassing the air-floated effluent water, and removing gas in the air-floated effluent water to obtain degassed effluent water. The invention utilizes the dissolved air flotation device to remove oil, suspended matters, impurities and the like in the produced water, and adopts the membrane degassing technology to remove carbon dioxide, oxygen and the like in the produced water. Compared with the conventional common medicament treatment method, the method has the advantages of no medicament consumption, greatly reduced treatment cost, no secondary pollution, small equipment floor area, convenience in operation, capability of effectively removing carbon dioxide in the oilfield produced water, reducing the influence on reinjection water, solving the corrosion and scaling problems of water injection facilities, reducing the treatment cost of the produced water, realizing effective reinjection of the produced water and ensuring normal and stable production of the oilfield.

Description

Method for treating carbon dioxide flooding oilfield produced water
Technical Field
The invention relates to a method for treating carbon dioxide flooding oilfield produced water, in particular to a method for treating the carbon dioxide flooding oilfield produced water for reinjection by adopting dissolved air flotation and degassing technologies.
Background
In the middle and later periods of exploitation of most oil fields in China, the water content of crude oil is higher and higher, the water content of produced liquid of some oil fields reaches 60% -90%, the water content of produced liquid of some oil fields reaches 97%, and the improvement of the recovery ratio of the crude oil becomes a technical problem of close attention in the exploitation of the crude oil. The gas injection oil displacement is one of the main technologies of tertiary oil recovery, and the carbon dioxide oil displacement is to inject carbon dioxide into an oil reservoir, so that the viscosity of crude oil can be reduced, the fluidity ratio of the crude oil to water is improved, the volume of the crude oil is greatly expanded, the expanded residual oil can be favorably separated from formation water and the surface of rock, and the recovery of the crude oil is improved. The carbon dioxide flooding technology is earlier researched and applied abroad, mainly in countries such as the United states, Canada, Britain and the like; a great deal of earlier researches on the carbon dioxide oil displacement technology are carried out in China, and field tests are carried out in oil fields of Jiangsu, China, Daqing, Shengli and the like, so that the recovery ratio can be improved by 8-16% again. The carbon dioxide oil displacement has good application prospect in the exploitation of low-permeability oil reservoirs and high-water-cut oil reservoirs, has important significance for reducing greenhouse effect and protecting ambient air, is the most potential oil displacement technology in tertiary oil recovery, and is increasingly widely applied to the exploitation of oil fields.
The carbon dioxide flooding oilfield produced water not only contains oil, suspended impurities, various anions and cations, surfactants and other pollutants contained in conventional produced water, but also contains a large amount of soluble carbon dioxide and other gases, and the problems of serious corrosion and scaling are accompanied while the recovery ratio is improved. The injection of a large amount of carbon dioxide can cause corrosion and scaling of near-well formations, perforation holes, underground oil pipes, pumps, ground equipment, pipelines and the like, so that the formations and the pipelines are blocked, and the normal production and development of oil fields are influenced. In addition, the existence of a large amount of carbon dioxide can cause the concentration of suspended matters in water to rise, influences the oil-water separation effect of a water injection station, causes the reinjection of water and oil and particles to be difficult to reach the reinjection standard, and can cause adverse effects on the surrounding soil environment.
At present, the treatment of the produced water of the carbon dioxide flooding oil field is mainly carried out by adding agents such as corrosion inhibitors and the like, the method only relieves the corrosion and scaling problems of water injection facilities from the surface, does not remove the carbon dioxide in the produced water, has large adding amount of the agents and higher treatment cost, and is easy to cause secondary pollution of reinjection water. In addition, methods such as a vacuum method and a supergravity process are in research, the vacuum method has a certain removal effect on carbon dioxide in water, but the equipment requirement is high, air extraction equipment and negative pressure operation are required, and the investment is high; the supergravity process technology is still not mature, the operation cost is high, and the actual industrial application is not carried out.
The patent CN106609371A, entitled "a corrosion inhibitor and a preparation method and application thereof", discloses a corrosion inhibitor and a preparation method and application thereof. The corrosion inhibitor comprises: 25-35 wt% of amphoteric surfactant, 20-28 wt% of sulfur-containing organic matter, 15-25 wt% of nitrogen-containing organic matter, 1-10 wt% of oxygen scavenger and 2-39 wt% of water. The corrosion inhibitor has the performances of corrosion inhibition, scale inhibition and sterilization, can effectively solve the corrosion problem of a crude oil gathering and transportation pipeline, can inhibit the corrosion of metal, also eliminates under-scale corrosion caused by scale formation and corrosion caused by microorganisms, and is suitable for the treatment of carbon dioxide flooding oilfield produced water. The corrosion inhibitor only relieves the corrosion problem of oilfield equipment from the surface, cannot completely remove carbon dioxide in produced water, has high medicament consumption cost and is easy to cause secondary pollution to water quality.
The patent CN104961287A, entitled "oil-containing sewage zero-discharge treatment method and system", discloses a method and system for oil-containing sewage zero-discharge treatment. The method comprises the steps of sequentially carrying out three-stage filtration treatment, resin deoiling treatment, nanofiltration membrane desalination, hardness removal treatment and reverse osmosis membrane desalination treatment on oilfield produced water after flocculation and precipitation. Carrying out chemical hardness removal, filtration and reverse osmosis desalination treatment on the generated primary concentrated water; and the second-stage concentrated water enters an MVR distillation system after vacuum deoxygenation and carbon dioxide removal treatment, the generated concentrated brine is crystallized to form salt, and the fresh water enters a steam injection boiler after fine de-hardening treatment or fine de-salting treatment and deoxidation treatment. The method adopts vacuum method to remove oxygen and carbon dioxide, has high requirement on equipment and higher investment.
Disclosure of Invention
Aiming at the defects of the existing treatment method, the invention provides a standard-reaching reinjection treatment method for carbon dioxide flooding oilfield produced water, which adopts a dissolved air flotation and membrane degassing technology, utilizes a dissolved air flotation device to remove oil, suspended matters, impurities and the like in the produced water, and adopts a membrane degassing technology to remove carbon dioxide, oxygen and the like in the produced water. Compared with the prior art, the invention combines the dissolved air flotation and the membrane degassing technology, can remove oil, suspended matters and the like in the produced water of the carbon dioxide flooding, has high carbon dioxide removal rate, can remove oxygen, and can ensure that the produced water can reach the reinjection standard; compared with the conventional common medicament treatment method, the method has the advantages of no medicament consumption, greatly reduced treatment cost, no secondary pollution, small equipment floor area, convenience in operation, capability of effectively removing carbon dioxide in the oilfield produced water, reducing the influence on reinjection water, solving the corrosion and scaling problems of water injection facilities, reducing the treatment cost of the produced water, realizing effective reinjection of the produced water and ensuring normal and stable production of the oilfield.
In order to achieve the aim of the invention, the invention provides a method for treating carbon dioxide flooding oilfield produced water, which comprises the following steps:
s1, carrying out dissolved air flotation treatment on the oilfield produced water to remove oil and solid suspended matters in the oilfield produced water to obtain air flotation effluent;
s2, degassing the air-floated effluent water, and removing gas in the air-floated effluent water to obtain degassed effluent water.
According to some embodiments of the present invention, in step S1, the oilfield produced water is subjected to a dissolved air flotation process using a dissolved air flotation assembly, preferably the dissolved air flotation assembly includes:
the air flotation tank is used for receiving oilfield produced water;
the dissolved gas tank is used for dissolving nitrogen in water to obtain saturated dissolved gas water;
and the other end of the dissolved air releaser is connected with the dissolved air tank and used for introducing saturated dissolved air water in the dissolved air tank into the air flotation tank.
The nitrogen gas sent into the dissolved gas tank is dissolved in water by pressurization to form saturated dissolved gas water which enters the air flotation tank. The air flotation tank is internally provided with a dissolved air releaser, saturated dissolved air water passes through the dissolved air releaser, air dissolved in water is separated out to form a large amount of micro bubbles, the micro bubbles are fully contacted and adhered with oil, suspended matters and the like in sewage, the micro bubbles with specific gravity larger than that of the water are periodically discharged from the bottom of the tank when the water sinks, and the micro bubbles with specific gravity smaller than that of the water float on the water surface under the action of buoyancy to form scum which is periodically cleaned.
According to the preferred embodiment of the invention, the operation pressure of the dissolved air tank is 0.3 to 0.5MPa, and the dissolved air flotation residence time is 20 to 40 min.
According to some embodiments of the invention, the air flotation effluent is degassed in step S2 by using a membrane module.
According to a preferred embodiment of the present invention, the membrane module is operated at a temperature of 5 to 40 ℃ and a vacuum degree of-0.06 to-0.1 MPa.
According to some embodiments of the invention, the membrane module comprises a degassing membrane which is a resinous material, hollow fiber membrane with a hydrophobic surface.
According to a preferred embodiment of the invention, the degassing membrane has a membrane external diameter of 0.4 to 2mm and a membrane internal diameter of 0.3 to 1.5 mm.
In some specific embodiments, the membrane module uses nitrogen as the purge gas.
In some specific embodiments, the air input of the membrane module is 1.5-5 m3H, water inflow of 1.5-4 m3/h。
The membrane filaments are woven into the filament cloth and rolled into a column shape to be filled into the membrane shell, so that the effective contact area is increased, and meanwhile, the membrane filaments are fixed, the filament breakage phenomenon cannot occur, and the stability of the effluent quality is ensured; the liquid forms jet flow on the surface of the membrane wire, so that the flow channel can be effectively improved, and the mass transfer efficiency is improved. The wall of the hollow fiber of the degassing membrane is provided with micro pores with the diameter of 5-20nm, water molecules can not pass through the micro pores, and gas molecules such as carbon dioxide, oxygen and the like can pass through the micro pores. When the membrane module is in operation, produced water enters from one side of the membrane module and passes through the outer side of the hollow fiber membrane, gases such as carbon dioxide and oxygen are continuously pumped away by the inner side of the hollow fiber membrane under the action of the vacuum pump, a certain negative pressure is formed, and the gases such as carbon dioxide and oxygen in the produced water continuously overflow from the water through the hollow fiber membrane, so that the gases are removed.
According to some embodiments of the invention, the oilfield produced water has a content of suspended matter of 5 to 150Mg/L, an oil content of 2 to 500Mg/L, a dissolved oxygen content of 0.01 to 1Mg/L, an aggressive carbon dioxide content of 1.8 to 70Mg/L, an average corrosion rate of 0.05 to 0.64 mm/year, Mg2+Ca in an amount of 10 to 1200mg/L2+The content is 50 to 3000 mg/L.
According to the 'clastic rock oil reservoir water injection quality recommendation index and analysis method' of oilfield produced water reinjection standard (SY/T5329-2012), when the average air permeability of an injection layer is less than or equal to 0.01 mu m2 (the water quality requirement is strictest), the main control indexes of the produced water reinjection water quality are that the suspended solid content is less than or equal to 1mg/L, the oil content is less than or equal to 5mg/L, the dissolved oxygen content is less than or equal to 0.1mg/L, the water is stable when the content of erosive carbon dioxide is-1 to 1mg/L (when the content of erosive carbon dioxide is equal to zero, the water can dissolve calcium carbonate and has an erosive effect on a water injection facility, when the content of erosive carbon dioxide is less than zero, carbonate precipitation.
According to a preferred embodiment of the invention, the degassed effluent has a content of suspended matter < 1mg/L, an oil content < 0.1mg/L, a dissolved oxygen content < 0.1mg/L, an aggressive carbon dioxide content < 1mg/L and an average corrosion rate < 0.076 mm/year.
According to some embodiments of the invention, the method further comprises the steps of:
and S3, delivering the degassed effluent to a water injection station for reinjection.
Compared with the existing oilfield produced water treatment method, the method has the following advantages:
(1) the carbon dioxide removal rate is high and can reach 85 to 95 percent, and simultaneously, the deoxidation can be carried out, and the treated effluent meets the reinjection requirement;
(2) the method is a pure physical process, has no chemical consumption and no secondary pollution;
(3) the medicament consumption in the produced water treatment process is greatly reduced, only a small amount of electric energy is consumed in the operation, and the equipment operation and treatment cost is low;
(4) the membrane degassing unit occupies a small area, is convenient to install, is modularized in equipment, does not need high-position installation, and is convenient to operate and manage;
(5) effectively solves the problem of corrosion and scaling of equipment of the carbon dioxide flooding oilfield produced water facility, and ensures normal and stable production of the oilfield.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
example 1:
the main water quality characteristics of the oilfield produced water used in the embodiment are as follows: 72Mg/L suspended matter, 499Mg/L oil content, 0.1Mg/L dissolved oxygen content, 10.8Mg/L aggressive carbon dioxide content, 0.29 mm/year average corrosion rate and Mg content2+Content of 190mg/L, Ca2+The content is 288 mg/L.
The processing steps are as follows:
step 1, treating oilfield produced water in a dissolved air floatation unit, wherein nitrogen is used as a gas source, the operation pressure of a dissolved air tank is 0.3MP, and the dissolved air floatation retention time is 20 min. And removing oil and suspended solid in the produced water through air floatation treatment to form air floatation water.
Under the condition, the content of suspended matters in the water discharged by the dissolved air flotation is 0.9mg/L, and the content of oil is 1 mg/L; and (4) collecting and treating the bottom mud and the scum subjected to air floatation regularly and intensively.
Step 2, enabling air-floated effluent to enter a membrane degassing unit to remove carbon dioxide, oxygen and the like in the produced water to form membrane degassing unit effluent; the operating conditions of the membrane module are as follows: water inlet pressure 0.08MPa, vacuum degree-0.097 MPa, nitrogen flow 1.55m3H, inflow 2m3H, the water inlet temperature is 18 ℃.
Under the condition, the suspended solid content of the effluent of the membrane degassing unit is 0.6mg/L, the oil content is 0.06mg/L, the dissolved oxygen content is 0.05mg/L, the aggressive carbon dioxide content is 0.08mg/L, the average corrosion rate is less than 0.076 mm/year, and the reinjection standard of the oilfield produced water is met.
And 3, enabling the water discharged from the membrane degassing unit to meet the reinjection water index requirement, and entering a water injection station for reinjection.
Example 2:
the main water quality characteristics of the oilfield produced water used in the embodiment are as follows: 120Mg/L suspended matter, 230Mg/L oil content, 0.4Mg/L dissolved oxygen content, 30Mg/L aggressive carbon dioxide content, 0.26 mm/year average corrosion rate, Mg2+Content 160mg/L, Ca2+The content is 1250 mg/L.
The processing steps are as follows:
step 1, treating oilfield produced water in a dissolved air flotation unit, wherein nitrogen is used as a gas source, the operation pressure of a dissolved air tank is 0.4MP, and the dissolved air flotation retention time is 30 min. And removing oil and suspended solid in the produced water through air floatation treatment to form air floatation water.
Under the condition, the content of suspended matters in the water discharged by the dissolved air flotation is 0.8mg/L, and the content of oil is 1 mg/L; and (4) collecting and treating the bottom mud and the scum subjected to air floatation regularly and intensively.
Step 2, enabling air-floated effluent to enter a membrane degassing unit to remove carbon dioxide, oxygen and the like in the produced water to form membrane degassing unit effluent; the operating conditions of the membrane module are as follows: water inlet pressure 0.2MPa, vacuum degree-0.094 MPa, nitrogen flow 1.8m3H, inflow of 3m3H, water inlet temperature of 30 DEG C
Under the condition, the content of suspended solids in the effluent of the membrane degassing unit is 0.8mg/L, the oil content is 0.06mg/L, the dissolved oxygen content is 0.035mg/L, the content of aggressive carbon dioxide is 0.07mg/L, the average corrosion rate is less than 0.076 mm/year, and the reinjection standard of the oilfield produced water is met.
And 3, enabling the water discharged from the membrane degassing unit to meet the reinjection water index requirement, and entering a water injection station for reinjection.
Example 3:
the main water quality characteristics of the oilfield produced water used in the embodiment are as follows: 25Mg/L suspended matter, 280Mg/L oil content, 0.12Mg/L dissolved oxygen content, 65Mg/L aggressive carbon dioxide content, 0.26 mm/year average corrosion rate and Mg content2+Content 450mg/L, Ca2+The content is 900 mg/L.
The processing steps are as follows:
step 1, treating oilfield produced water in a dissolved air floatation unit, wherein nitrogen is used as a gas source, the operation pressure of a dissolved air tank is 0.45MP, and the dissolved air floatation retention time is 40 min. And removing oil and suspended solid in the produced water through air floatation treatment to form air floatation water.
Under the condition, the content of suspended matters in the water discharged by the dissolved air flotation is 0.7mg/L, and the content of oil is 1 mg/L; and (4) collecting and treating the bottom mud and the scum subjected to air floatation regularly and intensively.
Step 2, enabling air-floated effluent to enter a membrane degassing unit to remove carbon dioxide, oxygen and the like in the produced water to form membrane degassing unit effluent; the operating conditions of the membrane module are as follows: water inlet pressure 0.3MPa, vacuum degree-0.097 MPa, nitrogen flow 2.0m3H, inflow 4m3H, water inlet temperature of 20 DEG C
Under the condition, the suspended solid content of the effluent of the membrane degassing unit is 0.7mg/L, the oil content is 0.05mg/L, the dissolved oxygen content is 0.05mg/L, the aggressive carbon dioxide content is 0.08mg/L, the average corrosion rate is less than 0.076 mm/year, and the reinjection standard of the oilfield produced water is met.
And 3, enabling the water discharged from the membrane degassing unit to meet the reinjection water index requirement, and entering a water injection station for reinjection.
Comparative example 1:
the water quality characteristics of the produced water of a certain oil field are the same as that of the example 2, and the difference between the comparative example 1 and the example 2 is that the air-float effluent enters a membrane degassing unit, and the operation condition of a membrane module is that the nitrogen flow is 1m3H, water quantity of 5m3H, other operating conditions were the same as in example 2; under the operating conditions, the content of suspended solid in the effluent of the membrane degassing unit is 0.85mg/L, the oil content is 0.07mg/L, the content of dissolved oxygen is 0.15mg/L, and the content of aggressive carbon dioxide is 8 mg/L.
From the comparison of example 2 with comparative example 1, it can be seen that the gas flow is less than 1.5m3H, water amount is more than 4m3Under the operation condition of/h, the removal rate of carbon dioxide is obviously reduced.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A method for treating carbon dioxide flooding oilfield produced water comprises the following steps:
s1, carrying out dissolved air flotation treatment on the oilfield produced water to remove oil and solid suspended matters in the oilfield produced water to obtain air flotation effluent;
s2, degassing the air-floated effluent water, and removing gas in the air-floated effluent water to obtain degassed effluent water.
2. The method according to claim 1, wherein in the step S1, the oilfield produced water is subjected to dissolved air flotation treatment by using a dissolved air flotation assembly, and preferably the dissolved air flotation assembly comprises:
the air flotation tank is used for receiving oilfield produced water;
the dissolved gas tank is used for dissolving nitrogen in water to obtain saturated dissolved gas water;
and the other end of the dissolved air releaser is connected with the dissolved air tank and used for introducing saturated dissolved air water in the dissolved air tank into the air flotation tank.
3. The method of claim 2, wherein the operating pressure of the dissolved air tank is 0.3 to 0.5MPa and the dissolved air flotation residence time is 20 to 40 min.
4. The method according to any one of claims 1 to 3, wherein the air-float effluent is degassed by a membrane module in step S2.
5. The method according to claim 4, wherein the membrane module is operated at a temperature of 5 to 40 ℃ and a vacuum of-0.06 to-0.1 MPa.
6. The method according to any one of claims 1 to 5, wherein the membrane module comprises a degassing membrane which is a hollow fiber membrane of a resinous material having a hydrophobic surface.
7. The method according to any one of claims 1 to 6, wherein the degassing membrane has an outer membrane diameter of 0.4 to 2mm and an inner membrane diameter of 0.3 to 1.5 mm.
8. The method of any one of claims 1 to 7 wherein the oilfield produced water has a content of suspended matter of 5 to 150mg/L, an oil content of 2 to 500mg/L, a dissolved oxygen content of 0.01 to 1mg/L, an aggressive carbon dioxide content of 1.8 to 70mg/L, and an average corrosion rate of 0.05 to 0.64 mm/year.
9. The method according to any one of claims 1-8, wherein the degassed effluent has a content of suspended matter < 1mg/L, an oil content < 0.1mg/L, a dissolved oxygen content < 0.1mg/L, an aggressive carbon dioxide content < 1mg/L, and an average corrosion rate < 0.076 mm/year.
10. The method according to any of claims 1-9, characterized in that the method further comprises the steps of:
and S3, delivering the degassed effluent to a water injection station for reinjection.
CN201811207144.9A 2018-10-17 2018-10-17 Method for treating carbon dioxide flooding oilfield produced water Pending CN111056650A (en)

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Application publication date: 20200424