CN104556281A - Method for removing carbon dioxide contained in water - Google Patents
Method for removing carbon dioxide contained in water Download PDFInfo
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- CN104556281A CN104556281A CN201410770011.8A CN201410770011A CN104556281A CN 104556281 A CN104556281 A CN 104556281A CN 201410770011 A CN201410770011 A CN 201410770011A CN 104556281 A CN104556281 A CN 104556281A
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a method for removing carbon dioxide contained in water and is particularly suitable for produced water for recycling in oil and gas fields for injecting carbon-dioxide flooding. The method mainly comprises the following three parts: 1, performing air stripping to remove carbon dioxide, wherein the oxygen content of water in the process is increased to be close to saturation; 2, performing nitrogen stripping to remove oxygen in the previous step; and 3, performing catalytic combustion and regeneration on nitrogen for stripping, pressurizing and recycling. The corrosion of the water from which carbon dioxide and oxygen are removed on the water equipment and pipelines is obviously reduced. According to the method, the traditional dosing treatment is avoided, secondary pollution is avoided, and the operating cost is low.
Description
Technical field
The present invention relates to a kind of method removing the carbonic acid gas contained in water, belong to oil-gas field technical field.
Background technology
Along with the increase of the exploitation time limit, most of oil field stressor layer reduces, and production rate declines.In order to improve oil recovery rate, fecund is oily, stable yields is oily, needs to maintain or improve reservoir pressure.Ensure that the most frequently used method of crude production rate is to stratum water filling, and recovered water re-injection is after treatment the optimal path at saving water source, oil field.All carbon dioxide is dissolved with in a lot of oil field extracted water of current China, in the recovered water in part oil field, carbon dioxide content is up to hundreds of mg/L, according to SY/T5329-94 " petroclastic rock reservoir water water quality fertilizer index " standard-required, in oil field reinjection water water quality standard, require that free carbon dioxide content is less than 10mg/L.This is because carbon dioxide is soluble in water, sewage entirety presents acidity, and under identical pH condition, it is also more serious than hydrochloric acid to the corrosion of iron and steel.Carbonic acid gas causes iron and steel general corrosion and serious local corrosion rapidly, makes equipment and down-hole pipe generation premature corrosion failure, and causes serious consequence.
At present, the main method processing carbon dioxide corrosion problem in oil field extracted water recycle system is chemical method, and other colleges and universities and research institution propose to adopt vacuum method, gravity Method and air-extraction.Various method all has its range of application and relative merits.
Chemical method adds inhibiter in sewage, relies on inhibiter to carry out control corrosion rate, and the action principle of inhibiter is filming control corrosion in metallic walls, and its major advantage is that construction investment is economized.Problems existing: inhibiter can not remove in sewage the factor causing corrosion completely.And because the consumption of medicament, guard space are limited, easily cause water pollution once again.
Vacuum method has the carbonic acid gas contained in water and necessarily removes ability, but high to equipment requirements, needs extraction equipment and negative-pressure operation, invests higher.
Hypergravity technique removes the successful of carbonic acid gas in water, but due to economic cause also not widespread uses in oil field wastewater treatment such as technology maturity and working cost height.
Current industry does not also find a kind of gratifying solution, therefore needs the mode of a kind of environmental protection, the carbon dioxide removal that efficient, high reliability, expense are low.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method removing the carbonic acid gas contained in water, being specially adapted to the production water for re-injection in oil-gas field.
The technical solution adopted for the present invention to solve the technical problems is: the method is: 1, air air lift carbon dioxide removal, and the oxygen level of water is increased to close to saturated in the process; 2, the oxygen of previous step is removed by nitrogen air lift; 3, carry out catalytic combustion regenerative to gas stripping gas nitrogen, then pressurized circulation utilizes.
Its concrete technology flow process is as follows:
1, carbonated recovered water is adjusted to higher than atmospheric pressure through force (forcing) pump or valve, enter decarbonation tower from top to bottom, gas blower is utilized to provide excessive air in the tripping device of direction under decarbonation tower, air and carbonated water carry out counter current contact air lift and go out carbonic acid gas, the air carrying carbonic acid gas is discharged to air from decarbonation tower upper air vent, and the water of carbon dioxide removal is discharged from decarbonation tower lower drain port, at this moment the gas concentration lwevel of discharging in water is reduced to below 10mg/L, oxygen concentration in water reaches or close to state of saturation,
The described built-in filler of decarbonation tower, filler is stainless steel dumped packing or the structured packing with acid resistance corrosion, for providing contacting of gas and liquid;
2, import to device for deoxidizing after being mixed with gas stripping gas nitrogen by the water of discharging in decarbonation tower, carry out deoxidation treatment.Water outlet through deoxygenation is discharged from water port below device for deoxidizing, and gas stripping gas nitrogen (hereinafter referred to as " oxygen enrichment the gas stripping gas ") spray catcher above deoxidation tower being rich in oxygen is discharged to venting port and entered gas stripping gas regenerative circuit;
The difference that described device for deoxidizing requires according to occupation of land and raw water quality, water outlet require can adopt one-level or secondary deoxidation.In general, the effect of two-stage is better than one-level.Every one-level deoxidation can take one of two kinds of forms again: a) counter current contact deoxidation tower; Or b) static mixer+gas-liquid separator.In general: the good separating effect of tower, but higher to the water purity requirements of process, require that water into deoxidation tower is through the process of oil removing, oil removal, and equipment size is large, more easily limited in application such as ocean platforms.Below 0.05mg/L can be reached through one-level deoxidation tower process water outlet oxygen level, water outlet oxygen level through the process of secondary deoxidation tower can reach below 0.02mg/L, and the water outlet oxygen level through the combined treatment of one-level static mixer, one-level gas-liquid separator and secondary static mixer, secondary gas-liquid separator can reach below 0.05mg/L.
Filler is established in described deoxidation tower, due to still some carbonic acid gas in water, therefore filler is stainless steel dumped packing or the structured packing with acid resistance corrosion, pending water enters from deoxidation tower top, gas stripping gas nitrogen enters from deoxidation tower bottom, and water and nitrogen are in filling batch counter current contact.
Described firsts and seconds gas-liquid separator can adopt horizontal or vertical structure.
3, the oxygen enrichment air lift conductance that venting port above device for deoxidizing is discharged is entered catalyticreactor, fuel is added in catalyticreactor, make oxygen enrichment gas stripping gas with under the effect of catalyzer with fuel reaction oxygen depleted, gas stripping gas nitrogen (hereinafter referred to as " oxygen deprivation gas stripping gas ") the self-catalyzed reaction device outlet removing oxygen is discharged, and recycles.And from catalyticreactor oxygen deprivation gas stripping gas out due to absorption reaction liberated heat, temperature is higher than entrance.So utilize by the part in the oxygen deprivation gas stripping gas of catalyticreactor high temperature out, enter interchanger by the gas stripping gas preheating before catalyticreactor, be convenient to stably catalyzed oxidizing reaction, remaining part utilizes T-valve to be discharged to gas stripping gas loop;
Catalyst bed established by described catalyticreactor, and with stagnant catalyst, catalyzer adopts the precious metal such as aluminium sesquioxide Supported Pt Nanoparticles or palladium as catalyzer;
Well heater is established, once the temperature in reactor lower than certain set(ting)value, to catalyticreactor supplementary heating in described catalyticreactor;
Described fuel is hydrogen.The fuel selecting hydrogen to do catalyticcombustion at oil-gas field is not a conventional selection.If the conventional device for deoxidizing of oil-gas field adopts air-extraction, almost all adopt methyl alcohol, ethanol or methane.But these fuel contain carbon, produce carbonic acid gas after burning.If employing old process, incite somebody to action introducing carbon dioxide again in the water after carbon dioxide removal, then the effect of the carbon dioxide removal before will be had a greatly reduced quality.And adopting hydrogen here, then not carbonated in products of combustion, avoids the problems referred to above.
4, utilize gas pressurized device to pressurize the oxygen deprivation gas stripping gas that device for deoxidizing is discharged and import gas stripping gas loop, recycle;
Described gas pressurized device can be roots blower, also can be other gas boosting equipment.
The invention has the beneficial effects as follows: this method can remove the carbonic acid gas in oilfield sewage, treatment effect is good, thus the acidity of recovered water can be reduced, the erosion rate of carbon steel is down to 0.02 below mm/a, reaches SY/T 5329-94 " petroclastic rock reservoir water water quality fertilizer index "; Adopt air air lift carbonic acid gas, although introduce oxygen, adopt nitrogen air lift to remove oxygen, gas stripping gas adopts the mode of catalyzed reaction to recycle, and deaerating effect is good, and reliability is high, and system does not have secondary pollution; System is without the need to adding corrosion inhibitor; Flow process of the present invention is simple, and reaction conditions is gentle, and be particularly suitable for processing carbonated oil field reinjection water, removing carbon dioxide efficiency is high, and working cost is low.
Deoxidization technique is used for carbon dioxide removal by the present invention, carries out deoxidation more afterwards, and according to the pipe material in downstream, selects hydrogen to do the fuel of nitrogen regeneration, again introduce the problem of carbonic acid gas after avoiding decarburization deoxidation flow process.
The present invention may be used for the industries such as oil-gas field, particularly relate to the technique carrying out removing re-injection again in Produced Water In Oil-gas Fields, Ngi containing carbonic acid gas, but also may be used for the field containing carbonic acid gas in other water, thus avoid the sour water containing carbonic acid gas to cause corrosion to e-quipment and pipe.
Accompanying drawing explanation
Fig. 1 is the inventive method technical process Fig. 1, adopts two-stage static mixer and separator to remove oxygen.
Fig. 2 is the inventive method technical process Fig. 2, adopts one-level static mixer and separator to remove oxygen.
Fig. 3 is the inventive method technical process Fig. 3, adopts two-stage deoxidation tower regeneration nitrogen.
Number in the figure:
1, gas blower, 2, decarbonation tower, 3, impeller pump, 4, one-level static mixer, 5, one-level gas-liquid separator, 6, interchanger, 7, catalyticreactor, 8, secondary static mixer, 9, secondary gas-liquid separator, 10, gas boosting equipment, 11, one-level deoxidation tower, 12, secondary deoxidation tower.
Embodiment
Embodiment 1
For energy more detailed description technical characterstic of the present invention, below in conjunction with Fig. 1 citing, use of the present invention is set forth.But the invention is not restricted to this example, can be combined with concrete application conditions according to technical scheme of the present invention and to determine embodiment.
With certain oil field day process 9600m
3extraction produced-water reinjection be treated to example, containing gas concentration lwevel about 500 mg/L in extraction sewage, oxygen level is about 1mg/L, oleaginousness about 1000 mg/L.When using of the present invention, first sewage enter decarbonation tower 2, and sewage enters from tower top, contacts with the air inversion blasted by gas blower 1 at the bottom of tower, carries out air lift decarbonation.Decarbonation tower 2 is packing tower, and the in bulk or structured packing of inner filling, can ensure that gas-liquid two-phase fully contacts, working pressure is close to normal pressure.Air air lift is discharged from tower top after going out the carbonic acid gas in sewage, and the sewage of carbon dioxide removal is centrifuged pump 3 suction deoxidation flow process at the bottom of tower.In the flow process of decarbonation, can the carbon dioxide content of water outlet at the bottom of control tower within the specific limits by the amount of blasting controlling air.Due to higher with oxygen level in the air of waste water, a large amount of oxygen of dissolution of contaminated water of decarbonation, makes oxygen level reach or close to saturated, for reaching waterflooding requirement, needs to carry out further deoxidation to sewage.
Pass into deoxidation flow process from the sewage of decarbonation tower 2 extraction and mix with the nitrogen as gas stripping gas, one-level static mixer 4 is entered after mixing, wherein arranging filler unit makes sewage fully contact with gas stripping gas, mixture flow flows into one-level gas-liquid separator 5 afterwards, this separator can be horizontal also can be vertical, and the component arranged through separator interior makes gas-liquid two-phase fully be separated.Now gas stripping gas nitrogen has taken away most oxygen in sewage, and make the sewage oxygen level flowed out from one-level gas-liquid separator 5 drop to 0.2-0.3mg/L, carbon dioxide content is substantially constant.Containing more oxygen in gas stripping gas now, need regeneration.Sour water after the nitrogen of gas stripping gas itself is processed absorbs a part, needs to supplement herein, but without the need to supplementary high pure nitrogen, and the nitrogen of replenish loss can be carried out by adding air, the oxygen carried can remove in the lump in the process of gas stripping gas regeneration.
Utilize hydrogen and oxygen containing nitrogen low-temperature burning under the katalysis of noble metal catalyst, remove oxygen, regeneration nitrogen heat release, react and carry out in catalyticreactor 7.For ensureing the minimum response temperature of catalyticreactor 7 and making full use of the heat of the high temperature gas stripping gas that burning produces, by the gas stripping gas that interchanger 6 makes the high temperature gas stripping gas preheating after regeneration not regenerate, make the gas stripping gas temperature after preheating reach the temperature of specifying and enter reactor again, wherein interchanger 6 uses plate-type heat exchanger, heat exchange efficiency is high, and floor space is little.The preheating temperature of gas stripping gas can be controlled by the three-way control valve regulating catalyticreactor 7 to export.
The oxygen in gas stripping gas is removed in catalyticreactor 7, pluralities of fuel can be applied, when using hydrogen for fuel, oxygen reaction in hydrogen and gas stripping gas, generate water vapour, releasing heat makes the temperature of catalyticreactor maintain higher than 100 DEG C, and the usage quantity of hydrogen needs Bound moisture flow to control with the flow replenishing air.In the gas stripping gas of regeneration, oxygen content increases, and needs to remove.For catalyticreactor, inside is provided with electric heater, can start and carry out pre-heating system, make it to reach desired reaction temperature in startup procedure, by changing loaded catalyst, regulating the means such as bullion content can regulate nitrogen regeneration effect.Gas stripping gas through regeneration mix with the sewage flowed out from one-level gas-liquid separator and passes into secondary static mixer 8, the further air lift through abundant contact, mixture inflow secondary gas-liquid separator 9.The gas stripping gas flowed out from secondary gas-liquid separator 9 is carried a small amount of oxygen and is got back to one-level static mixer 4 through the pressurization Posterior circle of gas boosting equipment 10 and carry out air lift deoxidation, gas boosting equipment 10 wherein can be roots blower or compressor, and it selects relevant with pressure drop concrete in system.From secondary gas-liquid separator 9 flow out sewage carbon dioxide content lower than 5mg/L, oxygen level, lower than 0.02mg/L, is all less than related specifications requirement.
Embodiment 2
In some applications, in such as land polymkeric substance water filling produce oil process, if less demanding to the oxygen level of production water, or the pipeline that production water enters has good oxytolerant performance, other flow processs then in embodiment 1 are constant, but two-stage static mixer+separator can be reduced to one-level, as shown in Figure 2.
Embodiment 3
In some applications, in the oilfield process of such as land high sulfur-bearing, if require higher to the oxygen level of production water, but do not have the device space to limit, two-stage or one-level air lift deoxidation tower can be adopted, replace two-stage or one-level static mixer+separator respectively, wherein the separation tower system flow of two-stage as shown in Figure 3.Because deoxidation tower makes gas stripping gas and oxygen-containing water counter current contact, better deoxidation effect can be obtained, but deoxidation tower often needs higher height than static mixer and separator, thus at sea oil-gas field etc. has limitation in floor space and the high application of requirement for height, but has better application potential by land.
The above is only situation of the present invention citing, is not do any pro forma restriction to the present invention, every according in technical spirit of the present invention to using any simple modification of doing and equivalent variations, all fall within protection scope of the present invention.
Claims (5)
1. remove a method for the carbonic acid gas contained in water, it is characterized in that: the concrete technology flow process of the method is as follows:
Carbonated water enters decarbonation tower, in the tripping device of lower direction, provide air, and air and carbonated water carry out counter current contact, and the gas concentration lwevel of discharging in water reduces, and the oxygen concentration in water reaches or close to state of saturation;
The water of discharging in decarbonation tower and nitrogen are imported to device for deoxidizing, nitrogen mixes with water and contacts, oxygen in water enters into nitrogen, the nitrogen (hereinafter referred to as " oxygen enrichment gas stripping gas ") being rich in oxygen is discharged from device for deoxidizing, and the water that the oxygenous concentration after process is little is discharged below device for deoxidizing;
The oxygen enrichment air lift conductance that venting port is discharged above device for deoxidizing enters catalyst oxidation reactor, adds fuel, make oxygen enrichment gas stripping gas and fuel reaction oxygen depleted in catalyticreactor; Nitrogen (hereinafter referred to as " oxygen deprivation gas stripping gas ") the self-catalyzed reaction device outlet removing oxygen is discharged; This deoxidation process protection one-level or secondary deoxidation;
Utilize gas boosting equipment to pressurize the oxygen deprivation gas stripping gas that device for deoxidizing is discharged and import gas stripping gas loop, recycle;
By partly or entirely entering an interchanger by the gas stripping gas preheating before catalyticreactor in the oxygen deprivation gas stripping gas of catalyticreactor high temperature out, remaining part utilizes T-valve to be discharged to gas stripping gas loop.
2. a kind of method removing the carbonic acid gas contained in water according to claim 1, is characterized in that: described gas boosting equipment is roots blower or other gas boosting equipment.
3. a kind of method removing the carbonic acid gas contained in water according to claim 1, is characterized in that: catalyst bed established by described catalyticreactor, and with stagnant catalyst, catalyzer adopts the precious metal such as aluminium sesquioxide Supported Pt Nanoparticles or palladium as catalyzer.
4. a kind of method removing the carbonic acid gas contained in water according to claim 1, is characterized in that: establish well heater in described catalyticreactor.
5. a kind of method removing the carbonic acid gas contained in water according to claim 1, is characterized in that: described fuel is hydrogen.
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| CN201410770011.8A CN104556281B (en) | 2014-12-15 | 2014-12-15 | A kind of method removing the carbon dioxide contained in water |
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| CN201410770011.8A CN104556281B (en) | 2014-12-15 | 2014-12-15 | A kind of method removing the carbon dioxide contained in water |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109869636A (en) * | 2019-03-26 | 2019-06-11 | 中国海洋石油集团有限公司 | A kind of outer output oil CO of reduction2The offshore platform process system and method for partial pressure |
| CN115583686A (en) * | 2022-10-13 | 2023-01-10 | 新疆敦华绿碳技术股份有限公司 | Produced water decarbonization treatment device and method |
| CN116639826A (en) * | 2022-10-26 | 2023-08-25 | 中国石油天然气股份有限公司 | CO (carbon monoxide) 2 Drive produced water reinjection treatment system and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116639826A (en) * | 2022-10-26 | 2023-08-25 | 中国石油天然气股份有限公司 | CO (carbon monoxide) 2 Drive produced water reinjection treatment system and method |
| CN116639826B (en) * | 2022-10-26 | 2024-03-08 | 中国石油天然气股份有限公司 | CO (carbon monoxide) 2 Drive produced water reinjection treatment system and method |
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