CN104556281B - A kind of method removing the carbon dioxide contained in water - Google Patents
A kind of method removing the carbon dioxide contained in water Download PDFInfo
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- CN104556281B CN104556281B CN201410770011.8A CN201410770011A CN104556281B CN 104556281 B CN104556281 B CN 104556281B CN 201410770011 A CN201410770011 A CN 201410770011A CN 104556281 B CN104556281 B CN 104556281B
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- water
- carbon dioxide
- gas
- oxygen
- nitrogen
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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
-
- 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
Abstract
The invention discloses and a kind of remove the method for carbon dioxide in water, be particularly well-suited in the oil gas field of the carbon dioxide injection displacement of reservoir oil output water for re-injection.The method mainly includes three parts: 1, air air stripping carbon dioxide removal, the oxygen content of water increases to close to saturated in the process；2, with the oxygen of nitrogen air stripping removing previous step；3, gas stripping gas nitrogen carrying out catalytic combustion regenerative, then pressurized circulation utilizes.The water of carbon dioxide removal and oxygen significantly reduces for the corrosivity of watering equipment and pipeline.This method avoid traditional agent-feeding treatment, non-secondary pollution, and operating cost is low.
Description
Technical field
A kind of method that the present invention relates to carbon dioxide removing and containing in water, belongs to oil gas field technical field.
Background technology
Along with the increase of the exploitation time limit, most of oil field drop in formation pressure, production rate declines.In order to improve rate of oil production, many oil-producings, stable yields oil, need to maintain or improve strata pressure.Ensure that crude output most common method is to stratum water filling, and recovered water re-injection after treatment is the optimal path at saving water source, oil field.At present all dissolved with carbon dioxide in a lot of oil field extracted water of China, in the recovered water in part oil field, carbon dioxide content is up to hundreds of mg/L, according to SY/T5329-94 " clastic rock reservoir water water quality fertilizer index " standard-required, oil field reinjection water water standard requiring, free carbon dioxide content is less than 10mg/L.This is because, carbon dioxide is soluble in water, and sewage entirety presents acidity, and under the conditions of identical pH, it is more serious than hydrochloric acid to the corrosion of iron and steel.Carbon dioxide causes the rapid general corrosion of iron and steel and serious local corrosion so that 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 re-injection system is chemical method, and other colleges and universities and research institution propose to use vacuum method, gravity Method and air-extraction.Various methods all have its range of application and pluses and minuses.
Chemical method is to add corrosion inhibiter in sewage, relies on corrosion inhibiter to carry out control corrosion rate, and the action principle of corrosion inhibiter is filming control corrosion in metallic walls, and its major advantage is that construction investment saves.The problem existed: corrosion inhibiter can not remove the factor causing corrosion in sewage completely.And because consumption, the guard space of medicament are limited, easily cause water pollution once again.
Vacuum method has certain removing ability to the carbon dioxide contained in water, but high to equipment requirements, needs air-extractor and negative-pressure operation, invests higher.
In hypergravity technique removing water, the effect of carbon dioxide is obvious, but owing to the economic causes such as technology maturity and operating cost height are not extensively applied in oil field wastewater treatment.
Industry does not the most find a kind of gratifying solution at present, it is therefore desirable to a kind of environmental protection, the mode of 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, a kind of method that the invention provides carbon dioxide removing and containing in water, it is particularly well-suited in oil gas field the output water for re-injection.
The technical solution adopted for the present invention to solve the technical problems is: the method is: 1, air air stripping carbon dioxide removal, the oxygen content of water increases to close to saturated in the process；2, with the oxygen of nitrogen air stripping removing previous step；3, gas stripping gas nitrogen carrying out catalytic combustion regenerative, then pressurized circulation utilizes.
Its concrete technology flow process is as follows:
1, carbonated recovered water is adjusted to the pressure of superatmospheric through force (forcing) pump or valve, enter carbon dioxide removal tower from top to bottom, utilize aerator that direction segregation apparatus provides under carbon dioxide removal tower the air of excess, air and carbonated water carry out counter current contacting air stripping and go out carbon dioxide, the air carrying carbon dioxide is discharged to air from carbon dioxide removal tower upper air vent, and the water of carbon dioxide removal is discharged from carbon dioxide removal tower lower drain port, at this moment the gas concentration lwevel discharged in water is reduced to below 10mg/L, oxygen concentration in water reaches or close to saturation；
The described built-in filler of carbon dioxide removal tower, filler is rustless steel dumped packing or the structured packing with acid resistance corrosion, for providing the contact of gas and liquid；
2, import to device for deoxidizing after being mixed with gas stripping gas nitrogen by the water discharged in carbon dioxide removal tower, carry out deoxidation treatment.Discharging through the water outlet of deoxygenation discharge outlet below device for deoxidizing, rich in the gas stripping gas nitrogen (hereinafter referred to as " oxygen-enriched gas stripping gas ") of oxygen, above deoxidation tower, mist eliminator to air vent is discharged into gas stripping gas regenerative circuit；
Described device for deoxidizing can use one-level or two grades of deoxidations according to taking up an area the difference requiring to require with raw water quality, water outlet.In general, the effect of two-stage is better than one-level.Every one-level deoxidation can take again one of two kinds of forms: a) counter current contacting deoxidation tower；Or b) static mixer+gas-liquid separator.In general: the good separating effect of tower, but higher to the water purity requirements processed, it is desirable to the water entering deoxidation tower passes through the process of oil removing, oil removal, and equipment size is big, is easier to limited in application such as ocean platforms.Process water outlet oxygen content through one-level deoxidation tower and can reach below 0.05mg/L, the water outlet oxygen content processed through two grades of deoxidation towers can reach below 0.02mg/L, and the water outlet oxygen content through one-level static mixer, one-level gas-liquid separator and two grades of static mixers, the combined treatment of two grades of gas-liquid separators can reach below 0.05mg/L.
Described deoxidation tower sets filler, due to still some carbon dioxide in water, therefore filler is rustless steel dumped packing or the structured packing with acid resistance corrosion, and 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 contacting.
Described firsts and seconds gas-liquid separator can use horizontal or vertical structure.
3, the oxygen-enriched air stripping conductance that air vent above device for deoxidizing is discharged is entered catalytic reactor, fuel is added in catalytic reactor, make oxygen-enriched gas stripping gas with under the effect of catalyst 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 catalytic reactor oxygen deprivation gas stripping gas out owing to absorbing reaction liberated heat, temperature is higher than entrance.So the part in utilizing the oxygen deprivation gas stripping gas by catalytic reactor high temperature out, enter heat exchanger and the gas stripping gas before catalytic reactor is preheated, it is simple to stably catalyzed oxidation reaction, remaining part utilizes three-way valve to be discharged to gas stripping gas loop；
Described catalytic reactor sets catalyst bed, and with fixed catalyst, catalyst uses the noble metal such as aluminium sesquioxide Supported Pt Nanoparticles or palladium as catalyst；
Heater is set, once the temperature in reactor less than certain setting value, to catalytic reactor supplementary heating in described catalytic reactor；
Described fuel is hydrogen.The fuel selecting hydrogen to do catalysis burning at oil gas field is not a conventional selection.If the conventional device for deoxidizing of oil gas field uses air-extraction, almost all uses methanol, ethanol or methane.But these fuel contain carbon, after burning, produce carbon dioxide.If employing old process, in the water after carbon dioxide removal will introducing carbon dioxide again, then before the effect of carbon dioxide removal will have a greatly reduced quality.And here use hydrogen, then not carbonated in combustion product, it is to avoid the problems referred to above.
4, the oxygen deprivation gas stripping gas that device for deoxidizing is discharged utilizes gas pressurized device pressurization import gas stripping gas loop, recycle；
Described gas pressurized device can be roots blower, it is also possible to be other gas boosting equipment.
The invention has the beneficial effects as follows: the method can remove the carbon dioxide in oilfield sewage, high treating effect, such that it is able to reduce the acidity of recovered water, the corrosion rate of carbon steel is down to 0.02 below mm/a, is reached SY/T 5329-94 " clastic rock reservoir water water quality fertilizer index "；Use air air stripping carbon dioxide, although introducing oxygen, but use nitrogen air stripping can remove oxygen, gas stripping gas uses the mode of catalytic reaction to recycle, and deaerating effect is good, and reliability is high, and system does not has secondary pollution；System is without adding corrosion inhibitor；Flow process of the present invention is simple, and reaction condition is gentle, is particularly suitable for processing carbonated oil field reinjection water, and removing carbon dioxide efficiency is high, and operating cost is low.
Deoxidization technique is used for carbon dioxide removal by the present invention, carries out deoxidation the most again, and according to the pipe material in downstream, select hydrogen to do the fuel of nitrogen regeneration, it is to avoid the problem being introduced back into carbon dioxide after decarburization deoxidation flow process.
The present invention may be used for the industries such as oil gas field, the technique particularly relating to be removed re-injection again containing carbon dioxide in Produced Water In Oil-gas Fields, Ngi, but can be used for the field containing carbon dioxide in other water, thus avoid the acid water containing carbon dioxide that equipment and pipeline are caused corrosion.
Accompanying drawing explanation
Fig. 1 is the inventive method technological process Fig. 1, uses two-stage static mixer and separator removing oxygen.
Fig. 2 is the inventive method technological process Fig. 2, uses one-level static mixer and separator removing oxygen.
Fig. 3 is the inventive method technological process Fig. 3, uses two-stage deoxidation tower regeneration nitrogen.
Label in figure:
1, aerator, 2, carbon dioxide removal tower, 3, centrifugal pump, 4, one-level static mixer, 5, one-level gas-liquid separator, 6, heat exchanger, 7, catalytic reactor, 8, two grades of static mixers, 9, two grades of gas-liquid separators, 10, gas boosting equipment, 11, one-level deoxidation tower, 12, two grades of deoxidation towers.
Detailed description of the invention
Embodiment 1
For the technical characterstic of the energy more detailed description present invention, below in conjunction with Fig. 1 citing, the use of the present invention is illustrated.But the invention is not restricted to this example, can be combined with concrete application conditions according to technical scheme and determine detailed description of the invention.
9600m is processed with certain oil field day3Extraction produced-water reinjection process as a example by, containing gas concentration lwevel about 500 mg/L, oxygen content about 1mg/L, oil content about 1000 mg/L in extraction sewage.When using the present invention, sewage initially enters carbon dioxide removal tower 2, and sewage enters from tower top, contacts with from the air inversion blasted by aerator 1 at the bottom of tower, carries out air stripping carbon dioxide removal.Carbon dioxide removal tower 2 is packed tower, the in bulk or structured packing of internal filling, can guarantee that gas-liquid two-phase is fully contacted, and operation pressure is close to normal pressure.Air air stripping goes out discharges from tower top after the carbon dioxide in sewage, the sewage of carbon dioxide removal from the bottom of tower by centrifugal pump 3 suction deoxidation flow process.In the flow process of carbon dioxide removal, 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 content in the air of waste water, a large amount of oxygen of the dissolution of contaminated water of carbon dioxide removal, make oxygen content reach or close to saturated, for reaching waterflooding requirement, need sewage is carried out further deoxidation.
It is passed through deoxidation flow process from the sewage of carbon dioxide removal tower 2 extraction and mixes with the nitrogen as gas stripping gas, one-level static mixer 4 is entered after mixing, being provided with filler unit makes sewage be fully contacted with gas stripping gas, mixing logistics afterwards flows into one-level gas-liquid separator 5, this separator can be horizontal can also be vertical, the component arranged through separator interior makes gas-liquid two-phase be sufficiently separated.Now gas stripping gas nitrogen has taken away most oxygen in sewage, makes the sewage oxygen content flowed out from one-level gas-liquid separator 5 drop to 0.2-0.3mg/L, and carbon dioxide content is basically unchanged.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 supplementary high pure nitrogen, and the nitrogen of loss can be supplemented by adding air, the oxygen carried can remove during gas stripping gas regenerates in the lump.
Utilizing hydrogen and oxygen containing nitrogen low-temperature burning under the catalytic action of noble metal catalyst, remove oxygen, regeneration nitrogen heat release, reaction is carried out in catalytic reactor 7.For ensureing the minimum response temperature of catalytic reactor 7 and making full use of the heat of the high temperature gas stripping gas that burning produces, the high temperature gas stripping gas after regeneration is made to preheat unregenerated gas stripping gas by heat exchanger 6, the temperature making the gas stripping gas temperature after preheating reach to specify enters back into reactor, wherein heat exchanger 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 of regulation catalytic reactor 7 outlet.
The oxygen in gas stripping gas is removed in catalytic reactor 7, pluralities of fuel can be applied, when being fuel when using hydrogen, hydrogen and the oxygen reaction in gas stripping gas, generate steam, releasing heat makes the temperature of catalytic reactor be maintained above 100 DEG C, and the usage amount of hydrogen need to control in conjunction with discharge and the flow replenishing air.In the gas stripping gas of regeneration, oxygen content increases, and needs to remove.For catalytic reactor, inside is provided with electric heater, can start and carry out pre-heating system, make up to desired reaction temperature in startup procedure, can regulate nitrogen regeneration effect by changing the means such as loaded catalyst, regulation bullion content.Gas stripping gas through regeneration mix be passed through two grades of static mixers 8 with the sewage flowed out from one-level gas-liquid separator, through being fully contacted and further air stripping, and mixture two grades of gas-liquid separators 9 of inflow.The gas stripping gas flowed out from two grades of gas-liquid separators 9 is carried a small amount of oxygen and is returned to one-level static mixer 4 through the pressurization Posterior circle of gas boosting equipment 10 and carry out air stripping deoxidation, gas boosting equipment 10 therein can be roots blower or compressor, and it selects the pressure drop concrete with system relevant.The sewage carbon dioxide content flowed out from two grades of gas-liquid separators 9 is less than 0.02mg/L, respectively less than related specifications requirement less than 5mg/L, oxygen content.
Embodiment 2
In some applications, during the most land polymer water filling oil-producing, if it is less demanding to the oxygen content of output water, or the pipeline that output water enters has preferable oxytolerant performance, then other flow processs 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 the most land high sulfur-bearing, if the oxygen content of output water is required higher, but do not have the device space to limit, two-stage or one-level air stripping deoxidation tower can be used, replacing two-stage or one-level static mixer+separator respectively, wherein the separation tower system flow of two-stage is as shown in Figure 3.Owing to deoxidation tower makes gas stripping gas and oxygenated water counter current contacting, more preferable deoxidation effect can be obtained, but deoxidation tower often needs higher height than static mixer and separator, thus the application that at sea oil gas field etc. are high to floor space and requirement for height has limitation, but there is more preferable application potential by land.
The above is only the situation citing of the present invention, is not that the present invention does any pro forma restriction, to using any simple modification and equivalent variations done, within each falling within protection scope of the present invention in every technical spirit according to the present invention.
Claims (5)
1. the method removing the carbon dioxide contained in water, it is characterised in that: the concrete technology flow process of the method is as follows:
Carbonated water enters carbon dioxide removal tower, provides air, air and carbonated water to carry out counter current contacting, discharge the gas concentration lwevel in water and reduce in the segregation apparatus of lower direction, and the oxygen concentration in water reaches or close to saturation；
Water and the nitrogen discharged in carbon dioxide removal tower import to device for deoxidizing, and nitrogen mixes with water and contacts, and the oxygen in water enters in nitrogen, and the nitrogen rich in oxygen is discharged from device for deoxidizing, and the water that oxygenous concentration after process is little is discharged below device for deoxidizing；
The nitrogen rich in oxygen that air vent is discharged above device for deoxidizing imports catalytic reactor, adds fuel, make the nitrogen rich in oxygen and fuel reaction oxygen depleted in catalytic reactor；The nitrogen self-catalyzed reaction device outlet removing oxygen is discharged；This deoxidation process protection one-level or two grades of deoxidations；
The nitrogen removing oxygen that device for deoxidizing is discharged utilizes the pressurization of gas boosting equipment import gas stripping gas loop, recycles；
Gas stripping gas before catalytic reactor being preheated by the heat exchanger that partly or entirely enters in the nitrogen removing oxygen of catalytic reactor high temperature out, remaining part utilizes three-way valve to be discharged to gas stripping gas loop.
A kind of method removing the carbon dioxide contained in water the most according to claim 1, it is characterised in that: described gas boosting equipment is roots blower or other gas boosting equipment.
A kind of method removing the carbon dioxide contained in water the most according to claim 1, it is characterised in that: described catalytic reactor sets catalyst bed, and with fixed catalyst, catalyst uses aluminium sesquioxide Supported Pt Nanoparticles or palladium noble metal as catalyst.
A kind of method removing the carbon dioxide contained in water the most according to claim 1, it is characterised in that: set heater in described catalytic reactor.
A kind of method removing the carbon dioxide contained in water the most according to claim 1, it is characterised in that: described fuel is hydrogen.
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| CN109869636B (en) * | 2019-03-26 | 2024-04-19 | 中国海洋石油集团有限公司 | Reducing CO of crude oil transported outwards2Partial pressure offshore platform process system and method |
| CN115583686B (en) * | 2022-10-13 | 2024-04-16 | 新疆敦华绿碳技术股份有限公司 | Device and method for decarbonizing produced water |
| 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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| CN1054402A (en) * | 1990-01-19 | 1991-09-11 | 波克集团股份有限公司 | The cryogenic purincation of gas |
| CN102380313A (en) * | 2010-08-31 | 2012-03-21 | 大阳日酸株式会社 | Gas purifying method and gas purifying apparatus |
| CN102641653A (en) * | 2012-04-25 | 2012-08-22 | 中国石油化工股份有限公司 | Technology of carbon dioxide removal from reaction recycle gas of vinyl acetate monomer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11262753A (en) * | 1998-03-17 | 1999-09-28 | Tokico Ltd | Method and apparatus for water treatment |
| JP2001129305A (en) * | 1999-11-09 | 2001-05-15 | Kurita Water Ind Ltd | Deoxidation and decarbonation apparatus |
| JP2003047950A (en) * | 2001-08-01 | 2003-02-18 | Kurita Water Ind Ltd | Deoxygenation and decarboxylation treatment apparatus and treatment method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054402A (en) * | 1990-01-19 | 1991-09-11 | 波克集团股份有限公司 | The cryogenic purincation of gas |
| CN102380313A (en) * | 2010-08-31 | 2012-03-21 | 大阳日酸株式会社 | Gas purifying method and gas purifying apparatus |
| CN102641653A (en) * | 2012-04-25 | 2012-08-22 | 中国石油化工股份有限公司 | Technology of carbon dioxide removal from reaction recycle gas of vinyl acetate monomer |
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