CN101708887A - Method for pre-oxidizing oil field waste water by using air - Google Patents
Method for pre-oxidizing oil field waste water by using air Download PDFInfo
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- CN101708887A CN101708887A CN200910193594A CN200910193594A CN101708887A CN 101708887 A CN101708887 A CN 101708887A CN 200910193594 A CN200910193594 A CN 200910193594A CN 200910193594 A CN200910193594 A CN 200910193594A CN 101708887 A CN101708887 A CN 101708887A
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Abstract
The invention discloses a method for pre-oxidizing oil field waste water by using the air, which comprises the following steps: introducing the air into oil field waste water to form free oxygen or dissolved oxygen in the oil field waste water; oxidizing the ferroins in the oil field waste water to form ferric ions by using the oxidization action of the free oxygen or dissolved oxygen, hydrolyzing the ferric ions to form Fex(OH)m(3x-m) and colloidal precipitate and oxidizing sulfides to form sulfur; and removing the sulfur by flocculation, sedimentation and filtration. The method has the advantages that: thermodynamic stability of the treated oil field waste water is improved, so that the water quality can keep constant and the suspended material content keeps constant and meets standards at a well mouth in the process of delivering the oil field waste water to a water distributing station and the well mouth; in the pre-oxidization process, no chemical is used, no extra sludge is produced, no pollution is produced and resources and cost are saved, so the pre-oxidization process is a 'green chemical' process; and the pre-oxidization process in which the operation is simple, convenient and safe, is easy to regulate and realize automation, has high adaptability to water volume and is convenient to promote and use.
Description
Technical field
The present invention relates to a kind of air that utilizes oilfield sewage is carried out the method for pre-oxidation treatment, belong to oil field produced water treatment field.
Background technology
In the Oil extraction process in oil field, claim " extraction liquid " or " output liquid " from the wet oil of underground extraction, the water of separating from extraction liquid is called " oil field extracted water ", also claims in " oil field output water " or " oilfield sewage ".
After the oil field enters waterflood stage, can produce a large amount of oilfield sewages.Oilfield sewage is a kind of heterogeneous system that integrates suspended solids, oil, gas dissolved and dissolved salt, wherein contains suspended solids, colloidal particle, dispersed oil and oil slick, emulsification wet goods impurity, with the tiny colloidal particle of water formation collosol state.For environment protection and the consideration that economizes on resources, need handle these sewage, manage suspended solids, colloid, dispersed oil and oil slick are removed, so that reinjection into reservoir is reused.In sewage treatment process, only utilize the gravity natural subsidence can not remove these particulates, must make colloidal sol take off in a different manner surely, condense or flocculate by chemical action, becoming could be settlement separate behind the bigger particle.Simultaneously, the corrodibility and the fouling tendency of kill bacteria, reduction sewage.
Oilfield sewage mainly adopts " syllogic " flow processing at present, promptly receives oil, sedimentation and filtration.Fe
2+, H
2S, HS
-, S
2-Solubleness in sewage is bigger, can't be removed by above-mentioned sedimentation and filtration.But Fe
2+Can oxidized gradually formation Fe
x(OH)
(3x-m) m+ colloidal solid; Simultaneously, Fe
2+Can also with the reduzate S of sulphate reducing bacteria (SRB)
2-Effect forms (FeS)
xBlack colloidal precipitation.About chemical reaction suc as formula (1) and (2).
Fe
2++O
2→Fe
x(OH)
(3x-m) m+↓????????(1)
xFe
2++xS
2-→(FeS)
x????????????????(2)
Fe
x(OH)
(3x-m) M+Colloid and (FeS)
xColloid mainly exists with the form of suspended solids and dirt in sewage, promptly generates new suspended solids (SS), makes water quality deterioration.Therefore can not all reach every standard (SY/T 5329-94 " petroclastic rock reservoir water water quality is recommended index and analytical procedure ") requirement of oilfield injection water by the oilfield sewage of this flow processing, even some index can be up to standard at sewage works, but owing to handle the poor heat stability of back sewage, can the longshore current journey worsen, when arriving water injection well, water quality is not up to standard yet, stops up the stratum.Therefore, want to improve the thermodynamic stability of handling back sewage, just need manage to remove the Fe in the decontaminated water
2+, H
2S, HS
-, S
2-Deng reducing substances.
Chemistry " preoxidation " and electrochemistry " preoxidation " all can be with the Fe in the sewage
2+Be oxidized to ferric ion, make it become the component useful sewage purification with cohesion, simultaneously can be with H
2S, HS
-, S
2-, the FeS sulfides is oxidized to elemental sulfur, separates removal by flocculation, sedimentation, filtration subsequently, improves the thermodynamic stability of handling back sewage.Simultaneously, make suspended substance, emulsification wet goods impurity small-particle in the sewage be gathered into macrobead, form the flco that volume is big, density is high, sedimentation is fast, sedimentation fully from water body, separate.Finally reach and purify water, kill bacteria, control burn into suppress fouling, make every index of handling back sewage all can satisfy oilfield injection water.Chemistry " preoxidation " is realized the preoxidation purpose by adding, use as the oxygen acid and the oxygenants such as salt, hydrogen peroxide thereof of chlorine, chlorine in sewage.This method needs the mass consumption chemical oxidizing agent in sewage treatment process, this oil field for produce hydrocarbons is extremely dangerous; Electrochemistry " preoxidation " is pointed to sewage energising electrolysis and is realized the preoxidation purpose, and as described in patent CN 1562781A " a kind of method of processing oil field sewage by electrolysing ", but this method needs consumed power.
At present at home, had the correlative study personnel that oilfield sewage is carried out aeration and handled, but its objective is that the sewage that makes after aeration is handled replaces clear water to come prepared polymer solution, and the present invention is reducing substances such as the Fe that makes in the sewage
2+, H
2S, HS
-And S
2-Oxidation, and separate from sewage by flocculating settling, improve the sewage thermodynamic stability, finally reach the purpose of stabilizing water quality, therefore still there is not the report that utilizes air (oxygen) oilfield sewage to be carried out " preoxidation " processing at present.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art part, the object of the present invention is to provide a kind of method of utilizing air oilfield sewage to be carried out pre-oxidation treatment.
Purpose of the present invention is achieved through the following technical solutions: a kind of air that utilizes carries out the method for pre-oxidation treatment to oilfield sewage, comprises following operation steps:
Air is introduced in the oilfield sewage, in oilfield sewage, formed free oxygen or dissolved oxygen; Utilize the oxidation capacity of free oxygen or dissolved oxygen, ferrous ion in the oilfield sewage is oxidized to iron ion, the iron ion hydrolysis generates the composition Fe useful to sewage disposal
x(OH)
m (3x-m)+Colloidal precipitation becomes elemental sulfur with sulfide oxidation simultaneously; Remove elemental sulfur by flocculation, sedimentation and filtration then.
The effective constituent of described air is oxygen; Described sulfide is hydrogen sulfide (H
2S), sulphur hydrogen radical ion (HS
-) and sulfonium ion (S
2-).
It is described that air is introduced oilfield sewage is to adopt pressurized air is introduced (as shown in Figure 1) in the oilfield sewage.
It is described that air is introduced oilfield sewage is to utilize the mobilization dynamic of oilfield sewage that air is sucked in the oilfield sewage.
Described suction is that the high flow rate of oilfield sewage sucks air in the oilfield sewage when oilfield sewage is flowed through stenosis; According to venturi principle, when flow one timing, flow velocity and sectional area are inverse ratio.Flow velocity is high more, and pressure is low more.Drainage flow just can suck air in the Sewage treatment systems, when flowing through thin neck place as shown in Figure 2.
Described suction is to utilize liquid level difference in slurry tank liquid level and the rising pipe, and oilfield sewage sucks air the oilfield sewage from slurry tank downward impact power when the rising pipe overflow; By the principle of work of diffusion pump as can be known, surrounding gas molecule carrier can be flowed together during liquid-flow.Sewage can carry air to the surging force of underflow stream from slurry tank and suck the Sewage treatment systems, as shown in Figure 3.
The present invention removes Fe in the decontaminated water by oxygenizement
2+, H
2S, HS
-, S
2-With reducing substanceses such as various sulfide, comprise making Fe
2+Change into the Fe of water purification effect
x(OH)
(3x-m) M+Simultaneously with H
2S, HS
-, S
2-Change into elemental sulfur with various sulfide, and they are separated from sewage by flocculation, sedimentation, filtration.Owing to handle in the sewage of back and do not contain matter Fe
2+, H
2S, HS
-, S
2-And various sulfide etc., thereby avoid handling back sewage in the well head course of conveying, regenerate Fe
x(OH)
(3x-m) M+, (FeS)
xDeng impurity, improve the purpose of handling back oilfield sewage thermodynamic stability to reach, make and handle back sewage in the course of conveying of water distributing station, water injection well, water quality does not change, sewage after the processing can not only (SY/T 5329-94) up to standard at sewage works, and also can be up to standard when transporting to well head outside.
The present invention can implement separately, its flow process as shown in Figure 4: air is introduced from the isolated oilfield sewage of triphase separator, reducing substances is carried out preoxidation, flocculate then, sedimentation and filtration, can fail outward, reinjection into reservoir.
When the oxidation capacity of air is not enough to the whole oxidations of the reducing substances in the sewage, the present invention can be used as prime oxidation and chemical preoxidation (Fig. 5) or electrochemistry preoxidation (Fig. 6) and is used.From the isolated oilfield sewage of triphase separator, at first carry out preoxidation, add a small amount of chemical oxidizing agent again or carry out electrochemistry " preoxidation ", with remaining reducing substances in the sewage whole " preoxidation " with air, flocculate at last, sedimentation and filtration, can fail outward, reinjection into reservoir.
Joining in the treating processes of polywater in tertiary oil recovery generally is to avoid oxidizing reaction, because join the material that generates after ferrous ion in the polywater and sulfide and the oxygen reaction viscosity of joining polywater is reduced; But the present invention creatively utilizes the oxygenizement of airborne oxygen in the process of handling oilfield sewage, carry out the material that produces after the oxidizing reaction with ferrous ion and sulfide, remove by flocculation, sedimentation and filter type, improved the stability of oilfield sewage.
The present invention compared with prior art has following advantage and beneficial effect: (1) employing the inventive method can be with very low cost with part, big portion even the oxidation of Restore All material in the sewage; (2) the inventive method has improved the thermodynamic stability of handling the back oilfield sewage, and it is not changed in water quality in the course of conveying of water distributing station, well head, and suspension content does not increase, and water quality does not worsen, still can be up to standard at well head; (3) in electrolysis step of the present invention, " chemical reagent " that works is airborne oxygen.In preoxidation process, do not use chemical agent, therefore have additionally do not produce mud, sludge quantity is few, pollution-free, helps economizing on resources and cost, meets " Green Chemistry " technology; (4) " preoxidation " of the present invention process, easy and simple to handle, safety is easy to regulation and control and realizes automatization, and water yield size, water quality difference are had adaptability widely, is easy to be extended and applied.
Description of drawings
Fig. 1 is pressurized air (oxygen) work exemplary flow.
Fig. 2 is the venturi principle exemplary flow.
Fig. 3 is that slurry tank is to underflow stream impact work synoptic diagram.
Fig. 4 is the technical process that the present invention uses separately.
Fig. 5 is the technical process that the present invention and chemical preoxidation are used.
Fig. 6 is the technical process that the present invention and electrochemistry preoxidation are used.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
Embodiment 1
Present embodiment adopts the method for the invention separately, utilizes air that oilfield sewage is carried out preoxidation, discharge of sewage 238m
3/ h, air is pressed into the sewage disposal flow process with air compressor.Air forms free oxygen or dissolved oxygen in oilfield sewage; Utilize the oxidation capacity of free oxygen or dissolved oxygen, ferrous ion in the oilfield sewage is oxidized to iron ion, the iron ion hydrolysis generates Fe
x(OH)
m (3x-m)+Colloidal precipitation becomes elemental sulfur with sulfide oxidation simultaneously; Remove elemental sulfur by flocculation, sedimentation and filtration then.
Water quality in standing and well head water quality are monitored, and the result is as shown in table 1.
Result among table 1 embodiment 1
| Sulfur-bearing mg/L | Suspended substance mg/L | Oil-containing mg/L | Median particle size μ m | ??∑Fe??mg/L | SRB/L | TGB/L | Erosion rate mm/a | |
| Standard | ??≤10 | ??≤3 | ??≤10 | ??≤1.8 | ??≤0.5 | ??≤10 | ??≤10 | ??≤0.076 |
| Air | ??0.2 | ??1.0 | ??3.4 | ??0.6 | ??0.31 | ??0 | ??0 | ??0.034 |
| Sulfur-bearing mg/L | Suspended substance mg/L | Oil-containing mg/L | Median particle size μ m | ??∑Fe??mg/L | SRB/L | TGB/L | Erosion rate mm/a | |
| Well head | ??0.2 | ??1.3 | ??1.5 | ??0.6 | ??0.31 | ??0 | ??0 | ??0.028 |
As shown in Table 1, adopt the method for the invention sewage disposal can not only be become satisfy fully the injection water up to standard that SY/T5329-94 requires, and water conditioning, also can be up to standard in well head water quality.
Embodiment 2
The method that present embodiment adopts electrochemical method, air to combine with electrochemistry is handled oilfield sewage, and the discharge of sewage is 154m
3/ h.Adopting the required consumed current of electrochemical method is 5760A; The method that adopts air to combine with electrochemistry promptly at first utilizes venturi principle that air is sucked Sewage treatment systems, adopts electrochemical method to carry out " preoxidation " then, and required electric current only needs 295A.
Air and anode are with reducing substances in the sewage, as H
2S, HS
-, S
2-, Fe
2+Be oxidized to colloid Fe with FeS etc.
x(OH)
(3x-m) M+With simple substance S, bacterium is killed fully, flocculates subsequently, sedimentation, filtration, and water quality in standing and well head water quality are monitored, and the result is as shown in table 2:
Table 2 embodiment 2 experimental results
| Sulfur-bearing mg/L | Suspended substance mg/L | Oil-containing mg/L | Median particle size μ m | ??∑Fe??mg/L | SRB/L | TGB/L | Erosion rate mm/a | |
| Standard | ??≤10 | ??≤3 | ??≤10 | ??≤1.8 | ??≤0.5 | ??≤10 | ??≤10 | ??≤0.076 |
| Electrochemistry | ??0.4 | ??1.4 | ??4.1 | ??0.7 | ??0.31 | ??0 | ??0 | ??0.027 |
| Air+electrochemistry | ??0.3 | ??1.1 | ??3.6 | ??0.6 | ??0.33 | ??0 | ??0 | ??0.031 |
| Well head | ??0.2 | ??1.3 | ??1.5 | ??0.6 | ??0.34 | ??0 | ??0 | ??0.026 |
By table 2 as seen, the method for the invention and electrochemistry " preoxidation " method is used, and sewage disposal can not only be become satisfy fully the injection water up to standard that SY/T 5329-94 requires, and water conditioning, also can be up to standard in well head water quality.
Embodiment 3
Present embodiment adopts chemical process, air and chemofacies bonded method to handle oilfield sewage, and the discharge of sewage is 338m
3/ h.Adopt chemical process per hour need consume the KClO of 12.19kg
3Adopt air and chemofacies bonded method, promptly at first utilize slurry tank air to be carried and suck in the Sewage treatment systems, adopt chemical process to carry out " preoxidation " then, the KClO of required consumption to the surging force of underflow stream
3Only be 0.455kg.
Air and chemical oxidizing agent are with reducing substances in the sewage, as H
2S, HS
-, S
2-, Fe
2+Be oxidized to colloid Fe with FeS etc.
x(OH)
(3x-m) M+With simple substance S, bacterium is killed fully, flocculates subsequently, sedimentation, filtration, and water quality in standing and well head water quality are monitored, and the result is as shown in table 3:
Table 3 embodiment 3 experimental results
| Sulfur-bearing mg/L | Suspended substance mg/L | Oil-containing mg/L | Median particle size μ m | ??∑Fe??mg/L | SRB/L | TGB/L | Erosion rate mm/a | |
| Standard | ??≤10 | ??≤3 | ??≤10 | ??≤1.8 | ??≤0.5 | ??≤10 | ??≤10 | ??≤0.076 |
| Chemistry | ??0.1 | ??1.6 | ??3.2 | ??0.6 | ??0.23 | ??0 | ??0 | ??0.041 |
| Air+electrochemistry | ??0 | ??1.2 | ??3.7 | ??0.6 | ??0.34 | ??0 | ??0 | ??0.037 |
| Well head | ??0.3 | ??1.7 | ??2.4 | ??0.7 | ??0.27 | ??0 | ??0 | ??0.038 |
By table 3 as seen, the method for the invention and chemistry " preoxidation " method is used, and sewage disposal can not only be become satisfy fully the injection water up to standard that SY/T 5329-94 requires, and water conditioning, also can be up to standard in well head water quality.
By the foregoing description as can be known, adopt the method for the invention, even can not be with the whole oxidations of the reducing substances in the sewage, be used with chemistry " preoxidation " or electrochemistry " preoxidation ", can save oxygenant or electric weight in a large number, economize on resources and cost, meet " Green Chemistry " technology.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. one kind is utilized air that oilfield sewage is carried out the method for pre-oxidation treatment, it is characterized in that comprising following operation steps:
Air is introduced in the oilfield sewage, in oilfield sewage, formed free oxygen or dissolved oxygen; Utilize the oxidation capacity of free oxygen or dissolved oxygen, ferrous ion in the oilfield sewage is oxidized to iron ion, the iron ion hydrolysis generates Fe
x(OH)
m (3x-m)+Colloidal precipitation becomes elemental sulfur with sulfide oxidation simultaneously; Remove elemental sulfur by flocculation, sedimentation and filtration then.
2. a kind of air that utilizes according to claim 1 carries out the method for pre-oxidation treatment to oilfield sewage, and it is characterized in that: the effective constituent of described air is oxygen; Described sulfide is hydrogen sulfide, sulphur hydrogen radical ion and sulfonium ion.
3. a kind of air that utilizes according to claim 1 carries out the method for pre-oxidation treatment to oilfield sewage, it is characterized in that: described air is introduced oilfield sewage is to adopt pressurized air is introduced in the oilfield sewage.
4. a kind of air that utilizes according to claim 1 carries out the method for pre-oxidation treatment to oilfield sewage, it is characterized in that: described air is introduced oilfield sewage is to utilize the mobilization dynamic of oilfield sewage that air is sucked in the oilfield sewage.
5. a kind of air that utilizes according to claim 4 carries out the method for pre-oxidation treatment to oilfield sewage, and it is characterized in that: described suction is that the high flow rate of oilfield sewage sucks air in the oilfield sewage when oilfield sewage is flowed through stenosis.
6. a kind of method of utilizing air oilfield sewage to be carried out pre-oxidation treatment according to claim 4, it is characterized in that: described suction is to utilize liquid level difference in slurry tank liquid level and the rising pipe, and oilfield sewage sucks air the oilfield sewage from slurry tank downward impact power when the rising pipe overflow.
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|---|---|---|---|
| CN200910193594A CN101708887A (en) | 2009-10-31 | 2009-10-31 | Method for pre-oxidizing oil field waste water by using air |
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103320621A (en) * | 2013-07-09 | 2013-09-25 | 中南大学 | Method for solidifying heavy metals in electrolytic manganese slags and co-producing sulphur |
| CN103816938A (en) * | 2012-11-19 | 2014-05-28 | 宝山钢铁股份有限公司 | Ferrous air oxidation reaction catalyst |
| CN108840483A (en) * | 2018-06-13 | 2018-11-20 | 四川奉泽水环境技术有限公司 | The method and system of hydrogen sulfide is removed from waste water |
| CN110510778A (en) * | 2019-09-10 | 2019-11-29 | 厦门嘉戎技术股份有限公司 | A kind of landfill leachate preprocess method and device |
| CN110590032A (en) * | 2019-09-17 | 2019-12-20 | 厦门嘉戎技术股份有限公司 | Pretreatment system and method for leachate treatment |
| CN110683670A (en) * | 2018-07-05 | 2020-01-14 | 中石化石油工程技术服务有限公司 | Aeration, desulfurization, iron removal and deoxidation device and method for oilfield polymer-blending sewage |
| CN113213685A (en) * | 2021-04-26 | 2021-08-06 | 萍乡市华星环保工程技术有限公司 | Desulfurization product sulfur recycling treatment process |
| CN114230064A (en) * | 2021-10-26 | 2022-03-25 | 克拉玛依市三达新技术股份有限公司 | Sewage desulphurization system and desulphurization method |
-
2009
- 2009-10-31 CN CN200910193594A patent/CN101708887A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816938A (en) * | 2012-11-19 | 2014-05-28 | 宝山钢铁股份有限公司 | Ferrous air oxidation reaction catalyst |
| CN103320621A (en) * | 2013-07-09 | 2013-09-25 | 中南大学 | Method for solidifying heavy metals in electrolytic manganese slags and co-producing sulphur |
| CN103320621B (en) * | 2013-07-09 | 2015-06-17 | 中南大学 | Method for solidifying heavy metals in electrolytic manganese slags and co-producing sulphur |
| CN108840483A (en) * | 2018-06-13 | 2018-11-20 | 四川奉泽水环境技术有限公司 | The method and system of hydrogen sulfide is removed from waste water |
| CN110683670A (en) * | 2018-07-05 | 2020-01-14 | 中石化石油工程技术服务有限公司 | Aeration, desulfurization, iron removal and deoxidation device and method for oilfield polymer-blending sewage |
| CN110510778A (en) * | 2019-09-10 | 2019-11-29 | 厦门嘉戎技术股份有限公司 | A kind of landfill leachate preprocess method and device |
| CN110590032A (en) * | 2019-09-17 | 2019-12-20 | 厦门嘉戎技术股份有限公司 | Pretreatment system and method for leachate treatment |
| CN113213685A (en) * | 2021-04-26 | 2021-08-06 | 萍乡市华星环保工程技术有限公司 | Desulfurization product sulfur recycling treatment process |
| CN114230064A (en) * | 2021-10-26 | 2022-03-25 | 克拉玛依市三达新技术股份有限公司 | Sewage desulphurization system and desulphurization method |
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Application publication date: 20100519 |