CN100546927C - The treatment process of oily(waste)water - Google Patents
The treatment process of oily(waste)water Download PDFInfo
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- CN100546927C CN100546927C CNB2006100860427A CN200610086042A CN100546927C CN 100546927 C CN100546927 C CN 100546927C CN B2006100860427 A CNB2006100860427 A CN B2006100860427A CN 200610086042 A CN200610086042 A CN 200610086042A CN 100546927 C CN100546927 C CN 100546927C
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Abstract
Oil-containing sewage treatment technique and equipment thereof.The treatment facility and the technology thereof that relate to oily(waste)water in a kind of oil field operation.It includes treater chamber, acid solution case, oxidation liquid case, lye tank and controller, and wherein the treater chamber is communicated with successively and is formed by micro-electrolysis reactor, Fenton reactor, settling vessel; The acid solution case connects water-in, and filler is equipped with at the micro-electrolysis reactor middle part, corresponding respectively Fenton reactor, the settling vessel of connecting of oxidation liquid case, lye tank; Import and export at each pipeline is respectively equipped with valve, and each valve, water pump link to each other with controller respectively.Treatment process of the present invention may further comprise the steps: 1) micro-electrolysis reaction; 2) Fenton reaction; 3) precipitation; 4) settling vessel water outlet input clean water basin.The present invention replaces ideal traditional, the disagreeableness walnut shell filter of treatment effect to select, and has that investment is little, the life-span is long, working cost is low and move easy characteristics, can solve the difficult problem that oil-field water pollutes effectively.
Description
Technical field
The present invention relates to the equipment and the treatment process thereof of water treatment, relate in particular to the treatment facility and the technology thereof of oily(waste)water in a kind of oil field operation.
Background technology
Tertiary oil recovery has been carried out in the oil field that has on a large scale, and alkaline surfactant polymer flooding oil-field technology has reached the industrial test stage at present.Owing to contain alkali, polymkeric substance, tensio-active agent, the water treatment difficulty is increased in the ternary composite flooding water extraction.Meeting general, oil, water are drawn back ground together in the oil pumping process.After oil, the water sepn, often be mixed with a spot of oil in the water, also contain alkali, polymkeric substance, tensio-active agent etc. in the water simultaneously, if directly discharging, could serious environment pollution.Consider to make full use of water resources, these water are generally understood recycle, continue to inject well.But can influence oil pump capacity after this sewage that contains a large amount of impurity injects the down-hole,, therefore need handle this sewage if discharging then pollutes the environment.At present, generally adopt walnut shell filter to handle this sewage, walnut shell filter mainly is to make sewage and the reaction of treatment agent composition by mixer means, and the mode by strainer filtering reaches processing intent again.It can be handled the suspended substance in the sewage effectively, but the plurality of impurities that still contains in the water can't make water be purified in the one-level treatment facility fully.
Summary of the invention
The present invention is directed to above defective a kind of treatment process that adopts reaction of high order to handle the oily(waste)water of oilfield sewage is provided.
Technical scheme of the present invention is: the treatment facility that it adopts includes intake pump, treater chamber, acid solution case, oxidation liquid case, lye tank, clean water basin and the controller that connects sewage lagoon, and wherein the treater chamber is communicated with successively and is formed by micro-electrolysis reactor, Fenton reactor, settling vessel; The water outlet of intake pump connects the water-in of the bottom of micro-electrolysis reactor, and the acid solution case connects this water-in, at the micro-electrolysis reactor middle part filler is housed, and micro-electrolysis reactor top is provided with the mouth that is communicated with the Fenton reactor; Fenton reactor top also is provided with another mouth that is communicated with settling vessel; Oxidation liquid case, lye tank are respectively by corresponding Fenton reactor, the settling vessel of connecting of pipeline; Import and export at each pipeline is respectively equipped with valve, and each valve, water pump link to each other with controller respectively; Settling vessel connects clean water basin;
Described treatment process carries out according to the following steps:
1), at first, sewage is equipped with the micro-electrolysis reactor of filler by the continuous suction one of intake pump, inject mineral acid simultaneously, when the pH of sewage value to 4.0～7.0, stop to inject mineral acid, sour water is the process of the motion from the micro-electrolysis reactor bottom toward top, by the filler at micro-electrolysis reactor middle part, adjust intake pump, valve, make the reaction times of sour water in micro-electrolysis reactor reach 30～60 minutes;
2), reacted sewage mouthful overflows into the Fenton reactor by micro-electrolysis reactor top, injects composite oxidant in the sewage in the Fenton reactor; Described composite oxidant comprises hydrogen peroxide and potassium bichromate, both mass ratios 1000～2000: 1; Composite oxidant and sewage volume ratio are 0.3%～0.5%, and by setting the volumetric ratio of Fenton reactor and micro-electrolysis reactor, making sewage reaction times in the Fenton reactor is 120～210 minutes;
3), reach the water of step reaction time, by Fenton reactor top mouthful overflow into settling vessel, in settling vessel, inject alkali lye, up to the pH value is 7.5～8.5 o'clock, stop to inject alkali lye,, make sewage in settling vessel, precipitate 2 hours by setting the volumetric ratio of Fenton reactor and settling vessel;
4), settling vessel water outlet input clean water basin, dispose.
The Fenton reactor is provided with reaction zone A and reaction zone B, and two districts are interconnected.
Also be provided with a gas blower, gas blower connects micro-electrolysis reactor, Fenton reactor respectively by pipeline.
Filler in the described micro-electrolysis reactor is iron plane flower or cast iron filing and inertia carbon granule.
Described inertia carbon granule is graphite, activated carbon, coke.
In the described acid solution case is mineral acid.
In the described lye tank is sodium hydroxide or aqua calcis.
Between settling vessel and clean water basin, also be provided with the air supporting flotation area.
The present invention adopts at first micro-electrolysis reaction, and the filler in the micro-electrolysis reactor forms countless galvanic cells under the acid solution effect, produces electrode reaction and caused thus a series of effects, has changed the character of pollutent in the sewage, forms nascent state Fe
2+Ion reaches first purpose of sewage disposal; In the Fenton reaction, under acidic conditions, Fenton reagent produces hydroxyl radical free radical (OH) attack organic molecule by catalytic decomposition, and making its mineralising is CO
2, H
2Inanimate matters such as O, thus reach another object of the present invention; By neutralization reaction, precipitation, make water reach emission standard at last.The small amount of impurities that precipitates and isolates, canned processing.
The present invention replaces ideal traditional, the disagreeableness walnut shell filter of treatment effect to select, and has that investment is little, the life-span is long, working cost is low and move easy characteristics, can solve the difficult problem that oil-field water pollutes effectively.
Description of drawings
Fig. 1 is the structural representation of present device
1 is water-in among the figure, the 2nd, and micro-electrolysis reactor, the 3rd, Fenton reactor A district, the 4th, Fenton reactor B district, the 5th, settling vessel, the 6th, water outlet;
Fig. 2 is a M-M view among Fig. 1
7 is acid-adding ports among the figure, the 8th, dividing plate, 9 fillers, the 10th, blast pipe, the 11st, micro-electrolysis reactor and Fenton reactor A district connected entrance, the 12nd, oxidizer mouth, the 13rd, blast pipe, the 14th, Fenton reactor B district and settling tank connected entrance, the 15th, add the alkali mouth, the 16th, Fenton reactor A district and Fenton reactor B district connected entrance;
Fig. 3 is the structural representation of another embodiment of present device
17 is air supporting flotation area among the figure;
Fig. 4 is a N-N view among Fig. 3
18 is dreg collecting slots among the figure, the 19th, and the perforation header.
Embodiment
Equipment of the present invention is that water-in 1 connects micro-electrolysis reactor 2, acid-adding port 7 is communicated with micro-electrolysis reactor 2 simultaneously, establish a dividing plate 8 that is furnished with mesh in the bottom of micro-electrolysis reactor 2 inner chambers, on dividing plate 8, put and establish filler 9, filler 9 can be iron plane flower or cast iron filing and inertia carbon granule, the inertia carbon granule can be selected graphite for use, activated carbon, coke loads on the inert particle, offer the Link Port 11 that is communicated with Fenton reactor A district 3 on the sidewall on reactor 2 tops, reactor 2 tops feed a blast pipe 10, blast pipe 10 passes filler 9 and dividing plate 8 bottom until reactor 2, in sewage, export high pressure gas, make reaction more abundant.
Fenton reactor A district 3 is communicated with by Link Port 16 with the bottom in Fenton reactor B district 4, blast pipe 13 stretches into the bottom in Fenton reactor two districts, establish oxidizer mouth 12 at 3 tops, Fenton reactor A district, add composite oxidant in the sewage of oxygenant mouth 12 in the Fenton reactor, composite oxidant comprises hydrogen peroxide and potassium bichromate; The high pressure gas of blast pipe 13 inputs make the reaction in Fenton reactor two districts more abundant, improve treatment effect.
The connected entrance 14 that is communicated with settling tank 5 is established on the top in Fenton reactor B district 4, and settling tank 5 tops are established and added alkali mouth 15, adds the sewage of alkali lye with step before neutralizing, and sets out the mouth of a river 6 in the bottom of settling tank 5, and water outlet 6 connects clean water basin.
Equipment of the present invention also has another embodiment, air supporting flotation area 17 promptly is set between settling tank 5 and clean water basin, because the water of handling out is through several order reactions, can produce some floating matters, in this district 17, gather up floating matter, gas foam etc. by this dreg collecting slot 18 of distinguishing the setting of 17 tops, further improve the quality of handling back water.The rising pipe of air supporting flotation area 17 bottoms is selected perforation header 19 for use.
Technology of the present invention is:
It may further comprise the steps:
1), sewage is carried out micro-electrolysis reaction, inject sulfuric acid in the sewage in the container, when the pH of sewage value to 4.0, stop to inject sulfuric acid, maintenance sewage reaction times in container is 45 minutes;
2), the sewage to last step carries out the Fenton reaction, inject composite oxidant in the sewage in the container, composite oxidant is hydrogen peroxide and potassium bichromate, and both mass ratioes are 1000: 1, composite oxidant and sewage volume ratio are 0.5%, and the reaction times is 210 minutes;
3) will go up the water outlet input settling vessel of step, again, and inject sodium hydroxide solution in settling vessel, the pH value of water is adjusted at 7.5 o'clock in the settling vessel, stops to inject sodium hydroxide solution, precipitates 2 hours;
4), the water input clean water basin exported in the settling vessel, dispose.
It may further comprise the steps:
1), sewage is carried out micro-electrolysis reaction, inject hydrochloric acid in the sewage in the container, when the pH of sewage value to 5.5, stop to inject hydrochloric acid, maintenance sewage reaction times in container is 50 minutes;
2), the sewage to last step carries out the Fenton reaction, inject composite oxidant in the sewage in the container, composite oxidant is hydrogen peroxide and potassium bichromate, and both mass ratioes are 1500: 1, composite oxidant and sewage volume ratio are 0.4%, and the reaction times is 165 minutes;
3) will go up the water outlet input settling vessel of step, again, and inject aqua calcis in settling vessel, the pH value of water is adjusted at 8 o'clock in the settling vessel, stops to inject aqua calcis, precipitates 2 hours;
4), the water input clean water basin exported in the settling vessel, dispose.
It may further comprise the steps:
1), sewage is carried out micro-electrolysis reaction, inject sulfuric acid in the sewage in the container, when the pH of sewage value to 4.0～7.0, stop to inject sulfuric acid, maintenance sewage reaction times in container is 55 minutes;
2), the sewage to last step carries out the Fenton reaction, inject composite oxidant in the sewage in the container, composite oxidant is hydrogen peroxide and potassium bichromate, and both mass ratioes are 2000: 1, composite oxidant and sewage volume ratio are 0.3%, and the reaction times is 120 minutes;
3) will go up the water outlet input settling vessel of step, again, and inject aqua calcis in settling vessel, the pH value of water is adjusted at 8.5 o'clock in the settling vessel, stops to inject aqua calcis, precipitates 2 hours;
4), the water input clean water basin exported in the settling vessel, dispose.
Little electrolysis (micro-electrolysis) among the present invention, be called interior electrolysis, iron reduction, iron carbon method etc. again, filler in the micro-electrolysis reactor forms countless galvanic cells, produce electrode reaction and caused thus a series of effects, change the character of pollutent in the sewage, reached the purpose of sewage disposal.
Main electrode reaction has:
Anode (Fe): Fe-2e → Fe
2+[E
0(Fe
2+/ Fe)=-0.44V]
Negative electrode (C):
Under the acidic conditions: 2H
++ 2e → 2[H] → H
2[E
0(H
+/ H
2)=0.00V]
Under the acid aerobic condition: O
2+ 4H
++ 4e → 2H
2O [E
0(O
2)=1.23V]
Under the neutrallty condition: O
2+ 2H
2O+4e → 4OH
-[E
0(O
2/ OH
-)=0.40V]
1894, the H.J.H.Fenton reported first was pointed out H
2O
2At Fe
2+Have the multiple organic ability of oxidation under the ionic katalysis, hydrogen peroxide is Fenton reagent, wherein Fe with combining of ferrous ion
2+Ion is mainly as the homogeneity catalyzer, and H
2O
2Play oxygenizement.On this basis, people have constantly carried out with H
2O
2Be the research of master's composite oxidant, utilize the strong oxidizing property of composite oxidant, general physics, chemistry, the reluctant industrial sewage of biochemical process are effectively handled.
Fenton among the present invention reacts, and under acidic conditions, Fenton reagent produces hydroxyl radical free radical (OH) attack organic molecule by catalytic decomposition, and making its mineralising is CO
2, H
2Inanimate matters such as O, oxidising process are the beginning that is produced as chain of chain reaction: OH, and other free radical and reaction intermediate have constituted the node of chain, between the various free radicals or the interaction of free radical and other material free radical is consumed, reaction chain stops.Reaction mechanism is summarized as follows:
The beginning of chain: Fe
2++ H
2O
2→ Fe
3++ OH
-+ OH
The transmission of chain: OH
-+ Fe
2+→ Fe
3++ OH
-
·OH+H
2O
2→HO
2·+H
2O
Fe
3++H
2O
2→Fe
2++HO
2·+H
2O
HO
2·+Fe
3+→Fe
2++O
2·+H
+
OH+R-H (organism) → R+H
2O
OH+R-H (organism) → [R-H]
++ HO
-
R+Fe
3++ HO
-→ P (product)+Fe
2++ OH
[R-H]
++ Fe
3++ HO
-→ P (product)+Fe
2++ HO
2+ [H]
End stopping of chain: 2OH → H
2O
2
HO
2·+HO
2·→H
2O
2+O
2
Fe
3++HO
2·→Fe
2++O
2
Fe
2++HO
2·+H
+→Fe
3++H
2O
2
HO
2·+O
2·+H
+→H
2O
2+O
2
Fe
2++O
2·+H
+→Fe
3++H
2O
2
[H]+HO
-+Fe
3+→H
2O+Fe
2+
The major control step that Fenton reagent participates in reaction be free radical especially OH exert an influence and with the interactional process of organism, calculation of thermodynamics in recent years shows, said Fe in the classical theory
2+With H
2O
2Between the out-shell electron shift reaction can not carry out because the intermediate HO of its reaction
2Be difficult to form easier formation Fe from mechanics
2+-H
2O
2Complex compound.Fe
2+The complex compound inner electron shift theory and think: in system, introduce the generation mechanism that suitable part can improve catalyzed reaction and free radical, improve reaction efficiency, improve reaction conditions, realize the preferential oxidation degraded of hard-degraded substance or toxic substance simultaneously; Therefore, it is the key that Fenton reagent is able to continuous research and development that the introducing part improves catalyzed reaction mechanism, also is the main difficult point of Fenton method treatment technology.The present invention adopts hydrogen peroxide and potassium bichromate preparation treatment agent, has obtained good effect.The small amount of impurities that the present invention precipitates and isolates, canned processing.
Claims (8)
1, the treatment process of oily(waste)water, the treatment facility that it adopts includes intake pump, treater chamber, acid solution case, oxidation liquid case, lye tank, clean water basin and the controller that connects sewage lagoon, and wherein the treater chamber is communicated with successively and is formed by micro-electrolysis reactor, Fenton reactor, settling vessel; The water outlet of intake pump connects the water-in of the bottom of micro-electrolysis reactor, and the acid solution case connects this water-in, at the micro-electrolysis reactor middle part filler is housed, and micro-electrolysis reactor top is provided with the mouth that is communicated with the Fenton reactor; Fenton reactor top also is provided with another mouth that is communicated with settling vessel; Oxidation liquid case, lye tank are respectively by corresponding Fenton reactor, the settling vessel of connecting of pipeline; Import and export at each pipeline is respectively equipped with valve, and each valve, water pump link to each other with controller respectively; Settling vessel connects clean water basin;
Described treatment process is characterised in that it carries out according to the following steps:
1), at first, sewage is equipped with the micro-electrolysis reactor of filler by the continuous suction one of intake pump, inject mineral acid simultaneously, when the pH of sewage value to 4.0～7.0, stop to inject mineral acid, sour water is the process of the motion from the micro-electrolysis reactor bottom toward top, by the filler at micro-electrolysis reactor middle part, adjust intake pump, valve, make the reaction times of sour water in micro-electrolysis reactor reach 30～60 minutes;
2), reacted sewage mouthful overflows into the Fenton reactor by micro-electrolysis reactor top, injects composite oxidant in the sewage in the Fenton reactor; Described composite oxidant comprises hydrogen peroxide and potassium bichromate, both mass ratios 1000～2000: 1; Composite oxidant and sewage volume ratio are 0.3%～0.5%, and by setting the volumetric ratio of Fenton reactor and micro-electrolysis reactor, making sewage reaction times in the Fenton reactor is 120～210 minutes;
3), reach the water of step reaction time, by Fenton reactor top mouthful overflow into settling vessel, in settling vessel, inject alkali lye, up to the pH value is 7.5～8.5 o'clock, stop to inject alkali lye,, make sewage in settling vessel, precipitate 2 hours by setting the volumetric ratio of Fenton reactor and settling vessel;
4), settling vessel water outlet input clean water basin, dispose.
2, the treatment process of oily(waste)water according to claim 1 is characterized in that, the Fenton reactor is provided with reaction zone A and reaction zone B, and two districts are interconnected.
3, the treatment process of oily(waste)water according to claim 1 is characterized in that, also is provided with a gas blower, and gas blower connects micro-electrolysis reactor, Fenton reactor respectively by pipeline.
4, the treatment process of oily(waste)water according to claim 1 is characterized in that, the filler in the described micro-electrolysis reactor is iron plane flower or cast iron filing and inertia carbon granule.
5, the treatment process of oily(waste)water according to claim 4 is characterized in that, described inertia carbon granule is graphite, activated carbon, coke.
6, the treatment process of oily(waste)water according to claim 1 is characterized in that, is mineral acid in the described acid solution case.
7, the treatment process of oily(waste)water according to claim 1 is characterized in that, is sodium hydroxide or aqua calcis in the described lye tank.
8, the treatment process of oily(waste)water according to claim 1 is characterized in that, also is provided with the air supporting flotation area between settling vessel and clean water basin.
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|---|---|---|---|
| CNB2006100860427A CN100546927C (en) | 2006-07-18 | 2006-07-18 | The treatment process of oily(waste)water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100860427A CN100546927C (en) | 2006-07-18 | 2006-07-18 | The treatment process of oily(waste)water |
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| Publication Number | Publication Date |
|---|---|
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| CN100546927C true CN100546927C (en) | 2009-10-07 |
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| CN102267771B (en) * | 2010-06-07 | 2013-09-04 | 鞍钢股份有限公司 | Pretreatment method of coking wastewater |
| CN102774897B (en) * | 2012-04-23 | 2014-01-22 | 克拉玛依市三达新技术开发有限责任公司 | Treatment method of polymer flooding and binary combination flooding-SP-sewage |
| CN102627378B (en) * | 2012-04-24 | 2013-07-10 | 湖北君集水处理有限公司 | Treatment method of oil field alkali-surfactant-polymer flooding oil extraction wastewater |
| CN102633413B (en) * | 2012-05-07 | 2013-05-22 | 黑龙江吉纳森生物工程股份有限公司 | Treatment process for wastewater of oilfield extracted by three compound combination flooding |
| CN102718348A (en) * | 2012-07-19 | 2012-10-10 | 太仓东能环保设备有限公司 | Oily sewage treatment device |
| CN103288251A (en) * | 2013-06-14 | 2013-09-11 | 西安建筑科技大学 | Iron-carbon micro-electrolysis processing method and device for oil field well site acid waste water |
| CN103395919B (en) * | 2013-08-03 | 2015-04-01 | 大连交通大学 | Equipment for pretreatment of high-concentration perfume wastewater and method |
| CN103496830B (en) * | 2013-10-23 | 2014-10-22 | 天津亿利科能源科技发展股份有限公司 | Movable integrated type multi-functional oily wastewater integrated treatment device |
| CN104230087B (en) * | 2014-09-30 | 2016-06-01 | 东莞市英硫净水服务有限公司 | The desalination treatment process of a kind of haline water |
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| CN109231647A (en) * | 2018-10-16 | 2019-01-18 | 章嘉华 | A kind of processing system of industrial chromium-containing waste water |
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| CN109708989B (en) * | 2018-12-28 | 2021-10-01 | 扬州大学 | Device for measuring contents of oil, water and particulate matters in gas and using method thereof |
| CN110054339A (en) * | 2019-05-17 | 2019-07-26 | 廊坊新奥龙河环保科技有限公司 | Integrated sealed formula high-concentration acidic wastewater danger waste liquor treatment equipment and processing method |
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2006
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