CN101497472B - Process for treating oilfield sulfur-containing sewerage - Google Patents
Process for treating oilfield sulfur-containing sewerage Download PDFInfo
- Publication number
- CN101497472B CN101497472B CN2009100259848A CN200910025984A CN101497472B CN 101497472 B CN101497472 B CN 101497472B CN 2009100259848 A CN2009100259848 A CN 2009100259848A CN 200910025984 A CN200910025984 A CN 200910025984A CN 101497472 B CN101497472 B CN 101497472B
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- CN
- China
- Prior art keywords
- wastewater
- sewage
- air
- sulfur
- vessel
- Prior art date
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Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 19
- 229910052717 sulfur Inorganic materials 0.000 title claims description 18
- 239000011593 sulfur Substances 0.000 title claims description 16
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 239000010865 sewage Substances 0.000 claims description 37
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 4
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract 10
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000019600 saltiness Nutrition 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
Abstract
The present invention discloses a process for treating sulfuric wastewater in an oil field. When the content of S<2-> of the sulfuric wastewater in the oil field is less than 30 mg/L, the wastewater is introduced to an open vessel; air is blown to the vessel for 25 to 40 minutes; the volume ratio of air to wastewater is controlled to be 2:1 to 8:1;when the content of S<2-> of the sulfuric wastewater in the oil field is more than or equal to 30 mg/L, the wastewater is introduced to the open vessel; thiosulfate as an evocating agent is added into the vessel; air is blown to the vessel for 25 to 40 minutes; and the volume ratio of air to wastewater is controlled to be 2:1 to 8:1. In the sulfuric wastewater of the oil field treated by the method, the content of the S<2-> can be reduced to be between 0 and 1.5 mg/L; compared with the viscosity of the wastewater which is not desulfurized and polymerized, the viscosity of the wastewater which is polymerized is improved by 30 to 40 percent, thereby greatly reducing consumption of polymer; and the treatment cost is 0.07 yuan/ton.
Description
Technical field
The present invention openly comes a kind of treatment process of oilfield sulfur-containing sewage, particularly utilizes the technology of airborne oxygen treatments applied sour water.
Background technology
Along with Oilfield developing, crude oil water containing constantly raises.In order to protect environment, to keep Oil extraction and stratum production capacity, become conventional with carrying out re-injection after the sewage disposal for many years.Part oil field block causes the water quality instability owing to sulfide content in the water raises gradually, has jeopardized the water flooding effect.According to the data that geology department provides, water injection well, the layer short or do not absorb water and list in 60% of retrofit work amount be because of injection water quality defective due to, this is seriously restricting the oil-field development benefit.Do not remove the sulfide function and design in the existing water conditioning process.Sulphur and sulfide in the output sewage of oil field with S, S
2-, SO
4 2-For principal mode exists, S and SO
4 2-Can both under the effect of sulphate reducing bacteria, be reduced into S
2-, S in the water
2-Because its out-shell electron very easily is out of shape, penetrativity is strong, and iron and steel is had the Cl of ratio
-Stronger corrodibility forms local corrosion or pitting corrosion at steel surface, finally makes the tube wall perforation, destroys sewage and water injection equipment.Because the corrosive product gluey FeS suspended substance that is water-fast black, excellent stability makes the rapid blackening of water quality after the processing smelly, and suspended substance increases; FeS is again a kind of oil in water emulsion stablizer simultaneously, and the oil removing difficulty is increased; Inject underground obstruction stratum, the oil reservoir water-retaining capacity is descended, water injection pressure constantly raises, and influences intensified injection of wells measure validity period and reduces, and increases measure cost.
Research and test in place show both at home and abroad, join poly-degraded of injecting with sewage to the polymers soln various degrees, sewage is to the major cause of polymkeric substance degraded, the high problem of the saltiness of sewage still not, main is the severely degrade that the active substance in the on-the-spot high-pressure sealed sewage produces polymkeric substance, cause the injection fluid viscosity not reach requirement, reduced the effect of polymer flooding.Along with the rising of reservoir temperature and salinity,, thereby obtain needed solution viscosity value in requisition for the implantation concentration that increases polymkeric substance.Can improve viscosity in aqueous solution though increase the implantation concentration of polymkeric substance, the corresponding production operation cost that increased makes polymer flooding be difficult to bring into play due value.If utilize oilfield sewage prepared polymer solution, will take appropriate measures and technology comes oilfield sewage is handled, to improve the viscosity of polymers soln, reach the requirement of injection.
In the prior art, for removing S
2-Following two kinds of methods are arranged: 1, chemical precipitation method, cost are too high, and the new metal ion of introducing to the reduction of polymkeric substance viscosity greater than S
2-Reduction to the polymkeric substance viscosity; 2, dioxygen water law, effect are with good, but hydrogen peroxide is a hazardous chemical, and cost is also up to 0.6 yuan/ton; 3, ozone method, effective but facility investment is big, processing cost is too up to 1.6 yuan/ton.
Summary of the invention
Goal of the invention: the objective of the invention is at the deficiencies in the prior art, a kind of treatment process of oilfield sulfur-containing sewage is provided.
Technical scheme: the treatment process that the invention discloses a kind of oilfield sulfur-containing sewage:
S when oilfield sulfur-containing sewage
2-Content feeds sewage in the open container during less than 30mg/L, drum air 25～40 minutes, and the volume ratio of control air and sewage is 2: 1～8: 1;
S when oilfield sulfur-containing sewage
2-Content feeds sewage in the open container during more than or equal to 30mg/L, adds the initiator thiosulphate, rouses air 25～40 minutes again, and the volume ratio of control air and sewage is 2: 1～8: 1.
Wherein, the adding quality of described thiosulphate is 1Kg/10000m with the volume of a container ratio
3
Wherein, described thiosulphate is a Sulfothiorine.
Wherein, the volume ratio of preferred control air and sewage is 5: 1～6.5: 1.Under inferior ratio, be treatment S
2-The optimum proportion of ionic concentration when 60mg/L.
Ultimate principle of the present invention is: with S
2-Form be present in sulfide in the sewage, contact with airborne oxygen, oxidation-reduction reaction promptly takes place, generate thiosulphate, the part thiosulphate is further oxidation again, generates vitriol.
2S
2-+2O
2+H
2O→S
2O
3 2-+2OH
-
2HS
-+2O
2→S
2O
3 2-+H
2O
S
2O
3 2-+2O
2+2OH-→2SO
4 2-+H
2O
A part of sulphur is oxidized under the effect of oxygen, but the process that key is any chemical reaction all has a reaction to cause, this process is according to the chemical property difference of reactive material, and the reaction conditions different time is also different, and the long weak point that has is arranged.Because the oxidisability of airborne oxygen is lower than the oxidisability of ozone and hydrogen peroxide, so the time of causing will be grown a lot, wherein the initiation time of 60mg/L content sewage is 8～10 hours, but in a single day causes, and chemical reaction will go on very normally.
Work as S
2-Ionic concentration is when 30mg/L is above, and air sweetening need spend long time, adds the speed that initiator can increase desulfurization greatly.
Beneficial effect: by the sewage that the inventive method is handled, its S
2-Content can drop to 0～1.5mg/L, poly-viscosity raising 30～40% is joined in the not desulfurization of ratio of viscosities of joining after gathering, and reduces the consumption of polymkeric substance greatly, handles the water yield and can reach 11000～12000 tons/day, processing cost is 0.07 yuan/ton, has industry using value and prospect.
Embodiment
Embodiment 1:
07 year, following two joint stations of Henan Oil Field, S in the oilfield sulfur-containing sewage
2-Be 12～20mg/L, the air water volume ratio is 1.4～1.8: 1,12000 tons of treatment capacities, and the residence time is 26min, the S after the processing
2-Be 0-1mg/L.
Embodiment 2:
08 year, following two joint stations of Henan Oil Field, S in the oilfield sulfur-containing sewage
2-Be 60mg/L, add Sulfothiorine 1Kg/10000m
3, the air water volume ratio is 5～6.5: 1,10000 tons of treatment capacities, and the residence time is 35min, the S after the processing
2-Be 0.5-1.0mg/L.
Through above-mentioned experimental results show that, the present invention has broken through in the past and thought the theoretic bias that air can't be operated in the theory on the spot in actual oilfield sewage sulfur removal technology, in fact through studies show that, as long as the volume ratio of control air and sewage is controlled to be 2: 1～and 8: 1 scope, can implement fully.Particularly, when sulphur content reached more than the 30mg/L particularly 60mg/L in running into sewage, traditional theory thought that atmospheric oxidation can't implement fully, and added the Sulfothiorine among the present invention as initiator after, can be that desulphurization reaction normally carries out.
The invention provides a kind of thinking and method of treatment process of oilfield sulfur-containing sewage; the method and the approach of this technical scheme of specific implementation are a lot; the above only is a preferred implementation of the present invention; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.The all available prior art of each component part not clear and definite in the present embodiment is realized.
Claims (4)
1. the treatment process of an oilfield sulfur-containing sewage is characterized in that:
S when oilfield sulfur-containing sewage
2-Content feeds sewage in the open container during more than or equal to 30mg/L, adds the initiator thiosulphate, rouses air 25～40 minutes again, and the volume ratio of control air and sewage is 2: 1～8: 1.
2. the treatment process of a kind of oilfield sulfur-containing sewage according to claim 1 is characterized in that, the adding quality of described thiosulphate is 1Kg/10000m with the volume of a container ratio
3
3. the treatment process of a kind of oilfield sulfur-containing sewage according to claim 1 and 2 is characterized in that described thiosulphate is a Sulfothiorine.
4. the treatment process of a kind of oilfield sulfur-containing sewage according to claim 1 is characterized in that, the volume ratio of control air and sewage is 5: 1～6.5: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100259848A CN101497472B (en) | 2009-03-16 | 2009-03-16 | Process for treating oilfield sulfur-containing sewerage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100259848A CN101497472B (en) | 2009-03-16 | 2009-03-16 | Process for treating oilfield sulfur-containing sewerage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101497472A CN101497472A (en) | 2009-08-05 |
| CN101497472B true CN101497472B (en) | 2011-09-07 |
Family
ID=40944776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100259848A Expired - Fee Related CN101497472B (en) | 2009-03-16 | 2009-03-16 | Process for treating oilfield sulfur-containing sewerage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497472B (en) |
-
2009
- 2009-03-16 CN CN2009100259848A patent/CN101497472B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101497472A (en) | 2009-08-05 |
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|---|---|---|---|
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160906 Address after: 214237 Wuxi, Jiangsu City, Yixing Province Zhang Zhu industrial concentration area Patentee after: Jiangsu, Environmental Engineering Co. Ltd. Address before: District Yixing Zijing Environmental Protection Equipment Co Ltd 214231 Jiangsu city of Yixing Province Zhang Zhu Zhen Industrial Patentee before: Amethyst Yixing Environmental Protection Equipment Co., Ltd. |
|
| CP03 | Change of name, title or address |
Address after: Zhang Zhu Zhen 214231 Jiangsu city in Wuxi Province, Yixing City, South Gate Village Patentee after: Jiangsu Dakai Environmental Engineering Co. Ltd. Address before: 214237 Wuxi, Jiangsu City, Yixing Province Zhang Zhu industrial concentration area Patentee before: Jiangsu, Environmental Engineering Co. Ltd. |
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| CP03 | Change of name, title or address | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180531 Address after: 710077 Xi'an, Yanta District, Shaanxi, north of Jinye two Road North yycui garden first a 6 unit, 21 floors 62102 rooms. Patentee after: Shaanxi Hai Ji Ya Environmental Protection Technology Co., Ltd. Address before: 214231 South Gate Village, Zhang Zhu Town, Yixing City, Wuxi, Jiangsu Patentee before: Jiangsu Dakai Environmental Engineering Co. Ltd. |
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| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110907 Termination date: 20190316 |
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| CF01 | Termination of patent right due to non-payment of annual fee |