CN104803425A - Method for removing hydrogen sulfide from high-sulfur oilfield produced water - Google Patents
Method for removing hydrogen sulfide from high-sulfur oilfield produced water Download PDFInfo
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- CN104803425A CN104803425A CN201410039118.5A CN201410039118A CN104803425A CN 104803425 A CN104803425 A CN 104803425A CN 201410039118 A CN201410039118 A CN 201410039118A CN 104803425 A CN104803425 A CN 104803425A
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Abstract
The invention discloses a method for removing hydrogen sulfide from high-sulfur oilfield produced water, and belongs to the field of hydrogen sulfide removal. The method adopting natural gas as a gas source and adopting a gas stripping technology to desulfurize comprises the following steps: determining the content of hydrogen sulfide in sulfur-containing oilfield produced water and the volume ratio of the natural gas to the sulfur-containing oilfield produced water; and adjusting the pH value of the produced water to 3-4 to make sulfur in the produced water exist as hydrogen sulfide, allowing the natural gas to contact with the produced water in a stripping tower in a countercurrent manner, and carrying out gas-liquid separation to remove hydrogen sulfide. The natural gas in an oilfield produced water treatment station is adopted as the gas source, and a stripping technology is adopted to remove sulfur in the sulfur-containing oilfield produced water, so the desulfurization rate is high, and compared with methods adopting steam as the gas source, the method disclosed in the invention has the advantages of no need of a steam boiler or a pipe network system, and low cost; the oilfield natural gas is sufficient, so the demand of hydrogen sulfide removal of large-scale oilfield produced water can be met; and removed hydrogen sulfide is conveyed to a natural gas processing station and is processed, so the processed hydrogen sulfide can be comprehensively utilized, and no waste liquid is discharged.
Description
Technical field
The present invention relates to hydrogen sulfide stripping field, particularly a kind of high sulfur-bearing oilfield recovered water removes the method for hydrogen sulfide.
Background technology
Oil field extracted water is the water produced in oil water flooding recovery process, wherein containing a large amount of ions being difficult to organic pollutant and the high density of degrading, does not reach the standard of re-injection and directly discharge, needs to process it, until reach emission standard.
Containing H2S in sulfur-bearing oil field extracted water, and H2S has corrosive nature, if directly sulfur-bearing oil field extracted water is passed into oil field produced water treatment device, can cause the corrosion of pipeline and equipment, causes a hidden trouble to safety in production.The simultaneously volatilization of H2S and precipitation, can have a strong impact on personnel safety.Therefore, need the sulphur removed wherein before sulfur-bearing oil field extracted water is processed, to ensure safety in production.Sulphur content all over the world in sulfur-bearing oil field extracted water is different, and in oil field at home recovered water, the content of sulphur is lower, is less than 20ppm, does not generally carry out desulfurization process.
At present, it is source of the gas that domestic refinery sulfur-containing waste water takes off H2S with steam, adopts single tower low pressure gas stripping process, and under the condition of pH value 7 ~ 8, vacuum tightness 0.09MPa-0.1MPa, extracting 20-30 minute, treatment scale is less.Realizing in process of the present invention, contriver finds that prior art at least exists following problem:
The content of Middle East sulfur-bearing oil field extracted water hydrogen sulfide is 150-600ppm, in recovered water, the content of hydrogen sulfide is high, adopt existing sulfur removal technology desulfurization degree low, the follow-up processing requirements of oil field extracted water cannot be met, bring the hidden danger of safety in production to subsequent disposal; Meanwhile, Middle East sulfur-bearing oil field extracted water amount is large, if using steam as source of the gas, adopt gas stripping process to remove hydrogen sulfide, the quantity of steam of needs is large, cannot meet the process that extensive oil field extracted water removes hydrogen sulfide; Need to build large-scale steam boiler and pipe network system simultaneously, expense and energy consumption large; And after air lift, generate a large amount of sulfur-containing waste waters, cause environmental pollution.
Summary of the invention
Can not meet to solve prior art the problem that Middle East sulfur-bearing oil field extracted water removes hydrogen sulfide technology needs, embodiments providing a kind of method that sulfur-bearing oil field extracted water removes hydrogen sulfide.Described technical scheme is as follows:
High sulfur-bearing oilfield recovered water removes a method for hydrogen sulfide, it is characterized in that, described method take Sweet natural gas as source of the gas, adopts air-extraction desulfurization, specifically operates as follows:
Analyze content, the saltiness of chlorion in sulfur-bearing oil field extracted water, and then determine the content of hydrogen sulfide in described sulfur-bearing oil field extracted water;
The volume ratio of described Sweet natural gas and described sulfur-bearing oil field extracted water is determined according to the content of hydrogen sulfide in described sulfur-bearing oil field extracted water;
The pH value regulating sulfur-bearing oil field extracted water is 3-4, then the sulfur-bearing oil field extracted water regulating pH value inputted from the top of gas stripping column and flow downward, the bottom input of Sweet natural gas from described gas stripping column is also upwards flowed, the Sweet natural gas counter current contact on the column plate of described gas stripping column making described sulfur-bearing oil field extracted water in the process of flowing downward and upwards flow, pass through gas liquid separating function, obtain sulfur-containing gas and desulfurization oil field extracted water, described sulfur-containing gas is discharged from the tower top of described gas stripping column, and described desulfurization oil field extracted water is discharged at the bottom of the tower of gas tower.
Concrete, described air-extraction is single tower pressurization stripping process.
Further, its pH value is adjusted to 7-8 with alkali lye after discharging at the bottom of the tower of gas stripping column by described desulfurization oil field extracted water, and enters next step processing unit, until reach the standard of re-injection or discharge.
Further, described sulfur-containing gas enters the process that sulfur-containing gas processing unit carries out next step after discharging from the tower top of described gas stripping column.
Concrete, the volume ratio of described Sweet natural gas and described sulfur-bearing oil field extracted water is (3-8): 1.
Concrete, the temperature of described sulfur-bearing oil field extracted water is 70 DEG C ~ 90 DEG C.
Concrete, the pressure of described gas stripping column is 200kpa-350kpa.
Concrete, in described sulfur-bearing oil field extracted water, the content of hydrogen sulfide is 150ppm-600ppm.
Concrete, described gas stripping column tower diameter is 2-3m.
Concrete, described gas stripping column adopts the combined trapezoid spray tray being applicable to oily(waste)water.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
First the present invention analyzes the content of chlorion in sulfur-bearing oil field extracted water, saltiness, determine the impact on hydrogen sulfide content in water of salt effect, to determine the solubleness of hydrogen sulfide in described sulfur-bearing oil field extracted water, and then determine the impact of salt effect on hydrogen sulfide content in water, take Sweet natural gas as source of the gas, employing gas stripping process removes the sulphur in sulfur-bearing oil field extracted water, by optimizing desulfurization process conditions, gas stripping gas is contacted in gas stripping column fully with high sulfur-bearing oilfield recovered water, not only desulfurization degree is high, can more than 90% be reached, and, sulphur content in sulfur-bearing oil field extracted water is higher, desulfurization degree is higher, simultaneously compared with using steam as source of the gas, without the need to building steam boiler and pipe network system, cost-saving, in the present invention with the Sweet natural gas in oil field produced water treatment station for source of the gas, not only tolerance is sufficient, the oil field produced water yield in Middle East can be met large, carry out the demand that extensive oil field extracted water removes hydrogen sulfide technology, and obtain after air lift can also transport to gas conditioning station containing the Sweet natural gas of hydrogen sulfide and carry out processing rear comprehensive utilization, without discharging of waste liquid, be conducive to environmental protection.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is that the sulfur-bearing oil field extracted water that the embodiment of the present invention provides removes hydrogen sulfide technology schema.
In figure, the implication of each symbol is as follows:
1 gas stripping column, 2 column plates, 3 sulfur-bearing oil field extracted waters, 4 Sweet natural gases, 5 sulfur-containing gas, 6 desulfurization recovered waters, 7 acid solutions, 8 alkali lye.
Embodiment
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
See Fig. 1, embodiments provide a kind of method that sulfur-bearing oil field extracted water removes hydrogen sulfide, the method comprises:
Described method take Sweet natural gas as source of the gas, adopts air-extraction desulfurization.Specifically operate in accordance with the following steps:
First analyze the content of saltiness and hydrogen sulfide in sulfur-bearing oil field extracted water 3, determine the volume ratio of described Sweet natural gas 4 and described sulfur-bearing oil field extracted water 3; Under the condition that other conditions are all identical, when in recovered water, saltiness is different, the solubleness of hydrogen sulfide is also by difference, therefore, first the saltiness of sulfur-bearing oil field extracted water 3 should be determined before the volume ratio determining Sweet natural gas 4 and sulfur-bearing oil field extracted water 3, correctly could simulate the hydrogen sulfide content of recovered water, and then determine the volume ratio of Sweet natural gas 4 and sulfur-bearing oil field extracted water 3, to improve the removal efficiency of hydrogen sulfide.
At present, remove H2S in various water and reckon without water intermediate ion and salt effect content for the concrete impact removing hydrogen sulfide.
Concrete, in described sulfur-bearing oil field extracted water 3, the content of hydrogen sulfide is 150ppm-600ppm.
Concrete, the volume ratio of described Sweet natural gas 4 and described sulfur-bearing oil field extracted water 3 is (3-8): 1, in gas stripping process, utilize gas-liquid separation principle to transfer in gas phase by the hydrogen sulfide in liquid phase, therefore, the amount of the gas phase needed is larger, and when gas-liquid volume ratio is (3-8): when 1, the decreasing ratio of hydrogen sulfide is the highest.
Then, the pH value regulating sulfur-bearing oil field extracted water 3 by acid solution 7 is 3-4, makes the sulphur in sulfur-bearing oil field extracted water 3 be dissolved in recovered water with the form of hydrogen sulfide;
Finally the above-mentioned sulfur-bearing oil field extracted water 3 regulating pH value entered gas stripping column 1 from the top of gas stripping column 1 and flow downward, Sweet natural gas enters gas stripping column 1 and upwards flows from the bottom of gas stripping column 1, sulfur-bearing oil field extracted water 3 in the process of flowing downward with Sweet natural gas 4 counter current contact on the column plate 2 of gas stripping column 1 upwards to flow, pass through gas liquid separating function, obtain sulfur-containing gas 5 and desulfurization oil field extracted water 6 respectively, described sulfur-containing gas 5 is discharged from the tower top of gas stripping column 1, enter sulfur-containing gas processing unit and remove hydrogen sulfide, the hydrogen sulfide removed can fully utilize, be conducive to environmental protection, desulfurization oil field extracted water 6 is discharged at the bottom of the tower of gas tower 1.According to the regulation of GB26983-2011-T " mensuration of crude oil hydrogen sulfide, methyl mercaptan and ethanethio " standard, chromatography is adopted to detect the content of hydrogen sulfide in desulfurization oil field extracted water 6, when the content of hydrogen sulfide in desulfurization oil field extracted water is at below 20ppm, hydrogen sulfide in desulfurization oil field extracted water 6 can not overflow from water, also can not cause obvious corrosion to equipment and pipeline, treatment Technology for Petroleum Water Flooding needs can be met.Therefore, after the pH value of desulfurization oil field extracted water 6 being adjusted to 7-8 with alkali lye 8, desulfurization oil field extracted water 6 is for further processing, until reach re-injection or emission standard.
Air-extraction is equivalent to underpressure distillation, due to the gas stripping gas added--and Sweet natural gas sulfur component dividing potential drop is in the gas phase very low, is equivalent to the dividing potential drop reducing sulfur component in gas phase when stagnation pressure is constant, is conducive to sulfur component from liquid phase to the mass transfer of gas phase.The feature of sulfur-bearing oil field extracted water air lift sulfur removal technology is along with the pH value value of recovered water reduces, sulfur component all exists with the form of H2S, gas stripping gas in tower in flow process with the recovered water counter current contact on column plate flowed downward, because the H2S dividing potential drop in gas phase is very low, in liquid phase, the content of H2S is high, under the effect of concentration difference, the H2S of liquid phase enters gas phase, thus realizes the object that sulfur-bearing oil field extracted water removes hydrogen sulfide.
Embodiment provided by the invention directly utilizes the Sweet natural gas in oil field produced water treatment station to be source of the gas, employing gas stripping process removes the sulphur in sulfur-bearing oil field extracted water, with steam as compared with source of the gas, without the need to building steam boiler and pipe network system, cost of investment and energy cost are saved, Oilfield Natural Gas Plant tolerance is sufficient simultaneously, can meet the demand that extensive oil field extracted water removes hydrogen sulfide; In addition, the hydrogen sulfide removed is transported to after gas conditioning station processes and can be fully utilized, and without discharging of waste liquid, is conducive to environmental protection.Compared with prior art, the method that the sulfur-bearing oil field extracted water that the embodiment of the present invention provides removes hydrogen sulfide has unexpected effect.
Concrete, the temperature of described sulfur-bearing oil field extracted water 3 is 60 DEG C ~ 80 DEG C.More the solubleness of high hydrogen sulfide in water is lower for temperature, therefore the content of hydrogen sulfide in water can be reduced by the method putting forward high sulfur-bearing oilfield recovered water 3 temperature, but when temperature is higher than 60 DEG C ~ 80 DEG C, continue the removal effect impact of raised temperature on hydrogen sulfide little, therefore the angle consideration of cost is increased from the power consumption that heats up, in air lift process, the temperature selecting sulfur-bearing oil field extracted water is 60 DEG C ~ 80 DEG C.
Concrete, the pressure of described gas stripping column is 200kpa-350kpa.The lower desulfuration efficiency of air pressure is higher, but reduction air pressure needs to consume a large amount of energy, and therefore when taking into account desulfuration efficiency and energy consumption two factors, the embodiment of the present invention selects air lift pressure to be 200kpa-350kpa.
Concrete, described gas stripping column 1 tower diameter is 2-3m.The treatment capacity of tower diameter Main Basis sulfur-bearing oil field extracted water 3 is determined, considers the restriction of transport condition simultaneously, the tower diameter of gas stripping column is chosen as 2-3 rice more suitable.
Concrete, described gas stripping column 1 adopts the combined trapezoid spray tray being applicable to oily(waste)water.It is large that combined trapezoid spray tray has flux, and the advantages such as separation efficiency is high, anti-clogging, are applicable to extensive oily(waste)water and remove hydrogen sulfide.
Embodiment 1
See Fig. 1, the embodiment of the present invention for source of the gas, adopts air-extraction to remove the hydrogen sulfide of sulfur-bearing oil field extracted water with the Sweet natural gas in oil vapor treatment station.
Gas stripping process flow process is as follows: first analysis temperature is the content of various ion and the content of hydrogen sulfide, wherein salts contg 190,000ppm in the sulfur-bearing oil field extracted water 3 of 65 DEG C, C 1 content 130,000ppm, hydrogen sulfide content 550ppm, in sulfur-bearing oil field extracted water 3, sulphur content is high, and corrodibility is large; In the sulfur-bearing oil field extracted water 3 of pH value 6.5, add acid solution 7, adjust its pH value, when the pH value of sulfur-bearing oil field extracted water is 3, sulfur-bearing oil field extracted water 3 is injected from the top of gas stripping column 1 according to the flow of 200T/h and makes it flow downward.Meanwhile, the Sweet natural gas 4 of 40 DEG C injects with the bottom of the flow of 1600Nm3/h from gas stripping column 1 and upwards flows, and gas stripping column 1 selects dual phase steel material, tower diameter 2.0m, tower height 12m, installs 12 blocks of column plates 2, air lift pressure 300kpa in tower.Sulfur-bearing oil field extracted water 3 in the process of flowing downward with Sweet natural gas 4 counter current contact on the column plate 2 of gas stripping column 1 upwards to flow, pass through gas liquid separating function, obtain sulfur-containing gas 5 and desulfurization oil field extracted water 10 respectively, described sulfur-containing gas 5 is discharged from the tower top of gas stripping column 1, enter the process that sulfur-containing gas processing unit carries out next step, the hydrogen sulfide removed fully utilizes, and is beneficial to environmental protection; Desulfurization oil field extracted water 6 is discharged at the bottom of the tower of gas stripping column 1, and according to the regulation of GB26983-2011-T " mensuration of crude oil hydrogen sulfide, methyl mercaptan and ethanethio " standard, the content adopting chromatography to detect hydrogen sulfide in desulfurization oil field extracted water 6 is 18ppm; Finally, after the pH value of desulfurization oil field extracted water 6 being adjusted to 7 with alkali lye 8, desulfurization oil field extracted water 6 is for further processing, until reach re-injection or emission standard.
Embodiment 2
See Fig. 1, the embodiment of the present invention for source of the gas, adopts air-extraction to remove the hydrogen sulfide of sulfur-bearing oil field extracted water with the Sweet natural gas in oil vapor treatment station.
Gas stripping process flow process is as follows: first analysis temperature is the content of various ion and the content of hydrogen sulfide, wherein salts contg 100,000ppm in the sulfur-bearing oil field extracted water 3 of 75 DEG C, C 1 content 60,000ppm, hydrogen sulfide content 150ppm, in sulfur-bearing oil field extracted water 3, sulphur content is higher, and corrodibility is larger; In the sulfur-bearing oil field extracted water 3 of pH value 6, add acid solution 7, adjust its pH value, when the pH value of sulfur-bearing oil field extracted water is 3.5, sulfur-bearing oil field extracted water 3 is injected from the top of gas stripping column 1 according to the flow of 500T/h and makes it flow downward.Meanwhile, the Sweet natural gas 4 of 40 DEG C injects with the bottom of the flow of 2500Nm3/h from gas stripping column 1 and upwards flows, and gas stripping column 1 selects dual phase steel material, tower diameter 2.4m, tower height 16m, installs 15 blocks of column plates 2, air lift pressure 350kpa in tower.Sulfur-bearing oil field extracted water 3 in the process of flowing downward with Sweet natural gas 4 counter current contact on the column plate 2 of gas stripping column 1 upwards to flow, pass through gas liquid separating function, obtain sulfur-containing gas 5 and desulfurization oil field extracted water 10 respectively, described sulfur-containing gas 5 is discharged from the tower top of gas stripping column 1, enter the process that sulfur-containing gas processing unit carries out next step, the hydrogen sulfide removed fully utilizes, and is beneficial to environmental protection; Desulfurization oil field extracted water 6 is discharged at the bottom of the tower of gas stripping column 1, and according to the regulation of GB26983-2011-T " mensuration of crude oil hydrogen sulfide, methyl mercaptan and ethanethio " standard, the content adopting chromatography to detect hydrogen sulfide in desulfurization oil field extracted water 6 is 13ppm; Finally, after the pH value of desulfurization oil field extracted water 6 being adjusted to 8 with alkali lye 8, desulfurization oil field extracted water 6 is for further processing, until reach re-injection or emission standard.
The invention described above embodiment sequence number, just to describing, does not represent the quality of embodiment.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. high sulfur-bearing oilfield recovered water removes a method for hydrogen sulfide, it is characterized in that, described method take Sweet natural gas as source of the gas, adopts air-extraction desulfurization, specifically operates as follows:
Analyze content, the saltiness of chlorion in sulfur-bearing oil field extracted water, and then determine the content of hydrogen sulfide in described sulfur-bearing oil field extracted water;
The volume ratio of described Sweet natural gas and described sulfur-bearing oil field extracted water is determined according to the content of hydrogen sulfide in described sulfur-bearing oil field extracted water;
The pH value regulating sulfur-bearing oil field extracted water is 3-4, then the sulfur-bearing oil field extracted water regulating pH value inputted from the top of gas stripping column and flow downward, the bottom input of Sweet natural gas from described gas stripping column is also upwards flowed, the Sweet natural gas counter current contact on the column plate of described gas stripping column making described sulfur-bearing oil field extracted water in the process of flowing downward and upwards flow, pass through gas liquid separating function, obtain sulfur-containing gas and desulfurization oil field extracted water, described sulfur-containing gas is discharged from the tower top of described gas stripping column, and described desulfurization oil field extracted water is discharged at the bottom of the tower of gas tower.
2. the method for claim 1, is characterized in that, described air-extraction is single tower pressurization stripping process.
3. the method for claim 1, is characterized in that, its pH value is adjusted to 7-8 with alkali lye after discharging at the bottom of the tower of gas stripping column by described desulfurization oil field extracted water, and enters next step processing unit, until reach the standard of re-injection or discharge.
4. the method for claim 1, is characterized in that, described sulfur-containing gas enters the process that sulfur-containing gas processing unit carries out next step after discharging from the tower top of described gas stripping column.
5. the method for claim 1, is characterized in that, the volume ratio of described Sweet natural gas and described sulfur-bearing oil field extracted water is (3-8): 1.
6. the method for claim 1, is characterized in that, the temperature of described sulfur-bearing oil field extracted water is 70 DEG C ~ 90 DEG C.
7. the method for claim 1, is characterized in that, the pressure of described gas stripping column is 200kpa-350kpa.
8. the method for claim 1, is characterized in that, in described sulfur-bearing oil field extracted water, the content of hydrogen sulfide is 150ppm-600ppm.
9. the method for claim 1, is characterized in that, described gas stripping column tower diameter is 2-3m.
10. the method for claim 1, is characterized in that, described gas stripping column adopts the combined trapezoid spray tray being applicable to oily(waste)water.
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| CN105000745A (en) * | 2015-09-02 | 2015-10-28 | 中国石油化工股份有限公司 | Sulfur gas field produced water treatment system |
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| CN116199293A (en) * | 2021-11-30 | 2023-06-02 | 中国石油化工股份有限公司 | Reinforced negative pressure gas stripping device and gas stripping method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105000745A (en) * | 2015-09-02 | 2015-10-28 | 中国石油化工股份有限公司 | Sulfur gas field produced water treatment system |
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| CN112645478A (en) * | 2019-10-10 | 2021-04-13 | 中国石油化工股份有限公司 | Desulfurization method and system for high-sulfur-content wastewater of oil and gas field |
| CN112053029A (en) * | 2020-07-28 | 2020-12-08 | 中国石油天然气股份有限公司 | Classification and classification method for gas production pipeline management of natural gas field |
| CN112053029B (en) * | 2020-07-28 | 2024-03-08 | 中国石油天然气股份有限公司 | Classification and classification method for natural gas field gas production pipeline management |
| CN116199293A (en) * | 2021-11-30 | 2023-06-02 | 中国石油化工股份有限公司 | Reinforced negative pressure gas stripping device and gas stripping method thereof |
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