CN117923719A - Gas field water desulfurization and electrooxidation sulfur recovery system and method - Google Patents
Gas field water desulfurization and electrooxidation sulfur recovery system and method Download PDFInfo
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- 238000011084 recovery Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006056 electrooxidation reaction Methods 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 74
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- 230000003750 conditioning effect Effects 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- -1 sulfur ions Chemical class 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
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- Treating Waste Gases (AREA)
Abstract
The invention provides a gas field water desulfurization and electrooxidation sulfur recovery system and method, wherein the system comprises a desulfurization reinjection system and an absorption liquid sulfur recovery system, wherein: the desulfurization reinjection system comprises a raw water regulating tank, a stripping tower, a second regulating tank and an air floatation device which are connected in sequence; the absorption liquid sulfur recovery system comprises an absorption tower, a primary electrocatalytic oxidation device, a sulfur precipitation device, a sulfur separation device and a secondary electrocatalytic oxidation device which are connected in sequence; the blowing and degassing outlet of the blowing and stripping tower is connected to the gas inlet of the absorption tower, and the outlet of the secondary electrocatalytic oxidation device is connected to the regulating tank. According to the gas field water desulfurization and electrooxidation sulfur recovery system and method provided by the invention, the gas field water desulfurization standard reinjection is realized by combining the gas field water blowing desulfurization reinjection process with the absorption liquid sulfur recovery process, and the recycling of sulfur elements in the gas field water is realized at the same time, so that the sulfur product is prepared.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a gas field water desulfurization and electrooxidation sulfur recovery system and method.
Background
A large amount of wastewater is formed in the natural gas exploitation process, and the wastewater has the characteristics of high mineralization degree, high suspended matters and high organic matters, and also contains a large amount of calcium, magnesium, barium, strontium and other ions easy to scale and sulfides. The high-concentration sulfur-containing wastewater has the following hazards that firstly, equipment pipelines are corroded, iron sulfide generated by the reaction of steel and sulfur ions in the pipelines corrodes and is blocked by pollution, and meanwhile, hydrogen ions are released to diffuse into the steel to cause metal defects so as to cause embrittlement of the steel; secondly, the ecological environment is influenced, more than 1ppm of gaseous hydrogen sulfide in the air can cause death of people, more than 0.5ppm of hydrogen sulfide in the water body can cause acute poisoning death of fish, so that microorganisms in a biochemical system lose activity, and growth of plant root systems is inhibited in soil. Therefore, the method has great significance in treating the wastewater with high sulfur content in the natural gas exploitation process.
Desulfurization in wastewater is mainly divided into two ideas, wherein one is to adopt a chemical method to precipitate or oxidize and remove sulfur ions, and common methods comprise a precipitation method, a medicament oxidation method, a biological method, an adsorption method, a gas stripping method and the like; the other is to recycle sulfur ions to prepare sulfur, including complex iron desulfurization, electrooxidation recovery of sulfur and the like; among them, the sulfide preparation sulfur recycling technology is the current widely focused direction.
CN218131057U discloses a desulfurization and regeneration device for complex iron, which utilizes the redox property of an alkaline complex iron catalyst to absorb hydrogen sulfide, the hydrogen sulfide is directly oxidized by the complex iron to generate elemental sulfur, and the complex iron is converted into complex ferrous iron; then air is blown into the regeneration settling tank, and the complex ferrous iron in the oxidized alkaline absorbent is converted into complex ferrous iron for regeneration and reuse. Simultaneously, sulfur is settled and separated to form sulfur slurry, and the sulfur slurry is sent to a filter for dehydration to form sulfur cakes. The complex iron desulfurization process has the advantages of high recovery rate, low energy consumption and the like, but has the defect of recovering the residual complex iron medicament in the sulfur, thereby affecting the purity of the sulfur.
The electrocatalytic oxidation process adopts electrochemical reaction, sulfide is oxidized on the anode and sulfur is recovered, and hydrogen is generated at the same time by the cathode, so that the electrocatalytic oxidation process has the advantages of no external chemical agent, no waste liquid, low energy consumption, complete oxidation and desulfurization, rapidness and high efficiency and high catalytic efficiency; CN219792623U and CN212770005U respectively disclose a device for electrochemical treatment of sulfur-containing wastewater. However, aiming at a gas field water system with high hardness and high sulfur content, a large amount of calcium, magnesium, barium, strontium and other easily-scaling ions exist in the wastewater, the scaling of the polar plate is easily caused, meanwhile, due to the fact that the wastewater contains volatile organic sulfur and other pollutants, the adaptability among different systems needs to be comprehensively considered, and the problem that the scaling of the polar plate is easily caused due to direct precipitation of sulfur by electrochemical oxidation is solved. Therefore, it is needed to provide a set of combined process for desulfurizing gas field water and recovering sulfur, and simultaneously realize sulfur recovery, organic sulfur treatment and standard reinjection of gas field water.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a system and a method for desulfurizing and electrooxidizing sulfur in gas field water, which simultaneously realize sulfur recovery, organic sulfur treatment and standard reinjection of the gas field water, and have the characteristics of no need of adding chemical agents, no generation of solid waste, small occupied area and high economical efficiency.
The technical scheme provided by the invention is as follows:
The utility model provides a gas field water desulfurization and electrooxidation sulphur recovery system, the system includes desulfurization reinjection system and absorption liquid sulphur recovery system, wherein:
The desulfurization reinjection system comprises a raw water regulating tank, a stripping tower, a second regulating tank and an air floatation device which are sequentially connected, wherein the desulfurization reinjection system is used for realizing standard reinjection of the gas field water after the gas field water sequentially passes through the raw water regulating tank to regulate pH, the stripping tower blows out sulfur-rich gas, the second regulating tank is used for homogenizing the gas field water and the air floatation device is used for removing suspended matters;
The absorption liquid sulfur recovery system comprises an absorption tower, a primary electrocatalytic oxidation device, a sulfur precipitation device, a sulfur separation device and a secondary electrocatalytic oxidation device which are connected in sequence; the blowing and degassing outlet of the blowing and degassing tower is connected to the gas inlet of the absorption tower, and the outlet of the secondary electrocatalytic oxidation device is connected to the regulating tank; the absorption liquid sulfur recovery system is used for sequentially absorbing sulfur-rich gas blown out by the blowing-off tower into sulfur-rich absorption liquid through the absorption tower through alkali washing, enabling the sulfur-rich absorption liquid to react through the primary electrocatalytic oxidation device to generate polysulfide, separating sulfur out through the sulfur separation device through carbon dioxide acidification reaction, separating the sulfur product through the sulfur separation device, and recycling separated filtrate into the second regulating tank after further deep oxidation desulfurization through the secondary electrocatalytic oxidation device.
The invention further provides that the desulfurization reinjection system further comprises a plate-and-frame filter pressing device, wherein the plate-and-frame filter pressing device is connected with the second regulating tank and the air floatation device and is used for separating precipitated solid slag generated in the second regulating tank and the air floatation device after plate-and-frame filter pressing.
The second aspect of the invention provides a gas field water desulfurization and electrooxidation sulfur recovery method adopting the system, which comprises the following steps:
Firstly, introducing gas field water into the raw water regulating tank to regulate the pH value, and then, introducing the gas field water into the stripping tower to strip sulfur-rich gas containing H 2 S; introducing the desulfurized gas field water into the second regulating tank, mixing with the waste liquid from the secondary electrocatalytic oxidation device, and carrying out homogenization regulation; then introducing the gas field water desulfurization solution into the air floatation device to remove suspended matters, and realizing standard reinjection of the gas field water desulfurization solution;
Introducing sulfur-rich gas blown out of the stripping tower into the absorption tower, and performing alkaline washing absorption to obtain sulfur-rich absorption liquid; introducing the sulfur-rich absorption liquid into the primary electrocatalytic oxidation device to react in an alkaline environment to generate polysulfide; then introducing the sulfur precipitation device, and performing acidification reaction with CO 2 gas to decompose polysulfide and precipitate sulfur to obtain sulfur mixed solution; introducing the sulfur mixed solution into the sulfur separation device for solid-liquid separation to obtain a sulfur product; and introducing the separated filtrate into the secondary electrocatalytic oxidation device, and recycling the waste liquid into the second regulating tank after deep oxidation desulfurization.
The invention is further arranged that the pH value of the raw water regulating tank is regulated to be 2-5 by adding acid liquor/alkali liquor, and the S 2- or HS - ions in the gas field water are regulated to form H 2 S.
The invention is further arranged that the air is introduced into the stripping tower to blow out H 2 S and organic sulfur gas in the gas field water, wherein the organic sulfur gas comprises substances such as mercaptan, thiophenol, thioether and the like in the gas field water; the ratio of gas to liquid introduced into the stripping tower is controlled to be 100: 1-500: 1,
The invention further provides that in the second regulating tank, gas field water is mixed with waste liquid which is from the second-stage electrocatalytic oxidation device and contains SO 4 2- for homogenization regulation, and calcium, barium and strontium plasma in the gas field water is regulated to form precipitates such as CaSO 4、BaSO4、SrSO4.
The invention further provides that a flocculating agent can be added into the air flotation device for removing suspended matters in the gas field water through air flotation and flocculation, and the residence time in the air flotation device is controlled to be 0.25-1 h.
The invention is further arranged that after the second regulating tank and the air floatation device treat gas field water, the solid phase generated by the filtration and separation of the plate-and-frame filter pressing device can be introduced into the next operation; namely, for the air floatation device, the gas field water is reinjected after being filtered by a plate-and-frame filter pressing device; and (5) carrying out outward treatment on mud cakes generated by plate and frame filter pressing.
The invention is further arranged that in the absorption tower, alkali liquor is in countercurrent contact with the sulfur-rich gas from the stripping tower for absorption, H 2 S enriched in gas phase is dissolved in the absorption liquid for conversion into S 2-, and organic sulfur is also dissolved in the absorption liquid.
The invention is further arranged that alkali liquor which is introduced into the absorption tower is preferably NaOH solution, H 2 S enriched in gas phase is converted into Na 2 S and is dissolved in the absorption liquid, the concentration of the alkali liquor is controlled to be 10-40% by mass fraction, and the ratio of gas to liquid which is introduced into the absorption tower is controlled to be 100: 1-500: 1.
The invention is further arranged that the current density of the primary electrocatalytic oxidation device is controlled to be 5-20 mA/cm 2, the pH value of the electrocatalytic oxidation reaction is controlled to be 9-13, and the residence time is controlled to be 2-6 h; the occurrence forms of polysulfide ions generated by the reaction in the primary electrocatalytic oxidation device comprise S 2 2-、S3 2-、S4 2-、S5 2- and the like; the electrode in the primary electrocatalytic oxidation device can adopt a reversed electrode operation to relieve the scaling phenomenon of sulfur on an electrocatalytic oxidation polar plate directly.
The invention is further arranged that the adding concentration of CO 2 gas in the sulfur precipitation device is controlled to be 5-25%, the partial pressure control range of CO 2 is controlled to be 0.15-0.5 MPa, the acidification reaction temperature is controlled to be 30-60 ℃, and the acidification reaction pH is controlled to be 5-8.
The invention further provides that the sulfur separation device can adopt plate-and-frame filter pressing equipment, belt filter pressing equipment, centrifugal separation equipment, sedimentation separation equipment and the like, and is preferably plate-and-frame filter pressing equipment.
The invention is further arranged that the current density of the secondary electrocatalytic oxidation device is controlled to be 20-50 mA/cm 2, the pH value of the electrocatalytic oxidation reaction is controlled to be 5-8, the residence time is controlled to be 2-4 h, and the secondary electrocatalytic oxidation device is used for deeply degrading organic sulfur pollutants in filtrate through the electrocatalytic oxidation reaction and deeply oxidizing HS - ions obtained through the acidification reaction. The produced waste liquid of the secondary electrocatalytic oxidation device is circularly conveyed to a second conveying regulating tank, so that the accumulation of pollutants such as inorganic salt and the like in the absorption liquid sulfur recovery system is avoided.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the gas field water desulfurization and electrooxidation sulfur recovery system and method provided by the invention, standard reinjection of treated gas field water is realized through the combination of the gas field water blowing desulfurization reinjection process and the absorption liquid sulfur recovery process, and the standard of gas field water reinjection technical Specification (QSY 01004-2016) is satisfied; meanwhile, the recycling of sulfur element in the gas field water is realized, and the sulfur product is prepared.
(2) The sulfur-rich absorption liquid obtained by stripping and alkaline washing absorption of the gas field water is recovered by adopting a two-step method; namely, polysulfide is prepared through an alkaline electrocatalytic oxidation process, sulfur is obtained through acidification under the carbon dioxide atmosphere, scaling caused by direct large-area adhesion of the sulfur on an electrocatalytic oxidation polar plate can be avoided, and current efficiency is improved; in addition, the primary electrocatalytic oxidation equipment adopts the reversed pole operation, so that the scaling of the polar plate can be synchronously and effectively relieved.
(3) The sulfur-rich absorption liquid is controlled in a grading way by adopting a two-stage electrocatalytic oxidation device, and the 85 percent sulfur conversion rate can be realized through one-stage electrocatalytic oxidation and acidification reaction; organic sulfur compounds in the absorption liquid are deeply treated through secondary electrocatalytic oxidation, so that the on-site malodor problem can be effectively relieved; meanwhile, HS - in the secondary electrocatalytic oxidation deep oxidation absorption liquid is SO 4 2- and is circulated to the second regulating tank, SO that the accumulation of pollutants such as inorganic salts and the like in the absorption liquid sulfur recovery system is avoided.
Drawings
FIG. 1 is a process flow diagram of a gas field water desulfurization and electrooxidation sulfur recovery system of the present invention.
Detailed Description
The technical scheme of the invention is clearly and completely described in the following by specific embodiments. It is to be understood that the described embodiments are only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.
Example 1
Referring to fig. 1, the invention discloses a gas field water desulfurization and electrooxidation sulfur recovery system, which comprises a desulfurization reinjection system and an absorption liquid sulfur recovery system, wherein:
the desulfurization reinjection system comprises a raw water regulating tank, a stripping tower, a second regulating tank and an air floatation device which are sequentially connected, wherein the desulfurization reinjection system is used for realizing standard reinjection of the gas field water after the gas field water sequentially passes through the raw water regulating tank to regulate pH, the stripping tower to strip hydrogen sulfide and organic sulfur gas, the second regulating tank to homogenize the gas field water and the air floatation device to remove suspended matters;
The absorption liquid sulfur recovery system comprises an absorption tower, a primary electrocatalytic oxidation device, a sulfur precipitation device, a sulfur separation device and a secondary electrocatalytic oxidation device which are connected in sequence; the blowing and degassing outlet of the blowing and degassing tower is connected to the gas inlet of the absorption tower, and the outlet of the secondary electrocatalytic oxidation device is connected to the regulating tank; the absorption liquid sulfur recovery system is used for sequentially absorbing sulfur-rich gas blown out by the blowing-off tower into sulfur-rich absorption liquid through the absorption tower through alkali washing, enabling the sulfur-rich absorption liquid to react through the primary electrocatalytic oxidation device to generate polysulfide, separating sulfur out through the sulfur separation device through carbon dioxide acidification reaction, separating the sulfur product through the sulfur separation device, and recycling separated filtrate into the second regulating tank after further deep oxidation desulfurization through the secondary electrocatalytic oxidation device.
Further, the desulfurization reinjection system further comprises a plate-and-frame filter pressing device, wherein the plate-and-frame filter pressing device is connected with the second regulating tank and the air floatation device and is used for filtering and separating sediment solid slag generated in the second regulating tank and the air floatation device through the plate-and-frame.
Specifically, the gas field water desulfurization and electrooxidation sulfur recovery method adopting the system provided by the invention comprises the following steps:
firstly, introducing gas field water into the raw water regulating tank, regulating the pH value to 2-5 by adding acid/alkali liquor, and regulating the pH value of S 2- or HS - ions in the gas field water to form H 2 S; introducing the gas field water subjected to raw water regulation into the stripping tower, and blowing out H 2 S and organic sulfur gas in the gas field water after air stripping; introducing the desulfurized gas field water into the second regulating tank, mixing the desulfurized gas field water with the waste liquid which is from the second-stage electrocatalytic oxidation device and contains SO 4 2-, carrying out homogenization regulation, and regulating calcium, barium and strontium plasma in the gas field water to form precipitates such as CaSO 4、BaSO4、SrSO4; introducing the homogenized and adjusted gas field water into the air floatation device to remove suspended matters by an air floatation method, so that standard reinjection of the desulfurized gas field water can be realized;
Introducing sulfur-rich gas blown out of the stripping tower into the absorption tower, countercurrent contacting and absorbing with alkali liquor, dissolving H 2 S enriched in gas phase into the absorption liquid to convert into S 2-, and dissolving organic sulfur into the absorption liquid through alkali washing and absorption to obtain sulfur-rich absorption liquid; the sulfur-rich absorption liquid is introduced into the primary electrocatalytic oxidation device through a delivery pump, polysulfide is generated through electrocatalytic oxidation reaction in an alkaline environment, wherein the occurrence forms of polysulfide ions comprise S 2 2-、S3 2-、S4 2-、S5 2- and the like; the produced water of the primary electrocatalytic oxidation device is conveyed to the sulfur precipitation device, CO 2 gas is introduced to carry out acidification reaction to decompose polysulfide and precipitate sulfur, and sulfur mixed solution is obtained; introducing the sulfur mixed solution into the sulfur separation device, performing solid-liquid separation to obtain a sulfur product, introducing the separated filtrate into the secondary electrocatalytic oxidation device, performing electrocatalytic oxidation reaction to deeply remove organic sulfur pollutants, and deeply oxidizing HS - obtained through the acidification reaction to convert the HS 3834 into SO 4 2-; the produced water of the secondary electrocatalytic oxidation device is circularly conveyed to a second conveying regulating tank, so that the accumulation of pollutants such as inorganic salts and the like in the absorption liquid sulfur recovery system is avoided.
Further, the ratio of gas to liquid introduced into the stripping tower is controlled to be 100: 1-500: and 1, the organic sulfur gas blown out of the stripping tower comprises mercaptan, thiophenol, thioether and other substances in gas field water.
Furthermore, flocculant can be added into the air flotation device for removing suspended matters in gas field water through air flotation and flocculation, and the residence time in the air flotation device is controlled to be 0.25-1 h.
Furthermore, after the gas field water is treated by the second regulating tank and the air floatation device, the solid phase generated by filtering and separating by the plate-and-frame filter pressing device can be introduced into the next operation; namely, for the air floatation device, the gas field water is reinjected after being filtered by a plate-and-frame filter pressing device; and (5) carrying out outward treatment on mud cakes generated by plate and frame filter pressing.
Further, the alkali liquor introduced into the absorption tower is preferably NaOH solution, so that the enriched H 2 S in the gas phase is converted into Na 2 S to be dissolved in the absorption liquid, the concentration of the alkali liquor is controlled to be 10-40% by mass fraction, and the gas-liquid ratio introduced into the absorption tower is controlled to be 100: 1-500: 1.
Further, the current density of the primary electrocatalytic oxidation device is controlled to be 5-20 mA/cm 2, the pH of the electrocatalytic oxidation reaction is controlled to be 9-13, and the residence time is controlled to be 2-6 h; the primary electrocatalytic oxidation device is operated in an alkaline atmosphere, so that sulfur can be prevented from being directly attached to the polar plate, the problem of scaling of the polar plate is solved, and the current efficiency is improved; the electrode in the primary electrocatalytic oxidation device can adopt the electrode reversing operation, and the electrode reversing operation is carried out once every 2-6 hours, so that the scaling phenomenon of sulfur on an electrocatalytic oxidation polar plate can be further relieved.
Further, the adding concentration of CO 2 gas in the sulfur precipitation device is controlled to be 5% -25%, the partial pressure control range of CO 2 is 0.15-0.5 MPa, the acidification reaction temperature is controlled to be 30-60 ℃, and the acidification reaction pH is controlled to be 5-8; the specific reaction equation of the acidification reaction of CO 2 gas introduced into the sulfur precipitation device is shown as follows:
S2 2-+H+→S↓+HS-
S3 2-+H+→2S↓+HS-
S4 2-+H+→3S↓+HS-
S5 2-+H+→4S↓+HS-
CO2+H2O→H++HCO3 -
HCO3 -→H++CO3 2-
Furthermore, the sulfur separation device can adopt plate-frame filter pressing equipment, belt filter pressing equipment, centrifugal separation equipment, sedimentation separation equipment and the like, and is preferably plate-frame filter pressing equipment.
Further, the current density of the secondary electrocatalytic oxidation device is controlled to be 20-50 mA/cm 2, the pH of the electrocatalytic oxidation reaction is controlled to be 5-8, the residence time is controlled to be 2-4 h, and the secondary electrocatalytic oxidation device is used for deeply degrading organic sulfur in filtrate and deeply oxidizing residual HS - ions.
Example 2
The concentration of sulfur ions in water inflow of the gas field is 312mg/L, the concentration of barium ions is 1000mg/L, the concentration of strontium ions is 800mg/L, and the total hard concentration is 2500mg/L.
The gas field water was treated using the system and method described in example 1, with a gas-to-liquid ratio in the stripping column controlled to 200:1, the concentration of the sulfur ions in the gas field water after stripping is less than 10mg/L, and the removal rate of the sulfur ions reaches more than 96 percent. The concentration of the alkali liquor introduced into the absorption tower is controlled to be 30%, and the gas-liquid ratio of the absorption tower is controlled to be 100:1, the concentration of sodium sulfide in the absorption liquid can reach 295g/L. The current density of the primary electrocatalytic oxidation was controlled to 10mA/cm 2, the reaction pH was controlled to 9 and the residence time was controlled to 4h. The concentration of carbon dioxide introduced into the sulfur precipitation device is controlled to be 10%, the partial pressure of carbon dioxide is controlled to be 0.2MPa, the reaction temperature is controlled to be 60 ℃, and the reaction pH is controlled to be 5. The current density of the secondary electrocatalytic oxidation is controlled at 25mA/cm 2, the reaction pH is controlled at 5, and the residence time is controlled at 4h. After the above-mentioned electrooxidation sulfur recovery treatment, the recovery rate of sulfur can be up to 85%.
Example 3
The concentration of sulfur ions in water inflow of the gas field is 80mg/L, the concentration of barium ions is 600mg/L, the concentration of strontium ions is 400mg/L, and the total hard concentration is 1200mg/L.
The system and method described in example 1 were used to treat gas field water, and the gas-liquid ratio in the stripping column was controlled at 100:1, the concentration of sulfur ions in the gas field water after stripping is less than 1mg/L, and the removal rate of the sulfur ions is more than 98 percent. The concentration of the alkali liquor introduced into the absorption tower is controlled to be 20%, and the gas-liquid ratio of the absorption tower is controlled to be 100:1, the concentration of sodium sulfide in the absorption liquid can reach 195g/L. The current density of the primary electrocatalytic oxidation was controlled to 5mA/cm 2, the reaction pH was controlled to 9 and the residence time was controlled to 2h. The concentration of carbon dioxide introduced into the sulfur precipitation device is controlled to be 5%, the partial pressure of carbon dioxide is controlled to be 0.15MPa, the reaction temperature is controlled to be 60 ℃, and the reaction pH is controlled to be 5. The current density of the secondary electrocatalytic oxidation is controlled to be 40mA/cm 2, the reaction pH is controlled to be 5, and the residence time is controlled to be 3h. After the above-mentioned electrooxidation sulfur recovery treatment, the sulfur recovery rate can be up to 85%.
The present application has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present application and to implement the same, but not to limit the scope of the present application, and all equivalent changes or modifications made according to the spirit of the present application should be covered in the scope of the present application.
Claims (10)
1. The utility model provides a gas field water desulfurization and electrooxidation sulphur recovery system which characterized in that, the system includes desulfurization reinjection system and absorption liquid sulphur recovery system, wherein:
The desulfurization reinjection system comprises a raw water regulating tank, a stripping tower, a second regulating tank and an air floatation device which are connected in sequence;
the absorption liquid sulfur recovery system comprises an absorption tower, a primary electrocatalytic oxidation device, a sulfur precipitation device, a sulfur separation device and a secondary electrocatalytic oxidation device which are connected in sequence;
the blowing and degassing outlet of the blowing and stripping tower is connected to the gas inlet of the absorption tower, and the outlet of the secondary electrocatalytic oxidation device is connected to the regulating tank.
2. The system of claim 1, wherein the desulfurization reinjection system further comprises a plate and frame filter press device, wherein the plate and frame filter press device is connected with the second regulating tank and the air floatation device and is used for separating precipitated solid slag generated in the second regulating tank and the air floatation device after the plate and frame filter press.
3. A method for desulfurizing gas field water and recovering electrooxidized sulfur by using the system of any one of claims 1-2, comprising the steps of:
Firstly, introducing gas field water into the raw water regulating tank to regulate the pH value, and then, introducing the gas field water into the stripping tower to strip sulfur-rich gas containing H 2 S; introducing the desulfurized gas field water into the second regulating tank, mixing with the waste liquid from the secondary electrocatalytic oxidation device, and carrying out homogenization regulation; then introducing the gas field water desulfurization solution into the air floatation device to remove suspended matters, and realizing standard reinjection of the gas field water desulfurization solution;
Introducing sulfur-rich gas blown out of the stripping tower into the absorption tower, and performing alkaline washing absorption to obtain sulfur-rich absorption liquid; introducing the sulfur-rich absorption liquid into the primary electrocatalytic oxidation device to react in an alkaline environment to generate polysulfide; then introducing the sulfur precipitation device, and performing acidification reaction with CO 2 gas to decompose polysulfide and precipitate sulfur to obtain sulfur mixed solution; introducing the sulfur mixed solution into the sulfur separation device for solid-liquid separation to obtain a sulfur product; and introducing the separated filtrate into the secondary electrocatalytic oxidation device, and recycling the waste liquid into the second regulating tank after deep oxidation desulfurization.
4. A system according to claim 3, wherein the pH is adjusted to 2-5 by adding an acid or alkali solution to the raw water adjustment tank.
5. A system according to claim 3, wherein the blow-off column is vented to blow off H 2 S and organic sulfur gases from the field water; the ratio of gas to liquid introduced into the stripping tower is controlled to be 100: 1-500: 1.
6. A system according to claim 3, wherein in the second conditioning tank, the gas field water is homogenized in combination with a waste stream from a secondary electrocatalytic oxidation device and containing SO 4 2-;
Adding a flocculating agent into the air flotation device, and removing suspended matters in gas field water through air flotation and flocculation, wherein the residence time in the air flotation device is controlled to be 0.25-1 h;
And after the second regulating tank and the air floatation device treat the gas field water, the solid phase generated by the filtration and separation treatment of the second regulating tank and the air floatation device is filtered and separated by the plate-and-frame filter pressing device and then is introduced into the next operation.
7. A system according to claim 3, wherein in the absorption tower, lye is countercurrently contacted with sulfur-rich gas from the stripping tower for absorption, the concentration of the lye is controlled to be 10% -40% by mass, and the gas-liquid ratio introduced into the absorption tower is controlled to be 100: 1-500: 1.
8. A system according to claim 3, wherein the current density of the primary electrocatalytic oxidation device is controlled to be 5-20 mA/cm 2, the pH of the electrocatalytic oxidation reaction is controlled to be 9-13, and the residence time is controlled to be 2-6 h; the electrode in the primary electrocatalytic oxidation device adopts a reversed electrode operation.
9. The system according to claim 3, wherein the addition concentration of CO 2 gas in the sulfur precipitation device is controlled to be 5% -25%, the partial pressure control range of CO 2 is 0.15-0.5 MPa, the acidification reaction temperature is controlled to be 30-60 ℃, and the acidification reaction pH is controlled to be 5-8.
10. A system according to claim 3, wherein the current density of the secondary electrocatalytic oxidation device is controlled to be 20-50 mA/cm 2, the pH of the electrocatalytic oxidation reaction is controlled to be 5-8, and the residence time is controlled to be 2-4 h.
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