CN115893711A - Method for treating organic sulfur in fracturing flow-back fluid suitable for oil and gas field - Google Patents
Method for treating organic sulfur in fracturing flow-back fluid suitable for oil and gas field Download PDFInfo
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- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 claims description 2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for treating organic sulfur in fracturing flow-back fluid of an oil and gas field, which comprises the steps of firstly adding a chelating agent and alkali liquor into the fracturing flow-back fluid to chemically absorb the organic sulfur, then adding a modified nano catalyst to carry out catalytic oxidation treatment on the organic sulfur and realize regeneration of the alkali liquor, then carrying out reabsorption treatment on residual organic sulfur by using a biomass desulfurizer, and finally obtaining the treated fracturing flow-back fluid by fine filtration.
Description
Technical Field
The invention relates to the field of oil-gas field water treatment, in particular to a method for treating organic sulfur in fracturing flow-back fluid of an oil-gas field.
Background
The sulfur exists in crude oil and natural gas mainly in the form of inorganic sulfur compounds such as hydrogen sulfide and organic sulfur compounds such as mercaptan, thioether, carbonyl sulfide, carbon disulfide and thiophene. Organosulfur is the second largest sulfur-containing component behind pyrite in sedimentary rocks. With the development of unconventional oil and gas resources, hydraulic fracturing technology has received widespread attention. Hydraulic fracturing is a stimulation or stimulation procedure in which a subterranean formation is pressed open with pressure to form a fracture and propped up with a proppant to reduce the resistance to fluid flow. After the hydraulic fracturing operation is finished, organic sulfur in the stratum can be dissolved or solubilized by alcohol and a surfactant solution in the fracturing flow-back fluid and flow back to the ground. The odor threshold of the organic sulfur is very low, for example, the odor threshold of methyl mercaptan is about 0.07ppb, and the value is smaller than the odor threshold of hydrogen sulfide (about 0.41 ppb), so the organic sulfur in the fracturing flowback fluid is not effectively treated, and the odor can generate stink and pungent odor to cause serious environmental protection events.
The domestic and foreign desulfurization technology mainly comprises: dry desulfurization, wet desulfurization, biological desulfurization, membrane desulfurization, pressure swing adsorption desulfurization and the like. They can be classified into physical, chemical and biological methods according to the desulfurization mechanism. The physical methods are mainly masking methods, physical adsorption and dilution diffusion methods, but sulfides are not fundamentally changed and still cause toxicological damage when entering human bodies according to toxicity accumulation effects. The biological method is to realize the absorption, decomposition and conversion of organic sulfur in natural gas by means of the self metabolic process of microorganisms, and then convert organic sulfur pollutants in the natural gas into substances harmless to the environment, and has the defects of strong pertinence, high cost, overlong microbial passage period, easy pollution and the like. The chemical treatment of organic sulfur is carried out in various ways, usually including two processes, i.e., enrichment and treatment, and depending on the way of treatment, chemical adsorption, solvent absorption, catalytic oxidation, low-temperature plasma, etc. are involved. The main desulfurization processes are the Sulfinol method and the Hybrisol method. The solvents used in the Sulfinol method are sulfolane, methyldiethanolamine (MDEA) and Diisopropanolamine (DIPA), wherein MDEA and DIPA can remove hydrogen sulfide in natural gas, and sulfolane can remove organic sulfur in natural gas, so that the desulfurization effect is good, and the method is similar to a sulphonylamine method for removing hydrogen sulfide. The absorption solvent adopted by the Hybrisol method is secondary amine and tertiary amine, and is matched with methanol, so that organic sulfur in natural gas can be removed by adding the methanol, and the absorption efficiency of the mixed solution on hydrogen sulfide in the natural gas can be improved.
However, the current desulfurization technology has the following three problems: 1) Hydrogen sulfide removal technologies are reported more, related technologies are mature, but organic sulfur removal technologies are reported less; 2) The reports of desulfurization technology in natural gas are more, but the reports of treatment technology of organic sulfur in water phases such as fracturing flowback fluid are less; 3) The reports of the organic sulfur treatment technology suitable for oil and gas field sites are less. Compared with hydrogen sulfide, the threshold value of organic sulfur is lower, so that the organic sulfur is easier to be sniffed by people, particularly, in the process of flowback of the fracturing fluid of an oil and gas field, foul smell is often generated, and the production life and the body health of field operators and nearby residents are seriously affected, wherein the cause of the foul smell is that the fracturing flowback fluid dissolves or solubilizes the organic sulfur in the stratum. The influence of organic sulfur on the surrounding environment is therefore likewise great, and it is necessary to remove it in a targeted manner during the production process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for treating organic sulfur in fracturing flow-back fluid of an oil and gas field, which solves the problem of influence of odor on the environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a treatment method for organic sulfur in fracturing flow-back fluid of an oil and gas field comprises the following steps:
(1) Adding a chelating agent and alkali liquor into the fracturing flow-back fluid to carry out chemical absorption on organic sulfur;
(2) Adding a modified nano catalyst into the fracturing flow-back fluid after chemical absorption to perform catalytic oxidation on organic sulfur;
(3) Adding a biomass desulfurizer into the fracturing flow-back fluid after catalytic oxidation in the step (2) to reabsorb residual organic sulfur;
(4) And (4) filtering the fracturing flow-back fluid after the biomass desulfurizer in the step (3) is reabsorbed.
The alkali liquor is mainly used for absorbing acid sulfur-containing compounds such as mercaptan, carbon-based sulfur, hydrogen sulfide and the like, so that organic sulfur is prevented from overflowing from a water body, and the overflow of odor is reduced. The chelating agent is mainly used for avoiding or reducing the generation of calcium and magnesium precipitates after alkali liquor is added into the fracturing flow-back fluid. Preferably, the chelating agent in step (1) is one or more of aminotrimethylene phosphonic acid, diethylenetriaminepentamethylene phosphonic acid, ethylene diamine tetraacetic acid and hydroxyethylidene diphosphonic acid; the alkali liquor is one or more of sodium hydroxide, potassium hydroxide, urea, polyethylene polyamine, diethylenetriamine, tetraethylenepentamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, diisopropanolamine, diglycolamine, hydroxyethyl hexahydro-s-triazine, 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine and 1,3, 5-tris (dimethylaminopropyl) hexahydro-triazine.
Preferably, the addition amount of the chelating agent is 50 mg/L-500 mg/L, and the addition amount of the alkali liquor is 3wt% -10 wt%.
Preferably, in the step (1), the fracturing flow-back fluid, the chelating agent and the alkali liquor are stirred in a sealed tank by a stirring device to carry out chemical absorption, wherein the stirring speed of the stirring device is 500-1500 r/min, and the stirring time is 5-15 min.
Preferably, the step (2) further comprises introducing air into the fracturing flow-back fluid after chemical absorption at a flow rate of 3-5L/min during the catalytic oxidation, wherein the catalytic oxidation time is 10min.
The modified nano catalyst is used for catalytic oxidation treatment of organic sulfur compounds, converts organic sulfur into sulfur or sulfur oxides through the catalytic oxidation effect of the modified nano catalyst, and meanwhile realizes regeneration of liquid caustic soda. In order to improve the adsorption capacity of the catalyst on organic sulfur and other substances and further effectively improve the catalytic oxidation efficiency, preferably, the modified nano-catalyst in the step (2) is a modified ferro-manganese bimetallic oxide, and the amount of the modified nano-catalyst is 1wt% -3 wt%.
Preferably, the preparation method of the modified ferro-manganese bimetallic oxide comprises the following steps: respectively with Fe (NO) 3 ) 3 ·9H 2 O and Mn (NO) 3 ) 2 ·4H 2 O is an iron and manganese precursor, and polyether amine is used as a template and a surface modifier for calcination; wherein, fe (NO) 3 ) 3 ·9H 2 O and Mn (NO) 3 ) 2 ·4H 2 The mass ratio of O is 4.
In order to avoid the existence of a small amount of residual organic sulfur in a water sample after catalytic oxidation, the invention also adds a biomass desulfurizer into the fracturing flow-back fluid after catalytic oxidation to carry out reabsorption treatment on the residual organic sulfur. Preferably, the amount of the biomass desulfurizer used in the step (3) is 0.5wt% to 1.0wt%.
Preferably, the preparation method of the biomass desulfurizer comprises the following steps: crushing wheat bran; and adding a surfactant into the crushed wheat bran, stirring for 24 hours, filtering the suspension, and then placing the filtered solid in a 65 ℃ drying oven for drying for 12 hours to obtain the biomass desulfurizer.
The surface active agent modification can improve the adsorption capacity of the biomass desulfurizer. Preferably, the surfactant is one or more of dodecyl dimethyl betaine, lauramidopropyl betaine, tetradecyl dimethyl betaine and cocamidopropyl betaine; the dosage ratio of the wheat bran to the surfactant is 1g:20 to 50mL.
The invention has the beneficial effects that:
according to the method, firstly, alkali liquor is used for absorbing acidic sulfur-containing compounds such as hydrogen sulfide and mercaptan, then, modified nano-catalyst is used for further catalyzing and oxidizing sulfur-containing substances such as hydrogen sulfide, mercaptan and thioether, so that the removal rate of foul smell reaches more than 99%, and when necessary, a biomass desulfurizer is used for physically adsorbing residual organic sulfur in a water body, so that the removal rate is further improved.
The method is mainly used for effectively removing the organic sulfur in the field fracturing flow-back process of the oil and gas field, and simultaneously, the hydrogen sulfide and the organic sulfur are always simultaneously considered, so that the hydrogen sulfide can be effectively removed, the odor of the field fracturing flow-back water is effectively solved, and the unnecessary environmental problem is avoided.
The alkali liquor can be regenerated, the biomass desulfurizer can also be regenerated after being treated, the cyclic utilization is realized, the resources are saved, and the cost is reduced.
Drawings
FIG. 1 is a fracturing flowback fluid before and after treatment in example 1;
FIG. 2 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in frac flowback fluid before and after treatment in example 1;
FIG. 3 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in the fracturing flow-back fluid before and after treatment in example 2;
FIG. 4 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in fracturing flow-back fluid before and after treatment of comparative example 1;
FIG. 5 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in the fracturing flow-back fluid before and after treatment of comparative example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort, fall within the protection scope of the present invention.
The invention provides a method for treating organic sulfur in fracturing flow-back fluid of an oil and gas field, which comprises the steps of firstly adding a chelating agent and alkali liquor into the fracturing flow-back fluid to carry out chemical absorption on the organic sulfur, adding a modified nano catalyst to carry out catalytic oxidation treatment on the organic sulfur and realize regeneration of the alkali liquor, then carrying out reabsorption treatment on residual organic sulfur by a biomass desulfurizer, finally realizing recycling of the fracturing flow-back fluid by fine filtration, and realizing regeneration of the biomass desulfurizer by proper treatment. The specific embodiment is as follows.
Example 1
A treatment method for organic sulfur in fracturing flow-back fluid of an oil and gas field comprises the following steps:
(1) In a sealed tank body with a stirring device, a chemical feeding pump is used for adding diethylenetriaminepentamethylenephosphonic acid and sodium hydroxide into the fracturing flowback fluid to carry out chemical absorption on organic sulfur. Wherein the concentration of the diethylenetriaminepentamethylenephosphonic acid in the fracturing flow-back fluid is 100mg/L, and the dosage of the sodium hydroxide is 10wt% of the fracturing flow-back fluid. The stirring speed of the stirring device is 1500r/min, and the stirring time is 15min.
(2) 100g of Fe (NO) was weighed out separately 3 ) 3 ·9H 2 O,100g of Mn (NO) 3 ) 2 ·4H 2 O and 20g of polyetheramine T-5000, at 600 ℃ for 12 hours. And then crushing the calcined catalyst to 20-50 meshes to obtain the modified ferro-manganese bimetal oxide.
(3) Pumping the fracturing flow-back fluid after chemical absorption in the step (1) into a second tank, adding 3wt% of modified ferro-manganese bimetallic oxide, introducing air according to the flow of 3L/min, and carrying out catalytic oxidation for 10min.
(4) 1000g of wheat bran was pulverized, and the resultant powder was sieved with 75-mesh and 100-mesh sieves. 20L of dodecyl dimethyl betaine with the concentration of 1mmol/L is prepared and mixed with wheat bran, and the mixture is magnetically stirred for 24 hours at the temperature of 30 ℃. And filtering the suspension, drying the filtered modified wheat bran in a 65 ℃ drying oven for 12 hours to obtain the biomass desulfurizer, and filling the biomass desulfurizer into a filter bag for later use.
(5) Pumping the fracturing flow-back fluid subjected to catalytic oxidation treatment in the step (3) into a third tank, and adding the prepared biomass desulfurizer into the fracturing flow-back fluid for treatment for 15min, wherein the use amount of the biomass desulfurizer is 0.5wt%.
(6) And taking out the filter bag filled with the biomass desulfurizer, drying for 3 hours at 100 ℃, and recovering the biomass desulfurizer.
(7) And (3) finely filtering the fracturing flow-back fluid which is sequentially subjected to chemical absorption, catalytic oxidation and biomass desulfurizer reabsorption by using a fiber ball filter to obtain the fracturing flow-back fluid without organic sulfur.
Figure 1 is a graph of fracturing flow-back fluid before and after treatment according to this example. From figure 1 it can be seen that the treated water sample was clear. FIG. 2 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in frac flowback fluid before and after treatment according to this example (FIG. 2a is before treatment, FIG. 2b is after treatment). As can be seen from FIG. 2, the fracturing flow-back fluid before treatment contains sulfur-containing substances such as hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl disulfide, and none of the sulfur-containing substances is detected after treatment, which shows that the organic sulfur treatment method provided by the invention can effectively remove organic sulfur in the fracturing flow-back fluid of an oil and gas field, and the treated water can be used in production links of the oil and gas field such as preparation of the fracturing fluid.
Example 2
A treatment method for organic sulfur in fracturing flow-back fluid of an oil and gas field comprises the following steps:
(1) In a sealed tank body with a stirring device, a dosing pump is used for adding ethylene diamine tetraacetic acid and diethanol amine into fracturing flowback liquid to carry out chemical absorption on organic sulfur. Wherein the concentration of the ethylene diamine tetraacetic acid in the fracturing flow-back fluid is 150mg/L, and the dosage of the diethanolamine is 5wt% of the fracturing flow-back fluid. The stirring speed of the stirring device is 1500r/min, and the stirring time is 15min.
(2) 125g of Fe (NO) were weighed out separately 3 ) 3 9H2O,75g of Mn (NO) 3 ) 2 ·4H 2 O and 30g of polyetheramine T-5000, calcined at 500 ℃ for 16 hours. And then crushing the calcined catalyst to 20-50 meshes to obtain the modified ferro-manganese bimetallic oxide.
(3) Pumping the fracturing flow-back fluid after chemical absorption in the step (1) into a second tank, adding 2wt% of modified ferro-manganese bimetallic oxide, introducing air according to the flow of 3L/min, and carrying out catalytic oxidation for 10min.
(4) 1000g of wheat bran was pulverized, and the resultant powder was sieved with 75-mesh and 100-mesh sieves. Mixing 30L tetradecyl dimethyl betaine with concentration of 1mmol/L with testa Tritici, and magnetically stirring at 30 deg.C for 24 hr. And then filtering the turbid liquid, and drying the filtered modified wheat bran in a 65 ℃ drying oven for 12 hours to obtain the biomass desulfurizer, and filling the biomass desulfurizer into a filter bag for later use.
(5) Pumping the fracturing flow-back fluid subjected to catalytic oxidation treatment in the step (3) into a third tank, and adding the prepared biomass desulfurizer into the fracturing flow-back fluid for treatment for 15min, wherein the use amount of the biomass desulfurizer is 1.0wt%.
(6) And taking out the filter bag filled with the biomass desulfurizer, drying for 3 hours at 100 ℃, and recovering the biomass desulfurizer.
(7) And (3) finely filtering the fracturing flow-back fluid which is sequentially subjected to chemical absorption, catalytic oxidation and biomass desulfurizer reabsorption by using a fiber ball filter to obtain the fracturing flow-back fluid without organic sulfur.
FIG. 3 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in frac flowback fluid before and after treatment in example 2 (FIG. 3a is before treatment, FIG. 3b is after treatment). As can be seen from FIG. 3, the fracturing flow-back fluid before treatment contains sulfur-containing substances such as hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl disulfide, and none of the sulfur-containing substances is detected after treatment, which indicates that the method of the invention can simultaneously remove the hydrogen sulfide and the organic sulfur in the fracturing flow-back fluid of the oil and gas field.
Comparative example 1
(1) In a sealed tank body with a stirring device, a chemical feeding pump is used for adding diethylenetriaminepentamethylenephosphonic acid and sodium hydroxide into the fracturing flowback fluid to carry out chemical absorption on organic sulfur. Wherein the concentration of the diethylenetriaminepentamethylenephosphonic acid in the fracturing flow-back fluid is 100mg/L, and the dosage of the sodium hydroxide is 10wt% of the fracturing flow-back fluid. The stirring speed of the stirring device is 1500r/min, and the stirring time is 15min.
(2) 1000g of wheat bran was pulverized, and the obtained powder was sieved with 75 mesh and 100 mesh sieves. 20L of dodecyl dimethyl betaine with the concentration of 1mmol/L is prepared and mixed with wheat bran, and the mixture is magnetically stirred for 24 hours at the temperature of 30 ℃. And then filtering the turbid liquid, and drying the filtered modified wheat bran in a 65 ℃ drying oven for 12 hours to obtain the biomass desulfurizer, and filling the biomass desulfurizer into a filter bag for later use.
(3) Pumping the fracturing flow-back fluid chemically absorbed in the step (1) into a second tank body, and adding the prepared biomass desulfurizer into the fracturing flow-back fluid for treatment for 15min, wherein the amount of the biomass desulfurizer is 0.5wt%.
(4) And (3) taking out the filter bag filled with the biomass desulfurizer, drying for 3 hours at 100 ℃, and recovering the biomass desulfurizer.
(5) And (3) finely filtering the fracturing flow-back fluid which is sequentially subjected to chemical absorption and biomass desulfurizer reabsorption by using a fiber ball filter to obtain the fracturing flow-back fluid without organic sulfur.
FIG. 4 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in frac flowback before and after treatment of comparative example 1 (FIG. 4a is before treatment, FIG. 4b is after treatment). As can be seen from FIG. 4, the fracturing flow-back fluid before treatment contains sulfur-containing substances such as hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl disulfide, and the methyl sulfide and the dimethyl disulfide are detected after treatment, which shows that the technical contribution of the invention to the catalytic oxidation of organic sulfur is made by adding the modified nano-catalyst into the fracturing flow-back fluid after chemical absorption.
Comparative example 2
(1) In a sealed tank with a stirring device, adding diethylenetriaminepentamethylenephosphonic acid and sodium hydroxide into the fracturing flowback fluid by using a dosing pump to carry out chemical absorption on organic sulfur. Wherein the concentration of the diethylenetriaminepentamethylenephosphonic acid in the fracturing flow-back fluid is 100mg/L, and the dosage of the sodium hydroxide is 10wt% of the fracturing flow-back fluid. The stirring speed of the stirring device is 1500r/min, and the stirring time is 15min.
(2) 100g of Fe (NO) was weighed out separately 3 ) 3 ·9H 2 O,100g of Mn (NO) 3 ) 2 ·4H 2 O and 20g of polyetheramine T-5000, at 600 ℃ for 12 hours. And then crushing the calcined catalyst to 20-50 meshes to obtain the modified ferro-manganese bimetal oxide.
(3) Pumping the fracturing flow-back fluid after chemical absorption in the step (1) into a second tank, adding 3wt% of modified ferro-manganese bimetallic oxide, introducing air according to the flow of 3L/min, and carrying out catalytic oxidation for 10min.
(4) And (3) finely filtering the fracturing flow-back fluid which is sequentially subjected to chemical absorption and catalytic oxidation by using a fiber ball filter to obtain the fracturing flow-back fluid with organic sulfur removed.
FIG. 5 is a gas chromatogram for detection of hydrogen sulfide and organic sulfur in frac flowback before and after treatment of comparative example 2 (FIG. 5a is before treatment, FIG. 5b is after treatment). As can be seen from fig. 5, the fracturing flow-back fluid before treatment contains sulfur-containing substances such as hydrogen sulfide, methyl mercaptan, methyl sulfide and dimethyl disulfide, and methyl sulfide and dimethyl disulfide are detected after treatment, which indicates that the technical contribution of adding a biomass desulfurizer to the fracturing flow-back fluid after catalytic oxidation to reabsorb residual organic sulfur.
According to the invention, firstly, a chelating agent and alkali liquor are added into the fracturing flow-back fluid to chemically absorb organic sulfur, then a modified nano catalyst is added to perform catalytic oxidation treatment on the organic sulfur and realize regeneration of the alkali liquor, and finally, a biomass desulfurizer is used for performing reabsorption treatment on residual organic sulfur, so that effective removal of hydrogen sulfide and organic sulfur in the fracturing flow-back fluid of an oil-gas field is realized, and the influence of odor to the environment is solved.
It should be noted that the above embodiments belong to the same inventive concept, and the description of each embodiment has a different emphasis, and reference may be made to the description in other embodiments where the description in individual embodiments is not detailed.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The method for treating organic sulfur in the fracturing flow-back fluid of the oil and gas field is characterized by comprising the following steps of:
(1) Adding a chelating agent and alkali liquor into the fracturing flow-back fluid to carry out chemical absorption on organic sulfur;
(2) Adding a modified nano catalyst into the fracturing flow-back fluid after chemical absorption in the step (1) to perform catalytic oxidation on organic sulfur;
(3) Adding a biomass desulfurizer into the fracturing flow-back fluid after catalytic oxidation in the step (2) to reabsorb residual organic sulfur;
(4) And (4) filtering the fracturing flow-back fluid after the biomass desulfurizer in the step (3) is reabsorbed.
2. The method for treating organic sulfur in oil and gas field fracturing flow-back fluid according to claim 1, wherein the chelating agent in step (1) is one or more of aminotrimethylene phosphonic acid, diethylenetriaminepentamethylene phosphonic acid, ethylene diamine tetraacetic acid and hydroxyethylidene diphosphonic acid; the alkali liquor is one or more of sodium hydroxide, potassium hydroxide, urea, polyethylene polyamine, diethylenetriamine, tetraethylenepentamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, diisopropanolamine, diglycolamine, hydroxyethyl hexahydro-s-triazine, 2-chloro-4, 6-dimethoxy-1, 3, 5-triazine and 1,3, 5-tris (dimethylaminopropyl) hexahydro-triazine.
3. The method for treating organic sulfur in oil and gas field fracturing flow-back fluid according to claim 1, wherein the chelating agent is added in an amount of 50mg/L to 500mg/L, and the alkali liquor is added in an amount of 3wt% to 10wt%.
4. The method for treating organic sulfur in fracturing flow-back fluid of oil and gas field according to claim 1, wherein the chemical absorption is performed by stirring the fracturing flow-back fluid, chelating agent and alkali liquor in a sealed tank by a stirring device in step (1), wherein the stirring speed of the stirring device is 500 r/min-1500 r/min, and the stirring time is 5 min-15 min.
5. The method for treating organic sulfur in the fracturing flow-back fluid of the oil and gas field according to claim 1, wherein the step (2) further comprises introducing air into the fracturing flow-back fluid after chemical absorption at a flow rate of 3-5L/min for 10min during the catalytic oxidation.
6. The method for treating organic sulfur in fracturing flowback fluid of oil and gas fields according to claim 1, wherein the modified nano-catalyst in step (2) is a modified ferro-manganese bimetallic oxide, and the amount of the modified nano-catalyst is 1-3 wt%.
7. The method for treating organic sulfur in fracturing flow-back fluid of oil and gas fields according to claim 6, wherein the modified ferro-manganese bi-metal oxide is prepared by the following steps: respectively with Fe (NO) 3 ) 3 ·9H 2 O and Mn (NO) 3 ) 2 ·4H 2 O is an iron and manganese precursor, and polyether amine is used as a template and a surface modifier for calcination; wherein, fe (NO) 3 ) 3 ·9H 2 O and Mn (NO) 3 ) 2 ·4H 2 The mass ratio of O is 4.
8. The method for treating organic sulfur in oil and gas field fracturing flow-back fluid according to claim 1, wherein the amount of the biomass desulfurizer used in the step (3) is 0.5wt% to 1.0wt%.
9. The method for treating organic sulfur in oil and gas field fracturing flow-back fluid according to claim 1, wherein the preparation method of the biomass desulfurizer in the step (3) comprises the following steps: crushing wheat bran; and adding a surfactant into the crushed wheat bran, stirring for 24 hours, filtering the suspension, and then drying the filtered solid in a 65 ℃ drying oven for 12 hours to obtain the biomass desulfurizer.
10. The method for treating organic sulfur in oil and gas field fracturing flow-back fluid, according to claim 9, is characterized in that the surfactant is one or more of dodecyl dimethyl betaine, lauramidopropyl betaine, tetradecyl dimethyl betaine and cocamidopropyl betaine; the using amount of the wheat bran and the surfactant is 1g:20 to 50mL.
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