CN111482187A - Preparation method of bismuth-rich composite photocatalyst for treating oilfield flowback fluid - Google Patents
Preparation method of bismuth-rich composite photocatalyst for treating oilfield flowback fluid Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 22
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000012530 fluid Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 48
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 30
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001103 potassium chloride Substances 0.000 claims abstract description 15
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
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- 239000000413 hydrolysate Substances 0.000 claims abstract description 6
- 108010009736 Protein Hydrolysates Proteins 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
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- 230000007062 hydrolysis Effects 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 239000000203 mixture Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 25
- 239000007788 liquid Substances 0.000 abstract description 9
- 229920013818 hydroxypropyl guar gum Polymers 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229940073609 bismuth oxychloride Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
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- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a preparation method of a bismuth-rich composite photocatalyst for treating oilfield flowback fluid, which comprises the following steps: s1, dissolving bismuth nitrate pentahydrate in glycerol, and dissolving potassium chloride in the other part of glycerol; s2, dropwise adding the potassium chloride solution into the bismuth nitrate pentahydrate solution, heating to 40-70 ℃, and stirring for 30-50 min; s3, reacting the reaction liquid at the temperature of 140-160 ℃ for 15-16h, filtering and drying to obtain a precursor; s4, adding the precursor into distilled water, heating in a water bath at 40-70 ℃, adjusting the pH of the water solution to 8-10 by using 20% ammonia water, carrying out hydrolysis reaction for 12-20h, filtering to obtain a hydrolysate, and drying; s5, calcining the dried hydrolysate in a muffle furnace at the constant temperature of 400-600 ℃ for 2-5h to obtain Bi3O4Cl/Bi24O31Cl10A composite photocatalyst is provided. The catalyst is compared with the prior Bi3O4Cl、Bi24O31Cl10The photocatalyst has better performance, and the catalyst can catalyze and oxidize the hydroxypropyl guar gum waste liquid in the oilfield fracturing flow-back fluid under visible light.
Description
Technical Field
The invention relates to the technical field of oil and gas field waste liquid treatment, in particular to a preparation method of a bismuth-rich composite photocatalyst for treating oil field flowback liquid through photocatalytic oxidation.
Background
The acid fracturing technology is an important technology for improving the yield and injection of an oil field, and is characterized in that a certain reagent is prepared into fracturing liquid with certain viscosity by a chemical method, and then the viscous liquid is injected into a stratum at high speed by using a high-pressure pump set. When the injection speed of the pump is higher than the absorption speed of the stratum, the stratum can form cracks, and oil and gas in a reservoir in the stratum are driven out under a certain acting force, so that the oil field recovery rate is improved. Meanwhile, the fracturing injected in oil and gas exploitation can also be discharged back to the ground, and the fracturing flow-back fluid has the characteristics of complex components, high viscosity, high turbidity, high stability and the like. The characteristics of the fracturing flow-back fluid determine the difficulty of treating the fracturing flow-back fluid, if the fracturing flow-back fluid is not directly discharged, great environmental pollution is caused to an oil field, and the development of the oil field is also restricted, so that the method for treating the fracturing flow-back fluid of the oil field by adopting the high-efficiency and environment-friendly method is the research technical core.
Since 1977, Carey J.H. by use of TiO2The photocatalyst degrades polychlorinated biphenyl, and the photocatalysis is applied to degrade organic matters for the first time, so that the photocatalyst becomes a pioneer for treating environmental problems by a photocatalysis technology. In recent years, bismuth oxyhalide rich in bismuth has been favored by researchers as a novel semiconductor photocatalytic material because of its properties such as high redox ability, chemical stability, and resistance to photo-corrosion. The bismuth-rich bismuth oxyhalide can be used as a photocatalyst for treating organic matters in oilfield fracturing flowback fluid. The bismuth oxyhalide rich in bismuth is used for regulating and controlling the position of a conduction band in an energy band by changing the position of the conduction band through controlling the values of halogen atoms and oxygen atoms in bismuth oxyhalide. BixOyClZIs a bismuth-rich bismuth oxychloride catalyst, such as Bi3O4Cl、Bi12O17Cl2、Bi24O31Cl10The method is reported successively, but the single bismuth-rich bismuth oxychloride has a fixed energy band structure and high electron-hole recombination efficiency, cannot improve the catalytic performance, and seriously restricts the application space of the bismuth oxychloride.
Disclosure of Invention
The invention aims to improve single bismuth-richThe technical problems of fixed energy band structure, higher electron-hole recombination efficiency and limited photocatalytic performance of bismuth oxychloride provide a simple and efficient preparation method of Bi3O4Cl/Bi24O31Cl10A method for preparing a composite photocatalyst. The photocatalyst performance of the composite photocatalyst is remarkably improved, and the composite photocatalyst can be used for photooxidation treatment of organic matters in oilfield fracturing flowback fluid.
The invention provides a preparation method of a bismuth-rich composite photocatalyst for treating oilfield flowback fluid, which comprises the following steps:
s1, dissolving bismuth nitrate pentahydrate in glycerol, and dissolving potassium chloride in another part of glycerol, wherein the molar weight of the bismuth nitrate pentahydrate and the molar weight of the potassium chloride are equal, the concentration of the bismuth nitrate pentahydrate in the glycerol is 0.06-0.15 mol/L, and the concentration of the potassium chloride in the glycerol is 0.06-0.15 mol/L.
S2, dropwise adding the potassium chloride solution into the bismuth nitrate pentahydrate solution, heating to 40-70 ℃, and stirring for 30-50 min;
s3, transferring the reaction liquid obtained in the step S2 into a reaction kettle, reacting at the constant temperature of 140 ℃ and 160 ℃ for 15-16h, filtering out a product, and drying to obtain a precursor;
s4, adding the precursor into distilled water, heating in a water bath at 40-70 ℃, starting stirring, adjusting the pH of the aqueous solution to 8-10 by using 20% ammonia water, then carrying out hydrolysis reaction at constant temperature for 12-20h, filtering to obtain a hydrolysate, and drying at 60-80 ℃;
s5, calcining the dried hydrolysis product in a muffle furnace at the constant temperature of 400-3O4Cl/Bi24O31Cl10A composite photocatalyst is provided.
Preferably, in step S2, the mixture is heated to 50 ℃ and stirred for 40 min.
Preferably, in step S3, the temperature is raised to 145 ℃ in a reaction kettle, the reaction is performed for 16 hours at a constant temperature, and after natural cooling, the product is filtered out and dried at 70 ℃ to obtain a precursor.
Preferably, in step S4, 2 to 5g of the precursor is added into 0.4 to 1L of distilled water, the mixture is heated at a water bath temperature of 50 ℃, the pH of the aqueous solution is adjusted to 9 by 20% ammonia water, then the mixture is hydrolyzed at a constant temperature for 16 hours, and the hydrolysate is obtained by filtration and dried at 70 ℃ for 12 hours.
Preferably, in step S5, the dried hydrolysate is calcined in a muffle furnace at 400 ℃ for 2h and then at 500 ℃ for 3h to obtain Bi3O4Cl/Bi24O31Cl10A composite photocatalyst is provided.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the bismuth-rich composite photocatalyst provided by the invention has the advantages that the process is simple, the cost is low, nontoxic and harmless raw material components are adopted, the harm to the health of a human body and the ecological environment is reduced, the environment-friendly technology is achieved, and the control and large-scale production are easy; the obtained photocatalyst has strong stability and high activity.
(2) The composite photocatalyst Bi of the invention3O4Cl/Bi24O31Cl10Relative to Bi3O4Cl、Bi24O31Cl10The monomer catalyst has stronger light absorption performance, greatly improves the utilization rate of visible light, has obvious effect and huge application space particularly in the aspect of processing the hydroxypropyl guar gum of the shale gas flow-back fluid, and has the removal rate of more than 90 percent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 shows Bi of example 13O4Cl/Bi24O31Cl10XRD spectrum of the composite photocatalyst.
FIG. 2 shows Bi in example 13O4Cl/Bi24O31Cl10Environmental scanning electron microscope image of composite photocatalyst
FIG. 3 shows Bi in example 13O4Cl/Bi24O31Cl10Transmission electron microscopy of the composite photocatalyst.
FIG. 4 shows Bi in example 13O4Cl/Bi24O31Cl10Ultraviolet-visible diffuse reflectance pattern of composite photocatalyst.
FIG. 5 shows Bi in example 13O4Cl/Bi24O31Cl10Band gap diagram of composite photocatalyst.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
Weighing 1.455g of bismuth nitrate pentahydrate by using an analytical balance, respectively dissolving the weighed bismuth nitrate pentahydrate in 30m L glycerol, weighing 0.223g of potassium chloride in 35m L glycerol, adding a potassium chloride solution into the glycerol solution of the bismuth nitrate pentahydrate by using a rubber head dropper, heating to 50 ℃, carrying out constant-temperature magnetic stirring for 40min, transferring the mixed solution into a reaction kettle, reacting for 16h in an oven at 160 ℃, naturally cooling, filtering, collecting precipitate, drying the precipitate in an oven at 70 ℃ for 12h to obtain a precursor, weighing 0.3g of the precursor, adding 100m L distilled water into the precursor, starting stirring, heating at 70 ℃ in a water bath, regulating the pH value of the hydrolyzed solution to 9 by using 20% of ammonia water, carrying out constant-temperature stirring hydrolysis for 16h, measuring the pH value of the hydrolyzed solution once every 2h in the hydrolysis process, if the pH value is changed, supplementing the ammonia water again to regulate the pH value to 9, filtering after the hydrolysis is finished, drying the hydrolyzed product at 70 ℃ for 12h, calcining the dried hydrolyzed product in a muffle furnace at 600 ℃ to obtain solid Bi powder, and calcining the Bi powder at 3h to obtain the dried hydrolyzed product3O4Cl/Bi24O31Cl10A composite photocatalyst.
FIG. 1 shows Bi prepared in example 13O4Cl/Bi24O31Cl10Composite photocatalyst and catalyst Bi3O4Cl、Bi24O31Cl10XRD spectrum of (1). Wherein, figure 1a is XRD pattern of photocatalyst at 2 theta 5-70 DEG and figure 1b is XRD pattern of photocatalyst at 2 theta 8-35 deg. After comparison, the catalyst Bi3O4Cl、Bi24O31Cl10Appearance of diffraction peaks of crystal planesAll in accordance with the position of the diffraction peak of the standard card. From the analysis in FIG. 1b, Bi3O4Cl/Bi24O31Cl10The diffraction peak 2 theta values of the catalyst are 9.6 degrees, 29.3 degrees, 29.8 degrees, 31.4 degrees and 31.8 degrees, and are corresponding to Bi3O4 Cl catalyst 002, 114, -114, 020, 022 crystal face, Bi3O4Cl/Bi24O31Cl10The diffraction peak 2 theta values of the catalyst are 10.8 degrees, 28.9 degrees, 30.2 degrees and 32.0 degrees, and are corresponding to Bi24O31Cl10Crystal planes of catalysts 102, 304, 213, 306, Bi3O4Cl/Bi24O31Cl10Catalyst simultaneous presence of Bi3O4Cl、Bi24O31Cl10Diffraction peaks of the catalyst, indicating successful preparation of Bi3O4Cl/Bi24O31Cl10And (3) compounding a catalyst.
FIG. 2 is an environmental scanning electron microscope for observing Bi3O4Cl/Bi24O31Cl10The morphology of the composite photocatalyst is shown, and Bi can be observed from the graph3O4Cl/Bi24O31Cl10The shape after hydrolysis and calcination is lamellar. In order to further study the crystal structure of the prepared composite catalyst, transmission electron microscopy was used for observation and analysis. From FIG. 3, it can be seen that Bi is produced3O4Cl/Bi24O31Cl10The inter-crystal distance between the medium 002 crystal face and Bi in the standard card is 0.921nm3O4The 002 crystal faces of the Cl catalyst have approximately the same crystal spacing, and Bi3O4Cl/Bi24O31Cl10The crystal spacing between the middle 102 crystal plane and Bi in the standard card is 0.812nm24O31Cl10The 002 crystal faces of the catalyst had roughly the same spacing, indicating that Bi was produced3O4Cl/Bi24O31Cl10The catalyst was a composite catalyst, which is consistent with the results of XRD pattern analysis.
FIG. 4 shows Bi according to the present invention3O4Cl/Bi24O31Cl10Composite photocatalystUltraviolet-visible diffuse reflectance pattern of (a). Fig. 5 is a band gap diagram. Bi3O4Cl/Bi24O31Cl10The maximum absorption wavelength of the catalyst is 487nm, Bi3O4The maximum absorption wavelength of the Cl catalyst is 450nm, and Bi24O31Cl10The maximum absorption wavelength of the catalyst was 439 nm. The band gap energy of the photocatalyst is closely related to the light absorption performance, so that the light absorption performance of the photocatalyst can be analyzed through an ultraviolet visible diffuse reflection spectrum, and further the band gap energy of the photocatalytic material can be analyzed. According to the formula
ahv＝A(hv-Eg)n/2
Wherein a is the light absorption coefficient/cm-1(ii) a h is the Planck constant/eV · s; v is photon frequency/Hz; a is a constant; egThe value of n depends on the transition type of the semiconductor material, namely the forbidden bandwidth/eV, and when the semiconductor material is a direct transition type, n is 1; when the semiconductor material is of the indirect transition type, n is 4. Bi3O4Cl/Bi24O31Cl10Is an indirect transition semiconductor, so n-4, according to the formula ahv-a (hv-E)g)2The coordinate value of the intersection point of the extension line of the straight line part of the measured absorption wavelength and the X axis can determine the band gap energy of the catalyst photocatalyst. From the graphs 4 and 5, Bi3O4Cl/Bi24O31Cl10Has a band gap value of 2.25eV, Bi3O4The band gap value of Cl is 2.44eV, Bi24O31Cl10The band gap value of (2.49 eV), the lower the band gap value of the composite catalyst, the higher the catalytic activity. The prepared photocatalyst can excite more photoproduction electrons under visible light, the electron-hole recombination rate is reduced, the photocatalytic activity is obviously improved, and the photocatalyst can be applied to oxidizing the hydroxypropyl guar gum solution in the oil field.
Example 2
Weighing 1.455g of bismuth nitrate pentahydrate by using an analytical balance, respectively dissolving the weighed bismuth nitrate pentahydrate into 30m L glycerol, weighing 0.223g of potassium chloride, dissolving the weighed potassium chloride into 35m L glycerol, adding a potassium chloride solution into the glycerol solution of the bismuth nitrate pentahydrate by using a rubber-tipped dropper, heating to 70 ℃, magnetically stirring at a constant temperature for 30min, and transferring the mixed solution to a containerReacting in a reaction kettle at 145 ℃ in an oven for 16h, naturally cooling, filtering, collecting precipitate, drying the precipitate in the oven at 70 ℃ for 12h to obtain a precursor, weighing 0.5g of the precursor, adding 100m L of distilled water, heating in a water bath at 50 ℃, regulating the pH value of a hydrolysis solution to 10 by using 20% ammonia water, stirring at constant temperature for hydrolysis reaction for 16h, measuring the pH value of the hydrolysis solution every 2 hours in the hydrolysis process, if the pH value is changed, supplementing the ammonia water again to regulate the pH value to 10, filtering after the hydrolysis is finished to obtain a hydrolysate, drying at 70 ℃ for 12h, calcining the dried hydrolysate in a muffle furnace at 400 constant temperature for 2h, calcining at 500 ℃ for 3h to obtain Bi3O4Cl/Bi24O31Cl10A composite photocatalyst is provided.
Bi prepared in example 1 and example 2 is added3O4Cl/Bi24O31Cl10Composite photocatalyst and catalyst Bi3O4Cl、Bi24O31Cl10The method comprises the steps of carrying out visible light photocatalytic activity test, adopting a hydroxypropyl guar gum aqueous solution as simulated oil field waste liquid, wherein the original concentration of the hydroxypropyl guar gum is 10 mg/L, adopting a 500W xenon lamp as a light source, adopting full wavelength, and the concentration content of a catalyst in the waste liquid is 0.5 g/L, measuring the concentration change of organic matters in the waste liquid before and after illumination by an ultraviolet visible spectrophotometer (UV-1600PC), and obtaining a test result shown in Table 13O4Cl/Bi24O31Cl10The efficiency of removing hydroxypropyl guar gum under illumination is Bi respectively3O4Cl、Bi24O31Cl101.7, 1.4 times, or even higher than the monomer. Thus, Bi prepared by the present invention3O4Cl/Bi24O31Cl10The composite photocatalyst has better catalytic performance and can be applied to the field of treating waste liquid of oil fields by a photocatalytic oxidation method.
TABLE 1 degradation efficiency of various photocatalysts for degrading oilfield organics
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a bismuth-rich composite photocatalyst for treating oilfield flowback fluid is characterized by comprising the following steps:
s1, dissolving bismuth nitrate pentahydrate in glycerol, and dissolving potassium chloride in the other part of glycerol, wherein the molar weight of the bismuth nitrate pentahydrate is equal to that of the potassium chloride;
s2, dropwise adding the potassium chloride solution into the bismuth nitrate pentahydrate solution, heating to 40-70 ℃, and stirring for 30-50 min;
s3, transferring the reaction liquid obtained in the step S2 into a reaction kettle, reacting at the constant temperature of 140 ℃ and 160 ℃ for 15-16h, filtering out a product, and drying to obtain a precursor;
s4, adding the precursor into distilled water, heating at the water bath temperature of 40-70 ℃, adjusting the pH of the aqueous solution to 8-10 by using 20% ammonia water, then carrying out hydrolysis reaction at constant temperature for 12-20h, filtering to obtain a hydrolysate, and drying at the temperature of 60-80 ℃;
s5, calcining the dried hydrolysis product in a muffle furnace at the constant temperature of 400-3O4Cl/Bi24O31Cl10A composite photocatalyst is provided.
2. The method for preparing the bismuth-rich composite photocatalyst for treating oilfield flowback fluid as defined in claim 1, wherein in the step S1, the concentration of bismuth nitrate pentahydrate in glycerol is 0.06-0.15 mol/L, and the concentration of potassium chloride in glycerol is 0.06-0.15 mol/L.
3. The method for preparing the bismuth-rich composite photocatalyst for treating oilfield flowback fluid as claimed in claim 2, wherein in step S2, the bismuth-rich composite photocatalyst is heated to 50 ℃ and stirred for 40 min.
4. The preparation method of the bismuth-rich composite photocatalyst for treating oilfield flowback fluid as claimed in claim 3, wherein in step S3, the temperature is raised to 145 ℃ in a reaction kettle, the reaction is carried out for 16h at constant temperature, and after natural cooling, the product is filtered out and dried at 70 ℃ to obtain a precursor.
5. The method for preparing the bismuth-rich composite photocatalyst for treating oilfield flowback fluid as claimed in claim 3, wherein in step S4, 2-5g of the precursor is added into 0.4-1L of distilled water, the mixture is heated at 50 ℃ of water bath, the pH of the aqueous solution is adjusted to 9 by 20% ammonia water, then the mixture is hydrolyzed at constant temperature for 16h, and the hydrolysate is obtained by filtering and dried at 70 ℃ for 12 h.
6. The method for preparing the bismuth-rich composite photocatalyst for treating oilfield flowback fluid according to claim 1, wherein in step S5, the dried hydrolysate is calcined in a muffle furnace at a constant temperature of 400 ℃ for 2h, and then at a constant temperature of 500 ℃ for 3h to obtain Bi3O4Cl/Bi24O31Cl10A composite photocatalyst is provided.
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Inventor after: Zhang Xu Inventor after: Yang Bo Inventor after: Zhang Ying Inventor after: Ye Changqing Inventor after: Liang Bing Inventor after: Sun Fengjing Inventor after: Wang Jie Inventor after: Lv Hong Inventor after: Liu Weihua Inventor after: Yang Ping Inventor after: Jiao Guoying Inventor after: Ding Zhongpei Inventor after: Shi Shuqiang Inventor after: Wang Jun Inventor after: Huang Xiaoliang Inventor after: Wang Qi Inventor before: Zhang Xu Inventor before: Yang Bo Inventor before: Zhang Ying Inventor before: Li Zuyou Inventor before: Ye Changqing Inventor before: Liang Bing Inventor before: Sun Fengjing Inventor before: Wang Jie Inventor before: Lv Hong Inventor before: Liu Weihua Inventor before: Yang Ping Inventor before: Jiao Guoying Inventor before: Ding Zhongpei Inventor before: Shi Shuqiang Inventor before: Wang Jun Inventor before: Huang Xiaoliang Inventor before: Wang Qi |