CN110918105A - Preparation method of photocatalyst for photocatalytic degradation of waste liquid of oil and gas field - Google Patents
Preparation method of photocatalyst for photocatalytic degradation of waste liquid of oil and gas field Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
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- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 18
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- 239000002243 precursor Substances 0.000 claims abstract description 21
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008103 glucose Substances 0.000 claims abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
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- 238000001035 drying Methods 0.000 claims abstract description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 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 description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- JDXXTKLHHZMVIO-UHFFFAOYSA-N 2-(3-hydroxypropyl)guanidine Chemical compound NC(=N)NCCCO JDXXTKLHHZMVIO-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a photocatalyst for photocatalytic degradation of waste liquid in oil and gas fields, which comprises the following steps: (1) dissolving a bismuth-containing compound in glycerol to obtain a solution A; dissolving a bromine-containing compound and a carbon-containing compound in another portion of glycerol to obtain a solution B; the carbon-containing compound is at least one of glucose, isopropanol and diethylenetriamine; (2) dropwise adding the solution B into the solution A, heating to 40-70 ℃, and stirring for 20-50 min to obtain a mixed solution; (3) heating the mixed solution to 140-180 ℃, and reacting for 14-18 h to obtain a precursor; (4) mixing the precursorAfter drying, adding the precursor into distilled water, hydrolyzing for 21-26 h at the water bath temperature of 40-70 ℃, and drying the hydrolysate to obtain solid powdery CDs-Bi4O5Br2A photocatalyst. CDs-Bi prepared by the invention4O5Br2The composite photocatalyst can catalyze and oxidize refractory organic matters in the oilfield fracturing flow-back fluid under visible light.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to CDs-Bi for degrading refractory organic matters in oil and gas field waste liquid by visible light4O5Br2A preparation method of the photocatalyst.
Background
The development of oil and gas fields is an important technology for promoting the economic progress of China, but the composition of flowback liquid in the exploitation of the oil and gas fields is complex, the main components of the flowback liquid comprise water, crude oil, soluble gas, suspended matters and various chemical additives, and the flowback liquid has the characteristics of high viscosity, high turbidity, high stability and the like. If the flowback liquid is directly discharged, the environment can be seriously polluted, the development of the industry in China is restricted, and the discharge of the flowback liquid is contrary to the green technology implemented in China. The use of the organic boron crosslinked hydroxypropyl guanidine gum fracturing fluid system can generate a large amount of flowback fluid, and if the flowback fluid is discharged without being treated, the flowback fluid can cause serious pollution to the surrounding environment, particularly crops and surface water systems. In the past, most oil and gas fields adopt a pit digging and burying or curing mode to treat return fluid or residual fracturing fluid, but the mode not only wastes resources, but also can generate great pollution or potential pollution to the environment, and the method is eliminated at present. At present, the domestic methods for treating the fracturing flow-back fluid mainly comprise chemical coagulation, chemical oxidation, biological treatment, physical treatment and the like, and can also adopt a plurality of methods for combined treatment according to experience and water quality analysis, although the treated wastewater can reach the standard discharge, the treatment cost of the methods is very high, and water resource waste is caused. The photocatalytic oxidation method is an advanced oxidation chemical method, is an environment-friendly treatment technology, has mild reaction conditions, strong oxidation capacity and wide application range, and has become a research hotspot at home and abroad for treating the organic pollutants which are difficult to degrade in the oil and gas field.
The photocatalysis technology means that the semiconductor photocatalyst can directly utilize solar energy, converts the light energy into chemical energy to promote the degradation of compounds, and utilizes oxidation reaction to mineralize pollutants completely without generating secondary pollution in a non-selective way, so that the photocatalysis technology is an ideal pollutant treatment technology and an energy-saving production technology, and is a core technology which urgently needs to solve the problems of environment and energy in the 21 st century. Among the numerous semiconductor catalysts, new bismuth-rich catalysts are in high interest to researchers. The bismuth-rich catalyst changes the position of a conduction band by controlling the values of halogen atoms and oxygen atoms in bismuth oxyhalide, and regulates the position of the conduction band in the energy band. The modification is an important method for improving the photocatalytic activity, and the main modification methods are as follows: noble metal deposition, semiconductor compounding, ion doping and the like. The forbidden bandwidth of the compound semiconductor is narrowed, and the separation of photo-generated electrons and holes can be effectively promoted, so that the catalytic activity is improved. Bi4O5Br2As typical bismuth-rich bismuth oxyhalide catalysts, there has been interest from researchers, such as Bi in recent years4O5Br2/ZIF-8、g-C3N4/Bi4O5Br2、Bi4O5Br2The composite catalysts such as/BiOBr and the like are reported, the catalytic performance of the composite catalysts still needs to be further improved, and the preparation method steps of the composite catalysts are mostly more complicated.
Disclosure of Invention
The invention aims to provide CDs-Bi for degrading oil and gas field waste liquid by visible light4O5Br2A preparation method of the photocatalyst. The CDs-Bi4O5Br2The composite photocatalyst is used for catalytically degrading organic matters which are difficult to degrade in the oil field waste liquid under the condition of visible light.
CDs-Bi provided by the invention4O5Br2The preparation method of the photocatalyst comprises the following steps:
(1) dissolving a bismuth-containing compound in glycerol to obtain a solution A; dissolving the bromine-containing compound and the carbon-containing compound in another portion of glycerol to obtain a solution B. Wherein the molar ratio of bismuth element of the bismuth-containing compound to bromine element of the bromine-containing compound is 1:1, and the molar ratio of bromine element of the bromine-containing compound to the carbon-containing compound is 1 (0.1-0.4). The carbon-containing compound is at least one of glucose, isopropanol and diethylenetriamine. Preferably, the carbon-containing compound is a mixture of isopropanol and diethylenetriamine in an equal molar ratio. The bismuth-containing compound is bismuth nitrate pentahydrate, and the bromine-containing compound is potassium bromide or sodium bromide.
(2) Dropwise adding the solution B into the solution A, heating to 40-70 ℃, and stirring for 20-50 min to obtain a mixed solution.
(3) Heating the mixed solution to 140-180 ℃, and reacting for 14-18 h to obtain a precursor.
(4) Drying the precursor, adding the precursor into distilled water, wherein the using amount ratio of the precursor to the distilled water is as follows: adding 3-6 g of the precursor into 1-3L of distilled water, hydrolyzing for 21-26 h at the water bath temperature of 40-70 ℃, and drying the hydrolysate to obtain solid powdery CDs-Bi4O5Br2A photocatalyst.
Preferably, when the carbon-containing compound is glucose, step (3) is specifically: heating the mixed solution to 160 ℃, and reacting for 16h at constant temperature to obtain a precursor.
It is also preferable that, when the carbon-containing compound is a mixture of isopropanol and diethylenetriamine in an equal molar ratio, the step (3) is specifically: the mixed solution is heated to 140 ℃ and reacts for 5 hours at constant temperature, then the temperature is increased to 180 ℃ and the reaction is carried out for 10 hours at constant temperature, and a precursor is obtained. In the step (4), the ratio of the mass of the precursor to the volume of the distilled water is 1 g: 400 mL; hydrolyzing at 50 deg.C in water bath for 24h, and drying the hydrolysate at 70 deg.C for 12 hr to obtain CDs-Bi4O5Br2A photocatalyst.
Compared with the prior art, the invention has the advantages that:
firstly, the invention prepares CDs-Bi by a one-step method4O5Br2A composite photocatalyst is provided. The existing method for preparing the composite catalyst mainly has two routes: firstly, preparing various composite components respectively, and then mixing and compounding; secondly, preparing a composite component and then storing the composite componentPreparing another composite component under the condition to obtain the composite. Compared with the prior art, the preparation method has the advantages of simple steps, easily controlled reaction conditions and simplified production process.
The introduction of the carbon-containing compound does not change Bi4O5Br2The crystal shape of (A) is used as a carrier, but the crystal shape can be based on the optical selectivity of the nano-scale quantum effect or different emission traps on the surface of the carbon quantum dot, can generate a plurality of defects and promote Bi under illumination4O5Br2The active group of the compound undergoes a redox photocatalytic reaction, thereby increasing Bi4O5Br2The catalytic activity of (3). CDs-Bi prepared by the invention4O5Br2The catalytic activity of the composite photocatalyst is superior to that of Bi4O5Br2The photocatalytic activity of the monomer. CDs-Bi4O5Br2The maximum absorption wavelength of the catalyst is 527nm, and Bi is4O5Br2The maximum absorption wavelength of the catalyst was 476nm, and CDs-Bi was calculated4O5Br2Has a band gap value of 2.11eV, Bi4O5Br2The band gap value of (2.41 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, and the photocatalytic activity is obviously improved. The organic boron catalyst can be used for catalytic oxidation degradation of organic matters in the oilfield fracturing flow-back fluid under visible light, and especially can be used for degrading organic boron which is difficult to degrade in the oilfield fracturing flow-back fluid.
Thirdly, the CDs-Bi using the invention4O5Br2The composite photocatalyst is prepared by irradiating visible light with the wavelength of more than 420nm by using 20mg/L of organic boron solution and CDs-Bi within 6h4O5Br2The removal rate is over 80 percent, and Bi is4O5Br2The removal rate is 34.50%, and the photocatalytic performance is obviously improved.
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 CDs-Bi prepared in examples 1, 3, 4 and 54O5Br2Photocatalyst and Bi4O5Br2XRD contrast pattern of monomer.
FIG. 2 is the CDs-Bi prepared in example 24O5Br2Ultraviolet-visible diffuse reflectance pattern of photocatalyst.
FIG. 3 is CDs-Bi prepared in example 24O5Br2Band gap diagram of the 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
CDs-Bi for photocatalytic degradation of waste liquid of oil and gas field4O5Br2The preparation method of the photocatalyst comprises the following steps:
0.9701g of bismuth nitrate pentahydrate is weighed by an analytical balance and respectively dissolved in 35mL of glycerol to obtain a solution A; weighing 0.238g of potassium bromide and 0.072g of glucose, and dissolving the potassium bromide and the glucose into another 35mL of glycerol to obtain a solution B; dropwise adding the solution B into the solution A by using a rubber head dropper, heating to 50 ℃, magnetically stirring for 40min, then transferring the mixed solution into a reaction kettle, reacting for 16h at 160 ℃, cleaning, and collecting precipitates to obtain a precursor. The precipitate was dried in an oven at 70 ℃ for 12 h. Weighing 0.5g of dry precursor, adding 200mL of distilled water, hydrolyzing at 50 ℃ in a water bath for 24h, drying the precipitate obtained by hydrolysis at 70 ℃ for 12h to obtain solid powder, namely 20% CDs-Bi4O5Br2A composite photocatalyst is provided. In the catalyst, 20% refers to the molar ratio of glucose to potassium bromide in the reaction raw materials is 0.2:1, and the written percentage is 20%.
Example 2
CDs-Bi for photocatalytic degradation of waste liquid of oil and gas field4O5Br2Photocatalyst and process for producing the sameThe preparation method comprises the following steps:
0.9701g of bismuth nitrate pentahydrate is weighed by an analytical balance and respectively dissolved in 35mL of glycerol to obtain a solution A; 0.238g of potassium bromide, 0.012g of isopropanol and 0.0206g of diethylenetriamine are weighed and dissolved in another 35mL of glycerol to obtain a solution B; dropwise adding the solution B into the solution A by using a rubber head dropper, heating to 50 ℃, magnetically stirring for 40min, transferring the mixed solution into a reaction kettle, reacting for 5h at 140 ℃, heating to 180 ℃, reacting for 10h, cleaning, and collecting precipitates to obtain a precursor. The precipitate was dried in an oven at 70 ℃ for 12 h. Weighing 0.5g of dry precursor, adding 200mL of distilled water, hydrolyzing at 50 ℃ in a water bath for 24h, drying the precipitate obtained by hydrolysis at 70 ℃ for 12h to obtain solid powder, namely 20% CDs-Bi4O5Br2A composite photocatalyst is provided. In the catalyst, 20 percent refers to that the molar ratio of the total mole number of the isopropanol and the diethylenetriamine to the mole number of the potassium bromide in the reaction raw materials is 0.2:1, and the written percentage is 20 percent.
Example 3
CDs-Bi for photocatalytic degradation of waste liquid of oil and gas field4O5Br2The procedure for the preparation of the photocatalyst was the same as in example 1. Except that the amount of glucose was 0.036 g. The final product obtained was 10% CDs-Bi4O5Br2A composite photocatalyst is provided. In the catalyst, 10% refers to the molar ratio of glucose to potassium bromide in the reaction raw materials is 0.1:1, and the written percentage is 10%.
Example 4
CDs-Bi for photocatalytic degradation of waste liquid of oil and gas field4O5Br2The procedure for the preparation of the photocatalyst was the same as in example 1. Except that the amount of glucose was 0.108 g. The final product obtained was 30% CDs-Bi4O5Br2A composite photocatalyst is provided. In the catalyst, 30% refers to the molar ratio of glucose to potassium bromide in the reaction raw materials is 0.3:1, and the written percentage is 30%.
Example 5
Be used for photocatalysis degradation oil gas field uselessLiquid CDs-Bi4O5Br2The procedure for the preparation of the photocatalyst was the same as in example 1. Except that the amount of glucose was 0.144 g. The final product obtained was 40% CDs-Bi4O5Br2A composite photocatalyst is provided. In the catalyst, 40% refers to that the molar ratio of glucose to potassium bromide in the reaction raw materials is 0.4:1, and the written percentage is 40%.
FIG. 1 shows CDs-Bi prepared in examples 1, 3, 4 and 54O5Br2Photocatalyst and Bi4O5Br2XRD contrast pattern of monomer. As can be seen from the figure, CDs-Bi4O5Br2In the photocatalyst, addition of the carbon-containing compound did not change Bi4O5Br2The crystal form of (1) which is used only as a carrier, is doped in a relatively small amount, and the photocatalytic active substance is Bi4O5Br2。
FIG. 2 is the CDs-Bi prepared in example 24O5Br2Ultraviolet-visible diffuse reflectance pattern of photocatalyst. It can be seen that4O5Br2Monomer ratio, CDs-Bi4O5Br2The absorption band edge of the composite photocatalyst is red shifted, the maximum absorption wavelength is 527nm, and Bi is4O5Br2The maximum absorption wavelength is 476nm, and the CDs-Bi is calculated4O5Br2Has a band gap value of 2.11eV, Bi4O5Br2The band gap value of (2.41 eV), the lower the band gap value of the composite catalyst, the higher the catalytic activity. The corresponding band gap diagram is shown in fig. 3.
CDs-Bi prepared in examples 1 and 24O5Br2The photocatalyst is used for carrying out photocatalytic performance test and selecting the existing Bi4O5Br2Monomer, Bi4O5Br2/ZIF-8 composite catalyst, CQDs/Bi prepared by other preparation methods4O5Br2Composite catalyst these three catalysts were used as comparative samples. Wherein, Bi4O5Br2the/ZIF-8 composite catalyst is from Master research student of Taiyuan university of technologyPaper "ZIF-8 reducibility to weak light (Bi)4O5Br2And Ag3PO4) Performance enhancement study of photocatalyst preparation method in page 18 of text. CQDs/Bi4O5Br2The composite catalyst is derived from the Master research and development academic paper CQDs/Bi of the Tai Yuan engineering university4O5Br2The compound is prepared by the preparation method of page 11 in the text of research on the photocatalytic degradation of resorcinol in water and the in vitro biological effect of lung cancer cells. The catalysts are tested for removing organic boron waste liquid in the oil field under visible light. A500W xenon lamp is used as a light source, visible light in the range of 420-780 nm is obtained through an optical filter, the dosage of the catalyst is 0.05g each time, the original concentration of the organic boron is 20mg/L, the total organic carbon content of the solution before illumination and after illumination for 6 hours is respectively measured, the organic boron removal rate is calculated through the change of the total organic carbon content, and the experimental result is shown in Table 1. The reduction of the total organic carbon content indicates that the organic boron is thoroughly decomposed into inorganic small molecules such as carbon dioxide, water and the like. Thus, the CDs-Bi of the present invention was demonstrated4O5Br2The composite catalyst can completely mineralize and decompose the organic boron into non-toxic and harmless inorganic small molecules under the condition of visible light.
TABLE 1 removal Rate data for various catalysts for organoboron 6h
| Example 1 | Example 2 | Bi4O5Br2 | Bi4O5Br2/ZIF-8 | CQDs/Bi4O5Br2 |
| 80.89％ | 85.46％ | 34.50％ | 45.13％ | 54.78％ |
As can be seen from Table 1, CDs-Bi of the present invention4O5Br2The efficiency of the photocatalyst in removing the organic boron under visible light is Bi4O5Br2More than 2 times of the monomer. And CDs-Bi4O5Br2The organic boron removal rate of the photocatalyst is obviously higher than that of Bi in the prior art4O5Br2ZIF-8 and CQDs/Bi4O5Br2The composite catalyst is 20-30% higher. Therefore, the photocatalyst has better visible light catalytic activity, and can be used for visible light catalytic degradation of refractory organic matters in waste liquid of oil and gas fields.
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 (10)
1. CDs-Bi for photocatalytic degradation of waste liquid of oil and gas field4O5Br2The preparation method of the photocatalyst is characterized by comprising the following steps:
(1) dissolving a bismuth-containing compound in glycerol to obtain a solution A; dissolving a bromine-containing compound and a carbon-containing compound in another portion of glycerol to obtain a solution B;
(2) dropwise adding the solution B into the solution A, heating to 40-70 ℃, and stirring for 20-50 min to obtain a mixed solution;
(3) heating the mixed solution to 140-180 ℃ and reacting for 14-18 h to obtain a precursor;
(4) drying the precursor, adding the precursor into distilled water, hydrolyzing at 40-70 ℃ in a water bath for 21-26 h, and drying the hydrolysate to obtain solid powdery CDs-Bi4O5Br2A photocatalyst.
2. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 14O5Br2The preparation method of the photocatalyst is characterized in that in step S1, the molar ratio of bismuth element of the bismuth-containing compound to bromine element of the bromine-containing compound is 1:1, and the molar ratio of bromine element of the bromine-containing compound to the carbon-containing compound is 1 (0.1-0.4).
3. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 24O5Br2The preparation method of the photocatalyst is characterized in that the carbon-containing compound is at least one of glucose, isopropanol and diethylenetriamine.
4. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 34O5Br2The preparation method of the photocatalyst is characterized in that the carbon-containing compound is a mixture of isopropanol and diethylenetriamine in an equal molar ratio.
5. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 44O5Br2The preparation method of the photocatalyst is characterized in that the step (3) is specifically as follows: the mixed solution is heated to 140 ℃ and reacts for 5 hours at constant temperature, then the temperature is increased to 180 ℃ and the reaction is carried out for 10 hours at constant temperature, and a precursor is obtained.
6. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 34O5Br2The preparation method of the photocatalyst is characterized in that when the carbon-containing compound is glucose, the step (3) is specifically as follows: heating the mixed solution to 160 ℃, and reacting for 16h at constant temperature to obtain a precursor.
7. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 14O5Br2The preparation method of the photocatalyst is characterized in that the bismuth-containing compound is bismuth nitrate pentahydrate, and the bromine-containing compound is potassium bromide or sodium bromide.
8. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 14O5Br2The preparation method of the photocatalyst is characterized in that in the step (4), the ratio of the mass of the precursor to the volume of the distilled water is (3-6 g): (1-3L).
9. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 54O5Br2The preparation method of the photocatalyst is characterized in that in the step (4), the ratio of the mass of the precursor to the volume of the distilled water is 1 g: 0.4L.
10. The CDs-Bi for photocatalytic degradation of oil and gas field effluents as claimed in claim 94O5Br2The preparation method of the photocatalyst is characterized in that in the step (4), the hydrolysis product is dried at 70 ℃ for 12 to obtain CDs-Bi after being hydrolyzed for 24 hours at the water bath temperature of 50 DEG C4O5Br2A photocatalyst.
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| CN112264059A (en) * | 2020-11-18 | 2021-01-26 | 安徽汇泽通环境技术有限公司 | Preparation method of acid orange 7 pollutant photodegradation composite photocatalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011048128A2 (en) * | 2009-10-22 | 2011-04-28 | Basf Se | Photocatalyst having increased daylight activity |
| CN106902810A (en) * | 2017-03-10 | 2017-06-30 | 湖南大学 | Individual layer Bismuth tungstate nano-sheet composite photo-catalyst of carbon quantum dot modification and its preparation method and application |
| CN107597151A (en) * | 2017-11-09 | 2018-01-19 | 西南石油大学 | The preparation method of Bi/Bi4O5X2 (X=Br, I) photochemical catalyst of organic boron is aoxidized under a kind of visible ray |
| CN107737600A (en) * | 2017-11-09 | 2018-02-27 | 西南石油大学 | A kind of ultra-thin Bi4O5Br2The preparation method and application of photochemical catalyst |
| CN108686658A (en) * | 2018-05-22 | 2018-10-23 | 三明学院 | A kind of C-QDs-Fe2O3/TiO2Composite photo-catalyst and preparation method thereof |
-
2019
- 2019-12-03 CN CN201911219971.4A patent/CN110918105A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011048128A2 (en) * | 2009-10-22 | 2011-04-28 | Basf Se | Photocatalyst having increased daylight activity |
| CN106902810A (en) * | 2017-03-10 | 2017-06-30 | 湖南大学 | Individual layer Bismuth tungstate nano-sheet composite photo-catalyst of carbon quantum dot modification and its preparation method and application |
| CN107597151A (en) * | 2017-11-09 | 2018-01-19 | 西南石油大学 | The preparation method of Bi/Bi4O5X2 (X=Br, I) photochemical catalyst of organic boron is aoxidized under a kind of visible ray |
| CN107737600A (en) * | 2017-11-09 | 2018-02-27 | 西南石油大学 | A kind of ultra-thin Bi4O5Br2The preparation method and application of photochemical catalyst |
| CN108686658A (en) * | 2018-05-22 | 2018-10-23 | 三明学院 | A kind of C-QDs-Fe2O3/TiO2Composite photo-catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 金海燕: ""QDs/Bi4O5Br2复合物对水中间苯二酚的光催化降解及对肺癌细胞的体外生物学效应研究"", 《中国优秀博硕士学位论文全文全文数据库医药卫生科技辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264059A (en) * | 2020-11-18 | 2021-01-26 | 安徽汇泽通环境技术有限公司 | Preparation method of acid orange 7 pollutant photodegradation composite photocatalyst |
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