CN110586141A - Preparation method of Ag-Bi solid solution composite photocatalyst for treating oil field waste liquid - Google Patents
Preparation method of Ag-Bi solid solution composite photocatalyst for treating oil field waste liquid Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000006104 solid solution Substances 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002699 waste material Substances 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000004332 silver Substances 0.000 claims abstract description 26
- 239000012153 distilled water Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000001678 irradiating effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 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 7
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 8
- -1 silver halide Chemical class 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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
- B01J27/08—Halides
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
-
- 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 an Ag-Bi solid solution composite photocatalyst for treating oil field waste liquid, which comprises the following steps: s1, dissolving the bismuth-containing compound in ethylene glycol to obtain a solution A; dissolving a bromine-containing compound and a chlorine-containing compound in the other part of ethylene glycol to obtain a solution B; s2, dropwise adding the solution B into the solution A, uniformly mixing, heating the mixed solution to 140-180 ℃, and reacting at constant temperature for 14-18 h to obtain BiOCl0.5Br0.5(ii) a S3, adding BiOCl0.5Br0.5Dissolving in distilled water, and adding silver-containing compound to obtainSolution C; s4, dissolving another chlorine-containing compound and a bromine-containing compound in distilled water to obtain a solution D, adding the solution D into the solution C, stirring for 1-3 h in the dark, centrifuging, and drying to obtain AgCl0.5Br0.5/BiOCl0.5Br0.5(ii) a S5, adding AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolving in distilled water, and irradiating under full-wavelength xenon lamp for 0.5-2 hr to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5A composite photocatalyst is provided. The catalyst disclosed by the invention has enhanced response to visible light, particularly has high activity in photocatalytic degradation of acrylamide, and can be applied to removal of acrylamide in oil fields.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a catalyst for photocatalytic oxidation in fracturing flowback fluidVisible light responsive Ag-AgCl of enamides0.5Br0.5/BiOCl0.5Br0.5A preparation method of a composite photocatalyst.
Background
In the production process of an oil field, the problem of water logging is often caused due to the heterogeneity of a bottom layer, and water plugging is needed, namely the seepage state of water in a stratum is changed, so that the aims of reducing the water production of the oil field, maintaining the energy of the stratum and improving the final recovery ratio of the oil field are fulfilled. The acrylamide chemical water shutoff agent has selectivity of permeability to oil and water, and the permeability to oil can be reduced by more than 10% at most, and the permeability to water can be reduced by more than 90%. The technical problem is also brought by the treatment fluid discharged from the oil field while the benefit of the oil field is improved. The fracturing flow-back fluid has complex components, contains various organic additives, and has the characteristics of high COD value, high viscosity, high turbidity, high stability and the like. If the fracturing flow-back fluid is directly discharged or reinjected into the stratum, serious pollution is caused to the underground environment and the natural environment, which is contrary to the green technology implemented in China. In order to meet the requirement of green economy, an environment-friendly technology for treating fracturing flow-back fluid is a core technology for continuous exploitation of oil fields.
The photocatalytic oxidation method is an advanced oxidation chemical method, is an environment-friendly treatment technology, and means that a semiconductor photocatalyst can directly utilize solar energy to convert the light energy into chemical energy to promote the degradation of a compound. The action mechanism is that active oxygen species with extremely strong activity are generated under the action of light of a semiconductor catalyst, and the active oxygen species can almost non-selectively oxidize and degrade organic pollutants which are difficult to degrade in the return liquid into non-toxic or low-toxic micromolecule substances and even directly mineralize carbon dioxide, water and other micromolecule carboxylic acids to achieve the harmless purpose. The technology has the advantages of no selectivity, strong oxidation capability, high reaction speed, high treatment efficiency, no secondary pollution and the like. The unique advantages of the photocatalysis technology enable the photocatalysis technology to have huge application prospects in treating fracturing flowback fluid of shale gas, the photocatalyst is the key of the photocatalysis technology, and the development of a novel photocatalyst is the core technology of the photocatalysis technology.
With the development of photocatalytic technology, a series of novel photocatalysts such as bismuth-based, silver-based, phosphorus-based and the like are reported, following the most classical titanium dioxide catalyst. In the development of catalysts, solid solution catalysts are the eye of researchers. Solid solutions refer to materials that are like crystals that produce a homogeneous, compositionally variable, like solution. Solid solution is an effective method for changing the electronic structure and energy band structure of semiconductors, and is formed by two semiconductors with similar radiuses, the same crystal structure and different wide forbidden bands and narrow forbidden bands. When the two substances form a solid solution, the structure of the semiconductor material is not changed, but the electronic structure of the semiconductor is changed due to the change of the constituent elements. Bismuth oxyhalide is a novel bismuth-based semiconductor material and has the characteristics of no toxicity, low price, strong oxidation-reduction capability, stable chemical property, light corrosion resistance and the like. The silver halide-based photocatalyst is also a novel semiconductor material, the activity of the silver halide-based photocatalyst is high, and the simple substance silver has a high-efficiency plasma effect. Based on the advantages of bismuth oxyhalide-based and silver halide-based photocatalysts, halogen atoms in the two photocatalysts meet the condition of forming a solid solution, so that a series of solid solution bismuth oxyhalide catalysts and solid solution silver halide catalysts are developed. The bismuth oxyhalide solid solution catalyst and the silver halide solid solution catalyst reported in the prior literature have stronger performance than the monomer, but the bismuth oxyhalide solid solution catalyst and the silver halide solid solution catalyst have not ideal utilization of solar energy, and the catalytic performance needs to be improved, so that further modification research on the bismuth oxyhalide solid solution catalyst and the silver halide solid solution catalyst is needed.
Disclosure of Invention
The invention aims to provide an Ag-Bi solid solution composite photocatalyst Ag-AgCl for treating oil field waste liquid0.5Br0.5/BiOCl0.5Br0.5The preparation method of (1).
The Ag-AgCl provided by the invention0.5Br0.5/BiOCl0.5Br0.5The preparation method of the composite solid-solution photocatalyst comprises the following steps:
s1, dissolving the bismuth-containing compound in ethylene glycol to obtain a solution A; mixing a bromine-containing compound and a chlorine-containing compound according to a molar ratio of Br: cl ═ 1:1 is dissolved in the other part of glycol to obtain solution B; wherein the amounts of the bromine-containing compound, the chlorine-containing compound and the bismuth-containing compound are equal; in the solution A, the concentration of the bismuth-containing compound is 0.07-0.2 mol/L; in the solution B, the concentrations of the bromine-containing compound and the chlorine-containing compound are the same, and the value range is 0.08-0.2 mol/L.
S2, dropwise adding the solution B into the solution A, stirring for 20-100 min, uniformly mixing, heating the mixed solution to 140-180 ℃, reacting at a constant temperature for 14-18 h, washing the product with absolute ethyl alcohol, and drying at 60-80 ℃ for 5-24 h to obtain BiOCl0.5Br0.5。
S3, adding BiOCl0.5Br0.5Adding into distilled water, stirring for 30min to dissolve completely, adding silver-containing compound, stirring at normal temperature for 20-100 min, BiOCl0.5Br0.5The molar ratio of the silver-containing compound to the silver-containing compound is 2:1, so as to obtain a solution C; in solution C, BiOCl0.5Br0.5The concentration is 0.04-0.1mol/L, and the concentration of the silver-containing compound is 0.02-0.05 mol/L. The silver-containing compound is preferably silver nitrate.
S4, dissolving another chlorine-containing compound and a bromine-containing compound in distilled water to obtain a solution D, wherein the molar ratio of the chlorine-containing compound to the silver-containing compound is 1:1, the molar ratio of the bromine-containing compound to the silver-containing compound is 0.5:1, and the concentration of the chlorine-containing compound in the solution D is 0.02-0.05 mol/L; the concentration of the bromine-containing compound is 0.01 to 0.025 mol/L. Adding the solution D into the solution C, stirring for 1-3 h in the dark, centrifuging, drying at 50-70 ℃ for 8-16 h to obtain AgCl0.5Br0.5/BiOCl0.5Br0.5；
S5, adding AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolving in distilled water, irradiating under full-wavelength xenon lamp for 0.5-2 hr, centrifuging, and drying to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5A composite photocatalyst is provided.
Preferably, the bismuth-containing compound is bismuth nitrate pentahydrate; the bromine-containing compound is potassium bromide or sodium bromide; the chlorine-containing compound is potassium chloride or sodium chloride.
Preferably, the step S5 may be performed as follows: 0.2-0.5 g of AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolving the mixture in 20-50 mL of distilled water, irradiating for 0.5-2h under a full-wavelength xenon lamp, centrifuging, and drying for 8-16 h at 50-70 ℃ to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5A composite photocatalyst is provided.
Ag-AgCl prepared by the method0.5Br0.5/BiOCl0.5Br0.5The composite photocatalyst is used for catalyzing, oxidizing and fracturing acrylamide in the flowback fluid under visible light.
Compared with the prior art, the invention has the advantages that:
first, the Ag-AgCl prepared by the invention0.5Br0.5/BiOCl0.5Br0.5The catalytic activity of the composite solid solution photocatalyst is superior to that of Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5The photocatalytic activity of the monomer. The prepared photocatalyst can excite more photoproduction electrons under visible light, the electron-hole recombination rate is reduced, the photocatalytic activity is obviously improved, especially, the acrylamide oxide has high activity, the preparation method is simple, the condition is mild, the purposes of reducing the cost and simplifying the production flow are achieved, and the photocatalyst can be applied to the acrylamide in the oxidative fracturing flowback fluid.
Secondly, the invention adopts nontoxic components, reduces the harm to the health of human bodies and the ecological environment, optimizes the preparation process of the photocatalyst and achieves the purposes of reducing the cost and simplifying the production flow. The photocatalyst prepared by the method does not need to be added with other chemical reagents and other preparation post-treatment, and the method is simple.
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 is Ag-AgCl prepared in example 10.5Br0.5/BiOCl0.5Br0.5Composite solid solution photocatalyst, Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5An XRD spectrum of (b) isFig. a is a partially enlarged view.
FIG. 2 is Ag-AgCl prepared in example 10.5Br0.5/BiOCl0.5Br0.5TEM spectra of the composite solid solution photocatalyst.
FIG. 3 is Ag-AgCl prepared in example 10.5Br0.5/BiOCl0.5Br0.5Composite solid solution photocatalyst, Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5Degradation efficiency of acrylamide.
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
Ag-AgCl for treating oil field waste liquid0.5Br0.5/BiOCl0.5Br0.5The preparation method of the composite photocatalyst comprises the following steps:
s1, weighing 1.9402g of bismuth nitrate pentahydrate by using an analytical balance, and dissolving the bismuth nitrate pentahydrate into 20mL of ethylene glycol to obtain a solution A; then 0.2982g of potassium chloride and 0.4760g of potassium bromide are dissolved in 60mL of ethylene glycol together to obtain a solution B;
s2, adding the solution B into the solution A, and stirring to react for 30 min; transferring the mixed solution into a reaction kettle to react for 16h at 160 ℃, washing with absolute ethyl alcohol, and drying for 12h at 60 ℃ to obtain BiOCl0.5Br0.5。
S3, mixing 2mmol of BiOCl0.5Br0.5Dissolving in distilled water, stirring for 30min, and adding 1mmol of silver nitrate to obtain solution C.
S4, dissolving 1mmol of potassium bromide and 0.5 mmol of potassium chloride in 30mL of distilled water together to obtain a solution D; adding the solution D into the solution C, and stirring and reacting for 2 hours in a dark place; washing with distilled water for centrifugation, and drying at 60 deg.C for 12 hr to obtain AgCl0.5Br0.5/BiOCl0.5Br0.5。
S5, adding 0.4g of AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolved in 30mL of distilled water inStirring and reacting for 1h under the illumination of 300w xenon lamp, centrifuging and drying for 12h at 60 ℃ to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5。
Example 2
Ag-AgCl for treating oil field waste liquid0.5Br0.5/BiOCl0.5Br0.5The preparation method of the composite photocatalyst comprises the following steps:
s1, dissolving 4mmol of bismuth nitrate pentahydrate in 40mL of ethylene glycol to obtain a solution A, and dissolving 4mmol of sodium bromide and 4mmol of sodium chloride in 40mL of ethylene glycol to obtain a solution B.
S2, adding the solution B into the solution A, and stirring for reaction for 30 min; transferring the mixed solution into a reaction kettle to react for 18h at the temperature of 140 ℃, washing with absolute ethyl alcohol, and drying for 10h at the temperature of 70 ℃ to obtain BiOCl0.5Br0.5。
S3, mixing 2mmol of BiOCl0.5Br0.5Dissolving in distilled water, stirring for 30min, and adding 1mmol of silver nitrate to obtain solution C.
S4, dissolving 1mmol of sodium bromide and 0.5 mmol of sodium chloride into 30mL of distilled water together to obtain a solution D; adding the solution D into the solution C, and stirring and reacting for 1h in a dark place; washing with distilled water for centrifugation, and drying at 50 deg.C for 16h to obtain AgCl0.5Br0.5/BiOCl0.5Br0.5。
S5, adding 0.4g of AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolving in 20mL of distilled water, stirring and reacting for 0.5h under the illumination of a 300w xenon lamp, centrifuging, and drying for 16h at 50 ℃ to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5。
Example 3
Ag-AgCl for treating oil field waste liquid0.5Br0.5/BiOCl0.5Br0.5The preparation method of the composite photocatalyst comprises the following steps:
s1, weighing 1.9402g of bismuth nitrate pentahydrate by using an analytical balance, and dissolving the bismuth nitrate pentahydrate into 20mL of ethylene glycol to obtain a solution A; then 0.2982g of potassium chloride and 0.4760g of potassium bromide are dissolved in 60mL of ethylene glycol together to obtain a solution B;
s2, adding the solution B into the solution A, and stirring to react for 30 min; transferring the mixed solution into a reaction kettle to react for 14h at 180 ℃, washing with absolute ethyl alcohol, and drying for 5h at 80 ℃ to obtain BiOCl0.5Br0.5。
S3, mixing 2mmol of BiOCl0.5Br0.5Dissolving in distilled water, stirring for 30min, and adding 1mmol of silver nitrate to obtain solution C.
S4, dissolving 1mmol of potassium bromide and 0.5 mmol of potassium chloride in 30mL of distilled water together to obtain a solution D; adding the solution D into the solution C, and stirring and reacting for 3 hours in a dark place; washing with distilled water for centrifugation, and drying at 70 deg.C for 8 hr to obtain AgCl0.5Br0.5/BiOCl0.5Br0.5。
S5, adding 0.4g of AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolving in 50mL of distilled water, stirring and reacting for 2h under the illumination of a 300w xenon lamp, centrifuging, and drying for 8h at 70 ℃ to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5。
And (3) performance characterization:
the Ag-AgCl prepared in example 10.5Br0.5/BiOCl0.5Br0.5XRD testing was performed and reacted with Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5The XRD patterns of the two parts are compared, and the result is shown in figure 1. As can be seen from the figure, Ag-AgCl prepared in example 10.5Br0.5/BiOCl0.5Br0.5The diffraction peak corresponding to the crystal face 102, 200 is BiOCl0.5Br0.5The single catalyst has diffraction peaks corresponding to crystal faces 200, 220 and 111 of Ag-AgCl0.5Br0.5The crystal faces of XRD pattern diffraction peaks of the monomer catalyst and the composite catalyst simultaneously contain the crystal faces of two monomer diffraction peaks, which indicates that Ag-AgCl is successfully prepared0.5Br0.5/BiOCl0.5Br0.5A composite photocatalyst is provided.
FIG. 2 is Ag-AgCl prepared in example 10.5Br0.5/BiOCl0.5Br0.5TEM spectra of the composite solid solution photocatalyst. BiOCl can be derived from the figure0.5Br0.5The interplanar spacing of the crystal plane (102) was 0.277nm, Ag-AgCl0.5Br0.5The interplanar spacing of the crystal plane (220) was 0.194nm, Ag-AgCl0.5Br0.5The spacing between crystal planes (200) was 0.272nm and Ag0The interplanar spacing of crystal plane (111) was 0.230 nm. Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5The TEM electron microscope projection image of (1) contains BiOCl0.5Br0.5、Ag-AgCl0.5Br0.5、Ag0The crystal face of (A) indicates that Ag-AgCl is successfully prepared0.5Br0.5/BiOCl0.5Br0.5A composite catalyst.
In addition, Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5、BiOCl0.5Br0.5And Ag-AgCl0.5Br0.5Has a band gap energy of 2.90eV and 2.62eV, respectively, and Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5The band gap energy of the composite was 2.71 eV.
The Ag-AgCl prepared in example 10.5Br0.5/BiOCl0.5Br0.5And Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5And carrying out a test experiment for visible light catalytic degradation of acrylamide. The photocatalytic activity test is characterized by removing oil field acrylamide through oxidation under visible light, wherein a 500W 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 a catalyst is 0.05g each time, the original concentration of an acrylamide solution is 20mg/L, the absorbance after catalytic oxidation is measured by an ultraviolet visible spectrophotometer (model UV-1600PC), and the sampling amount is 2 mL. The results of the experiment are shown in FIG. 3, and it can be seen that Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5The degradation effect of the composite photocatalyst on acrylamide is obviously superior to that of Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5. Acrylamide removal Rate at 4h, BiOCl0.5Br0.5Is 34.8%, Ag-AgCl0.5Br0.5Is 36.9%, Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5The composite photocatalyst is 40.1%. Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5The efficiency of the composite solid solution photocatalyst for removing acrylamide under visible light is Ag-AgCl0.5Br0.5、BiOCl0.5Br0.51.2 times of the total weight of the powder. Further obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5The catalytic activity of the composite photocatalyst is higher than that of Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5。
In conclusion, the invention provides a method for preparing Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5The method for preparing the composite photocatalyst reduces the production cost and simplifies the production process. Compared with the existing Ag-AgCl0.5Br0.5、BiOCl0.5Br0.5The solid solution photocatalyst has better performance, and can catalyze and oxidize acrylamide in the fracturing flow-back fluid under visible light.
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 (8)
1. A preparation method of an Ag-Bi solid solution composite photocatalyst for treating oil field waste liquid is characterized by comprising the following steps:
s1, dissolving the bismuth-containing compound in ethylene glycol to obtain a solution A; dissolving a bromine-containing compound and a chlorine-containing compound which are equal in molar weight to the bismuth-containing compound in another part of ethylene glycol to obtain a solution B;
s2, dropwise adding the solution B into the solution A, uniformly mixing, and then heating the mixed solution to 140EReacting at 180 ℃ for 14-18 h at constant temperature to obtain BiOCl0.5Br0.5；
S3, adding BiOCl0.5Br0.5Dissolving the mixture in distilled water, adding a silver-containing compound, stirring at normal temperature for 20-100 min, and stirring BiOCl0.5Br0.5The molar ratio of the silver-containing compound to the silver-containing compound is 2:1, so as to obtain a solution C;
s4, dissolving another chlorine-containing compound and a bromine-containing compound in distilled water to obtain a solution D, wherein the molar ratio of the chlorine-containing compound to the silver-containing compound is 1:1, and the molar ratio of the bromine-containing compound to the silver-containing compound is 0.5:1, adding the solution D into the solution C, stirring for 1-3 h in a dark place, centrifuging, and drying to obtain AgCl0.5Br0.5/BiOCl0.5Br0.5；
S5, adding AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolving in distilled water, irradiating under full-wavelength xenon lamp for 0.5-2 hr, centrifuging, and drying to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5A composite photocatalyst is provided.
2. The preparation method of the Ag-Bi solid solution composite photocatalyst for treating the oilfield waste liquid as claimed in claim 1, wherein in the solution A, the concentration of the bismuth-containing compound is 0.07-0.2 mol/L; in the solution B, the concentrations of the bromine-containing compound and the chlorine-containing compound are the same, and the value range is 0.08-0.2 mol/L.
3. The method for preparing the Ag-Bi solid solution composite photocatalyst for treating the oilfield waste liquid according to claim 2, wherein the bismuth-containing compound is bismuth nitrate pentahydrate; the bromine-containing compound is potassium bromide or sodium bromide; the chlorine-containing compound is potassium chloride or sodium chloride.
4. The method for preparing the Ag-Bi solid solution composite photocatalyst for treating the oilfield waste liquid according to claim 1, wherein the step S2 is specifically as follows: dropwise adding the solution B into the solution A, stirring for 20-100 min, heating the mixed solution to 160 ℃, reacting at constant temperature for 16h, washing the product with absolute ethyl alcohol, and reacting at 6 DEGDrying for 5-24 h at 0-80 ℃ to obtain BiOCl0.5Br0.5。
5. The method for preparing the Ag-Bi solid solution composite photocatalyst for treating the oilfield waste liquid as claimed in claim 4, wherein the step S3 is specifically as follows: adding BiOCl0.5Br0.5Adding into distilled water, stirring for 30min to dissolve completely, adding silver-containing compound, stirring at room temperature for 60min, and adding BiOCl0.5Br0.5The molar ratio of the silver-containing compound to the silver-containing compound is 2:1, so as to obtain a solution C; in solution C, BiOCl0.5Br0.5The concentration is 0.04-0.1mol/L, and the concentration of the silver-containing compound is 0.02-0.05 mol/L.
6. The method for preparing the Ag-Bi solid solution composite photocatalyst for treating the oilfield waste liquid as claimed in claim 5, wherein in the step S4, the concentration of the chlorine-containing compound in the solution D is 0.02-0.05 mol/L; the concentration of the bromine-containing compound is 0.01 to 0.025 mol/L; the drying temperature is 50-70 ℃, and the drying time is 8-16 h.
7. The method for preparing the Ag-Bi solid solution composite photocatalyst for treating the oilfield waste liquid according to claim 1, wherein the step S5 is specifically as follows: 0.2-0.5 g of AgCl0.5Br0.5/BiOCl0.5Br0.5Dissolving the mixture in 20-50 mL of distilled water, irradiating for 0.5-2h under a full-wavelength xenon lamp, centrifuging, and drying for 8-16 h at 50-70 ℃ to obtain Ag-AgCl0.5Br0.5/BiOCl0.5Br0.5A composite photocatalyst is provided.
8. A method for preparing a composite photocatalyst as claimed in any one of claims 1 to 7, wherein the Ag-AgCl is prepared0.5Br0.5/BiOCl0.5Br0.5The composite photocatalyst is used for catalyzing, oxidizing and fracturing acrylamide in the flowback fluid under visible light.
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| CN111229268A (en) * | 2020-02-13 | 2020-06-05 | 中国石油大学(华东) | Full-spectrum response bismuth oxide/silver phosphate/carbon nanotube sponge composite photocatalyst for well drilling waste liquid treatment, and preparation method and application thereof |
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