CN113189268A - Method for degrading organic pollutants by catalytic ozone - Google Patents
Method for degrading organic pollutants by catalytic ozone Download PDFInfo
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- CN113189268A CN113189268A CN202110642848.4A CN202110642848A CN113189268A CN 113189268 A CN113189268 A CN 113189268A CN 202110642848 A CN202110642848 A CN 202110642848A CN 113189268 A CN113189268 A CN 113189268A
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- oxalic acid
- ceo
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- ozone
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 12
- 230000000593 degrading effect Effects 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 title abstract description 32
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 376
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 125
- 239000003054 catalyst Substances 0.000 claims abstract description 101
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 65
- 238000006731 degradation reaction Methods 0.000 claims abstract description 44
- 230000015556 catabolic process Effects 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 14
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims abstract description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011218 binary composite Substances 0.000 claims abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 56
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 40
- 230000000694 effects Effects 0.000 claims description 36
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 33
- 238000002474 experimental method Methods 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 238000002386 leaching Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 230000007246 mechanism Effects 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- 230000033558 biomineral tissue development Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 241000894007 species Species 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
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- 238000003756 stirring Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000012512 characterization method Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
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- 238000011835 investigation Methods 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
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- 238000000746 purification Methods 0.000 claims 1
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- 238000006385 ozonation reaction Methods 0.000 abstract description 19
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 5
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- 150000003254 radicals Chemical class 0.000 description 6
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- 238000006555 catalytic reaction Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 102000019197 Superoxide Dismutase Human genes 0.000 description 4
- 108010012715 Superoxide dismutase Proteins 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 4
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- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
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- 230000002195 synergetic effect Effects 0.000 description 3
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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Abstract
The invention discloses a method for degrading organic pollutants by catalyzing ozone, which comprises the following steps: adopts a hydrothermal-roasting method to synthesize a copper-cerium binary composite catalyst (CuO-CeO)2) And characterized by X-ray diffractometry (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). Using oxalic acid as model compound and CuO-CeO2Is carried out continuouslyThe oxalic acid removal rate reaches 97.66 percent after 25min and is far higher than O in a flow catalytic ozonation test3(2.66％)、CuO/O3(7.38%) and CeO2/O3(5.47%) and other systems have the oxalic acid removal rate of 95.21%; CuO-CeO2/O3The optimal reaction conditions of the system are as follows: the mass concentration of ozone is 30mg/L, the adding amount of the catalyst is 0.20g/L, and the pH value of the solution is 7; CuO-CeO2More than 90% of oxalic acid can be removed after 5 times of recycling, and the oxalic acid has excellent stability and reusability. CuO-CeO2Catalytic O3Hydroxyl radicals are produced but not dominantly in the process, singlet oxygen being the major active oxidizing species responsible for the degradation of oxalic acid.
Description
Technical Field
The invention relates to the technical field of organic matter degradation experiments, in particular to a method for degrading organic pollutants by catalyzing ozone.
Background
The catalytic ozonization technology mainly depends on a catalyst to improve the amount of active free radicals generated by ozone, has simple process, easy operation and low investment cost, and is an advanced oxidation technology with good application prospect. Most of the commonly used catalytic ozonation techniques rely on hydroxyl radicals (·OH) to effect removal of refractory organics, many metal oxides (e.g., MnO)2、Co3O4、Fe2O3、TiO2) Supported on carbon-based materials (activated carbon, biochar, graphene, etc.) or inorganic minerals (volcanic rock, montmorillonite, alumina, gravels, etc.) as catalysts, which generally rely on catalyzing ozone production·OH dominates the removal of organic matter. In fact, it is possible to use,·the reaction rate of OH with saturated hydrophilic organics (e.g., ozone oxidation products) is lower than it does with ozone and HCO3 -/CO3 2-Resulting in very low removal efficiency for such saturated organics. The wastewater often contains a large amount of inorganic salt anions (such as Cl)-、HPO4 2-Etc.), they are paired·OH has a strong quenching effect. These·The presence of OH capture species not only greatly reduces catalytic oxidation efficiency, but also increases the use cost of ozone and catalyst. In view of this, based on·The ozone advanced oxidation technology of OH is probably more suitable for removing hydrophilic refractory organic matters in a complex matrix, and the key point of the technology lies in the development of a catalyst.
Copper oxide (CuO) is a p-type semiconductor oxide with a narrow band gap, and its unique properties make it interesting and applicable in many fields such as biomedicine, electricity, optics and environmental management. CuO has shown good results in catalyzing ozone to remove contaminants, but requires higher pH conditions, which limits its applications. Cerium oxide (CeO)2) Is an n-type semiconductor material with fluorite structure, is often used as a carrier material, and can improve the mechanical property and the thermal stability of the catalyst and improve the activity and the selectivity of the catalyst. CeO (CeO)2Has good oxygen storage and release capacity and is also proved to be capable of catalyzing ozone to degrade organic pollutants. Thus, CeO is added2The CuO and the binary heterogeneous material are compounded to form a binary heterogeneous material which is applied to catalytic ozonization, and is expected to generate a synergistic effect, improve the catalytic activity and generate a non-free radical action form. Although CuO-CeO2The composite material has good application in the fields of automobile exhaust ternary catalysis, CO oxidation in hydrogen-rich gas and the like, shows excellent catalytic activity, but the research on the application of the copper-cerium composite catalyst in ozone catalysis for removing refractory organic matters is less, particularly the research on the application of the copper-cerium composite catalyst in non-ozone catalysis·OH-dominated catalytic ozonation studies are rarely reported.
Disclosure of Invention
Low molecular weight organic acids (e.g., oxalic acid, pyruvic acid, succinic acid, etc.) are poorly oxidized by. OH, so they can be used to test for non-OH·And (4) OH oxidation process. Oxalic acid is generated in ozone oxidation products of most organic matters, and ozone per se has poor removal effect on the organic matters, so the oxalic acid is selected as a model compound for catalyzing ozone oxidation. Synthesis of copper-cerium binary composite catalyst (CuO-CeO) by hydrothermal-roasting method2) Applied to catalytic ozonization and adopts a continuous flow dynamic test to explore CuO-CeO2The feasibility of catalyzing ozone to degrade oxalic acid is realized by exploring the influence of initial pH, ozone concentration and catalyst addition amount on the removal of oxalic acid, exploring the active oxidation species and the catalysis action mechanism in the catalytic ozonation process and adopting CuO-CeO2Catalytic ozonation research and engineering practices provide references.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of catalyzing the degradation of organic pollutants by ozone comprising the steps of:
1. preparing reagent materials
Ce (NO3) 3.6H 2O, cupric nitrate solution, glycerol, urea, oxalic acid, tert-butyl alcohol (TBA), absolute ethyl alcohol, diammonium hydrogen phosphate, superoxide dismutase (SOD), furfuryl alcohol (FFA) and methanol (chromatographic purity), wherein reagents used in the experiment are all analytically pure and above, are not further purified, and are prepared into solution by deionized water;
2. preparation and characterization of the catalyst
Adopts a hydrothermal-roasting method to synthesize a copper-cerium binary composite catalyst (CuO-CeO)2) (ii) a Namely, cerium nitrate and urea are prepared into solution according to the molar ratio of 1:3 and added into a round-bottom flask, glycerol is used as a dispersing agent, and the mixture is refluxed and heated for 4 hours at the temperature of 140 ℃ to obtain CeO2White precursor powder is then dipped in copper nitrate solution and roasted for 4h at 550 ℃ to obtain CuO-CeO2A composite catalyst; measuring CuO-CeO by flame atomic absorption spectrophotometer2The content of the copper oxide is 50% (wt.); CuO is obtained by direct roasting of dried solid copper nitrate at 550 deg.C, CeO2Directly roasting the white precursor for 4 hours at 450 ℃; in addition, to better compare the effect of different firing temperatures on the material properties, CeO impregnated with copper nitrate was fired at 450 deg.C2Obtaining CuCe-450 from the precursor, and roasting pure CeO at 550 DEG C2White precursor to obtain CeO2-550。
The crystal structure composition of the catalyst was measured by an X-ray diffractometer (XRD, Rigaku corporation, japan), with a Cu target (K α 1) λ 0.15405nm, an acceleration voltage of 40kV, and a tube current of 40 mA; the morphology structure of the catalyst is characterized by adopting a scanning electron microscope (SEM, JSM-7800, Japan) and a transmission scanning electron microscope (TEM, JEM-2800, Japan);
3. experimental procedures and measurement methods
The oxalic acid degradation reaction is carried out in a 500mL glass flask, and 250mL oxalic acid solution with the molar concentration of 1mmol/L and a certain amount of catalyst are contained. Ozone is from an air source ozone generator (Qingdao national forest FL815Y), aeration is continuously carried out on the solution through a rotor flow meter, the flask is placed in a constant temperature heating magnetic stirrer with the constant temperature of 25 ℃, stirring is continuously carried out, the suspension state of the catalyst is ensured, and the experimental device is shown in figure 1. Sampling at intervals, immediately blowing off residual ozone in the sample solution by using nitrogen, and preserving to be tested after passing through a membrane. Changing a single condition, probing separatelyThe degradation condition of oxalic acid under the conditions that the initial pH value is 1, 3, 5, 7, 9 and 11, the ozone concentration is 5, 15, 30 and 45mg/L, and the adding amount of the catalyst is 0.05, 0.10, 0.20, 0.30 and 0.40 g/L; in addition, catalyst stability and reusability experiments are carried out, and the test is carried out under optimized experimental conditions under the condition of ensuring that the addition amount of Cu is consistent; (ii) use of t-butanol and furfuryl alcohol as. OH and singlet oxygen, respectively (ii)1O2) The capture agent of (2) is used for carrying out active oxidation species investigation experiments; repeating the experiments in each group for 3 times to obtain an average value; the ozone concentration in the reaction solution is determined by an iodine titration method; the concentration of oxalic acid in the solution was measured by a high performance liquid chromatography (proeutectoid L600) with a column of C18(5 μm. times.250 mm. times.4.6 mm), a UV detector wavelength of 210nm, and a mobile phase of 0.2% diammonium hydrogen phosphate solution (pH 2.6) with methanol 98:2 at a flow rate of 0.7 mL/min; the content of copper oxide and the leaching concentration of copper ions in the catalyst are measured by a flame atomic spectrophotometer (Pujintan TAS-990), and the zero charge point (pH) of the catalyst is measuredpzc) It was determined to be 6.97 by mass titration. The mineralization effect of oxalic acid was studied using a Total Organic Carbon (TOC) analyzer.
The experimental device comprises an ozone generator, a rotor flow meter, a constant-temperature heating magnetic stirrer, a flask and a conical flask, wherein the ozone generator is connected with one end of the rotor flow meter, the other end of the rotor flow meter is communicated to the bottom in the flask through a first conduit, the flask and the conical flask are communicated through a second conduit, one end of the second conduit is positioned at the upper part of the flask, the other end of the second conduit is positioned at the bottom of the conical flask, and bottle openings of the flask and the conical flask are sealed by rubber bottle stoppers; constant temperature heating magnetic stirrers includes the water bath heating tank and sets up in the magnetic stirring mechanism of water bath heating tank lower part, the water bath heating tank is put into to the flask, and the magneton has been put to flask inside, and magnetic stirring mechanism leans on magnetic drive magneton to rotate to stir the solution in the flask.
The device also comprises a high performance liquid chromatography analyzer for measuring the concentration of oxalic acid, a flame atomic spectrophotometer for measuring the content of catalyst copper oxide and the leaching concentration of copper ions, and a total organic carbon analyzer for researching the mineralization effect of oxalic acid.
The flask has a capacity of 500mL, and 250mL of oxalic acid solution with a molar concentration of 1mmol/L and a catalyst are contained. The flask was a flat bottom flask.
According to the experimental device for degrading oxalic acid by catalyzing ozone through the copper-cerium binary material, potassium iodide absorption liquid is contained in the conical flask.
The invention has the technical effects and advantages that:
(1) CuO and CeO2The catalyst formed by compounding has excellent ozone catalytic activity, and the removal rate of oxalic acid is as high as 97.66 percent and is far higher than O3(2.66％)、O3CuO (7.38%) and O3/CeO2(5.47%) and the like. Meanwhile, the oxalic acid has good mineralization capability, and the TOC removal rate of oxalic acid after 25min reaches 95.21%.
(2)CuO-CeO2Catalytic O3The optimal reaction conditions are as follows: the ozone concentration is 30mg/L, the catalyst dosage is 0.20g/L, and the solution pH is 7. CuO-CeO2After five times of circulation, more than 90% of oxalic acid can be removed, and good stability and reusability are shown.
(3) TBA capture experiment shows that oxalic acid is degraded·The participation of OH does not play a dominant role, and the synergistic effect of copper and cerium promotes O3Surface oxidation process, non-radical active oxidizing species generated in the process1O2Dominates the degradation of oxalic acid.
Drawings
FIG. 1 is a schematic structural diagram of the experimental apparatus;
FIG. 2 CuO-CeO2XRD spectrum of (1);
FIG. 3 CuO-CeO2SEM picture of (a);
FIG. 4 CuO-CeO2A TEM picture of (4);
FIG. 5 catalytic ozonation effect of different catalysts on oxalic acid ([ oxalic acid ]]1mmol/L, [ catalyst ]]＝0.20g/L，[O3]30mg/L (except for fig. a), pH 7);
FIG. 6 Effect of different initial pH values on oxalic acid degradation ([ oxalic acid ]]1mmol/L, [ catalyst ]]＝0.20g/L，[O3]＝30mg/L)；
FIG. 7 different ozone concentrations (a) and catalyst dosages (b) versus oxalate reductionInfluence of solution ([ oxalic acid ]]1mmol/L, [ catalyst ]]0.20g/L (except for fig. b), [ O ]3]30mg/L (except for fig. a), pH 7);
FIG. 8 Effect of Capture on catalytic ozonation of oxalic acid ([ oxalic acid ]]1mmol/L, [ catalyst ]]＝0.20g/L，[O3]＝30mg/L，[TBA]＝50mmol/L，[FFA]＝50mmol/L，pH＝7)；
Figure 9 shows the mechanism of action of catalytic ozonation of oxalic acid.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A method of catalyzing the degradation of organic pollutants by ozone comprising the steps of:
1. preparing reagent materials
Ce (NO3) 3.6H 2O, cupric nitrate solution, glycerol, urea, oxalic acid, tert-butyl alcohol (TBA), absolute ethyl alcohol, diammonium hydrogen phosphate, superoxide dismutase (SOD), furfuryl alcohol (FFA) and methanol (chromatographic purity), wherein reagents used in the experiment are all analytically pure and above, are not further purified, and are prepared into solution by deionized water;
2. preparation and characterization of the catalyst
Adopts a hydrothermal-roasting method to synthesize a copper-cerium binary composite catalyst (CuO-CeO)2) (ii) a Namely, cerium nitrate and urea are prepared into solution according to the molar ratio of 1:3 and added into a round-bottom flask, glycerol is used as a dispersing agent, and the mixture is refluxed and heated for 4 hours at the temperature of 140 ℃ to obtain CeO2White precursor powder is then dipped in copper nitrate solution and roasted for 4h at 550 ℃ to obtain CuO-CeO2A composite catalyst; measuring CuO-CeO by flame atomic absorption spectrophotometer2The content of the copper oxide is 50% (wt.); CuO is obtained by direct roasting of dried solid copper nitrate at 550 deg.C, CeO2Directly roasting the white precursor for 4 hours at 450 ℃; in addition, in order to betterThe CeO impregnated with copper nitrate is roasted at 450 ℃ compared with the influence of different roasting temperatures on the material performance2Obtaining CuCe-450 from the precursor, and roasting pure CeO at 550 DEG C2White precursor to obtain CeO2-550。
The crystal structure composition of the catalyst was measured by an X-ray diffractometer (XRD, Rigaku corporation, japan), with a Cu target (K α 1) λ 0.15405nm, an acceleration voltage of 40kV, and a tube current of 40 mA; the morphology structure of the catalyst is characterized by adopting a scanning electron microscope (SEM, JSM-7800, Japan) and a transmission scanning electron microscope (TEM, JEM-2800, Japan);
3. experimental procedures and measurement methods
The oxalic acid degradation reaction is carried out in a 500mL glass flask, and 250mL oxalic acid solution with the molar concentration of 1mmol/L and a certain amount of catalyst are contained. Ozone is from an air source ozone generator (Qingdao national forest FL815Y), aeration is continuously carried out on the solution through a rotor flow meter, the flask is placed in a constant temperature heating magnetic stirrer with the constant temperature of 25 ℃, stirring is continuously carried out, the suspension state of the catalyst is ensured, and the experimental device is shown in figure 1. Sampling at intervals, immediately blowing off residual ozone in the sample solution by using nitrogen, and preserving to be tested after passing through a membrane. Changing single conditions, and respectively exploring the degradation conditions of oxalic acid under the conditions that the initial pH values are 1, 3, 5, 7, 9 and 11, the ozone concentrations are 5, 15, 30 and 45mg/L, and the adding amounts of the catalyst are 0.05, 0.10, 0.20, 0.30 and 0.40 g/L; in addition, catalyst stability and reusability experiments are carried out, and the test is carried out under optimized experimental conditions under the condition of ensuring that the addition amount of Cu is consistent; (ii) use of t-butanol and furfuryl alcohol as. OH and singlet oxygen, respectively (ii)1O2) The capture agent of (2) is used for carrying out active oxidation species investigation experiments; repeating the experiments in each group for 3 times to obtain an average value; the ozone concentration in the reaction solution is determined by an iodine titration method; the concentration of oxalic acid in the solution was measured by a high performance liquid chromatography (proeutectoid L600) with a column of C18(5 μm. times.250 mm. times.4.6 mm), a UV detector wavelength of 210nm, and a mobile phase of 0.2% diammonium hydrogen phosphate solution (pH 2.6) with methanol 98:2 at a flow rate of 0.7 mL/min; the content of copper oxide and the leaching concentration of copper ions in the catalyst are measured by a flame atomic spectrophotometer (Pujintan TAS-990), and the zero charge point (pH) of the catalyst is measuredpzc) It was determined to be 6.97 by mass titration. The mineralization effect of oxalic acid was studied using a Total Organic Carbon (TOC) analyzer.
The experimental device shown in fig. 1 comprises an ozone generator 1, a rotameter 2, a constant-temperature heating magnetic stirrer, a flask 4 and a conical flask 5, wherein the ozone generator 1 is connected with one end of the rotameter 2, the other end of the rotameter 2 is communicated to the bottom in the flask 4 through a first conduit a, the flask 4 and the conical flask 5 are communicated through a second conduit b, one end of the second conduit b is positioned at the upper part of the flask, the other end of the second conduit b is positioned at the bottom of the conical flask 5, and bottle openings of the flask and the conical flask are sealed by rubber bottle stoppers; constant temperature heating magnetic stirrers includes water bath heating tank 31 and sets up in the magnetic stirring mechanism 32 of water bath heating tank lower part, in water bath heating tank 31 was put into to flask 4, the inside magnon 9 of having put of flask 4, magnetic stirring mechanism 32 leans on magnetic drive magnon to rotate 9 to stir the solution in the flask. The device also comprises a high performance liquid chromatography analyzer 6 for measuring the concentration of oxalic acid, a flame atomic spectrophotometer 7 for measuring the content of catalyst copper oxide and the leaching concentration of copper ions, and a total organic carbon analyzer 8 for researching the mineralization effect of oxalic acid.
Experimental results and discussion
1.1 characterization of the catalyst
FIG. 2 shows CuO-CeO as catalysts2From the XRD spectrum of (A), it can be seen that the peaks with 2 theta values of 28.50 DEG, 33.04 DEG, 47.42 DEG and 56.30 DEG are cubic CeO2Corresponding to the (111), (200), (220) and (311) crystal planes, in agreement with literature reports[13,14]Proves that the catalyst contains CeO2. Peaks appearing at 2 θ values of 35.48 °, 38.68 °, 38.88 ° and 48.72 ° are characteristic peaks of a monoclinic phase CuO, corresponding to (-111), (200) and (-202) crystal planes, respectively, thereby proving that the catalyst contains a CuO phase. No other miscellaneous peak is found by comparing with a card of The Joint Committee on Powder Diffraction Standards (JCPDS), which indicates that CuO-CeO is successfully synthesized2And (3) compounding a catalyst.
From CuO-CeO2The scanning electron micrograph (FIG. 3) of CuO-CeO was observed2Composite catalystThe agent consists of dispersed CuO nanospheres and aggregated CeO2Sheet layer composition; CuO and CeO were observed by transmission electron microscopy (FIG. 4)2Are all solid structures, and CuO nanospheres are embedded in CeO2The sheets are relatively uniformly dispersed, and a heterostructure is formed.
1.2 Activity of the catalyst
To investigate the catalytic ozonization effect of the prepared material, oxalic acid degradation experiments were performed in different reaction systems, and the results are shown in fig. 5. CuO and CeO only adding catalyst without introducing ozone2、CeO2-550、CuO-CeO2And the adsorption degradation curve of CuCe-450 to oxalic acid is shown in FIG. 5 a. As can be seen, CuO has almost no adsorption removal effect on oxalic acid, and CeO obtained by roasting at 450 ℃ and 550 DEG C2And CeO2The adsorption removal effect of the-550 on oxalic acid is similar, the removal rate of oxalic acid is maintained to be about 2.20% in 25 minutes, and CuCe-450 and CuO-CeO obtained by roasting at the two temperatures2Has better adsorption effect on oxalic acid than single CeO2The components, which may be CuO, are added to form a complex with oxalic acid, which promotes adsorption, with oxalic acid removal rates of 3.90% and 3.98%, respectively. When ozone was introduced without catalyst, it was found that the degradation effect of ozone on oxalic acid was poor, and only 2.66% was removed in 25min, as shown in fig. 5 b. In the CuO/O3And CeO2/O3In the reaction system, the oxalic acid degradation curve is reduced, but the effect is not obvious, and the removal rate is only 7.38 percent and 5.47 percent. CeO (CeO)2And CeO2The effect of 550 catalyzing the ozone to degrade the oxalic acid is not very different, which shows that the temperature change from 450 ℃ to 550 ℃ is applied to the CeO2The catalytic performance of (a) does not change much. When adding CuO-CeO2After the catalyst is used, the residual oxalic acid amount is greatly reduced, and the oxalic acid removal rate reaches 97.66 percent after 25 min. The activity of the copper-cerium composite catalyst obtained by roasting at 450 ℃ is weaker than that of the catalyst obtained at 550 ℃, which is probably because the roasting temperature influences the CuO in CeO2Crystallization on the surface and the formation of heterostructures. The degradation of oxalic acid in the above six reaction systems satisfies the quasi-first order reaction kinetics, and its degradation rate constant (k) is recorded in fig. 5 c. From which canTo be seen in CuO-CeO2/O3The oxalic acid degradation rate in the reaction system is far higher than that in O3、CuO/O3And CeO2/O3In the system, 101.34 times, 34.63 times and 51.14 times of the total weight of the components. The mineralization rate of the oxalic acid is CuO-CeO2/O395.21% was achieved in the reaction system, which is much higher than other catalytic reaction systems (see FIG. 5 d). From this, it can be seen that CuO and CeO2The composite greatly improves the catalytic activity of single metal oxides, shows synergistic effect, has excellent removal effect on ozone refractory organic oxalic acid, and has good application potential in the aspect. Since CeO2And CeO2The treatment effect of-550 is similar, while the activity of CuCe-450 is weaker than that of CuO-CeO2CeO will be temporarily disregarded in the following experiments2-550 and CuCe-450 catalysts.
1.3 influencing factors
1.3.1 Effect of initial pH
CuO and CuO-CeO under different initial pH conditions2The effect of catalytic ozonization on oxalic acid degradation is shown in fig. 6. The CuO is used for catalyzing ozonization to degrade the oxalic acid, the pH is changed from 1 to 11, and the removal rate of the oxalic acid is not changed greatly after 25min, which shows that the efficiency of catalyzing ozone to degrade the oxalic acid by the CuO is still very low under various pH conditions. When CuO-CeO is used2In the case of ozone, the residual oxalic acid ratio was slightly increased under the peracid (pH 1) or the overbase (pH 9 and 11), but was lower than that of CuO under the same conditions, further illustrating that CeO2The catalytic activity of CuO is enhanced. As can be seen, either CuO or CuO-CeO2The optimal pH conditions for catalyzing the ozone degradation of oxalic acid are all 7.
The existence forms of oxalic acid are different under different pH conditions, the pKa1 and the pKa2 of the oxalic acid are 1.23 and 4.19 respectively as dibasic acid, the oxalic acid exists in the form of oxalic acid molecules when the pH of the solution is less than 1.23, the oxalic acid is subjected to first-order dissociation when the pH is more than 1.23, and the oxalic acid is completely dissociated into C when the pH is more than 4.192O4 2-Ion(s)[15]. While the catalyst CuO-CeO2pH of (1)pzcIs 6.97, when the pH of the solution is less than its pHpzcWhen it is neededThe surface of the catalyst is positively charged, and the catalyst can adsorb oxalate ions with negative charges through electrostatic action, so that the oxalic acid degradation effect is very good when the pH is 5 or 7; when the pH is less than 1.23, the oxalic acid exists in a molecular form, the surface action of the oxalic acid and the catalyst is weakened, and the ratio of the residual oxalic acid is increased; when the pH of the solution is more than 7, the surface of the catalyst is negatively charged, and electrostatic repulsion exists between the catalyst and oxalate ions, so that the degradation of the catalyst is not facilitated, and on the other hand, ozone is decomposed rapidly under alkaline conditions, so that the ratio of residual oxalic acid is increased. Changes in pH can also have an effect on catalyst stability, and studies on this are discussed further in section 2.4.
1.3.2 Effect of ozone amount and catalyst dosage
In order to investigate the influence of the ozone concentration and the catalyst addition amount on the degradation of oxalic acid, single-factor batch experiments were performed on the ozone concentration and the catalyst addition amount, respectively, and the experimental results are shown in fig. 7. As can be seen from FIG. 7a, when the ozone concentration is 5mg/L, the residual oxalic acid content after 25min is 56.88%, and less than half of the oxalic acid is removed; along with the increase of the ozone concentration, the degradation rate and the removal degree of the oxalic acid are obviously increased, and especially when the ozone concentration reaches 45mg/L, the residual oxalic acid content is only 0.37 percent after 25min, and the complete removal of the oxalic acid is almost realized. The ozone concentration is respectively 5, 15, 30 and 45mg/L, the rate constants of oxalic acid degradation are respectively 0.025, 0.064, 0.110 and 0.115min-1. Although the oxalic acid removal rate and the ozone concentration are in positive correlation, economic cost needs to be considered in practical application, the operation cost is increased due to the excessively high ozone concentration, the ozone concentration is increased from 30mg/L to 45mg/L, the oxalic acid removal rate is only increased by 2%, the degradation rate is not increased too much, and the effective utilization rate and the treatment cost of ozone are considered, so that the ozone concentration of 30mg/L is reasonable in the research.
The adding amount of the catalyst is also a key factor influencing the oxalic acid removing effect. As shown in FIG. 7b, the oxalic acid removing effect becomes better as the amount of the catalyst added increases. The adding amount of the catalyst is increased from 0.05g/L to 0.20g/L, the increasing amplitude of the oxalic acid degradation rate constant is large, and the rate constant is slowly increased along with the continuous increase of the adding amount of the catalyst to 0.40g/L, which shows that the catalyst achieves the best utilization effect after the adding amount of the catalyst is increased to 0.20 g/L. Thereafter, the catalyst dosage was increased to 0.40g/L, and the degradation rate of oxalic acid did not increase significantly, which is limited by the ozone concentration, so that 0.20g/L should be the optimum catalyst dosage in this study.
1.4 stability and Recycling
In the process of treating wastewater by catalytic oxidation of ozone, the stability and the recycling property of the catalyst are important parameters for investigating the quality of the catalyst. The pH of the solution had a large influence on the stability of the metal oxide material, and therefore, this study was conducted with CuO and CuO-CeO at initial reaction solution pH values of 1, 3, 5, 7, 9 and 11, respectively2Experiment for degrading oxalic acid by catalyzing ozone, CuO-CeO2The addition amount of (B) is 0.200g/L, since CuO-CeO2The copper content in the solution was 50% (wt.), and in order to keep the Cu content consistent, the amount of CuO added was 0.125g/L for Cu in the solution after the experiment2+The leaching solubility was measured and the results are shown in table 1. From Table 1, it can be seen that Cu2+The leaching concentration gradually decreases with the increase of pH, and the leaching amount under the acidic condition is obviously higher than that under the neutral and alkaline conditions. The leaching concentration of copper ions of CuO is far higher than that of CuO-CeO within the pH range of 1-112Indicating the leaching concentration of CeO2The introduction of the CuO reduces the solubility of the CuO under lower pH, reduces the corrosion of acid to the CuO and greatly improves the stability of the CuO.
Table 1 catalysts Cu at different pH2+In the case of leaching
Table 1 The Cu2+leaching amount of catalysts at various pH
To investigate CeO2The contribution to improving the stability of CuO is large, and the used CuO and CuO-CeO2The catalytic materials are respectively recovered by centrifugation, washed by distilled water and absolute ethyl alcohol for multiple times and dried in an oven, and then the next catalytic ozone experiment is carried out. Ensuring the consistent copper content in the added catalyst, for CuO and CuO-CeO2The catalytic material was subjected to five cycles of oxalic acid degradation, the results of which are shown in table 2. It can be seen that after the 2 nd cycle test, the removal rate of CuO to oxalic acid is reduced to 2.68%, and the catalytic effect is reduced by 63.69% compared with the original catalytic effect, while the CuO-CeO2The composite material still has the oxalic acid removal rate of 91.04 percent after being recycled for the 5 th time. CuO and CuO — CeO after the 5 th cycle experiment were applied at pH 72The copper ion leaching concentrations of the catalyst are measured to be 4.67 mg/L and 0.04mg/L respectively, and CuO-CeO2The leaching concentration of the copper ions is far lower than that of CuO. The above results show that CeO2The combination of CuO and CuO greatly improves the catalytic activity and stability of the material, has good recycling performance, and can obviously reduce the operation cost in practical application.
TABLE 2 influence of the number of catalyst cycles on the oxalic acid removal rate
Table 2 Influence of recycling runs on the oxalic acid degradation.
1.5 reaction mechanism
Many free radicals are generated in the process of catalyzing the ozone to degrade the oxalic acid,·OH may be a more influential reactive free radical, in order to verify this experimental study·The effect of OH, a capture experiment was performed with TBA to examine the degradation of oxalic acid with and without a catalyst, as shown in FIG. 8. It can be seen that for the single ozonation process, the oxalic acid degradation was totally inhibited after addition of TBA, indicating that in the reaction where ozone alone oxidizes oxalic acid,·OH is the main reactive radical; in the CuO/O3ReactantAfter TBA was added to the system, the oxalic acid removal rate was reduced from 7.38% to 2.25%, indicating that in this system,·OH dominates the degradation of oxalic acid; in the presence of CuO-CeO2/O3After TBA was added to the reaction system, oxalic acid degradation was slightly inhibited and 91.95% of the oxalic acid was removed. As can be seen from this, in the case of CuO-CeO2/O3In the reaction system·OH generation, but the degradation of oxalic acid is mainly dependent on·OH oxidation. The non-layer·The OH catalytic process may comprise two ways, one is a direct oxidation process of ozone molecules, ozone is directly contacted with oxalic acid ions in a liquid phase to generate oxidation, but the oxalic acid degradation effect of the process is weaker; secondly, in the surface oxidation process of the catalyst, oxalic acid and ozone molecules are adsorbed to CuO-CeO2Catalyst surface, CeO2The CuO and the oxalic acid on the copper oxide can also form a Cu (II) -oxalic acid complex to strengthen the adsorption effect[16]CuO and CeO2Has stronger electron transfer function, strengthens the catalytic activity of CuO, and CeO2Has strong oxygen storage and release capacity, and accelerates the oxidation of oxalic acid by ozone. DAI and the like[17]And XING and the like[18]It has also been found that surface oxidation occurs during catalytic ozonation, and that surface oxidation of the catalyst is the primary mode of action for ozonation of oxalic acid.
It has been shown that singlet oxygen is produced during catalytic ozonation (1O2)[19]. To verify1O2Mainly degrading oxalic acid, and selecting FFA as1O2The quenching agent of (1)[20]Are added to CuO/O respectively3And CuO-CeO2/O3In the reaction system. The experimental result shows that after FFA is added, CuO-CeO2/O3The oxalic acid degradation in the reaction system is inhibited to a great extent, the oxalic acid removal rate is only 6.29 percent, and the ratio of CuO/O3The oxalic acid degradation in the reaction system was almost unchanged, which indicates that1O2Is caused by CuO-CeO2/O3The main active oxide species for oxalic acid degradation in the reaction system. CeO (CeO)2Has good oxygen storage and release capacity, and is easy to generate oxygen vacancy (O) in the action of copper and ceriumV)[21]The ozone decomposes on the catalyst surface to produce O2(formula 1) and simultaneously combines with electrons transferred on the surface of the catalyst to generate O2 ·-(as shown in formulas 2 and 3)[22]. Water molecules in the solution are adsorbed on the surface of the catalyst and O2 ·-Function is to form1O2Finally, the oxalic acid is degraded (formula 4), and the action mechanism of catalyzing ozonization of oxalic acid is shown in figure 9.
Cu2+-OV-Ce3++O3→Cu+-O2--Ce4++O2 (1)
Cu++Ce4+→Cu2++Ce3+ (2)
e-+O2→O2 ·- (3)
2O2 ·-+2H2O→1O2+H2O2+2OH- (4)
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.
Claims (5)
1. A method for degrading organic pollutants by catalyzing ozone is characterized by comprising the following steps: the method comprises the following steps:
s1 preparation of reagent Material
Cerium nitrate, copper nitrate solution, glycerol, urea, oxalic acid, tert-butyl alcohol, absolute ethyl alcohol, diammonium hydrogen phosphate, furfuryl alcohol and methanol;
s2 preparation and characterization of catalyst
Adopts a hydrothermal-roasting method to synthesize a copper-cerium binary composite catalyst (CuO-CeO)2) (ii) a Namely, cerium nitrate and urea are prepared into solution according to the molar ratio of 1:3 and added into a round-bottom flask, glycerol is used as a dispersing agent, and the mixture is refluxed and heated for 4 hours at the temperature of 140 ℃ to obtain CeO2White precursor powder, then soaking in copper nitrate solution at 550 deg.CRoasting for 4 hours to obtain CuO-CeO2A composite catalyst; measuring CuO-CeO by flame atomic absorption spectrophotometer2The content of the copper oxide is 50% (wt.); CuO is obtained by direct roasting of dried solid copper nitrate at 550 deg.C, CeO2Directly roasting the white precursor for 4 hours at 450 ℃; the crystal structure composition of the catalyst was measured by an X-ray diffractometer using a Cu target (K α 1) λ 0.15405nm, an acceleration voltage of 40kV, and a tube current of 40 mA; characterizing the morphology structure of the catalyst by adopting a scanning electron microscope and a transmission scanning electron microscope;
s3, experimental process and determination method
Oxalic acid degradation reaction is carried out in a 500mL flask, 250mL of oxalic acid solution with the molar concentration of 1mmol/L and a certain amount of catalyst are contained; the ozone comes from an air source ozone generator, continuously aerates the solution through a rotor flow meter, and the flask is placed in a constant-temperature heating magnetic stirrer and continuously stirred to ensure the suspension state of the catalyst; sampling at intervals, immediately blowing off residual ozone in the sample solution by using nitrogen, and preserving to be tested after passing through a membrane; changing single conditions, and respectively exploring the degradation conditions of oxalic acid under the conditions that the initial pH values are 1, 3, 5, 7, 9 and 11, the ozone concentrations are 5, 15, 30 and 45mg/L, and the adding amounts of the catalyst are 0.05, 0.10, 0.20, 0.30 and 0.40 g/L; in addition, catalyst stability and reusability experiments are carried out, and the test is carried out under optimized experimental conditions under the condition of ensuring that the addition amount of Cu is consistent; respectively adopting tert-butyl alcohol and furfuryl alcohol as·OH and singlet oxygen: (1O2) The capture agent is subjected to active oxidation species investigation experiments, and each group of experiments are repeated for 3 times to obtain an average value; the ozone concentration in the reaction solution is determined by an iodine titration method; the concentration of oxalic acid in the solution is measured by a high performance liquid chromatography analyzer, the chromatographic column is C18(5 mu m is multiplied by 250mm is multiplied by 4.6mm), the wavelength of an ultraviolet detector is 210nm, the mobile phase is 0.2 percent diammonium hydrogen phosphate solution (pH is 2.6), methanol is 98:2, and the flow rate is 0.7 mL/min; the content of copper oxide and the leaching concentration of copper ions in the catalyst are measured by a flame atomic spectrophotometer, and the zero charge point (pH) of the catalystpzc) 6.97 by mass titration; and (3) researching the mineralization effect of the oxalic acid by adopting a total organic carbon analyzer.
2. The method of claim 1, wherein the ozone degradation is catalyzed by the organic pollutant: in the step S1, in order to better compare the influence of different baking temperatures on the material properties, CeO impregnated with copper nitrate was baked at 450 deg.C2Obtaining CuCe-450 from the precursor, and roasting pure CeO at 550 DEG C2White precursor to obtain CeO2-550。
3. The method of claim 1, wherein the ozone degradation is catalyzed by the organic pollutant: the ozone generator is connected with one end of the rotor flow meter, the other end of the rotor flow meter is communicated to the bottom in the flask through a first guide pipe, the flask is communicated with the space between the conical flasks through a second guide pipe, one end of the second guide pipe is positioned at the upper part of the flask, the other end of the second guide pipe is positioned at the bottom of the conical flask, and bottle openings of the flask and the conical flasks are sealed by rubber bottle stoppers; constant temperature heating magnetic stirrers includes the water bath heating tank and sets up in the magnetic stirring mechanism of water bath heating tank lower part, the water bath heating tank is put into to the flask, and the magneton has been put to flask inside, and magnetic stirring mechanism leans on magnetic drive magneton to rotate to stir the solution in the flask.
4. A method of catalyzing the degradation of organic pollutants by ozone as in claim 3, wherein: according to the experimental device for degrading oxalic acid by catalyzing ozone through the copper-cerium binary material, potassium iodide absorption liquid is contained in the conical flask.
5. The method of claim 1, wherein the ozone degradation is catalyzed by the organic pollutant: in step S1, all reagents used were of analytical grade and above, and were used to prepare solutions with deionized water without further purification.
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| CN115350708A (en) * | 2022-09-16 | 2022-11-18 | 清华大学 | Composite catalyst and preparation method and application thereof |
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