CN115245832B - Preparation method, product and application of fluorine doped metal oxide catalyst - Google Patents

Preparation method, product and application of fluorine doped metal oxide catalyst Download PDF

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CN115245832B
CN115245832B CN202111626901.8A CN202111626901A CN115245832B CN 115245832 B CN115245832 B CN 115245832B CN 202111626901 A CN202111626901 A CN 202111626901A CN 115245832 B CN115245832 B CN 115245832B
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metal oxide
fluorine
oxide catalyst
doped metal
catalyst
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CN115245832A (en
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余德游
王姗丽
张明燕
吴明华
胡倩
徐李聪
蒋文斌
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Zhejiang Sci Tech University ZSTU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • 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
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • 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
    • 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
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Environmental & Geological Engineering (AREA)
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Abstract

本发明提供一种氟掺杂金属氧化物催化剂的制备方法、产品及应用。上述制备方法，包括：将金属氧化物分散于水中，加入含氟试剂进行反应，反应结束后，干燥后煅烧，得所述氟掺杂金属氧化物催化剂。本发明的制备方法采用煅烧法制备氟掺杂金属氧化物催化剂，通过引入氟降低金属上的电子云密度，增强金属氧化物的Lewis酸性，强化金属氧化物与O3的相互作用，催化O3快速分解产生更多的羟基自由基，增强对水中有机污染物的氧化降解，显著提高有机污染物的矿化程度。The invention provides a preparation method, product and application of a fluorine-doped metal oxide catalyst. The above preparation method includes: dispersing the metal oxide in water, adding a fluorine-containing reagent to react, and after the reaction is completed, drying and calcining to obtain the fluorine-doped metal oxide catalyst. The preparation method of the present invention adopts a calcination method to prepare a fluorine-doped metal oxide catalyst. By introducing fluorine, the electron cloud density on the metal is reduced, the Lewis acidity of the metal oxide is enhanced, the interaction between the metal oxide and O 3 is strengthened, and O 3 is catalyzed Rapid decomposition produces more hydroxyl radicals, enhances the oxidative degradation of organic pollutants in water, and significantly increases the degree of mineralization of organic pollutants.

Description

Preparation method, product and application of fluorine doped metal oxide catalyst
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a preparation method, a product and application of a fluorine doped metal oxide catalyst.
Background
The catalytic ozonation technology is an efficient and green advanced oxidation technology (AOPs), and is widely applied to the field of water pollution treatment because the technology can efficiently degrade organic pollutants. Compared with the single ozone oxidation technology, the heterogeneous catalytic ozone oxidation technology has high efficiency, and the solid catalyst can be recycled, so that secondary pollution caused by the catalyst is avoided or weakened, and the use cost of the catalyst is also reduced. The preparation of a high-efficiency stable solid catalyst is the key point of heterogeneous catalytic ozone technology.
The heterogeneous ozone catalyst which is used at present is mainly metal oxide represented by alumina, titanium oxide and the like, and the metal oxide can catalyze ozone to decompose and convert into active oxygen species with higher oxidizing capability, so that the capability of oxidizing and degrading organic pollutants is enhanced. In the prior art, lewis acidity of a metal oxide serving as a catalyst is weak, so that the action efficiency of a catalytic active site is low, and the catalytic performance of the metal oxide catalyst is influenced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method, a product and application of a fluorine doped metal oxide catalyst. The preparation method disclosed by the invention is simple in process, low in cost and easy to obtain raw materials, and has higher universality and adjustability; the fluorine doped metal oxide catalyst prepared by the preparation method has good catalytic effect and is applied to O 3 In the oxidative decomposition of organic pollutants, can effectively catalyze O 3 And more hydroxyl radicals are generated by rapid decomposition, so that the oxidative degradation of organic pollutants in water is enhanced, and the mineralization degree of the organic pollutants is remarkably improved.
A method of preparing a fluorine doped metal oxide catalyst comprising:
dispersing metal oxide in water, adding fluorine-containing reagent for reaction, drying and calcining after the reaction is finished to obtain the fluorine-doped metal oxide catalyst.
The reaction mechanism of metal oxide catalytic ozonation mainly takes surface hydroxyl groups as active sites to decompose ozone to generate oxygen-containing free radicals, and absorbs organic matters to reduce the activation energy of direct reaction of ozone and the organic matters. The catalytic activity of the metal oxide is related to the Lewis acid site on the surface of the metal oxide, so that the catalytic treatment effect is improved by improving the Lewis acid site on the surface of the metal oxide.
According to the preparation method disclosed by the invention, fluorine with the strongest electronegativity is doped into the metal oxide, ozone decomposition is promoted to generate active oxygen free radicals by regulating and controlling the electronic structure of the metal oxide, the activity of the metal oxide in catalyzing ozone is improved, and a new possibility is provided for enhancing the practical application of ozone oxidation to degrade organic pollutants.
Preferably, the molar volume ratio of the metal oxide to water is 1 mol/(0.5 to 10) L. Further preferably 1 mol/(0.5 to 5) L. Still more preferably 1 mol/(1 to 3) L.
Preferably, the molar ratio of fluorine to metal oxide in the fluorine-containing reagent is 1: (0.1-30).
Further preferably 1: (0.5-15). Still more preferably 1/(0.5 to 5).
Preferably, the metal oxide is one or more of aluminum oxide, cerium oxide, titanium oxide and manganese oxide.
Preferably, the fluorine-containing reagent is one or more of hydrofluoric acid, ammonium fluoride solution and sodium fluoride solution.
The drying may be natural drying or heat drying. When the heating drying is selected, the drying temperature is preferably 40 to 80 ℃, and the drying time is preferably 8 to 15 hours. More preferably, the drying temperature is 55 to 65 ℃ and the drying time is 11 to 13 hours.
Preferably, the reaction time is 1 to 12 hours. After the fluorine-containing reagent is added, the contact between reactants is increased by stirring or standing after ultrasonic treatment, so that the reaction rate and the effect are improved.
As a further preferable example, when the reaction is stirred after the addition of the fluorine-containing reagent, the stirring time is 2 to 12 hours. More preferably 2 to 4 hours.
As a further preferable mode, when the fluorine-containing reagent is added and then the ultrasonic treatment is carried out, the ultrasonic treatment time is 10 to 120 minutes and the standing time is 1 to 12 hours.
As a further preferable scheme, the ultrasonic time is 10-60 min, and the standing time is 4-12 h. More preferably, the ultrasonic treatment time is 20 to 40 minutes and the standing time is 6 to 10 hours.
Preferably, the calcination temperature is 100-1000 ℃ and the calcination time is 2-48 h.
When the fluorine-containing reagent is selected to be added, ultrasonic treatment is performed first and then standing is performed, the calcination temperature is preferably 100-500 ℃, and the calcination time is preferably 2-24 hours. More preferably, the calcination temperature is 200 to 400℃and the calcination time is 2 to 6 hours.
When stirring reaction is carried out after the fluorine-containing reagent is selectively added, the calcination temperature is preferably 400-900 ℃, and the calcination time is preferably 5-24 h. More preferably, the calcination temperature is 500 to 800 ℃ and the calcination time is 10 to 12 hours.
Preferably, after the calcination is finished, the obtained calcination product is washed and dried by ethanol and deionized water, and the fluorine doped metal oxide catalyst is obtained.
The calcination can be performed in a muffle furnace, and after the calcination is performed for a set time at a set temperature, the catalyst is washed and dried to obtain the fluorine doped metal oxide catalyst.
A fluorine doped metal oxide catalyst prepared by the method of any one of the above. The fluorine-doped metal oxide catalyst of the invention can improve ozone degradation reaction and catalyze O 3 Effectively decompose into hydroxyl free radicals, can improve the efficiency of ozone reaction degradation and mineralization of organic pollutants in water, and can be applied to the field of water pollution strengthening treatment.
An application of the fluorine doped metal oxide catalyst in degrading organic pollutants in wastewater.
Preferably, the organic contaminant is salicylic acid, p-nitrophenol, ofloxacin, tetracycline, or an analog of any of the above.
Preferably, the fluorine-doped metal oxide catalyst is added to wastewater containing organic pollutants, ozone is introduced, and ozone catalytic oxidation is performed.
Preferably, the concentration of the organic pollutant in the wastewater is 10-300 ppm. Further preferably 10 to 200ppm. Still more preferably 10 to 100ppm.
Preferably, the amount of fluorine-doped metal oxide catalyst added is 0.1 to 20. 20g L -1 . Further preferably 0.1 to 10. 10g L -1 . More preferably 0.1 to 5. 5g L -1 。
Preferably, the concentration of ozone is 0.001 to 1. 1g L -1 The flow rate is 10-200 mL min -1 . More preferably, the ozone concentration is 0.001 to 0.1. 0.1g L -1 The flow rate is 40-120 mL min -1 。
Compared with the prior art, the invention has the beneficial effects that:
the fluorine-doped metal oxide ozone catalyst is prepared by fully contacting a fluorine-containing reagent with metal oxide in water and then evaporating and calcining. The electron cloud density on the metal is reduced by introducing fluorine, the Lewis acidity of the active metal is enhanced, and the metal oxide and O are enhanced 3 Is to catalyze the interaction of O 3 And more hydroxyl radicals are generated by rapid decomposition, so that the oxidative degradation of organic pollutants in water is enhanced, and the mineralization degree of the organic pollutants is remarkably improved.
Drawings
FIG. 1 is an SEM morphology of the fluorine doped manganese oxide catalyst prepared in example 1;
FIG. 2 is a graph comparing the residual rate of fluorine-doped manganese oxide catalyst, pure manganese oxide and ozone oxidized p-nitrophenol without catalyst prepared in example 1 with time;
FIG. 3 is a graph comparing the residual rate of the fluorine-doped alumina catalyst prepared in examples 2 and 3 and the ozone oxidized p-nitrophenol without catalyst with time.
Detailed Description
The technical scheme of the present invention will be further described by the following examples.
Example 1
A method for preparing fluorine doped manganese oxide catalyst, comprising:
evenly stirring (dispersing) manganese oxide in deionized water, adding hydrofluoric acid solution for soaking, evaporating, drying, calcining, and performing aftertreatment to obtain the fluorine-doped manganese oxide catalyst.
The specific process is as follows:
a preparation method of fluorine doped manganese oxide catalyst comprises the following steps:
(1) 0.01mol of manganese oxide was dissolved in 20mL of deionized water, stirred, 0.43mL of hydrofluoric acid solution (containing 0.005mol of hydrogen fluoride) was added, stirred at 25℃for 4 hours, and the solvent (60℃for 12 hours) was evaporated to obtain a precursor solid.
(2) And (3) placing the precursor solid into a crucible to react for 12 hours at 700 ℃ in a muffle furnace, cleaning the obtained solid by ethanol and deionized water, drying, and drying at a low temperature to obtain the high-efficiency ozone catalyst fluorine-doped manganese oxide (fluorine-doped manganese oxide catalyst).
The SEM morphology graph of the prepared high-efficiency ozone catalyst fluorine doped manganese oxide is shown in figure 1, and the prepared high-efficiency ozone catalyst fluorine doped manganese oxide mainly consists of needles and particles.
Degradation Performance test
300mL of 10mg L -1 Placing p-nitrophenol solution (water as solvent) in beaker, placing in heat collecting magnetic stirrer, regulating temperature of heat collecting magnetic stirrer to 25deg.C, and rotating at 200rpm for min -1 . 120mg of catalyst (fluorine doped manganese oxide catalyst, pure manganese oxide catalyst, no catalyst added prepared in this example) was accurately weighed, added into the above p-nitrophenol solution, and O was introduced into the system 3 (concentration is 3mg L) -1 The flow rate is 120mL min -1 ) The ozonation reaction is triggered. 5mL (0 min, 5min, 10min, 15min, 20min, 25min, 30 min) was sampled every 5min, filtered through a 0.22 μm needle filter, and residual ozone and reactive oxygen species in the filtrate were rapidly quenched with 10. Mu.L t-butanol.Each set of experiments was repeated three times.
The concentration of p-nitrophenol is measured by adopting an Agilent 1260 type high performance liquid chromatograph, and the analysis conditions are as follows: agilent ZORBAX Eclipse XDB-C18 chromatographic column (3.5 μm, 4.6X105 mm) is used as stationary phase, column temperature is 30deg.C, mobile phase is mixed solution of water and methanol (30/70), and flow rate and sample injection amount are respectively 0.8mL min -1 And 20. Mu.L. The retention time of p-nitrophenol was 2.14min.
The concentration C of the sample is sampled at the time points of 0min, 5min, 10min, 15min, 20min, 25min and 30min t With the initial concentration C of the p-nitrophenol solution 0 The ratio of (2) is plotted on the ordinate and the time point is plotted on the abscissa, and the result is shown in FIG. 2. As can be seen from FIG. 2, after 30min of reaction, the high-efficiency ozone catalyst prepared in this example was fluorine doped manganese oxide (shown as HF-MnO in the figure 2 +O 3 ) The degradation rate of the p-nitrophenol solution is 98.28 percent, and the degradation rate is obviously superior to that of the pure manganese oxide catalyst (shown as pure MnO in the figure) 2 +O 3 ) And no catalyst (shown as O in the figure) 3 ) Is a degradation rate of (a).
Example 2
The procedure was the same as in example 1, except that the manganese oxide in example 1 was replaced with alumina to prepare a fluorine-doped alumina catalyst.
Example 3
The preparation method of the fluorine doped alumina ozone catalyst prepared from ammonium fluoride comprises the following steps:
(1) 0.01mol of alumina was dissolved in 10mL of deionized water, and 0.005mol of NH was added 4 F, ultrasonic treatment is carried out for 40min.
(2) And standing the sample for 10 hours, drying at 60 ℃ for 12 hours, placing the sample into a crucible to react for 2 hours at 300 ℃ in a muffle furnace, cleaning the obtained solid by ethanol and deionized water, drying the solid, and drying the solid at a low temperature to obtain the fluorine-doped alumina ozone catalyst.
The catalytic degradation rate of p-nitrophenol of the fluorine-doped alumina catalyst prepared in examples 2 and 3 was compared with that of the catalyst without catalyst by using the degradation performance test in example 1, and the test results are shown in FIG. 3Shown. As can be seen from FIG. 3, after 30min of reaction, the fluorine doped alumina catalysts prepared in examples 2 and 3 (shown as F respectively in the figures) HF -Al+O 3 、F NH4F -Al+O 3 ) The degradation rates of the p-nitrophenol solution are 97.50% and 97.49% respectively.
Example 4
A preparation method of fluorine doped titanium oxide catalyst comprises the following steps:
(1) 0.02mol of titanium oxide was dissolved in 30mL of deionized water and stirred, 0.86mL of ammonium fluoride solution (0.01 mol) was added, stirring was performed at 25℃for 4 hours, and the solvent (60℃for 12 hours) was evaporated to obtain a precursor solid.
(2) And placing the precursor solid into a crucible to react for 12 hours at 700 ℃ in a muffle furnace, washing and drying the obtained solid by ethanol and deionized water, and drying at a low temperature to obtain the fluorine-doped titanium oxide catalyst.
The degradation rate of the fluorine doped titanium oxide catalyst prepared in the embodiment was 97.36% after 30min of reaction by the degradation performance test method in the embodiment 1.

Claims (3)

1. The application of a fluorine-doped metal oxide catalyst in degrading organic pollutants in wastewater is that the fluorine-doped metal oxide catalyst is added into the wastewater containing the organic pollutants, and ozone is introduced; wherein the concentration of organic pollutants in the wastewater is 10-300 ppm; the input amount of the fluorine doped metal oxide catalyst is 0.1-20 g L -1 The method comprises the steps of carrying out a first treatment on the surface of the Ozone is introduced to a concentration of 0.001-1 g L -1 The flow rate is 10-200 mL min -1 ；
The preparation method of the fluorine doped metal oxide catalyst comprises the following steps:
dispersing metal oxide in water, adding a fluorine-containing reagent for reaction, and drying and calcining after the reaction is finished to obtain the fluorine-doped metal oxide catalyst;
the calcination temperature is 300-700 ℃, and the calcination time is 2-48 h;
the molar volume ratio of the metal oxide to the water is 1 mol/(0.5-10) L;
the molar ratio of fluorine to metal oxide in the fluorine-containing reagent is 1: (0.1-30);
the metal oxide is alumina;
the fluorine-containing reagent is an ammonium fluoride solution.
2. The application of the fluorine-doped metal oxide catalyst according to claim 1 in degrading organic pollutants in wastewater, wherein the reaction time is 1-12 h.
3. The use of a fluorine-doped metal oxide catalyst according to claim 1 for degrading organic contaminants in wastewater, wherein the organic contaminants are salicylic acid, p-nitrophenol, ofloxacin, tetracycline or analogues of any of the above.
CN202111626901.8A 2021-12-28 2021-12-28 Preparation method, product and application of fluorine doped metal oxide catalyst Active CN115245832B (en)

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