CN113181911A - Preparation method of noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst - Google Patents

Preparation method of noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst Download PDF

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CN113181911A
CN113181911A CN202110305149.0A CN202110305149A CN113181911A CN 113181911 A CN113181911 A CN 113181911A CN 202110305149 A CN202110305149 A CN 202110305149A CN 113181911 A CN113181911 A CN 113181911A
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noble metal
silicotungstic acid
temperature
metal platinum
hours
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陈希
叶蕾蕾
王梦凡
任立涵
邓捷
张学军
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Shenyang University of Chemical Technology
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Shenyang University of Chemical Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56Platinum group metals
    • B01J23/64Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652Chromium, molybdenum or tungsten
    • B01J23/6527Tungsten
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8668Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B01J35/613
    • B01J35/643
    • B01J35/647

Abstract

A preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst relates to a preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst, and comprises the following steps: fully dissolving a proper amount of cerium acetate, a proper amount of urea, a certain amount of silicotungstic acid and chloroplatinic acid solutions with different mass fractions in a solvent to obtain a noble metal platinum modified silicotungstic acid loaded cerium dioxide precursor solution; placing the noble metal platinum modified silicotungstic acid loaded cerium dioxide precursor solution in a hydrothermal reaction kettle, and obtaining a product after hydrothermal reaction; and step three, drying the product, then calcining at high temperature, and finally obtaining the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst with the particle size of 40-60 meshes by screening. The invention is used for catalytic oxidation of chlorobenzene, has the advantages of high catalytic activity, simple preparation process and the like, and provides a new idea for industrial application.

Description

Preparation method of noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst
Technical Field
The invention relates to a preparation method of a catalyst, in particular to a preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst.
Background
In industrial production, halogenated organic volatile matters frequently emitted by industries such as medicine, pesticide, light industry, packaging industry and the like are in wide concern due to the durability and potential toxicity of the halogenated organic volatile matters in the environment. In which the chlorinated radicals have a higher toxicity
Volatile Organic Compounds (CVOCs) not only destroy the atmosphere, but also have a persistent and cumulative impact on human health and ecosystem. Chlorobenzene has been a chlorinated organic volatile gas of great interest to researchers due to its properties of being difficult to degrade and toxic.
With the development of science and technology, various methods are adopted at home and abroad to treat chlorobenzene pollution, such as biodegradation, absorption/adsorption, membrane separation technology, photocatalysis, ozone oxidation, thermal combustion, catalytic combustion and the like; of these technologies, catalytic combustion is a promising treatment because it reduces the temperature and energy consumption during oxidation and converts chlorobenzene to H2O, HCl, CO2, etc. end products at lower temperatures, and thus is considered an environmentally friendly, green, efficient chlorobenzene treatment. At present, the key research of catalytic oxidation of chlorobenzene at home and abroad mainly focuses on screening and optimizing catalytic materials. The noble metal has obvious effect of improving the performance of catalytic oxidation of chlorobenzene. CeO2 is modified by heteropoly acid, so that the heteropoly acid has good oxidation-reduction capability and more surface acid sites. In the process of catalytic oxidation of chlorobenzene, CeO2 is modified by heteropoly acid, so that the catalytic activity and stability of the CeO2 catalyst in the catalytic oxidation of chlorobenzene are improved. More surface acidity can dissociate C-Cl of chlorobenzene, and stronger redox ability can continuously crack benzene rings and further deeply oxidize the benzene rings into short-chain intermediate products, so that the chlorobenzene is subjected to harmless treatment.
Disclosure of Invention
The invention aims to provide a preparation method of a noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst, the oxidation-reduction performance and the surface acidity of the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst are obviously improved compared with those of the silicotungstic acid modified cerium dioxide catalyst, and the catalytic oxidation of chlorobenzene is proved to have excellent catalytic performance by an activity test, and the preparation method is simple and economic and has great significance in industrial application.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst comprises the following preparation processes:
1) putting 8-10 mmol of cerium acetate and 15-30 mmol of urea in 25-50 mL of solvent, adding 0.08-0.14 mmol of silicotungstic acid and 7.7mmol/L of chloroplatinic acid solution after full dissolution, and stirring for 0.5-2 hours;
2) placing the obtained solution in a hydrothermal reaction kettle, and keeping the hydrothermal temperature of 80-170 ℃ for 6-42 hours;
3) washing and filtering a product obtained through the hydrothermal reaction, and moving the product into a drying oven with the temperature of 50-100 ℃ for 12-48 hours;
4) and (3) transferring the dried solid to a muffle furnace, firstly heating to 250-350 ℃ from room temperature through a program of 1-5 ℃ per minute, keeping the temperature for 1-2 hours, then heating to 500-700 ℃ through a program of 1-5 ℃ per minute, and keeping the temperature for 2-4 hours.
According to the preparation method of the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst, the solvent used in the step 1) is water, glycol, ethanol and methanol.
In the preparation method of the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst, the chloroplatinic acid solution in the step 1) is prepared by respectively adding 4mL of H with the concentration of 7.7mmol/L2PtCl6·6H2O, the mass fraction of the platinum oxide after roasting accounts for 0.5 percent of the catalyst; 8mL of H with a concentration of 7.7mmol/L was added2PtCl6·6H2O, the mass fraction of the platinum oxide after roasting accounts for 1 percent of the catalyst; 12mL of H with a concentration of 7.7mmol/L was added2PtCl6·6H2O, the mass fraction of the platinum oxide after roasting accounts for 1.5 percent of the catalyst; add 16mL of concentrateDegree of 7.7 mmol/L2% H2PtCl6·6H2And O, wherein the mass fraction of the platinum oxide after roasting accounts for 2 percent of the catalyst.
According to the preparation method of the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst, the hydrothermal temperature in the step 2) is 80-170 ℃, and the hydrothermal time is 6-42 hours.
According to the preparation method of the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst, the dried solid is calcined in the following two stages:
(1) the temperature is programmed to be increased from room temperature to 250-350 ℃ at 1-5 ℃ per min, and the temperature is kept for 1-2 hours;
(2) and (4) continuing programming at 1-5 ℃ per min until the temperature reaches 500-700 ℃, and keeping the temperature for 2-4 hours.
The preparation method of the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst comprises the step of preparing the catalyst with the specific surface area of 30.023-95.475 m2The pore diameter is 1.67-8.35 nm.
The invention has the advantages and effects that:
1. the heteropoly acid HSiW is used for the reaction of CeO2The modification can simultaneously improve the oxidation performance, the surface acidity and the catalytic activity and the stability in the catalytic oxidation of chlorobenzene.
2. The catalyst of the invention has low preparation cost and simple and convenient preparation method, and is suitable for large-scale production and utilization.
3. The high stability and excellent anti-carbon deposition capability of the catalyst show that the catalyst has the ideal effect of preventing chlorine adsorption from forming oxychloride on the surface and poisoning and degrading chlorobenzene pollution in the process of continuously catalyzing chlorobenzene for a long time.
4. The catalytic performance of the catalyst is further improved after the catalyst is doped with noble metal.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of silicotungstic acid modified ceria loaded with different mass fractions of platinum in the examples according to the invention;
FIG. 2 shows the conversion of a silicotungstic acid modified ceria catalyst loaded with different mass fractions of platinum for catalytic oxidation of chlorobenzene in the examples of the present invention.
Detailed Description
The present invention will be described in detail with reference to the embodiments shown in the drawings.
Example one
A preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst for catalytic oxidation of chlorobenzene comprises the following steps:
1) completely dissolving 8mmol of cerium acetate and 15mmol of urea in 25mL of ethylene glycol, and then adding 0.08mmol of silicotungstic acid and 4mL of H with the concentration of 7.7mmol/L2PtCl6·6H2O, and stirring for 1 hour;
2) placing the obtained solution in a hydrothermal reaction kettle, keeping the hydrothermal temperature of 180 ℃, and carrying out hydrothermal reaction for 12 hours;
3) washing and filtering a product obtained through the hydrothermal reaction, and moving the product into a drying oven with the temperature of 105 ℃ for 12 hours;
4) and transferring the dried solid to a muffle furnace, firstly raising the temperature from room temperature to 350 ℃ through a 2 ℃ C/min program, keeping the temperature for 2 hours, and then raising the temperature to 550 ℃ through a 2 ℃ C/min program, and keeping the temperature for 3 hours.
Example two
A preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst for catalytic oxidation of chlorobenzene comprises the following steps:
1) completely dissolving 8mmol of cerium acetate and 15mmol of urea in 25mL of ethylene glycol, and then adding 0.08mmol of silicotungstic acid and 8mL of H with the concentration of 7.7mmol/L2PtCl6·6H2O, and stirring for 1 hour;
2) placing the obtained solution in a hydrothermal reaction kettle, keeping the hydrothermal temperature of 180 ℃, and carrying out hydrothermal reaction for 12 hours;
3) washing and filtering a product obtained through the hydrothermal reaction, and moving the product into a drying oven with the temperature of 105 ℃ for 12 hours;
4) and transferring the dried solid to a muffle furnace, firstly raising the temperature from room temperature to 350 ℃ through a 2 ℃ C/min program, keeping the temperature for 2 hours, and then raising the temperature to 550 ℃ through a 2 ℃ C/min program, and keeping the temperature for 3 hours.
EXAMPLE III
A preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst for catalytic oxidation of chlorobenzene comprises the following steps:
1) completely dissolving 8mmol of cerium acetate and 15mmol of urea in 25mL of ethylene glycol, and then adding 0.08mmol of silicotungstic acid and 12mL of H with the concentration of 7.7mmol/L2PtCl6·6H2O, and stirring for 1 hour;
2) placing the obtained solution in a hydrothermal reaction kettle, keeping the hydrothermal temperature of 180 ℃ and carrying out hydrothermal reaction for 12 hours;
3) washing and filtering a product obtained through the hydrothermal reaction, and moving the product into a drying oven with the temperature of 105 ℃ for 12 hours;
4) and transferring the dried solid to a muffle furnace, firstly raising the temperature from room temperature to 350 ℃ through a 2 ℃ C/min program, keeping the temperature for 2 hours, and then raising the temperature to 550 ℃ through a 2 ℃ C/min program, and keeping the temperature for 3 hours.
Example four
A preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst for catalytic oxidation of chlorobenzene comprises the following steps:
1) completely dissolving 8mmol of cerium acetate and 15mmol of urea in 25mL of ethylene glycol, and then adding 0.08mmol of silicotungstic acid and 16mL of H with the concentration of 7.7mmol/L2PtCl6·6H2O, and stirring for 1 hour;
2) placing the obtained solution in a hydrothermal reaction kettle, keeping the hydrothermal temperature of 180 ℃ and carrying out hydrothermal reaction for 12 hours;
3) washing and filtering a product obtained through the hydrothermal reaction, and moving the product into a drying oven with the temperature of 105 ℃ for 12 hours;
4) and transferring the dried solid to a muffle furnace, firstly raising the temperature from room temperature to 350 ℃ through a 2 ℃ C/min program, keeping the temperature for 2 hours, and then raising the temperature to 550 ℃ through a 2 ℃ C/min program, and keeping the temperature for 3 hours.
The preferred embodiments of the present invention are shown above, but the embodiments are not limited to the examples, and the protection scope of the present invention includes: various modifications, changes, combinations, substitutions, etc. can be made in the embodiments without departing from the spirit and scope of the claims.

Claims (6)

1. A preparation method of a noble metal platinum modified silicotungstic acid loaded cerium dioxide catalyst is characterized by comprising the following preparation processes:
1) putting 8-10 mmol of cerium acetate and 15-30 mmol of urea in 25-50 mL of solvent, adding 0.08-0.14 mmol of silicotungstic acid and 7.7mmol/L of chloroplatinic acid solution after full dissolution, and stirring for 0.5-2 hours;
2) placing the obtained solution in a hydrothermal reaction kettle, and keeping the hydrothermal temperature of 80-170 ℃ for 6-42 hours;
3) washing and filtering a product obtained through the hydrothermal reaction, and moving the product into a drying oven with the temperature of 50-100 ℃ for 12-48 hours;
4) and (3) transferring the dried solid to a muffle furnace, firstly heating to 250-350 ℃ from room temperature through a program of 1-5 ℃ per minute, keeping the temperature for 1-2 hours, then heating to 500-700 ℃ through a program of 1-5 ℃ per minute, and keeping the temperature for 2-4 hours.
2. The preparation method of the noble metal platinum modified silicotungstic acid supported cerium oxide catalyst according to claim 1, wherein the solvent used in the step 1) is water, ethylene glycol, ethanol or methanol.
3. The method for preparing the noble metal platinum modified silicotungstic acid supported cerium oxide catalyst according to claim 1, wherein the chloroplatinic acid solution in the step 1) is prepared by respectively adding 4mL of H with the concentration of 7.7mmol/L2PtCl6·6H2O, the mass fraction of the platinum oxide after roasting accounts for 0.5 percent of the catalyst; 8mL of H with a concentration of 7.7mmol/L was added2PtCl6·6H2O, the mass fraction of the platinum oxide after roasting accounts for 1 percent of the catalyst; 12mL of H with a concentration of 7.7mmol/L was added2PtCl6·6H2O, the mass fraction of the platinum oxide after roasting accounts for 1.5 percent of the catalyst; 16mL of 2% H at a concentration of 7.7mmol/L was added2PtCl6·6H2And O, wherein the mass fraction of the platinum oxide after roasting accounts for 2 percent of the catalyst.
4. The preparation method of the noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst according to claim 1, wherein the hydrothermal temperature in the step 2) is 80-170 ℃ and the hydrothermal time is 6-42 hours.
5. The method for preparing a noble metal platinum modified silicotungstic acid supported cerium oxide catalyst according to claim 1, wherein the dried solid is calcined in two stages:
(1) the temperature is programmed to be increased from room temperature to 250-350 ℃ at 1-5 ℃ per min, and the temperature is kept for 1-2 hours;
(2) and (4) continuing programming at 1-5 ℃ per min until the temperature reaches 500-700 ℃, and keeping the temperature for 2-4 hours.
6. The preparation method of the noble metal platinum modified silicotungstic acid supported cerium oxide catalyst according to claim 1, wherein the prepared catalyst has a specific surface area of 30.023-95.475 m2The pore diameter is 1.67-8.35 nm.
CN202110305149.0A 2021-03-23 2021-03-23 Preparation method of noble metal platinum modified silicotungstic acid supported cerium dioxide catalyst Withdrawn CN113181911A (en)

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Publication number Priority date Publication date Assignee Title
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CN103143719A (en) * 2012-12-21 2013-06-12 浙江理工大学 Preparation method of platinum nanoparticle loaded platinum nanoparticle crystals
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CN111330606A (en) * 2020-04-14 2020-06-26 浙江大学 Catalyst for efficiently degrading chlorine-containing organic waste gas at low temperature and preparation method and application thereof

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Application publication date: 20210730