CN114011419B - Anti-sintering VOC (volatile organic compound) s Preparation method of combustion catalyst, product and application thereof - Google Patents
Anti-sintering VOC (volatile organic compound) s Preparation method of combustion catalyst, product and application thereof Download PDFInfo
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- CN114011419B CN114011419B CN202111348808.5A CN202111348808A CN114011419B CN 114011419 B CN114011419 B CN 114011419B CN 202111348808 A CN202111348808 A CN 202111348808A CN 114011419 B CN114011419 B CN 114011419B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
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Abstract
The invention discloses a preparation method of a sintering-resistant VOCs combustion catalyst, a product and application thereofThe catalyst is Fe 3+ Ion doped Ca 3 Co 4 O 9 A catalyst. Fe (Fe) 3+ Substitution can reduce Ca 3 Co 4 O 9 The valence state of Co ions is medium, lattice defects are introduced, and the catalytic combustion activity of VOCs of the catalyst is obviously improved; ca (Ca) 3 Co 4 O 9 The layered oxide structure of the catalyst has anisotropic growth characteristics, and the high-temperature stability of the catalyst is improved. The novel anti-sintering VOCs combustion catalyst prepared by the method is simple in preparation process, easy to produce in a large scale and has good application prospect.
Description
Technical Field
The invention relates to the field of environmental protection catalysis, in particular to a preparation method of a sintering-resistant VOCs combustion catalyst, a product and application thereof.
Background
VOCs are secondary particulate matter, SO 2 And the other main air pollutant after NOx, most VOCs have carcinogenic, teratogenic and mutagenic properties, and directly harm human health. Meanwhile, VOCs can also generate ozone and secondary aerosol through photochemical reaction, and the human health and the ecological environment are seriously influenced. Therefore, effective management of VOCs is of great significance.
Catalytic combustion is an effective means of controlling VOCs emissions. The cobaltosic oxide has weak metal-oxygen bond and has excellent activity which is comparable to that of a noble metal catalyst in the field of VOCs catalytic combustion. However, co 3 O 4 High temperature is easy to sinter, resulting in poor reaction stability of the catalyst. Co enhancement 3 O 4 The anti-sintering performance of the alloy has a great promotion effect on the large-scale application of the alloy.
Ca 3 Co 4 O 9 The cobalt-based layered oxide has a layered material similar to a superlattice structure and has specific anisotropic growth characteristics, so that the cobalt-based layered oxide still maintains excellent stability under high-temperature conditions. But Ca 3 Co 4 O 9 VOCs catalytic combustion performance of the material is not ideal and can be matched with Ca 3 Co 4 O 9 Co in (C) is Co 4+ Related to the following. Stronger Co 4+ O bond is such that Co 4+ /Co 3+ Between redox cycles and Co 3+ /Co 2+ Is more difficult to realize, resulting in Ca 3 Co 4 O 9 The catalytic combustion performance of VOCs is poor.
Disclosure of Invention
The invention aims to provide a preparation method of a sintering-resistant VOCs combustion catalyst.
Still another object of the present invention is: there is provided a product prepared by the above method.
Yet another object of the present invention is: there is provided the use of the above product.
The invention aims at realizing the following scheme: a preparation method of a sintering-resistant VOCs combustion catalyst, wherein the catalyst is a Fe < 3+ > ion doped Ca < 3 > Co < 4 > O < 9 > catalyst, the layered structure of the catalyst endows the catalyst with high stability, and Fe < 3+ > doping endows the catalyst with high activity, and the preparation method comprises the following steps:
weighing calcium nitrate tetrahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate and citric acid monohydrate with proper molar ratio, dissolving in deionized water, and stirring at room temperature for 60 min to obtain a solution, wherein the molar ratio of the cobalt nitrate hexahydrate to the ferric nitrate nonahydrate is (2-9): 1; the solubility of the total metal ions of the calcium, the cobalt and the iron is 1.5-2 mol/L; the mole ratio of the citric acid to the total metal ions of calcium, cobalt and iron is (1-1.5): 1;
and (3) rapidly heating to boiling, maintaining the reactant in a gel state, reacting for 12 h in a 120 ℃ blast drying box, and roasting for 12 h in a 800 ℃ muffle furnace to obtain the sintering-resistant VOCs combustion catalyst.
The invention also provides a sintering-resistant VOCs combustion catalyst which is prepared by the method.
The invention provides an application of a catalyst in catalytic combustion of VOCs.
The test conditions were as follows: VOCs contaminants were simulated using 1000 ppm of refractory short-chain propane with balance air at a flow rate of 30000 mL/g/h.
The principle of the invention is as follows: by ion dopingWith Fe 3+ Substituted Ca 3 Co 4 O 9 CdI of (2) 2 CoO (CoO) 2 Co in layer 3+ /Co 4+ The valence state of Co ions is regulated, so that the catalytic combustion activity of VOCs of the catalyst is obviously improved; fe (Fe) 3+ Substitution can reduce the valence state of Co ions, introduce lattice defects, improve the oxidation-reduction characteristics of the catalyst, and further remarkably improve the catalytic combustion activity of VOCs of the catalyst; the catalyst still maintains Ca after doping 3 Co 4 O 9 The layered oxide structure of the catalyst is improved.
The invention has the following advantages:
(1) The catalyst has a cobalt layered oxide structure and anisotropic growth characteristics, so that the catalyst has excellent high-temperature stability.
(2) The catalyst of the patent utilizes Fe 3+ Substitution can reduce Ca 3 Co 4 O 9 And in the valence state of Co ions, lattice defects are introduced, so that the oxidation-reduction characteristic of the catalyst is improved, and the catalytic combustion activity of VOCs of the catalyst is remarkably improved.
(3) The preparation process is simple, is easy for large-scale production, and has good application prospect.
Drawings
Figure 1 XRD patterns of the catalyst of example 2 and comparative example 1.
Detailed Description
The following describes embodiments of the present invention in detail: the present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments.
Example 1
An anti-sintering VOCs combustion catalyst is Fe 3+ Ion doped Ca 3 Co 4 O 9 Catalyst, its lamellar structure imparts high stability to the catalyst, fe 3+ Doping imparts high activity to the catalyst, and is prepared by the following steps:
0.015 mol of calcium nitrate tetrahydrate, 0.018 mol of cobalt nitrate hexahydrate, 0.002 mol of ferric nitrate nonahydrate and 0.0455 mol of citric acid monohydrate are weighed and dissolved in 20 mL deionized water, and the mixture is stirred at room temperature for 60 minutes to obtain a solution;
rapidly heating the solution to boil, maintaining the reactant in gel state, reacting in a 120 ℃ blast drying oven for 12 h, and roasting in a 800 ℃ muffle furnace for 12 h to obtain the sintering-resistant VOCs combustion catalyst Ca 3 Co 3.6 Fe 0.4 O 9 The catalytic combustion performance of VOCs is shown in Table 1.
Example 2
A sintering resistant VOCs combustion catalyst, similar to the procedure of example 1, prepared by the steps of:
dissolving 0.015 mol of calcium nitrate tetrahydrate, 0.016 mol of cobalt nitrate hexahydrate, 0.004 mol of ferric nitrate nonahydrate and 0.0455 mol of citric acid monohydrate in 20 mL deionized water, and stirring at room temperature for 60 min;
quickly heating to boiling, maintaining the reactant in gel state, reacting in a 120 deg.C air drying oven for 12 h, and calcining in a 800 deg.C muffle furnace for 12 h to obtain Ca 3 Co 3.2 Fe 0.8 O 9 The catalytic combustion performance of the catalyst VOCs is shown in table 1, and XRD characterization is shown in figure 1.
Example 3
A sintering resistant VOCs combustion catalyst, similar to the procedure of example 1, prepared by the steps of:
dissolving 0.015 mol of calcium nitrate tetrahydrate, 0.014 mol of cobalt nitrate hexahydrate, 0.006 mol of ferric nitrate nonahydrate and 0.0455 mol of citric acid monohydrate in 20 mL deionized water, and stirring at room temperature for 60 min to obtain a solution;
rapidly heating the solution to boil, maintaining the reactant in gel state, reacting in a drying oven at 120deg.C for 12 h, and calcining in a muffle furnace at 800 deg.C for 12 h to obtain Ca 3 Co 2.8 Fe 1.2 O 9 The catalytic combustion performance of the catalyst, VOCs, is shown in Table 1.
Comparative example 1:
a sintering resistant VOCs combustion catalyst, similar to the steps of examples 1 to 3, was prepared by the steps of:
dissolving 0.015 mol of calcium nitrate tetrahydrate, 0.020 mol of cobalt nitrate hexahydrate and 0.0455 mol of citric acid monohydrate in 20 mL deionized water, stirring at room temperature for 60 min, and rapidly addingHeating to boiling, maintaining the reactant in gel state, reacting in a drying oven at 120deg.C for 12 hr, and calcining in a muffle furnace at 800 deg.C for 12 h to obtain Ca 3 Co 4 O 9 The catalytic combustion performance of the catalyst VOCs is shown in table 1, and XRD characterization is shown in figure 1.
Application example:
the catalysts of examples 1-3 and comparative example 1 were used to test the catalytic combustion performance of VOCs, respectively. The test conditions were as follows: VOCs contaminants were simulated using 1000 ppm of refractory short-chain propane with balance air at a flow rate of 30000 mL/g/h. In each of the examples and comparative examples, the reaction temperature T90 at which the propane conversion was 90% was:
Claims (4)
1. the application of the sintering-resistant VOCs combustion catalyst in the catalytic combustion of VOCs is characterized in that the catalyst is Fe 3+ Ion doped Ca 3 Co 4 O 9 Catalyst, its lamellar structure imparts high stability to the catalyst, fe 3+ Doping imparts high activity to the catalyst, and the preparation method comprises the following steps:
weighing calcium nitrate tetrahydrate, cobalt nitrate hexahydrate, ferric nitrate nonahydrate and citric acid monohydrate, dissolving in deionized water, and stirring at room temperature for 60 min to obtain a solution, wherein the molar ratio of the cobalt nitrate hexahydrate to the ferric nitrate nonahydrate is (2-9): 1, the solubility of total metal ions of calcium, cobalt and iron in the solution is 1.5-2 mol/L, and the molar ratio of the citric acid to the total metal ions of calcium, cobalt and iron is (1-1.5): 1;
and (3) rapidly heating the solution to boiling, maintaining the heating until the reactant is in a gel state, reacting for 12 h in a 120 ℃ blast drying box, and roasting for 12 h in a 800 ℃ muffle furnace to obtain the sintering-resistant VOCs combustion catalyst.
2. Use of the sintering-resistant VOCs combustion catalyst according to claim 1 for the catalytic combustion of VOCs, wherein the sintering-resistant VOCs combustion catalyst is prepared by the steps of:
0.015 mol of calcium nitrate tetrahydrate, 0.018 mol of cobalt nitrate hexahydrate, 0.002 mol of ferric nitrate nonahydrate and 0.0455 mol of citric acid monohydrate are weighed and dissolved in 20 mL deionized water, and the mixture is stirred at room temperature for 60 minutes to obtain a solution;
rapidly heating the solution to boil, maintaining the reactant in gel state, reacting in a 120 ℃ blast drying oven for 12 h, and roasting in a 800 ℃ muffle furnace for 12 h to obtain the sintering-resistant VOCs combustion catalyst Ca 3 Co 3.6 Fe 0.4 O 9 。
3. Use of the sintering-resistant VOCs combustion catalyst according to claim 1 for the catalytic combustion of VOCs, wherein the sintering-resistant VOCs combustion catalyst is prepared by the steps of:
dissolving 0.015 mol of calcium nitrate tetrahydrate, 0.016 mol of cobalt nitrate hexahydrate, 0.004 mol of ferric nitrate nonahydrate and 0.0455 mol of citric acid monohydrate in 20 mL deionized water, and stirring at room temperature for 60 min;
quickly heating to boiling, maintaining the reactant in gel state, reacting in a 120 deg.C air drying oven for 12 h, and calcining in a 800 deg.C muffle furnace for 12 h to obtain Ca 3 Co 3.2 Fe 0.8 O 9 A catalyst.
4. Use of the sintering-resistant VOCs combustion catalyst according to claim 1 for the catalytic combustion of VOCs, wherein the sintering-resistant VOCs combustion catalyst is prepared by the steps of:
dissolving 0.015 mol of calcium nitrate tetrahydrate, 0.014 mol of cobalt nitrate hexahydrate, 0.006 mol of ferric nitrate nonahydrate and 0.0455 mol of citric acid monohydrate in 20 mL deionized water, and stirring at room temperature for 60 min to obtain a solution;
rapidly heating the solution to boil, maintaining the reactant in gel state, reacting in a drying oven at 120deg.C for 12 h, and calcining in a muffle furnace at 800 deg.C for 12 h to obtain Ca 3 Co 2.8 Fe 1.2 O 9 A catalyst.
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