CN113751014A - Monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance and preparation method thereof - Google Patents
Monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 39
- 239000011593 sulfur Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 17
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000005287 vanadyl group Chemical group 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229920001690 polydopamine Polymers 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract 2
- 238000006116 polymerization reaction Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract 2
- MCHZKGNHFPNZDP-UHFFFAOYSA-N 2-aminoethane-1,1,1-triol;hydrochloride Chemical compound Cl.NCC(O)(O)O MCHZKGNHFPNZDP-UHFFFAOYSA-N 0.000 abstract 1
- 229960003638 dopamine Drugs 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
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- 241000282414 Homo sapiens Species 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
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- 238000005265 energy consumption Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910052720 vanadium Inorganic materials 0.000 description 1
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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
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance and a preparation method thereof. The monatomic vanadyl is anchored on dopamine hydrochloride, the hydrochloric dopamine is subjected to polymerization reaction by using a trihydroxymethyl aminomethane-hydrochloric acid solution to adjust the pH value, an iron oxide carrier is tightly wrapped, the polydopamine is carbonized through high-temperature calcination, and the ferric oxide is removed through acid washing, so that the monodispersed spindle-shaped monatomic vanadyl catalyst is finally formed.
Description
Technical Field
The invention belongs to the technical field of functional special-shaped monatomic catalysts, and particularly relates to a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance and a preparation method thereof.
Background
Energy is the fundamental power of economic development, but is also the source of pollution. Since the human beings enter the industrialized society, the social productivity is rapidly developed, the development amount and the use amount of energy are gradually increased, especially in recent decades, the industrialized process is continuously accelerated, the energy consumption and the pollutant discharge amount are sharply increased, and the health of the human lives and property and the social progress are seriously influenced. The global environmental problem is increasingly prominent, and becomes a focus of general attention of the public. The environmental pollution includes air pollution, water environment pollution, soil pollution and the like, wherein the problem of air pollution is already a difficult problem which must be faced in the industrialization process of countries all over the world. The atmospheric environmental pollution causes harm to human health and various organisms to different degrees, the physical and mental health and the life quality of human beings are seriously affected, and huge loss is caused to the society.
The report of BP world energy statistics yearbook in 2018 shows that the proportion of the global energy consumption and the increase of the energy consumption in 2017 in China is 23.2% and 33.6% respectively. And the world is in the leaderboard of energy growth for 17 years continuously. After the coal consumption in 2014-2016 in China continuously decreases for three years, the increase of 0.5% is reproduced in 2017. Meanwhile, the coal yield is increased by 3.6 percent compared with 2016. Coal yields and consumption account for 46.4% and 50.7% of the world. Coal accounts for 27.6% of the global primary energy consumption in 2017. Although the proportion of coal in our national energy structure is reduced from 73.6% ten years ago and 62.0% 2016 to 60.4% 2017, the proportion is still far higher than the average level in the world, as shown in fig. 1-1. This fully indicates that coal still occupies a significant proportion in the energy structure of our country.
The metal is dispersed in nitrogen-doped carbon material in the form of single atom to form M-NxA monatomic catalyst of the type C (M being a metal monatomic, x being the coordination number of the N atom). It is well known that the surface free energy and specific activity of nanomaterials increase dramatically with decreasing particle size, and therefore monatomic catalysts (SACs) have many unique characteristicsAdvantages such as the metal elements are dispersed on the substrate material in an atomic scale, fully exposing all active sites, thereby facilitating the improvement of the activity of the catalyst and achieving the highest atomic utilization; a single metal atom with an extremely large surface free energy and high activity may cause a quantum size effect. In addition, the specific interaction between the metal atom and the substrate may promote charge transfer, or provide an unsaturated coordination environment for the metal atom, which is beneficial for improving catalytic activity and selectivity. Typical SACs are dispersed primarily on oxide, sulfide, carbon-based materials, or metal supports. Nowadays, the monatomic catalyst has been the focus of research in various fields by virtue of its unique advantages, and has been widely applied to a series of redox reaction systems, such as CO oxidation and CO2Reduction, oxygen reduction reaction (0RR), selective hydrogenation, photocatalyst and the like, but no suitable technology has been provided for successfully applying the monatomic catalyst to the field of denitration and sulfur resistance.
Disclosure of Invention
The invention aims to load a high-efficiency denitration sulfur-resistant monatomic catalyst on iron oxide, and then remove a monodisperse spindle-shaped iron oxide template to prepare the spindle-shaped monatomic catalyst. Due to the monodisperse spindle-shaped ferric oxide carrier, the monatomic catalyst is uniformly dispersed and has a spindle shape with a large specific surface area.
The technical scheme adopted by the invention is as follows:
the monodisperse spindle-shaped iron oxide can be prepared by the following method:
1) 0.5g ferric chloride hexahydrate is added into a 100mL beaker, 30mL deionized water is added, stirring is carried out for 30min at room temperature, 5.5mL triethylamine is added, the pH is adjusted to 8-9, and stirring is carried out until the ferric chloride hexahydrate is fully dissolved. And transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 180 ℃ for 10 hours, and cooling at room temperature after the reaction is finished.
2) And (3) filtering and washing the reaction solution after reaction by using 100mL of deionized water and ethanol, and drying the obtained product at 70 ℃ for 5 hours for later use.
More specifically, the monodisperse spindle-shaped monatomic catalyst can be prepared by the following method:
(1) accurately weighing 0.1g of monodisperse spindle-shaped iron oxide sample, dissolving in 50mL of deionized water to prepare an iron oxide solution, and ultrasonically dispersing for 20min to mark as A solution.
(2) Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride into 50mL of deionized water, adding ethylene acetone vanadyl oxide (0.2-0.8 mg) with different masses, and carrying out ultrasonic dispersion for 30min to mark as a solution B.
(3) Adding the solution B into the solution A, stirring at room temperature for 30min, adding 40mL of tris (hydroxymethyl) aminomethane-hydrochloric acid solution (wherein tris (hydroxymethyl) aminomethane is 0.24 g, hydrochloric acid is 6 mL, and deionized water is 34 mL), continuing stirring at room temperature for 12h, repeatedly filtering the reaction solution after the reaction is finished, and drying for later use.
(4) And placing the dried sample in a muffle furnace under the protection of nitrogen at 900 ℃ for calcining for 2h to remove organic impurities, placing the calcined sample in a 5wt% dilute hydrochloric acid solution after cooling for repeatedly pickling to remove ferric oxide, performing suction filtration washing on the pickled sample by using deionized water, and finally drying to obtain the spindle-shaped monatomic catalyst.
The advantages of the invention are as follows:
1. by using the spindle-shaped iron oxide as a template, the synthesized single-atom catalyst with the monodisperse spindle-shaped structure can more effectively increase the specific surface area and the reaction active site of the catalyst compared with the existing (sheet-shaped, rod-shaped and spherical) single-atom catalyst, can ensure that the catalyst is more stable and more efficient in denitration and sulfur resistance, and is beneficial to prolonging the service life of the catalyst.
2. Compared with other denitration and sulfur-resistant catalysts, the monatomic vanadyl greatly reduces the cost for preparing the catalyst, and can exert the catalytic capability of active substances to the maximum extent, namely, the effect of the original commercial catalyst can be achieved only by using one thousandth of the amount of the monatomic vanadyl.
3. Compared with common monatomic catalysts such as monatomic manganese, cobalt, iron and the like, monatomic vanadyl has higher chemical valence, and the higher valence is favorable for oxidizing NO in the denitrified gas to form NO2And the denitration reaction is accelerated.
4. The whole synthesis is carried out in a low-temperature environment, the reaction synthesis method and operation are simple, the reaction is rapid, no specific requirements are required on a reaction vessel, and the synthetic substances have no pollution to the environment.
Drawings
FIG. 1 is a diagram of a self-made tubular SCR reactor device in a catalyst activity test; in the figure, 1 is a gas source; 2 is a pressure reducing valve; 3 is a mass flow meter; 4 is a mixer; 5 is an air preheater; 6 is a catalyst bed; 7 is a composite material; 8 is a flue gas analyzer;
FIG. 2 is a scanning electron micrograph of a monodisperse spindle-shaped monatomic catalyst of example 3;
FIG. 3 is an EDX elemental scan of the monodisperse spindle-shaped monatomic catalyst of example 3;
FIG. 4 is a graph showing the catalytic stability analysis of the monodispersed spindle-shaped monatomic catalyst of example 3.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Accurately weighing 0.1g of monodisperse spindle-shaped iron oxide sample, dissolving in 50mL of deionized water to prepare an iron oxide solution, and ultrasonically dispersing for 20min to mark as A solution. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL of deionized water, adding 0.2mg of ethylene acetone vanadyl, performing ultrasonic dispersion for 30min, and marking as a solution B. And adding the solution B into the solution A, stirring at room temperature for 30min, adding 40mL of tris (hydroxymethyl) aminomethane-hydrochloric acid solution (wherein tris (hydroxymethyl) aminomethane is 0.24 g, hydrochloric acid is 6 mL, and deionized water is 34 mL), continuing stirring at room temperature for 12h, repeatedly filtering the reaction solution after the reaction is finished, and drying for later use. And placing the dried sample in a muffle furnace under the protection of nitrogen at 900 ℃ for calcining for 2h to remove organic impurities, placing the calcined sample in a 5% dilute hydrochloric acid solution after cooling for repeatedly pickling to remove ferric oxide, performing suction filtration washing on the pickled sample by using deionized water, and finally drying to obtain the spindle-shaped monatomic catalyst to be tested.
Composite material denitration and sulfur resistance in self-made pipeEvaluation was carried out in a SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is set to be 180 ℃, and the denitration rate is 57.1 percent by using a British KM940 flue gas analyzer; the temperature is set to be 200 ℃, the denitration rate is 61.5%, the temperature is set to be 220 ℃, the denitration sulfur resistance rate is 70.8%, the temperature is set to be 240 ℃, the denitration sulfur resistance rate is 81.1%, the temperature is set to be 260 ℃, and the denitration sulfur resistance rate is 77.2%; introducing SO at 240 DEG C2The test is carried out at intervals of 30min, and finally the final denitration rate is basically stabilized at 54.4 percent.
Example 2
Accurately weighing 0.1g of monodisperse spindle-shaped iron oxide sample, dissolving in 50mL of deionized water to prepare an iron oxide solution, and ultrasonically dispersing for 20min to mark as A solution. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL of deionized water, adding 0.4mg of ethylene acetone vanadyl, performing ultrasonic dispersion for 30min, and marking as a solution B. And adding the solution B into the solution A, stirring at room temperature for 30min, adding 40mL of tris (hydroxymethyl) aminomethane-hydrochloric acid solution (wherein tris (hydroxymethyl) aminomethane is 0.24 g, hydrochloric acid is 6 mL, and deionized water is 34 mL), continuing stirring at room temperature for 12h, repeatedly filtering the reaction solution after the reaction is finished, and drying for later use. And placing the dried sample in a muffle furnace under the protection of nitrogen at 900 ℃ for calcining for 2h to remove organic impurities, placing the calcined sample in a 5% dilute hydrochloric acid solution after cooling for repeatedly pickling to remove ferric oxide, performing suction filtration washing on the pickled sample by using deionized water, and finally drying to obtain the spindle-shaped monatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is set to be 180 ℃, and the denitration rate is 59.2 percent by using a British KM940 flue gas analyzer; the temperature is set to be 200 ℃, the denitration rate is 66.3%, the temperature is set to be 220 ℃, the denitration sulfur resistance rate is 72.2%, the temperature is set to be 240 ℃, the denitration sulfur resistance rate is 86.8%, the temperature is set to be 260 ℃, and the denitration sulfur resistance rate is 79.1%; introducing SO at 240 DEG C2Testing at intervals of 30min, and finallyThe out-of-stock ratio is basically stabilized at 60.1%.
Example 3
Accurately weighing 0.1g of monodisperse spindle-shaped iron oxide sample, dissolving in 50mL of deionized water to prepare an iron oxide solution, and ultrasonically dispersing for 20min to mark as A solution. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL of deionized water, adding 0.6mg of ethylene acetone vanadyl, performing ultrasonic dispersion for 30min, and marking as a solution B. And adding the solution B into the solution A, stirring at room temperature for 30min, adding 40mL of tris (hydroxymethyl) aminomethane-hydrochloric acid solution (wherein tris (hydroxymethyl) aminomethane is 0.24 g, hydrochloric acid is 6 mL, and deionized water is 34 mL), continuing stirring at room temperature for 12h, repeatedly filtering the reaction solution after the reaction is finished, and drying for later use. And placing the dried sample in a muffle furnace under the protection of nitrogen at 900 ℃ for calcining for 2h to remove organic impurities, placing the calcined sample in a 5% dilute hydrochloric acid solution after cooling for repeatedly pickling to remove ferric oxide, performing suction filtration washing on the pickled sample by using deionized water, and finally drying to obtain the spindle-shaped monatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is set to be 180 ℃, and the denitration rate measured by a British KM940 flue gas analyzer is 65.5 percent; the temperature is set to be 200 ℃, the denitration rate is 71.6 percent, the temperature is set to be 220 ℃, the denitration sulfur resistance rate is 82.6 percent, the temperature is set to be 240 ℃, the denitration sulfur resistance rate is 93.4 percent, the temperature is set to be 260 ℃, and the denitration sulfur resistance rate is 81.1 percent; introducing SO at 240 DEG C2The test is carried out at intervals of 30min, and finally the final denitration rate is basically stabilized at 69.9 percent.
FIG. 2 is a scanned graph of a monodisperse spindle-shaped monatomic catalyst, which can be seen to have better dispersibility and structural stability; FIG. 3 is an EDX (scanning EDX) elemental scan of a monodisperse spindle-shaped monatomic catalyst, and it can be seen that several elements of O, V, C and N are uniformly loaded on the surface of the catalyst, which illustrates that monatomic vanadyl is successfully loaded on the surface of polydopamine; FIG. 4 is a graph of analysis of catalytic stability of a monodisperse spindle-shaped monatomic catalyst, and it can be seen that the catalyst has good stability within 20 hours, and the denitration rate can be maintained at about 88%.
Example 4
Accurately weighing 0.1g of monodisperse spindle-shaped iron oxide sample, dissolving in 50mL of deionized water to prepare an iron oxide solution, and ultrasonically dispersing for 20min to mark as A solution. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL of deionized water, adding 0.6mg of ethylene acetone vanadyl, performing ultrasonic dispersion for 30min, and marking as a solution B. And adding the solution B into the solution A, stirring at room temperature for 30min, adding 40mL of tris (hydroxymethyl) aminomethane-hydrochloric acid solution (wherein tris (hydroxymethyl) aminomethane is 0.24 g, hydrochloric acid is 6 mL, and deionized water is 34 mL), continuing stirring at room temperature for 12h, repeatedly filtering the reaction solution after the reaction is finished, and drying for later use. And placing the dried sample in a muffle furnace under the protection of nitrogen at 900 ℃ for calcining for 2h to remove organic impurities, placing the calcined sample in a 5% dilute hydrochloric acid solution after cooling for repeatedly pickling to remove ferric oxide, performing suction filtration washing on the pickled sample by using deionized water, and finally drying to obtain the spindle-shaped monatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is set to be 180 ℃, and the denitration rate is 60.7 percent by using a British KM940 flue gas analyzer; the temperature is set to be 200 ℃, the denitration rate is 66.5%, the temperature is set to be 220 ℃, the denitration sulfur-resistant rate is 75.3%, the temperature is set to be 240 ℃, the denitration sulfur-resistant rate is 88.9%, the temperature is set to be 260 ℃, and the denitration sulfur-resistant rate is 80.2%; introducing SO at 240 DEG C2The test is carried out at intervals of 30min, and finally the final denitration rate is basically stabilized at 63.3 percent.
Example 5
Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL of deionized water, adding 0.6mg of ethylene vanadyl acetonate, ultrasonically dispersing for 30min, stirring at room temperature for 30min, adding 40mL of tris (hydroxymethyl) aminomethane-hydrochloric acid solution (0.24 g of tris (hydroxymethyl) aminomethane, 6 mL of hydrochloric acid and 34mL of deionized water), continuously stirring at room temperature for 12h, and repeatedly filtering, filtering and drying the reaction solution for later use after the reaction is finished. And placing the dried sample in a 900 ℃ nitrogen protection muffle furnace to be calcined for 2h to remove organic impurities, performing suction filtration and washing on the calcined sample by using deionized water, and finally drying to obtain the non-carrier monatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH3Volume fractions of 0.05% and O2The volume fraction is 5 percent, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is set to be 180 ℃, and the denitration rate is 55.1 percent by using a British KM940 flue gas analyzer; the temperature is set to be 200 ℃, the denitration rate is 61.5%, the temperature is set to be 220 ℃, the denitration sulfur-resistant rate is 66.7%, the temperature is set to be 240 ℃, the denitration sulfur-resistant rate is 74.8%, the temperature is set to be 260 ℃, and the denitration sulfur-resistant rate is 71.2%; introducing SO at 240 DEG C2The test is carried out at intervals of 30min, and finally the out-of-stock rate is basically stabilized at 47.8 percent. Activity evaluation: the catalyst was evaluated in a self-made tubular SCR reactor. The reactor is electrically heated externally, a thermocouple is arranged beside a catalyst bed layer of the reaction tube to measure the temperature, and the flow of the experimental device is shown in figure 1. Simulating the composition of flue gas by using a steel gas cylinder, wherein the flue gas comprises NO and O2、N2、NH3To reduce gas, NO and NH3Volume fraction of 0.04-0.06%, O2The volume fraction is 4-6%, and the rest is N2The gas flow rate is 700 mL/min-1The temperature is controlled between 120 ℃ and 200 ℃, and the gas flow and the gas composition are regulated and controlled by a mass flow meter. Gas analysis adopts a British KM940 smoke gas analyzer, and each working condition is stable for at least 30min in order to ensure the stability and accuracy of data.
TABLE 1 influence of various factors on the denitration sulfur resistance of the composite material (reaction temperature 240 ℃ C.)
As can be seen from the data in Table 1, at 240 ℃, with the increasing of the quality of vanadyl acetylacetonate, the denitration sulfur resistance rate tends to increase first and then decrease, which is caused by the increase of the content of monatomic vanadyl, but excessive addition causes agglomeration of vanadyl, resulting in the reduction of the denitration rate at the later stage. A maximum value occurs at a mass of 0.6mg of vanadyl acetylacetonate. And the sulfur resistance is also maximized.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance is characterized by comprising the following steps: the catalyst is a precursor and a coating body which take monodisperse spindle-shaped ferric oxide as a carrier, dopamine hydrochloride as a carbon source and a nitrogen source, vanadyl acetylacetonate as a source of vanadyl, vanadyl is anchored on polydopamine through polymerization reaction of the dopamine hydrochloride and coats ferric oxide at the same time, and unreacted organic matters and ferric oxide are removed through calcination and acid washing, so that the monodisperse spindle-shaped monatomic catalyst is finally obtained.
2. The method of preparing a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance according to claim 1, wherein: the monodisperse spindle-shaped ferric oxide carrier is obtained by the following method:
(1) adding 0.5g of ferric chloride hexahydrate into a 100mL beaker, adding 30mL of deionized water, stirring at room temperature for 30min, adding 5.5mL of triethylamine to adjust the pH value to 8-9, and stirring until the ferric chloride hexahydrate is fully dissolved; then transferring the reaction solution into a polytetrafluoroethylene inner container, carrying out hydrothermal reaction at 180 ℃ for 10h, and cooling at room temperature after the reaction is finished;
(2) and (3) pumping, filtering and cleaning the reaction solution after reaction by using 100mL of deionized water and ethanol, and drying the obtained product at 70 ℃ for 5h to obtain the monodisperse spindle-shaped ferric oxide carrier.
3. The method of preparing a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance according to claim 1, wherein: the preparation method comprises the following steps:
(1) dissolving monodisperse spindle-shaped ferric oxide in deionized water to prepare ferric oxide solution, and ultrasonically dispersing for 20min to mark as A solution;
(2) dissolving dopamine hydrochloride in deionized water, adding 0.2-0.8mg of vanadyl ethylene acetone, and ultrasonically dispersing for 30min to obtain solution B;
(3) adding the solution B into the solution A, stirring at room temperature for 30min, adding a tris (hydroxymethyl) aminomethane-hydrochloric acid solution, continuing stirring at room temperature for 12h, and repeatedly filtering, filtering and drying the reaction solution for later use after the reaction is finished;
(4) and (3) placing the dried sample in the step (3) in a nitrogen protection muffle furnace at 900 ℃ for calcining for 2h to remove organic impurities, placing the calcined sample in a 5wt% dilute hydrochloric acid solution after cooling for repeatedly pickling to remove ferric oxide, performing suction filtration washing on the pickled sample by using deionized water, and finally drying to obtain the monodisperse spindle-shaped monatomic catalyst.
4. The method of preparing a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance according to claim 3, wherein: the mass of the monodisperse spindle-shaped iron oxide in the step (1) is 0.1g, and the volume of the deionized water is 50 mL.
5. The method of preparing a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance according to claim 3, wherein: in the step (2), the mass of the dopamine hydrochloride is 0.15g, and the volume of the deionized water is 50 mL.
6. The method of preparing a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance according to claim 3, wherein: the volume of the tris-hydroxymethyl aminomethane-hydrochloric acid solution in the step (3) is 40mL, wherein the mass of tris-hydroxymethyl aminomethane is 0.24 g, the volume of hydrochloric acid is 6 mL, and the volume of deionized water is 34 mL.
7. The method of preparing a monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance according to claim 3, wherein: the mass of vanadyl acetylacetonate is 0.2mg, 0.4mg, 0.6mg or 0.8 mg.
8. A monodisperse spindle-shaped monatomic catalyst for denitration and sulfur resistance, which is produced by the production method according to any one of claims 1 to 7.
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