CN113751014B - Monodisperse spindle-shaped monoatomic catalyst for denitration and sulfur resistance and preparation method thereof - Google Patents
Monodisperse spindle-shaped monoatomic 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 47
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 34
- 239000011593 sulfur Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 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
- 125000005287 vanadyl group Chemical group 0.000 claims abstract description 13
- 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 abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000005554 pickling Methods 0.000 claims abstract description 7
- 229920001690 polydopamine Polymers 0.000 claims abstract description 3
- 238000004873 anchoring Methods 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 32
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 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
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 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 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 229910000831 Steel Inorganic materials 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 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
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 230000005476 size effect Effects 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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)
-
- 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
Abstract
The invention discloses a monodisperse spindle-shaped single-atom catalyst for denitration and sulfur resistance and a preparation method thereof. In anchoring monoatomic vanadyl on dopamine hydrochloride, utilizing a tris-hydrochloric acid solution to adjust the pH value is to enable dopamine hydrochloride to undergo a polymerization reaction so as to tightly wrap an iron oxide carrier, calcining at a high temperature to enable polydopamine to be carbonized, and then pickling to remove iron oxide, so that a monodisperse spindle-shaped monoatomic vanadyl catalyst is finally formed.
Description
Technical Field
The invention belongs to the technical field of functional special-shaped monoatomic catalysts, and particularly relates to a monodisperse spindle-shaped monoatomic catalyst for denitration and sulfur resistance and a preparation method thereof.
Background
Energy is the fundamental power for economic development, but is also the source of pollution. Since human beings enter an industrialized society, the social productivity is rapidly developed, the development amount and the use amount of energy are gradually increased, and especially in recent decades, the industrialization process is continuously accelerated, the energy consumption amount and the pollutant emission amount are rapidly increased, and the life and property health and social progress of human beings are seriously affected. Global environmental problems are increasingly prominent, and become a focus of general attention for the masses. Environmental pollution includes atmospheric pollution, water environmental pollution, soil pollution, etc., wherein the atmospheric pollution problem has been a problem that must be faced in the industrialized process all over the world. The atmospheric environmental pollution causes different degrees of harm to human health and various organisms, has seriously affected the physical and psychological health and the quality of life of human beings, and causes great loss to society.
2018. The annual report of BP world energy statistics annual book shows that China accounts for 23.2% and 33.6% of the global energy consumption and the energy consumption increase in 2017 respectively. And live in the global energy growth list for 17 years. After the consumption of coal in China is continuously reduced for three years from 2014 to 2016, the increase of 0.5% is reappeared in 2017. Meanwhile, the coal yield is increased by 3.6% compared with 2016 years. Coal yield and consumption account for 46.4% and 50.7% of the world. 2017. Annual coal has fallen to 27.6% in once-a-year energy consumption. Although the coal ratio in our country energy structure has fallen from 73.6% by ten years and 62.0% by 2016 to 60.4% by 2017, it is still much higher than the world average level, as shown in fig. 1-1. This fully shows that in our country's energy structure, coal still occupies a large specific gravity.
Dispersing metal in the form of single atom in nitrogen-doped carbon material to form M-N x Monoatomic catalysts of the type C (M is a metal monoatom and x is the coordination number of the N atom). It is known that the surface free energy and specific activity of nanomaterials are drastically increased with the decrease of particle size, so that monoatomic catalysts (SACs) have many unique advantages, such as the dispersion of metal elements on a substrate material in an atomic scale, and the full exposure of all active sites, thereby contributing to the improvement of the catalyst activity and the realization of the highest atomic utilization; a single metal atom with a very large surface free energy and high activity may cause quantum size effects. In addition, the specific interactions between the metal atoms and the substrate may promote charge transfer or provide an unsaturated coordination environment for the metal atoms, which is advantageous for improving catalytic activity and selectivity. Typical SACs are mainly dispersed in oxides, sulfides, and carbon-based materialsOr on a metal support. Today, single-atom catalysts, which by virtue of their unique advantages, are the hot spot of research in various fields, have been widely used in a range of redox reaction systems, such as CO oxidation, CO 2 Reduction, oxygen reduction reaction (0 RR), selective hydrogenation, photocatalysts, etc., but there is no suitable technology for successfully applying a single-atom catalyst to the denitration sulfur-resistant field.
Disclosure of Invention
The invention aims to load a high-efficiency denitration sulfur-resistant monoatomic catalyst on ferric oxide, and then remove a monodisperse spindle-shaped ferric oxide template to prepare a spindle-shaped monoatomic catalyst. The monodispersed spindle-shaped ferric oxide carrier ensures that the monoatomic catalyst is uniformly dispersed and has a spindle shape with larger 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 of ferric trichloride hexahydrate is added into a 100mL beaker, 30mL of deionized water is added, stirring is carried out for 30min at room temperature, 5.5mL of triethylamine is added again, the pH is adjusted to 8-9, and stirring is carried out until the solution is fully dissolved. And transferring the reaction solution into a polytetrafluoroethylene liner, performing hydrothermal reaction at 180 ℃ for 10 hours, and cooling at room temperature after the reaction is finished.
2) And (3) filtering and cleaning the reacted reaction liquid with 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 monoatomic catalyst can be prepared by the following method:
(1) Accurately weighing 0.1g of monodisperse spindle-shaped ferric oxide sample, dissolving in 50mL of deionized water to prepare ferric oxide solution, performing ultrasonic dispersion for 20min, and marking as solution A.
(2) Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL deionized water, adding different mass of ethylene-acetone vanadyl (0.2-0.8 mg), and performing ultrasonic dispersion for 30min to obtain a B solution.
(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), continuously stirring at room temperature for 12h, and repeatedly carrying out suction filtration and drying on the reaction solution after the reaction is finished for later use.
(4) And (3) calcining the dried sample in a muffle furnace protected by nitrogen at 900 ℃ for 2 hours to remove organic impurities, cooling, then, repeatedly pickling the calcined sample in a dilute hydrochloric acid solution with the concentration of 5wt% to remove ferric oxide, filtering and washing the pickled sample with deionized water, and finally, drying to obtain the spindle-shaped monoatomic catalyst.
The invention has the advantages that:
1. compared with the existing (lamellar, rod-shaped and spherical) single-atom catalyst, the single-atom catalyst with the synthesized monodisperse spindle-shaped structure can more effectively increase the specific surface area and the reactive sites of the catalyst, can make the catalyst 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 sulfur-resistant catalysts, the monoatomic vanadyl is greatly reduced in cost for preparing the catalyst, and the catalytic capability of active substances can be exerted to the greatest extent, namely, the effect of the original commercial catalyst can be achieved by only using one thousandth of the dosage.
3. As the monoatomic vanadyl has higher chemical valence state compared with common monoatomic catalysts such as monoatomic manganese, cobalt, iron and the like, the higher valence state is favorable for oxidizing NO in the denitration gas to form NO 2 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 requirement is imposed on a reaction container, and the synthetic substance has no pollution to the environment.
Drawings
FIG. 1 is a schematic diagram of a self-made tubular SCR reactor apparatus in a catalyst activity test; in the figure, 1 is an air source; 2 is a pressure reducing valve; 3 is a mass flowmeter; 4 is a mixer; 5 is an air preheater; 6 is a catalytic bed; 7 is a composite material; 8 is a flue gas analyzer;
FIG. 2 is a scanning electron microscope image of a monodisperse spindle-shaped monoatomic catalyst of example 3;
FIG. 3 is an EDX elemental scan of the monodisperse spindle-shaped monoatomic catalyst of example 3;
FIG. 4 is a graph of the catalytic stability analysis of the monodispersed spindle-shaped monoatomic catalyst of example 3.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
Accurately weighing 0.1g of monodisperse spindle-shaped ferric oxide sample, dissolving in 50mL of deionized water to prepare ferric oxide solution, performing ultrasonic dispersion for 20min, and marking as solution A. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL deionized water, adding 0.2mg of ethylene vanadyl acetonate, performing ultrasonic dispersion for 30min, and marking as solution B. 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), continuously stirring at room temperature for 12h, and repeatedly performing suction filtration and drying on the reaction solution after the reaction is finished for later use. And (3) calcining the dried sample in a muffle furnace protected by nitrogen at 900 ℃ for 2 hours to remove organic impurities, cooling, then, repeatedly pickling the calcined sample in a 5% dilute hydrochloric acid solution to remove ferric oxide, filtering and washing the pickled sample with deionized water, and finally, drying to obtain the spindle-shaped monoatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH 3 Volume fractions were 0.05%, O 2 Volume fraction 5% and balance N 2 The gas flow rate was 700 mL/min -1 The temperature is set to 180 ℃, and the denitration rate is 57.1 percent measured by a British KM940 flue gas analyzer; the temperature is set to 200 ℃, the denitration rate is 61.5%, the temperature is set to 220 ℃, the denitration sulfur resistance is 70.8%, the temperature is set to 240 ℃, the denitration sulfur resistance is 81.1%, the temperature is set to 260 ℃, and the denitration sulfur resistance is 77.2%; introducing SO at 240 DEG C 2 Interval 30The min test shows that the final out-of-stock rate is basically stabilized at 54.4%.
Example 2
Accurately weighing 0.1g of monodisperse spindle-shaped ferric oxide sample, dissolving in 50mL of deionized water to prepare ferric oxide solution, performing ultrasonic dispersion for 20min, and marking as solution A. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL deionized water, adding 0.4mg of ethylene vanadyl acetone, performing ultrasonic dispersion for 30min, and marking as solution B. 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), continuously stirring at room temperature for 12h, and repeatedly performing suction filtration and drying on the reaction solution after the reaction is finished for later use. And (3) calcining the dried sample in a muffle furnace protected by nitrogen at 900 ℃ for 2 hours to remove organic impurities, cooling, then, repeatedly pickling the calcined sample in a 5% dilute hydrochloric acid solution to remove ferric oxide, filtering and washing the pickled sample with deionized water, and finally, drying to obtain the spindle-shaped monoatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH 3 Volume fractions were 0.05%, O 2 Volume fraction 5% and balance N 2 The gas flow rate was 700 mL/min -1 The temperature is set to 180 ℃, and the denitration rate is 59.2% measured by using a British KM940 flue gas analyzer; the temperature is set to 200 ℃, the denitration rate is 66.3%, the temperature is set to 220 ℃, the denitration sulfur resistance is 72.2%, the temperature is set to 240 ℃, the denitration sulfur resistance is 86.8%, the temperature is set to 260 ℃, and the denitration sulfur resistance is 79.1%; introducing SO at 240 DEG C 2 The test is carried out at intervals of 30 minutes, and the final out-of-stock rate is basically stabilized at 60.1 percent.
Example 3
Accurately weighing 0.1g of monodisperse spindle-shaped ferric oxide sample, dissolving in 50mL of deionized water to prepare ferric oxide solution, performing ultrasonic dispersion for 20min, and marking as solution A. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL deionized water, adding 0.6mg of ethylene vanadyl acetone, performing ultrasonic dispersion for 30min, and marking as solution B. 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), continuously stirring at room temperature for 12h, and repeatedly performing suction filtration and drying on the reaction solution after the reaction is finished for later use. And (3) calcining the dried sample in a muffle furnace protected by nitrogen at 900 ℃ for 2 hours to remove organic impurities, cooling, then, repeatedly pickling the calcined sample in a 5% dilute hydrochloric acid solution to remove ferric oxide, filtering and washing the pickled sample with deionized water, and finally, drying to obtain the spindle-shaped monoatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH 3 Volume fractions were 0.05%, O 2 Volume fraction 5% and balance N 2 The gas flow rate was 700 mL/min -1 The temperature is set to 180 ℃, and the denitration rate is 65.5 percent measured by a British KM940 flue gas analyzer; the temperature is set to 200 ℃, the denitration rate is 71.6%, the temperature is set to 220 ℃, the denitration sulfur resistance is 82.6%, the temperature is set to 240 ℃, the denitration sulfur resistance is 93.4%, the temperature is set to 260 ℃, and the denitration sulfur resistance is 81.1%; introducing SO at 240 DEG C 2 The final out-of-stock rate was substantially stabilized at 69.9% for 30min testing intervals.
FIG. 2 is a scan of a monodisperse spindle-shaped monoatomic catalyst, which can be seen to have better dispersibility and structural stability; FIG. 3 is an EDX element scan of a monodisperse spindle-shaped monoatomic catalyst, which shows that the surface of the catalyst is uniformly loaded with several elements of O, V, C and N, and illustrates that monoatomic vanadyl is successfully loaded on the surface of polydopamine; fig. 4 is a graph of the catalytic stability analysis of a monodisperse spindle-shaped monoatomic catalyst, and it can be seen that the catalyst has better stability within 20h, and the denitration rate can be kept at about 88%.
Example 4
Accurately weighing 0.1g of monodisperse spindle-shaped ferric oxide sample, dissolving in 50mL of deionized water to prepare ferric oxide solution, performing ultrasonic dispersion for 20min, and marking as solution A. Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL deionized water, adding 0.6mg of ethylene vanadyl acetone, performing ultrasonic dispersion for 30min, and marking as solution B. 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), continuously stirring at room temperature for 12h, and repeatedly performing suction filtration and drying on the reaction solution after the reaction is finished for later use. And (3) calcining the dried sample in a muffle furnace protected by nitrogen at 900 ℃ for 2 hours to remove organic impurities, cooling, then, repeatedly pickling the calcined sample in a 5% dilute hydrochloric acid solution to remove ferric oxide, filtering and washing the pickled sample with deionized water, and finally, drying to obtain the spindle-shaped monoatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH 3 Volume fractions were 0.05%, O 2 Volume fraction 5% and balance N 2 The gas flow rate was 700 mL/min -1 The temperature is set to 180 ℃, and the denitration rate is 60.7% measured by using a British KM940 flue gas analyzer; the temperature is set to 200 ℃, the denitration rate is 66.5%, the temperature is set to 220 ℃, the denitration sulfur resistance is 75.3%, the temperature is set to 240 ℃, the denitration sulfur resistance is 88.9%, the temperature is set to 260 ℃, and the denitration sulfur resistance is 80.2%; introducing SO at 240 DEG C 2 The final out-of-stock rate was substantially stabilized at 63.3% for 30min testing intervals.
Example 5
Accurately weighing 0.15g of dopamine hydrochloride, dissolving the dopamine hydrochloride in 50mL deionized water, adding 0.6mg of vinyl acetone vanadyl, ultrasonically dispersing for 30min, stirring for 30min at room temperature, adding 40mL tris-hydroxymethyl aminomethane-hydrochloric acid solution (wherein tris is 0.24 g, hydrochloric acid 6 mL and deionized water 34 mL), continuously stirring for 12h at room temperature, and repeatedly performing suction filtration and drying on the reaction solution after the reaction is finished for standby. And (3) placing the dried sample in a nitrogen protection muffle furnace at 900 ℃ for calcining for 2 hours to remove organic impurities, filtering and washing the calcined sample with deionized water, and finally drying to obtain the carrier-free monoatomic catalyst to be tested.
The denitration and sulfur resistance of the composite material is evaluated in a self-made tubular SCR reactor. NO and NH 3 Volume fractions were 0.05%, O 2 Volume fraction 5% and balance N 2 The gas flow rate was 700 mL/min -1 The temperature is set to 180 ℃, and British KM940 smoke is usedThe denitration rate measured by the gas analyzer is 55.1%; the temperature is set to 200 ℃, the denitration rate is 61.5%, the temperature is set to 220 ℃, the denitration sulfur resistance is 66.7%, the temperature is set to 240 ℃, the denitration sulfur resistance is 74.8%, the temperature is set to 260 ℃, and the denitration sulfur resistance is 71.2%; introducing SO at 240 DEG C 2 The final out-of-stock rate was substantially stabilized at 47.8% for 30min testing intervals. Evaluation of Activity: the catalyst was evaluated in a home-made tubular SCR reactor. The reactor is externally electrically heated, a thermocouple is placed beside the catalyst bed of the reaction tube to measure the temperature, and the flow of the experimental device is shown in figure 1. The steel gas cylinder simulates the composition of smoke, wherein the smoke comprises NO and O 2 、N 2 、NH 3 For reducing gases, NO and NH 3 The volume fractions are 0.04-0.06%, O 2 The volume fraction is 4-6%, the rest is N 2 The gas flow rate was 700 mL/min -1 The temperature is controlled between 120 ℃ and 200 ℃, and the gas flow and composition are regulated and controlled by a mass flowmeter. The gas analysis adopts a British KM940 flue 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 composite materials (reaction temperature 240 ℃ C.)
As can be seen from the data in table 1, at 240 ℃, with the increasing quality of vanadyl acetylacetonate, the denitration sulfur resistance tends to increase and decrease, which is caused by the increase of the content of monoatomic vanadyl, but excessive addition can lead to agglomeration of vanadyl, resulting in the decrease of the denitration rate in the later stage. A maximum value occurs at a vanadyl acetylacetonate mass of 0.6 mg. And the sulfur resistance also reaches a maximum.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (3)
1. A preparation method of a monodisperse spindle-shaped monoatomic catalyst for denitration and sulfur resistance is characterized by comprising the following steps of: the catalyst is prepared by taking monodisperse spindle-shaped ferric oxide as a carrier, dopamine hydrochloride as a carbon source, a precursor and a coating of a nitrogen source, vanadyl acetylacetonate as a vanadyl monoatomic source, anchoring vanadyl to polydopamine through polymerization reaction of dopamine hydrochloride and simultaneously coating the ferric oxide, and finally removing unreacted organic matters and ferric oxide through calcination and acid washing to obtain the monodisperse spindle-shaped monoatomic catalyst;
the preparation method comprises the following steps:
(1) 0.1g of monodisperse spindle-shaped ferric oxide is dissolved in 50mL of deionized water to prepare ferric oxide solution, and the ferric oxide solution is subjected to ultrasonic dispersion for 20min and marked as solution A;
(2) Dissolving 0.15g of dopamine hydrochloride in 50mL of deionized water, adding 0.6mg of ethylene-acetone vanadyl, and performing ultrasonic dispersion for 30min to obtain a B solution;
(3) Adding the solution B into the solution A, stirring for 30min at room temperature, adding a tris (hydroxymethyl) aminomethane-hydrochloric acid solution, continuously stirring for 12h at room temperature, and repeatedly carrying out suction filtration and drying on the reaction solution after the reaction is finished for later use;
(4) Calcining the dried sample in the step (3) in a muffle furnace protected by nitrogen at 900 ℃ for 2 hours to remove organic impurities, cooling, then repeatedly pickling the calcined sample in a dilute hydrochloric acid solution with the weight of 5% to remove ferric oxide, filtering and washing the pickled sample with deionized water, and finally drying to obtain the monodisperse spindle-shaped monoatomic catalyst;
the monodisperse spindle-shaped ferric oxide carrier is prepared by the following steps:
1) Adding 0.5g of ferric trichloride 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 to 8-9, and stirring until the solution is fully dissolved; transferring the reaction solution into a polytetrafluoroethylene liner, performing hydrothermal reaction at 180 ℃ for 10 hours, and cooling at room temperature after the reaction is finished;
2) And (3) filtering and cleaning the reacted reaction liquid with 100mL of deionized water and ethanol, and drying the obtained product at 70 ℃ for 5 hours to obtain the monodisperse spindle-shaped ferric oxide carrier.
2. The method for preparing the monodisperse spindle-shaped monoatomic catalyst for denitration and sulfur resistance as claimed in claim 1, wherein the method comprises the following steps: the volume of the tris-hydrochloric acid solution of step (3) was 40mL, wherein the tris mass was 0.24 g, the hydrochloric acid volume was 6 mL, and the deionized water volume was 34mL.
3. A monodisperse spindle-shaped monoatomic catalyst for denitration and sulfur resistance prepared by the preparation method as claimed in any one of claims 1 to 2.
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