CN114272949A - M1 type molybdenum molecular sieve denitration catalyst with low-temperature ABS poisoning resistance and preparation method thereof - Google Patents
M1 type molybdenum molecular sieve denitration catalyst with low-temperature ABS poisoning resistance and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 231100000572 poisoning Toxicity 0.000 title claims abstract description 26
- 230000000607 poisoning effect Effects 0.000 title claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 13
- 239000011733 molybdenum Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000006184 cosolvent Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003546 flue gas Substances 0.000 abstract description 11
- 229910001868 water Inorganic materials 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 239000002982 water resistant material Substances 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
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Abstract
The invention discloses a low-temperature ABS poisoning resistant M1 type molybdenum molecular sieve denitration catalyst and a preparation method thereof6Octahedra and AO6Octahedron, wherein the element A is one or more of V and Nb, Sb, Te, AO6Octahedron atomic level dispersed in MoO6In the octahedral molecular sieve framework, AO6Octahedron as catalytically active center, MoO6The octahedron is an ABS decomposition center, and the pore structure of the molecular sieve promotes the decomposition of the ABS. Has the advantages that: the defect that the traditional SCR catalyst is easy to deactivate due to ABS deposition at low temperature is effectively overcome, the low-temperature stability of the catalyst is improved, and the energy consumption and the cost for catalyst regeneration are reduced. Molybdenum of type M1 under the conditions of 150 ℃ and 250 ℃ of water containing and sulfur containingThe denitration efficiency of the molecular sieve catalyst can be stably maintained to be more than 80 percent, and N is2The selectivity can reach more than 95 percent, and the method is suitable for controlling the emission of nitrogen oxides in the flue gas of various industrial sources.
Description
Technical Field
The invention relates to the technical field of air pollution control, in particular to a low-temperature ABS poisoning resistant M1 type molybdenum molecular sieve denitration catalyst and a preparation method thereof.
Background
Nitrogen oxide (NOx) is the current primary atmospheric pollutant, relates to a plurality of environmental problems, is an important cause for acid rain, ozone layer destruction, photochemical smog and greenhouse effect, is an important precursor of PM2.5, and brings serious threats to human health and climate environment. Currently, Selective Catalytic Reduction (SCR) technology for NOx and ammonia is one of the most effective, the most mature, and the most widely used emission reduction measures for NOx from both stationary and mobile sources. According to 2011-2015 national environmental statistics bulletin and 2017 Chinese statistics yearbook, the NOx emission in the power industry of China is effectively controlled, wherein the V2O5-WO3/TiO2 catalyst is the most commonly used SCR catalyst in a coal-fired power plant. However, the emission amount of NOx in non-electric industries (such as steel coking, glass cement, garbage incineration and the like) still tends to increase, because the temperature of flue gas in the non-electric industries is low (<300 ℃), SO2 and H2O in the flue gas react with NH3 to generate ammonium hydrogen sulfate (ABS), the ABS is deposited and covered on the surface of the catalyst, active sites of the catalyst are blocked, the catalyst is inactivated, and the service life of the traditional SCR catalyst is remarkably shortened.
At present, the common ABS poisoning resistance method for industrial flue gas denitration utilizes extra energy to heat and decompose ABS so as to achieve the effect of catalyst regeneration, but the energy consumption and the cost of the method are very high. Therefore, the research and development of the novel low-temperature anti-ABS poisoning denitration catalyst has great scientific significance and practical value in the fields of environment and energy. Recently, great progress has been made in developing catalysts having sulfur resistance, and researchers have reduced SO by reducing the redox ability of the catalyst2To reduce SO3Thereby suppressing the generation of ABS. However, the reduction of the redox ability of the catalyst also leads to the reduction of the low-temperature activity, and in addition, ABS is still accumulated slowly, so that the problem of ABS poisoning of the catalyst cannot be fundamentally solved. The development of high-efficiency denitration catalyst for resisting ABS poisoning at low temperature still faces a huge situationThe challenge of (2).
An effective solution to the problems in the related art has not been proposed yet.
Disclosure of Invention
The invention aims to provide a low-temperature ABS poisoning resistant M1 type molybdenum molecular sieve denitration catalyst and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a low-temperature ABS poisoning-resistant M1 type molybdenum molecular sieve denitration catalyst comprises a molecular sieve structure, wherein a molecular sieve framework is composed of MoO6Octahedra and AO6Octahedron, wherein the element A is one or more of V and Nb, Sb, Te, AO6Octahedron atomic level dispersed in MoO6In the octahedral molecular sieve framework, AO6Octahedron as catalytically active center, MoO6The octahedron is an ABS decomposition center, and the pore structure of the molecular sieve promotes the decomposition of the ABS.
Furthermore, the content of V element in the A element is 0.5-15 atom% relative to Mo element, the content of Nb, Sb, Te and other elements is 0-10 atom%, the A site is dispersed in the molecular sieve framework in an atomic level, and the relative content of the A element does not influence the whole structure of the molecular sieve.
According to another aspect of the invention, a preparation method of a low-temperature ABS poisoning resistant M1 type molybdenum molecular sieve denitration catalyst comprises the following steps:
(1) will be (NH)4)6Mo7O24·4H2Dissolving O in ultrapure water to form a clear solution;
(2) dissolving a required amount of soluble precursor salt of the element A in ultrapure water to prepare a clear solution, wherein part of precursor salt with low solubility needs to be added with a cosolvent (such as oxalic acid, ethanol and the like) for dissolution;
(3) mixing the A precursor solution prepared in the step (2) with the Mo precursor solution obtained in the step (1);
(4) taking the sample in the step (3) for a certain time of high-temperature hydrothermal reaction;
(5) and (3) centrifugally separating the solid obtained by the hydrothermal reaction, washing, drying, grinding into fine powder, and calcining to obtain the low-temperature ABS poisoning-resistant denitration catalyst.
Further, the hydrothermal reaction temperature of the step (4) is 150 ℃ and 250 ℃, and the time is 20-48 h.
Further, the low-temperature drying in the step (5) is carried out at the temperature of 80-120 ℃ for 8-12 h.
Further, the calcining conditions in the step (5) are as follows: raising the temperature to 400-500 ℃ at the speed of 5-10 ℃/min, preserving the heat for 2-6h, and then naturally cooling to the room temperature.
Compared with the prior art, the invention has the following beneficial effects:
1. VO is introduced into the reactor6The octahedron atomic level is dispersed in MoO6The low-temperature ABS poisoning resistant denitration catalyst is prepared on a molecular sieve framework structure. Wherein the M1 type molybdenum-oxygen molecular sieve has excellent sulfur-resistant water poisoning-resistant performance and low-temperature ABS decomposition performance, and the low-temperature denitration activity is determined by VO6The octahedron is provided, so that the catalyst can keep excellent stability and activity under the condition of medium-low temperature water-containing sulfur-containing flue gas;
2. comparison of the present invention to commercial V2O5-WO3/TiO2The denitration catalyst has better low-temperature SCR catalytic activity and more excellent sulfur resistance and water resistance;
3. the preparation method adopts a hydrothermal method, and is simple in operation process and high in repeatability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is one of graphs of experimental results of low-temperature ABS poisoning-resistant denitration catalysts prepared in embodiments 1 and 2 of the present invention.
Fig. 2 is a second graph of the experimental results of the low-temperature ABS poisoning-resistant denitration catalyst prepared in example 1 of the present invention.
Fig. 3 is a third graph of the experimental result of the low-temperature ABS poisoning-resistant denitration catalyst prepared in example 2 of the present invention.
Fig. 4 is a graph showing the results of the ammonium bisulfate poisoning resistance test of the VWTi catalyst prepared in example 3 of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and detailed description:
example 1
(1) 3.6 g (NH)4)6Mo7O24·4H2Dissolving O in 30mL of ultrapure water;
(2) take 0.07 g NH4VO3And 0.3 g of cosolvent (oxalic acid) was dissolved in 30mL of ultrapure water;
(3) mixing the materials obtained in the step (1) and the step (2), carrying out hydrothermal reaction at 175 ℃ for 48h, carrying out centrifugal separation and washing on solid powder after the reaction is finished, and drying the solid powder in an oven overnight;
(4) grinding the solid into fine powder, pouring the fine powder into a crucible, and putting the crucible into a muffle furnace for sealed roasting, wherein the sealed roasting specifically comprises the following steps: raising the temperature to 400 ℃ at the speed of 5 ℃/min, preserving the temperature for 4h, and then naturally cooling to room temperature to obtain a powder sample.
The SCR denitration performance of the catalyst was evaluated in a fixed bed reactor. The reaction fume conditions were set to 600 ppm NO and 600 ppm NH3,3 vol% O2,200 ppm SO2(when used), 10 vol% H2O (when used), N2Balance gas, total gas flow is 600 mL/min. And (3) introducing the simulated flue gas into a reaction furnace filled with 0.5 g of the low-temperature ABS poisoning-resistant denitration catalyst, setting the temperature of the reactor to be programmed, and monitoring the gas-phase concentration of each component on line in real time by using a flue gas analyzer. The denitration performance results are shown in fig. 1. As can be seen from fig. 1, the catalyst has good low-temperature denitration catalytic activity. The reactor was programmed to 210 ℃ and held steady, the change in NO concentration at the outlet was recorded, and the NO conversion was calculated. As can be seen from FIG. 2, the NO conversion is stable in the stability test at 210 deg.CAbout 80 percent, the high-performance sulfur-resistant and water-resistant material shows strong sulfur-resistant and water-resistant performance.
Example 2
(1) 3.6 g (NH)4)6Mo7O24·4H2Dissolving O in 30mL of ultrapure water;
(2) taking 0.1g of VOSO4And 0.1g C10H5NbO20·xH2O (MW = 538.04) was dissolved in 30mL of ultrapure water;
(3) mixing the materials obtained in the step (1) and the step (2), carrying out hydrothermal reaction at 180 ℃ for 48h, carrying out centrifugal separation and washing on solid powder after the reaction is finished, and drying the solid powder in an oven overnight;
(4) grinding the solid into fine powder, pouring the fine powder into a crucible, and putting the crucible into a muffle furnace for sealed roasting, wherein the sealed roasting specifically comprises the following steps: raising the temperature to 400 ℃ at the speed of 5 ℃/min, preserving the temperature for 4h, and then naturally cooling to room temperature to obtain a powder sample.
The SCR denitration performance of the catalyst was evaluated in a fixed bed reactor. The reaction fume conditions were set to 600 ppm NO and 600 ppm NH3,3 vol% O2,200 ppm SO2(when used), 10 vol% H2O (when used), N2Balance gas, total gas flow is 600 mL/min. And (3) introducing the simulated flue gas into a reaction furnace filled with 0.5 g of the low-temperature ABS poisoning-resistant denitration catalyst, setting the temperature of the reactor to be programmed, and monitoring the gas-phase concentration of each component on line in real time by using a flue gas analyzer. The denitration performance results are shown in fig. 1. As can be seen from fig. 1, the catalyst has good low-temperature denitration catalytic activity. The reactor was programmed to 210 ℃ and held steady, the change in NO concentration at the outlet was recorded, and the NO conversion was calculated. As can be seen from FIG. 3, in the stability test at 210 ℃, the NO conversion rate is stabilized at about 88%, and the sulfur-resistant and water-resistant performance is shown.
Example 3
For commercial V in fixed bed reactor2O5-WO3/TiO2The SCR denitration performance of the catalyst was evaluated. The reaction fume conditions were set to 600 ppm NO and 600 ppm NH3,3 vol% O2,200 ppm SO2(when used), 10 vol% H2O (when used), N2Balance gas, total gas flow is 600 mL/min. The simulated flue gas was introduced into a commercial V cell containing 0.5 g of2O5-WO3/TiO2In the reaction furnace of the catalyst, the temperature of the reactor is programmed to 230 ℃ and kept stable, and the gas phase concentration of each component is monitored on line in real time by a flue gas analyzer. The results are shown in FIG. 4, and it can be seen from FIG. 4 that the NO conversion rate gradually decreases in the 230 ℃ stability test, indicating that the conventional commercial V2O5-WO3/TiO2The catalyst is deactivated under low temperature conditions comprising water and sulfur.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the invention as defined by the appended claims. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The M1 type molybdenum molecular sieve denitration catalyst with low temperature and ABS poisoning resistance is characterized by comprising a molecular sieve structure, wherein the molecular sieve skeleton is MoO6Octahedra and AO6Octahedron, wherein the element A is one or more of V, Nb, Sb and Te, AO6Octahedron atomic level dispersed in MoO6In the octahedral molecular sieve framework, AO6Octahedron as catalytically active center, MoO6The octahedron is an ABS decomposition center.
2. The denitration catalyst of M1 type Mo molecular sieve based on claim 1, wherein the content of V element relative to Mo element in A element is 0.5-15 atom%, the content of Nb, Sb and Te element is 0-10 atom%, and A site is atomically dispersed in the molecular sieve skeleton.
3. A preparation method of a low-temperature ABS poisoning resistant M1 type molybdenum molecular sieve denitration catalyst is characterized by comprising the following steps:
(1) will be (NH)4)6Mo7O24·4H2Dissolving O in ultrapure water to form a clear solution;
(2) dissolving a required amount of soluble precursor salt of the element A in ultrapure water to prepare a clear solution, wherein part of precursor salt with low solubility needs to be added with a cosolvent (such as oxalic acid, ethanol and the like) for dissolution;
(3) mixing the A precursor solution prepared in the step (2) with the Mo precursor solution obtained in the step (1);
(4) taking the sample in the step (3) for a certain time of high-temperature hydrothermal reaction;
(5) and (3) centrifugally separating the solid obtained by the hydrothermal reaction, washing, drying, grinding into fine powder, and calcining to obtain the low-temperature ABS poisoning-resistant denitration catalyst.
4. The preparation method of the low-temperature ABS poisoning resistant M1 type molybdenum molecular sieve denitration catalyst as claimed in claim 3, wherein the hydrothermal reaction temperature in the step (4) is 150-250 ℃ and the time is 20-48 h.
5. The preparation method of the M1-type molybdenum molecular sieve denitration catalyst with low temperature resistance to ABS poisoning as claimed in claim 3, wherein the low temperature drying in step (5) is carried out at 80-120 ℃ for 8-12 h.
6. The preparation method of the low-temperature ABS poisoning resistant M1 type molybdenum molecular sieve denitration catalyst as claimed in claim 3, wherein the calcination in step (5) is carried out under the following specific conditions: raising the temperature to 400-500 ℃ at the speed of 5-10 ℃/min, preserving the heat for 2-6h, and then naturally cooling to the room temperature.
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