CN114160122A - A kind of fly ash-based anti-ammonium hydrogen sulfate poisoning wide temperature area SCR catalyst and its preparation method and application - Google Patents
A kind of fly ash-based anti-ammonium hydrogen sulfate poisoning wide temperature area SCR catalyst and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
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- 239000011159 matrix material Substances 0.000 claims abstract description 31
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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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Abstract
The invention discloses an ammonium bisulfate poisoning prevention wide-temperature-zone SCR catalyst taking fly ash as a substrate, and a preparation method and application thereof. The preparation method comprises the steps of mixing the porous fly ash and the wide-temperature-zone SCR catalyst, and grinding to obtain the catalyst. The wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning, which takes the fly ash as the matrix, can effectively prevent the ammonium bisulfate poisoning within a wider temperature range, effectively broadens the use temperature zone of the SCR catalyst, is suitable for medium-low-temperature SCR denitration, is easy to regenerate in the actual use process, can realize the recycling of the catalyst without stopping the machine, has high use value and good application prospect, and has very important significance for effectively improving the flue gas denitration efficiency of a coal-fired power plant. The preparation method of the catalyst has the advantages of simple process, convenient operation and the like, does not need special equipment, and is easy to realize industrial production.
Description
Technical Field
The invention belongs to the field of tail flue gas denitration, and relates to an ammonium bisulfate poisoning prevention wide-temperature-zone SCR catalyst taking fly ash as a substrate, and a preparation method and application thereof.
Background
Currently, NO in flue gas of coal-fired power plantsxThe removal is usually performed by selective catalytic reduction denitration (SCR) technology, and is often a "high temperature + high dust" arrangement. Along with the adjustment of the energy structure, the coal-electric unit faces a heavier peak regulation task, and the low-load operation and the deep peak regulation of the coal-electric unit become normal states. Method for removing NO in flue gas of coal-fired power plant by SCR technologyxIn the process, the commercial denitration catalyst, such as V-W/Ti SCR catalyst, is used, and the operation temperature range is 320-420 ℃. When the coal-electric unit operates at low load, the smoke temperature at the SCR inlet is lower than the catalyst activity temperature window, which can cause the activity of the catalyst to be reduced and can intensify SO2Poisoning, in turn, causing NOxAnd (5) excessive emission. In fact, the catalyst activity decreases and SO is generated under low temperature conditions2The root cause of the poisoning is due to SO in the coal-fired flue gas3And NH3The reaction produces Ammonium Bisulfate (ABS). ABS can be deposited in a liquid state in a microscopic pore structure of the catalyst under low temperature conditions to cause pore blocking to cover active sites, and the deposition of ABS in catalyst channels conforms to the capillary condensation effect, so that higher temperature is required for decomposing the ABS deposited in the pores. After ABS is deposited, the ABS can further interact with the catalyst to sulfate the active components of the catalyst, so that the catalyst is deactivated, and the denitration efficiency is reduced. Therefore, the coal-fired power plant usually sets the lowest ammonia injection temperature (about 320 ℃), and the denitration system is not operated when the flue gas temperature is lower than the lowest ammonia injection temperature, so that the NOx is discharged out of limits. Flue gas temperature of coal-fired power plant under low load conditionThe necessary reduction and the key for ensuring high-efficiency denitration are to improve the low-temperature activity and the sulfur resistance of the catalyst. Based on this, the prior art realizes the optimal performance of the SCR denitration catalyst under low load mainly by improving the SCR inlet smoke temperature, but the problems of high modification cost, long shutdown period, low boiler efficiency, poor system reliability and the like exist by adopting a smoke reheating system to heat the SCR inlet smoke temperature.
The development of wide-temperature-range catalysts for preventing ABS poisoning is a key for overcoming the economic and environmental challenges under the current deep peak regulation by the SCR denitration technology at present. The improvement of the low-temperature activity of the catalyst has been reported. For example, catalysts with Cu or Mn oxides as active components have good low temperature NH3SCR activity, but its active site is very labile in SO2And the sulfation occurs under the environment, which leads to serious chemical deactivation, and finally, the catalyst cannot adapt to the treatment conditions of most industrial waste gases. As another example, low temperature catalysts based on Cu-based molecular sieves have better SO2Tolerance, but because the preparation method is complex, the regeneration temperature is as high as 650 ℃, the problems of catalyst blockage and poisoning caused by ABS deposition cannot be effectively relieved, and thus commercialization is difficult to realize in the field of coal burning. Therefore, the high-activity wide-temperature-zone SCR catalyst which can effectively prevent ABS poisoning and is easy to regenerate is obtained, and has very important significance for improving the flue gas denitration efficiency of a coal-fired power plant.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the wide-temperature-region SCR catalyst which can effectively prevent ABS poisoning and is easy to regenerate and takes fly ash as a substrate, and the preparation method and the application thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an ammonium bisulfate poisoning prevention wide-temperature-zone SCR catalyst with fly ash as a substrate takes porous fly ash as a substrate; and a wide-temperature-zone SCR catalyst is attached to the surface of the porous fly ash.
The wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning and taking the fly ash as the matrix is further improved, and the porous fly ash is prepared by treating the fly ash with a sodium hydroxide solution.
The wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning, which takes the fly ash as a substrate, is further improved, and is a V-W/Ti series SCR catalyst.
The wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning by taking the fly ash as the matrix is further improved, and the V-W/Ti series SCR catalyst is V-W-Mn/TiO2-SiO2Catalyst, V-W/TiO2At least one of a catalyst and a Mn/Ce catalyst.
The V-W-Mn/TiO wide-temperature-zone SCR catalyst taking the fly ash as the matrix and preventing ammonium bisulfate poisoning is further improved2-SiO2The catalyst is TiO2-SiO2The composite oxide is used as a carrier, and the TiO2-SiO2The composite oxide is loaded with an active component V, an active component Mn and an active auxiliary agent W; the V-W-Mn/TiO2-SiO2In the catalyst, the mass fraction of an active component V is 1-1.5%, the mass fraction of an active component Mn is 5-10%, the mass fraction of an active auxiliary agent W is 6-8%, and the balance is TiO2-SiO2A composite oxide; the active component V is V2O5(ii) a The active component Mn is MnO2(ii) a The coagent W is WO3(ii) a The TiO is2-SiO2SiO in composite oxide2The occupied mole fraction is 5 percent to 20 percent.
As a general technical concept, the invention also provides a preparation method of the wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning by taking the fly ash as a substrate, which comprises the following steps: and mixing and grinding the porous fly ash and the wide-temperature-zone SCR catalyst to obtain the wide-temperature-zone SCR catalyst which takes the fly ash as a substrate and prevents ammonium bisulfate poisoning.
The preparation method is further improved, and the mass ratio of the porous fly ash to the wide-temperature-zone SCR catalyst is 1: 2-3.
In the preparation method, the porous fly ash is further improved by the following preparation method: mixing the fly ash with a sodium hydroxide solution, stirring, cleaning to be neutral, drying, grinding and sieving to obtain porous fly ash; the solid-liquid ratio of the fly ash to the sodium hydroxide solution is 1 g-2 g: 10 mL; the particle size of the fly ash is less than 0.1 mm; the concentration of the sodium hydroxide solution is 0.2 mol/L; the stirring is carried out at a temperature of 80 ℃; the stirring time is 1 h.
In the preparation method, the SCR catalyst in the wide temperature zone is V-W-Mn/TiO2-SiO2When the catalyst is prepared by the following method:
(1) dissolving titanyl sulfate and neutral silica sol in deionized water;
(2) dropwise adding ammonia water into the solution obtained in the step (1), stirring until the pH value of the solution reaches 10, standing and aging at 30-40 ℃ for 10 hours, filtering, washing the obtained precipitate with deionized water, and drying at 150 ℃ for 10 hours;
(3) heating the precipitate dried in the step (2) to 500 ℃ in the air atmosphere, and roasting for 3 hours to obtain TiO2-SiO2A composite oxide.
(4) Dissolving manganese acetate, ammonium metavanadate and ammonium tungstate in a citric acid solution, and adding the TiO obtained in the step (3)2-SiO2Mixing the composite oxide for 1 hour;
(5) heating the mixed solution obtained after stirring in the step (4) to 100 ℃ until the water is evaporated to dryness;
(6) drying the solid mixture obtained in the step (5) after the moisture is evaporated to dryness at the temperature of 120 ℃ for 10 hours, and calcining the solid mixture at the temperature of 500 ℃ for 3 hours to obtain V-W-Mn/TiO2-SiO2A catalyst.
As a general technical concept, the invention also provides an application of the wide-temperature-region SCR catalyst for preventing ammonium bisulfate poisoning by taking the fly ash as the matrix or the wide-temperature-region SCR catalyst for preventing ammonium bisulfate poisoning by taking the fly ash as the matrix, which is prepared by the preparation method, in coal-fired flue gas denitration.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides an ammonium bisulfate poisoning prevention wide-temperature-zone SCR catalyst taking fly ash as a substrate. According to the invention, the SCR catalyst with the wide temperature zone is attached to the porous fly ash, the microscopic pore structure in the porous fly ash can be utilized to adsorb and deposit ABS in the catalyst main body, and the ABS is gathered in the internal pores of the porous fly ash, so that the deposition and blockage of the ABS in the pores of the catalyst main body can be effectively avoided, the inactivation caused by the fact that the catalyst is covered by the ABS or sulfated can be avoided, the problem of catalyst poisoning caused by the ABS can be effectively solved, the catalyst has higher water-resistant sulfur-resistant and denitration activity within the temperature of 180 ℃ plus 420 ℃, and the stability of the catalyst is high; furthermore, the liquid ABS deposited in the porous fly ash can start to decompose at about 350 ℃, so that the catalyst can be subjected to real-time online cyclic regeneration in a normal SCR operation temperature region, and the catalyst can be recycled without stopping the machine. Therefore, the wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning, which takes the fly ash as the matrix, can effectively prevent the ammonium bisulfate poisoning within a wider temperature range, effectively broadens the use temperature zone of the SCR catalyst, is suitable for medium-low-temperature SCR denitration, is easy to regenerate in the actual use process, can realize the recycling of the catalyst without stopping, has high use value and good application prospect, and has very important significance for effectively improving the flue gas denitration efficiency of a coal-fired power plant.
(2) In the wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning, which takes fly ash as a substrate, the adopted porous fly ash is obtained by modifying the fly ash with a sodium hydroxide solution, the fly ash is treated with the sodium hydroxide solution, Si-OH on the surface of the fly ash can be neutralized, the modification of the surface of the fly ash is realized, the surface activity is increased, Si-Si bonds in the fly ash can be destroyed, and a porous structure is formed in the fly ash by dissolving corresponding components in the fly ash, namely the porous fly ash. Compared with other matrix materials (such as porous activated carbon and porous molecular sieve), the invention takes the porous fly ash as the matrix, has lower preparation cost, richer and adjustable pore structure and wider temperature zone, is easier to realize the in-situ regeneration of the catalyst, does not need to carry out redundant regeneration operation, and has lower regeneration period and cost.
(3) In the wide-temperature-zone SCR catalyst for preventing ABS poisoning and taking fly ash as a substrate, the adopted wide-temperature-zone SCR catalyst is V-W-Mn/TiO2-SiO2A catalyst. Compared with the traditional catalyst (V-W/TiO)2) V-W-Mn/TiO adopted by the invention2-SiO2In the catalyst, with TiO2-SiO2The composite oxide is used as a carrier, wherein SiO is introduced into the carrier material2Inhibition of SO on the catalyst2To SO3The catalytic oxidation reaction of (1) and the improvement of the SO resistance of the catalyst2Poisoning properties, and SiO added2The pore structure of the catalyst can be regulated, the deposition of ABS in the pores of the catalyst is reduced, and the physical and chemical poisoning of the catalyst caused by ABS is effectively relieved; meanwhile, the added active component Mn can improve the low-temperature activity of the catalyst and widen the active temperature region of the catalyst, thereby ensuring that the catalyst has better denitration activity under the condition of low load, realizing high-efficiency denitration within the wide temperature region range of 180-420 ℃, and having higher NOx conversion rate. Furthermore, by optimizing the mass fraction of the active component Mn in the catalyst to be 5-10%, the agglomeration of the active component can be avoided on the premise of effectively improving the activity of the catalyst, because the low content of the active component of the catalyst and the low activity of the catalyst can be caused when the content of Mn is too low, and the dispersion loading of the active component on the surface of the carrier is not facilitated when the content of the active component is too high, and the agglomeration phenomenon of the excessive active component on the surface of the carrier is caused, but the denitration activity of the catalyst is not facilitated to be improved.
(4) The invention provides a preparation method of an ammonium bisulfate poisoning-prevention wide-temperature-zone SCR catalyst by taking fly ash as a substrate, which has the advantages of simple process, convenient operation, mild reaction conditions and the like, does not need special chemical equipment, and is easy to realize industrial production.
(5) In the preparation method, the mass ratio of the porous fly ash to the wide-temperature-zone SCR catalyst is 1: 2-3, so that the catalyst can be effectively loaded on the surface of the porous fly ash to the maximum extent, and the catalyst can be uniformly dispersed on the surface of the porous fly ash, thereby being beneficial to obtaining better catalytic activity; meanwhile, the pore structure of the porous fly ash cannot be blocked, and ABS can be ensured to smoothly enter the porous fly ash, so that the catalyst poisoning can be prevented more favorably. In addition, the subsequent regeneration process of the catalyst is easier to realize by optimizing the using amount of the catalyst, the regeneration operation is simpler, the regeneration period is shorter, and the regeneration cost is lower.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a flow chart of a preparation process of an ammonium bisulfate poisoning prevention wide-temperature-zone SCR catalyst using fly ash as a substrate in example 1 of the present invention.
FIG. 2 shows that the fly ash-based wide temperature range SCR catalyst (A, B, C, D) for preventing ammonium bisulfate poisoning, the porous fly ash (a) and V-W-Mn/TiO prepared under different mass ratios of the porous fly ash to the wide temperature range SCR catalyst in example 1 of the present invention2-SiO2SEM image of catalyst (b).
FIG. 3 shows V-W-Mn/TiO concentrations of various active ingredients prepared in example 1 of the present invention2-SiO2Catalyst pair SO3Conversion is plotted.
FIG. 4 shows V-W/TiO deposited with ABS of the present invention2An infrared spectrogram of the porous fly ash composite catalyst.
FIG. 5 shows V-W/TiO deposited with ABS of the present invention2TG-MS diagram of porous fly ash composite catalyst.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
Example 1
The wide temperature zone SCR catalyst for preventing ammonium bisulfate poisoning with flyash as base material has porous flyash as base material and wide temperature zone SCR catalyst adhered to the surface of the porous flyash.
In this example, the SCR catalyst in the wide temperature zone was V-W-Mn/TiO2-SiO2A catalyst. The V-W-Mn/TiO2-SiO2The catalyst is TiO2-SiO2Composite oxide as carrier, TiO2-SiO2The composite oxide is loaded with an active component V, an active component Mn and a coagent W, wherein the active component V is V2O5Mn as an active component is MnO2The coagent W is WO3(ii) a The V-W-Mn/TiO2-SiO2The mass fraction of an active component V in the catalyst is 1.096%, the mass fraction of an active component Mn is 5.019%, the mass fraction of an active auxiliary agent W is 6.29%, and the balance is TiO2-SiO2A composite oxide; TiO 22-SiO2SiO in composite oxide2The occupied mole fraction is 20%.
A preparation method of the wide temperature zone SCR catalyst for preventing ammonium bisulfate poisoning using fly ash in the embodiment is shown in fig. 1, and includes the following steps:
(1) preparation of the catalyst body: 3mL of neutral silica Sol (SiO) having a mass concentration of 30% and a relative density of 1.2 was added to 10mL of deionized water2The molar masses were 2.8mL × 1.2g/mL × 30%/60 ═ 0.018mol) and 28.944g of titanium sulfate Ti (SO)4)2·9H2O(TiO2The molar weight of 28.944g/402g/mol is 0.072mol), stirring till complete dissolution, continuously stirring, dropwise adding ammonia water into the solution until the pH value reaches 10, standing and aging for 10h at 35 ℃, filtering and washing the precipitate to be neutral after formation, and drying in an oven at 150 ℃ for 10 h. Then placing the precipitate into a muffle furnace, and roasting for 3 hours at 500 ℃ in the air atmosphere to obtain TiO2-SiO2Composite oxide (TiO)2-SiO2Composite support) of SiO2Is 20%. 0.11g of ammonium metavanadate NH was weighed4VO(0.11g/117g/mol＝0.9401×10-3mol) and 0.55g ammonium tungstate (NH)4)10W12O41·4H2O(0.55g/3114.58g/mol＝0.1765×10-3mol) and 1.13g of manganese nitrate Mn (NO)3)2·4H2O (1.13g/251g/mol＝0.4501×10-2mol) dissolved in 60mL of citric acid 10 wt.% C6H2O7·H2Stirring to dissolve completely in O, adding TiO2-SiO2The composite oxide was stirred at room temperature for 1 hour. Transferring the solution into a rotary evaporator, evaporating to remove water in a water bath at 100 ℃, transferring the product after evaporation to a drying oven, drying at 120 ℃ for 10h, placing the obtained solid mixture into a muffle furnace, calcining at 500 ℃ in an air atmosphere for 3h, grinding, granulating, and sieving to 40-60 meshes to obtain 7.8096g V-W-Mn/TiO2-SiO2A catalyst.
(2) Preparing a porous fly ash matrix: weighing 6.5g of fly ash with the particle size of less than 0.1mm, placing the fly ash in 50mL of NaOH solution with the concentration of 0.2mol/L, magnetically stirring for 1h at the temperature of 80 ℃, filtering, reacting and repeatedly washing precipitates with deionized water until the precipitates are neutral, then transferring the precipitates into an oven to dry at the temperature of 110 ℃, grinding and sieving to obtain 3.9g of porous fly ash.
(3) Preparing a catalyst: the prepared V-W-Mn/TiO is mixed according to the mass ratio of 2: 12-SiO2And (3) mechanically mixing the catalyst and the porous fly ash in a mortar, and fully grinding and mixing to obtain the wide-temperature-zone SCR catalyst which takes the fly ash as a substrate and prevents ammonium bisulfate poisoning, wherein the number of the SCR catalyst is A.
An application of the ammonium hydrogen sulfate poisoning prevention wide-temperature-region SCR catalyst using fly ash as the matrix in the denitration of coal-fired flue gas in the embodiment is specifically to use the ammonium hydrogen sulfate poisoning prevention wide-temperature-region SCR catalyst using fly ash as the matrix to remove Nitrogen Oxides (NO) in coal-fired flue gasx) Performing selective catalytic reduction treatment to remove Nitrogen Oxides (NO)x) Converted to nitrogen and water.
In the embodiment 1 of the invention, porous fly ash is used as a substrate, and a wide-temperature-zone SCR catalyst (V-W-Mn/TiO) is attached to the surface of the substrate2-SiO2A catalyst). When the flue gas is subjected to denitration treatmentFrom SO3And NH3The Ammonium Bisulfate (ABS) is generated by reaction and is firstly deposited in the catalyst main body, so that the microscopic pore structure in the porous fly ash can be utilized to adsorb and deposit the ABS in the catalyst main body, and the ABS is gathered in the internal pores of the porous fly ash, thereby effectively avoiding the deposition and blockage of the ABS in the pores of the catalyst main body, avoiding the inactivation caused by the covering or sulfation of the catalyst by the ABS, effectively solving the problem of catalyst poisoning caused by the ABS, and leading the catalyst to have higher water-resistant sulfur-resistant and denitration activity within the temperature of 420 ℃ of 180-; furthermore, the liquid ABS deposited in the porous fly ash can start to decompose at 350 ℃, so that the catalyst can be subjected to real-time online cyclic regeneration in a normal SCR operation temperature region, and the catalyst can be recycled without stopping the machine. Therefore, the wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning, which takes the fly ash as the matrix, can effectively prevent ammonium bisulfate poisoning within a wider temperature range, effectively broadens the use temperature zone of the SCR catalyst, is suitable for medium-low-temperature SCR denitration, is easy to regenerate in the actual use process, can realize the recycling of the catalyst without stopping, has high use value and application prospect, and has very important significance for effectively improving the flue gas denitration efficiency of a coal-fired power plant.
In the embodiment, the wide-temperature-zone SCR catalyst which takes the fly ash as the matrix and is used for preventing ammonium bisulfate poisoning and is prepared under the condition of different mass ratios of the porous fly ash to the wide-temperature-zone SCR catalyst, wherein V-W-Mn/TiO2-SiO2The mass ratio of the catalyst to the porous fly ash is 1: 3, 1: 2 and 1: 1 respectively, and the serial numbers are B, C, D.
FIG. 2 shows that the fly ash-based wide temperature zone SCR catalyst (A, B, C, D) for preventing ammonium bisulfate poisoning, the porous fly ash (a) and V-W-Mn/TiO prepared under different mass ratios of the porous fly ash to the wide temperature zone SCR catalyst in example 1 of the present invention2-SiO2SEM image of catalyst (b). In FIG. 2, a is porous fly ash and b is V-W-Mn/TiO2-SiO2A catalyst. As can be seen from FIG. 2, V-W-Mn/TiO2-SiO2When the mass ratio of the catalyst to the porous fly ash is 2: 1V-W-Mn/TiO in the prepared wide-temperature-zone SCR catalyst (A) for preventing ammonium bisulfate poisoning by taking fly ash as a substrate2-SiO2The catalyst can better wrap porous fly ash particles and is V-W-Mn/TiO2-SiO2The active components of the catalyst are uniformly covered on the surface of the porous fly ash, so that more active components can directly participate in the denitration reaction in the catalyst prepared under the condition, and the catalyst with excellent catalytic activity can be obtained more easily. However, when V-W-Mn/TiO2-SiO2After the mass ratio of the catalyst to the porous fly ash is increased to 1: 1, namely after the using amount of the porous fly ash is increased, V-W-Mn/TiO2-SiO2The catalyst begins to be difficult to coat with the larger size beads in the fly ash. After the usage amount of the porous fly ash is further increased, the relative content of the catalyst is less, and the fly ash particles cannot be effectively wrapped and are dispersed with the fly ash microbeads. It is clear that the same V-W-Mn/TiO ratio increases with the amount of the porous fly ash2-SiO2Under the condition of the using amount of the catalyst, the content of active components capable of participating in denitration reaction is reduced, and the fly ash particles cannot be fully wrapped by the catalyst components, so that the fly ash without denitration performance is exposed in flue gas, the denitration effect cannot be exerted, and the denitration performance of the finished catalyst is influenced.
In the embodiment 1 of the invention, V-W-Mn/TiO with five different active component contents of A-E are also prepared2-SiO2Catalyst, except for the active ingredient content, other conditions were the same as those of the medium V-W-Mn/TiO prepared in example 12-SiO2The catalyst was the same. Simultaneously considers the content of Si in the active component V and the catalyst to SO3The influence of the conversion is, in particular: using the above catalyst for the treatment of SO2The catalytic reaction of the flue gas is carried out, and the result is shown in figure 3. FIG. 3 shows V-W-Mn/TiO concentrations of various active ingredients prepared in example 1 of the present invention2-SiO2Catalyst pair SO3Conversion is plotted. As can be seen from FIG. 3, V-W-Mn/TiO2-SiO2SO on the surface of the catalyst2To SO3The conversion rate of the catalyst is positively correlated with the content of the active component V, and V-W-Mn/TiO2-SiO2Increase of Si content and SO content in catalyst3The conversion is in a negative correlation, which indicates that increasing the content of active component V favors SO3While the addition of Si can suppress SO on the surface of the catalyst3Thereby being beneficial to improving the sulfur resistance of the catalyst.
In the invention, the influence of different porous matrix materials on the performance of the catalyst is also considered, for example, when porous activated carbon and porous molecular sieve are used as matrixes, the following adverse factors exist: (a1) the porous activated carbon and the porous molecular sieve have higher relative cost, and the matrix has high denitration reaction and SO in the matrix2To SO3The role of the transformation side reaction is not clear. (a2) Other porous materials, especially zeolite molecular sieves and the like are mostly prepared by adopting a template agent, the pore structure is single and cannot be regulated, and the adopted porous activated carbon material is not suitable for a high-temperature denitration environment and is only suitable for preparing a low-temperature catalyst. Compared with the conventional porous matrix material, the porous fly ash is used as the matrix in the application, and the application has the following advantages: (b1) the fly ash has wide source and is easy to obtain, and the sodium hydroxide solution is adopted to modify the fly ash, so that the preparation cost is relatively lower; (b2) the main substance in the porous fly ash is SiO2，SiO2The presence of (B) inhibits SO2To SO3Therefore, the porous fly ash is used as a substrate, and the activity of the catalyst is not negatively influenced; (b3) the porous fly ash is obtained by modifying the sodium hydroxide solution, so that the surface activity of the porous fly ash can be increased, the porous structure in the fly ash is rich, and the porous structure is easy to regulate and control; (b4) the porous fly ash has a stable structure and excellent high temperature resistance, can be used under a high temperature condition, is beneficial to widening the application temperature zone of the catalyst, is more beneficial to decomposing absorbed ABS by heating, is easy to realize in-situ regeneration of the catalyst, does not need to carry out redundant regeneration operation, and has a lower regeneration period and lower cost.
In the present invention, the effect on catalyst performance was also examined when porous fly ash was used as the substrate, e.g., the porous fly ash prepared in example 1 was used as V-W/TiO2A substrate for a catalyst, the V-W/TiO2In the preparation method of the porous fly ash composite catalyst, porous fly ash and V-W/TiO2Quality of the catalystThe ratio is 1: 2. At the same time, examine SO2For V-W/TiO2Poisoning effect of porous fly ash composite catalyst and V-W/TiO2Porous fly ash composite catalyst with pore structure characteristic and V-W/TiO2The decomposition characteristic of ABS in the porous fly ash composite catalyst.
First, examine SO2For V-W/TiO2Poisoning effect of porous coal ash composite catalyst, continuously introducing SO at 280 DEG C2+O2+NH3Gas, study SO2For V-W/TiO2The poisoning effect of the porous fly ash composite catalyst is shown in fig. 4.
FIG. 4 shows V-W/TiO deposited with ABS of the present invention2An infrared spectrogram of the porous fly ash composite catalyst. In FIG. 4, (a) is a V-W/TiO ABS-supported by dipping method2Catalyst, ABS mass content 5%; (b) SO at 280 DEG C2+O2+NH3V-W/TiO for generating deposited ABS under atmosphere2A catalyst; (c) V-W/TiO for loading ABS by dipping method2Catalyst, ABS mass content is 1%; (d) SO at 280 DEG C2+O2+NH3V-W/TiO for generating deposited ABS under atmosphere2Porous coal ash composite catalyst. As can be seen from FIG. 4, for the conventional V-W/Ti catalyst (b), the resultant is indeed deposited on the surface of the catalyst in the form of ABS, and is substantially consistent with the surface chemical characteristics of the catalyst supporting ABS by the impregnation method (a and c). And for the catalyst (d) using the porous fly ash as the matrix, the catalyst has substantially no ABS deposition after the reaction under the same conditions, which shows that: the porous fly ash is used as a matrix to effectively inhibit the deposition of ABS on the V-W/Ti catalyst, and the following also shows that: when the porous fly ash is used as a substrate, the ABS can be effectively inhibited in V-W-Mn/TiO2-SiO2Deposition on the catalyst.
Second, V-W/TiO2Porous fly ash composite catalyst with pore structure characteristic and SO2+O2+NH3V-W/TiO after gas reaction2The porous fly ash composite catalyst is characterized, and the results are shown in table 1.
As can be seen from Table 1, for the conventional V-W/Ti catalyst (V-W)/TiO2Catalyst), with SO2+O2+NH3After reaction, the generated ABS can cause the blockage of catalyst pores after deposition, and the V-W/TiO with porous fly ash as a substrate2The pore blockage of the porous fly ash composite catalyst is relieved. With V-W/TiO2The porous fly ash composite catalyst is obviously different from the porous fly ash composite catalyst in that the fly ash-based wide-temperature-zone SCR catalyst capable of preventing ammonium bisulfate poisoning, which is prepared in example 1, can better solve the problem of pore blockage, and the fundamental reason is that silicon dioxide is added into the catalyst.
TABLE 1 post ABS deposition V-W/TiO2Physical structure characteristic of porous fly ash composite catalyst
| Sample (I) | Specific surface area (m)2/g) | Pore volume (cm)3/g) | Average pore diameter (nm) |
| V-W/TiO2Porous coal ash composite catalyst | 40.04 | 0.24 | 20.11 |
| V-W/TiO2Catalyst and process for preparing same | 29.63 | 0.23 | 31.48 |
Third, V-W/TiO2Decomposition characteristic of ABS in porous fly ash composite catalyst, V-W/TiO after ABS deposition2The thermal analysis of the porous fly ash composite catalyst is carried out under different temperature conditions, and the result is shown in figure 5.
FIG. 5 shows V-W/TiO deposited with ABS of the present invention2TG-MS diagram of porous fly ash composite catalyst. In FIG. 5, (a) is V-W/TiO deposited with ABS2Catalyst, (b) is V-W/TiO deposited with ABS2Porous coal ash composite catalyst. As can be seen from FIG. 5, for the conventional catalyst (V-W/TiO)2Catalyst), ABS can take place the interact with catalyst after the deposit, change ABS decomposition characteristic, make ABS present multistage decomposition characteristic at the catalyst surface, show the decomposition temperature who improves catalyst. For V-W/TiO using porous fly ash as matrix2For the porous fly ash composite catalyst, after ABS is deposited, the decomposition characteristic of the ABS is basically unchanged, the ABS still has a single decomposition characteristic, and the decomposition temperature is relatively low. Therefore, the porous fly ash is used as a matrix, which is beneficial to the decomposition of ABS, and is more beneficial to the realization of the regeneration of the catalyst.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. An ammonium bisulfate poisoning prevention wide-temperature-zone SCR catalyst taking fly ash as a substrate is characterized in that porous fly ash is taken as the substrate; and a wide-temperature-zone SCR catalyst is attached to the surface of the porous fly ash.
2. The wide-temperature-zone SCR catalyst capable of preventing ammonium bisulfate poisoning and taking fly ash as a substrate according to claim 1, wherein the porous fly ash is prepared by treating fly ash with a sodium hydroxide solution.
3. The wide-temperature-zone SCR catalyst taking fly ash as the matrix and preventing ammonium bisulfate poisoning as claimed in claim 1 or 2, wherein the wide-temperature-zone SCR catalyst is a V-W/Ti series SCR catalyst.
4. The wide-temperature-zone SCR catalyst taking fly ash as matrix and preventing ammonium bisulfate poisoning as claimed in claim 3, wherein the V-W/Ti series SCR catalyst is V-W-Mn/TiO2-SiO2Catalyst, V-W/TiO2At least one of a catalyst and a Mn/Ce catalyst.
5. The wide-temperature-zone SCR catalyst taking fly ash as matrix and preventing ammonium bisulfate poisoning as claimed in claim 4, wherein the V-W-Mn/TiO catalyst2-SiO2The catalyst is TiO2-SiO2The composite oxide is used as a carrier, and the TiO2-SiO2The composite oxide is loaded with an active component V, an active component Mn and an active auxiliary agent W; the V-W-Mn/TiO2-SiO2In the catalyst, the mass fraction of an active component V is 1-1.5%, the mass fraction of an active component Mn is 5-10%, the mass fraction of an active auxiliary agent W is 6-8%, and the balance is TiO2-SiO2A composite oxide; the active component V is V2O5(ii) a The active component Mn is MnO2(ii) a The coagent W is WO3(ii) a The TiO is2-SiO2SiO in composite oxide2The occupied mole fraction is 5 percent to 20 percent.
6. The preparation method of the wide-temperature-zone SCR catalyst taking the fly ash as the matrix and preventing the ammonium bisulfate poisoning as the matrix as claimed in any one of claims 1 to 5, is characterized by comprising the following steps: and mixing and grinding the porous fly ash and the wide-temperature-zone SCR catalyst to obtain the wide-temperature-zone SCR catalyst which takes the fly ash as a substrate and prevents ammonium bisulfate poisoning.
7. The preparation method according to claim 6, wherein the mass ratio of the porous fly ash to the wide-temperature-zone SCR catalyst is 1: 2-3.
8. The preparation method according to claim 6, wherein the porous fly ash is prepared by the following preparation method: mixing the fly ash with a sodium hydroxide solution, stirring, cleaning to be neutral, drying, grinding and sieving to obtain porous fly ash; the solid-liquid ratio of the fly ash to the sodium hydroxide solution is 1 g-2 g: 10 mL; the particle size of the fly ash is less than 0.1 mm; the concentration of the sodium hydroxide solution is 0.2 mol/L; the stirring is carried out at a temperature of 80 ℃; the stirring time is 1 h.
9. The preparation method according to any one of claims 6 to 8, wherein the wide temperature zone SCR catalyst is V-W-Mn/TiO2-SiO2When the catalyst is prepared by the following method:
(1) dissolving titanyl sulfate and neutral silica sol in deionized water;
(2) dropwise adding ammonia water into the solution obtained in the step (1), stirring until the pH value of the solution reaches 10, standing and aging at 30-40 ℃ for 10 hours, filtering, washing the obtained precipitate with deionized water, and drying at 150 ℃ for 10 hours;
(3) heating the precipitate dried in the step (2) to 500 ℃ in the air atmosphere, and roasting for 3 hours to obtain TiO2-SiO2A composite oxide.
(4) Dissolving manganese acetate, ammonium metavanadate and ammonium tungstate in a citric acid solution, and adding the TiO obtained in the step (3)2-SiO2Mixing the composite oxide for 1 hour;
(5) heating the mixed solution obtained after stirring in the step (4) to 100 ℃ until the water is evaporated to dryness;
(6) drying the solid mixture obtained in the step (5) after the moisture is evaporated to dryness at the temperature of 120 ℃ for 10 hours, and calcining the solid mixture at the temperature of 500 ℃ for 3 hours to obtain V-W-Mn/TiO2-SiO2A catalyst.
10. The application of the wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning and taking fly ash as the matrix according to any one of claims 1 to 5 or the wide-temperature-zone SCR catalyst for preventing ammonium bisulfate poisoning and taking fly ash as the matrix prepared by the preparation method according to any one of claims 6 to 9 in coal-fired flue gas denitration.
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| DONG YE ET AL., 《ACS OMEGA》 NEW INSIGHTS INTO THE DECOMPOSITION BEHAVIOR OF NH4HSO4 ON THE SIO2-DECORATED SCR CATALYST AND ITS ENHANCED SO2-RESISTANT ABILITY, vol. 4, pages 4927 * |
| 刘向辉 等, 《西华大学学报（自然科学版）》粉煤灰基NH3-SCR 脱硝催化剂研究进展, vol. 39, no. 2, pages 79 - 87 * |
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