CN111617801A - Preparation method of hierarchical porous Cu/SAPO-34 catalyst - Google Patents
Preparation method of hierarchical porous Cu/SAPO-34 catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 66
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 17
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 21
- 239000002808 molecular sieve Substances 0.000 abstract description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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Abstract
A preparation method of a hierarchical pore Cu/SAPO-34 catalyst relates to a preparation method of a denitration catalyst, and belongs to the field of catalyst preparation. The invention aims to solve the technical problem that the preparation process of the existing hierarchical pore Cu-based molecular sieve catalyst is complicated, and the method comprises the following steps: firstly, adding pseudo-boehmite into water, adding phosphoric acid, a silicon source, triethylamine, copper citrate and CaCO3Obtaining sol; secondly, transferring the sol into a hydrothermal kettle, heating the sol in a high-temperature oven, finishing crystallization of the product, washing the product with hydrochloric acid, washing the product with distilled water, and drying the product to obtain a sample; thirdly, grinding the sample, then placing the sample in a muffle furnace, heating to 600 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 5h at 600 ℃, cooling to room temperature,and grinding, tabletting and granulating to obtain the 40-60-mesh hierarchical porous Cu/SAPO-34 catalyst. The multi-stage pore Cu/SAPO-34 catalyst for selectively catalytically reducing nitrogen oxides prepared by the one-step method has the advantages of environment-friendly raw materials, stable structure, low price and simple and convenient method.
Description
Technical Field
The invention relates to a preparation method of a denitration catalyst, and belongs to the field of catalyst preparation.
Background
The nitrogen oxide is one of main pollutants causing atmospheric pollution at present, can cause serious harm to the environment and human bodies, and is very easy to cause secondary pollution photochemical smog under sunlight. At present, the sources of nitrogen oxides generated by human activities are mainly divided into fixed sources such as thermal power plants and cement plants and mobile sources such as motor vehicles. Among the existing denitration techniques, ammonia selective catalytic reduction (NH)3SCR) is certainly one of the most efficient techniques. Metal oxide catalysts, as represented by V-W-Ti and V-Mo-Ti, have been commercially available as fixed source nitrogen oxide removal catalysts many years ago, but due to their narrow operating temperature window and V-Mo-Ti2O5The catalyst is not suitable for being applied to a mobile source denitration reaction due to the fact that the species has certain biological toxicity and the like.
The molecular sieve is used as a solid acid with abundant acid sites and large specific surface area, and is very suitable to be used as a carrier of a denitration catalyst. In recent years, small pore molecular sieves represented by SAPO-34 and SSZ-13 have been increasingly used as carriers for denitration catalysts, and such catalysts exhibit excellent denitration performance by supporting a transition metal such as Cu or Mn as an active component. The SAPO-34 with the hierarchical pore structure reserves the original microporous system and introduces a large number of mesoporous structures into the molecular sieve, and the hierarchical pores can increase the surface area of the catalyst and simultaneously improve the diffusion rate of reaction gas in the catalyst, thereby further improving the denitration performance of the catalyst. It is worth considering that the preparation of the current molecular sieve catalyst has many problems, for example, the hydrothermal synthesis conditions of the molecular sieve carrier are harsh, the ammonium exchange ion exchange process is tedious and takes long time, and needs to be calcined for many times, and these problems seriously hinder the further development of the molecular sieve denitration catalyst.
Disclosure of Invention
The invention aims to solve the technical problem that the existing hierarchical pore Cu-based molecular sieve catalyst is complicated in preparation process, and provides a preparation method of a hierarchical pore Cu/SAPO-34 catalyst.
The preparation method of the hierarchical pore Cu/SAPO-34 catalyst comprises the following steps:
firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 2-3h, then adding 3.3mL of phosphoric acid, stirring for 2-3h, then adding 0.5-2.5g of silicon source, stirring for 2-3h, then adding 5-8mL of triethylamine, stirring for 2-3h, adding 0.223g-0.100g of copper citrate, stirring for 8-12h, and finally adding 1-2g of CaCO3Stirring for 4-8h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, placing the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at the temperature of 180 ℃ and 200 ℃, washing the product for 3 to 5 times by using hydrochloric acid with the concentration of 0.3 to 0.5mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 6.5 to 7, and then drying the product at the temperature of 110 ℃ to obtain a sample;
and thirdly, grinding the sample, then placing the sample in a muffle furnace, heating the sample to 600 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 5 hours at the temperature of 600 ℃, cooling the sample to room temperature, and then grinding, tabletting and granulating the sample to obtain the 40-60-mesh hierarchical pore Cu/SAPO-34 catalyst.
In the step one, the silicon source is white carbon black.
The hierarchical porous Cu/SAPO-34 catalyst prepared by the invention is applied to selective catalytic reduction of nitrogen oxides at 480 ℃ and 150 ℃, and the mass of Cu in the hierarchical porous Cu/SAPO-34 catalyst is 0.8-5.5 wt.%.
In order to simplify the complex operation process, the invention selects and utilizes copper citrate as a copper source to synthesize the multi-level pore Cu/SAPO-34 by a one-step method, and the multi-level pore Cu/SAPO-34 catalyst for selectively catalytically reducing nitrogen oxides prepared by the one-step method has the advantages of environment-friendly raw materials, stable structure, low price and simple and convenient method. The catalyst prepared by the method is suitable for a wider temperature range (170--1) The catalyst prepared by the method has outstanding hydrothermal stability and water and sulfur resistance.
Drawings
FIG. 1 is a graph comparing NO conversion for multiwell Cu/SAPO-34 catalysts of varying Cu loadings;
FIG. 2 is a graph of NO conversion versus multi-stage pore 4.1 wt.% Cu/SAPO-34 catalyst at different space velocities for experiment three;
FIG. 3 is a graph of NO conversion versus multi-stage pore 4.1 wt.% Cu/SAPO-34 catalyst at different space velocities for experiment three;
FIG. 4 is a graph of multi-stage pore 4.1 wt.% Cu/SAPO-34 catalyst at various concentrations of H in experiment three2O and SO2NO conversion under conditions is plotted;
FIG. 5 is a graph comparing the conversion of the multi-pore 4.1 wt.% Cu/SAPO-34 catalyst of experiment three with a 3.8% Cu/SAPO-34 catalyst prepared by ion exchange.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the preparation method of the hierarchical pore Cu/SAPO-34 catalyst in the embodiment comprises the following steps:
firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 2-3h, then adding 3.3mL of phosphoric acid, stirring for 2-3h, then adding 0.5-2.5g of silicon source, stirring for 2-3h, then adding 5-8mL of triethylamine, stirring for 2-3h, adding 0.223g-0.100g of copper citrate, stirring for 8-12h, and finally adding 1-2g of CaCO3Stirring for 4-8h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, placing the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at the temperature of 180 ℃ and 200 ℃, washing the product for 3 to 5 times by using hydrochloric acid with the concentration of 0.3 to 0.5mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 6.5 to 7, and then drying the product at the temperature of 110 ℃ to obtain a sample;
and thirdly, grinding the sample, then placing the sample in a muffle furnace, heating the sample to 600 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 5 hours at the temperature of 600 ℃, cooling the sample to room temperature, and then grinding, tabletting and granulating the sample to obtain the 40-60-mesh hierarchical pore Cu/SAPO-34 catalyst.
The hierarchical porous Cu/SAPO-34 catalyst prepared by the embodiment is applied to selective catalytic reduction of nitrogen oxides at 480 ℃ and 150 ℃, and the mass of Cu in the hierarchical porous Cu/SAPO-34 catalyst is 0.8-5.5 wt.%.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the silicon source in the first step is white carbon black. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment differs from the first or second embodiment in that 1.5g of the silicon source is added to the first step and stirred for 3 hours. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is that 0.670 copper citrate is added and stirred for 12 hours in the first step. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is that the heating at 190 ℃ is performed for 48 hours in the second step. The rest is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: this embodiment differs from one of the first to fifth embodiments in that washing with hydrochloric acid at a concentration of 0.4mol/L in step two is carried out 4 times. The rest is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is that the temperature is raised to 600 ℃ in the third step at a temperature raising rate of 2-9 ℃/min. The rest is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the difference between the first embodiment and the seventh embodiment is that the temperature is raised to 600 ℃ in the third step at a heating rate of 3-8 ℃/min. The rest is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment is different from the first to eighth embodiments in that the temperature is raised to 600 ℃ at a temperature raising rate of 4-7 ℃/min in the third step. The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment is different from the first to ninth embodiments in that the temperature is raised to 600 ℃ at a temperature raising rate of 5 ℃/min in the third step. The rest is the same as one of the first to ninth embodiments.
The following experiments are adopted to verify the effect of the invention:
experiment one:
the preparation method of the 0.8 wt.% hierarchical pore Cu/SAPO-34 catalyst was carried out according to the following steps:
firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 2h, then adding 3.3mL of phosphoric acid, stirring for 2h, then adding 1.5g of white carbon black, stirring for 2h, then adding 7.0mL of triethylamine, stirring for 3h, adding 0.223g of copper citrate, stirring for 12h, and finally adding 2g of CaCO3Stirring for 4h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, putting the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at 180 ℃, washing the product for 5 times by using hydrochloric acid with the concentration of 0.3mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 7, and drying the product at 110 ℃ to obtain a sample;
and thirdly, grinding the sample, then placing the sample in a muffle furnace, heating the sample to 600 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 5 hours at the temperature of 600 ℃, cooling the sample to room temperature, and then grinding, tabletting and granulating the sample to obtain the Cu/SAPO-34 catalyst with the hierarchical pores of 40-60 meshes and the content of 0.8 wt.%.
Experiment two:
the preparation method of the hierarchical pore 2.6 wt.% Cu/SAPO-34 catalyst is carried out according to the following steps:
firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 3h, then adding 3.3mL of phosphoric acid, stirring for 3h, then adding 1.5g of white carbon black, stirring for 3h, then adding 7.0mL of triethylamine, stirring for 2.5h, adding 0.446g of copper citrate, stirring for 12h, and finally adding 2g of CaCO3Stirring for 4h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, putting the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at 190 ℃, washing the product for 3 times by using hydrochloric acid with the concentration of 0.4mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 7, and drying the product at 110 ℃ to obtain a sample;
and thirdly, grinding the sample, then placing the sample in a muffle furnace, heating the sample to 600 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 5 hours at the temperature of 600 ℃, cooling the sample to room temperature, and then grinding, tabletting and granulating the sample to obtain the Cu/SAPO-34 catalyst with the hierarchical pores of 2.6 wt.% of 40-60 meshes.
Experiment three:
the preparation method of the hierarchical pore 4.1 wt.% Cu/SAPO-34 catalyst is carried out according to the following steps:
firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 3h, then adding 3.3mL of phosphoric acid, stirring for 3h, then adding 1.5g of white carbon black, stirring for 3h, then adding 7.0mL of triethylamine, stirring for 3h, adding 0.670g of copper citrate, stirring for 12h, and finally adding 2g of CaCO3Stirring for 8h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, putting the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at 200 ℃, washing the product for 4 times by using hydrochloric acid with the concentration of 0.5mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 7, and drying the product at 110 ℃ to obtain a sample;
and thirdly, grinding the sample, then placing the sample in a muffle furnace, heating the sample to 600 ℃ at the heating rate of 8 ℃/min, keeping the temperature for 5 hours at the temperature of 600 ℃, cooling the sample to room temperature, and then grinding, tabletting and granulating the sample to obtain the 40-60-mesh Cu/SAPO-34 catalyst with the hierarchical pores of 4.1 wt.%.
The multi-stage pore 4.1 wt.% Cu/SAPO-34 catalyst is added at the NO concentration of 400-3The concentration is 400-2Volume concentration of 2-5% and N2As balance gas, H2The volume concentration of O is 3-12%, and the space velocity is 40,000--1And the temperature is 25-500 ℃.
The hierarchical pore 4.1 wt.% Cu/SAPO-34 catalyst is added in H2O volume concentration of 5-12% and SO2The concentration of (1) is 100-200ppm, the NO concentration is 400-1100ppm, NH3The concentration is 400-2Volume concentration of 2-5% and N2As balance gas, with space velocity of 40,000--1And treating at 200 deg.C for 10-60 h.
The hierarchical pore 4.1 wt.% Cu/SAPO-34 catalyst is added in H2Treating for 10-12h at 80 ℃ and 700 ℃ under the condition that the volume concentration of O is 5-10%, and then treating for 1100ppm and NH at the concentration of NO of 400-3The concentration is 400-2Volume concentration of 2-5%, H2O volume concentration of 3-12% and N2As balance gas, space velocity is 40,000h-1And the temperature is 25-500 ℃.
NO conversion of the multi-stage pore 4.1 wt.% Cu/SAPO-34 catalyst at different space velocities (GHSV) as shown in Table 1, reaction conditions [ NO]＝[NH3]＝1000ppm，[O2]＝3％，10％H2O,GHSV＝40,000–240,000h-1。
TABLE 1
Multi-stage pore 4.1 wt.% NO conversion of Cu/SAPO-34 catalyst by hydrothermal treatment under various conditions, as shown in Table 2, reaction conditions [ NO: [ NO ] NO]＝1000ppm,[NH3]＝1000ppm，[O2]＝3％,GHSV＝40,000h-1。
TABLE 2
Multi-pore 4.1 wt.% Cu/SAPO-34 catalyst resistant to H under various conditions2O, anti-SO2NO conversion as in table 3.
TABLE 3
The multistage pore 4.1 wt.% Cu/SAPO-34 at space velocity of 40,000h-1Under the conditions of (1), NO conversion rate: (>90%) is 170-500 ℃. While exhibiting excellent H resistance at 200 deg.C2O anti-SO2Performance, and 10% H in volume fraction2The catalyst treated at 80 ℃ and 700 ℃ respectively in the presence of O still can show the denitration performance which is comparable with that of a fresh catalyst. Through a series of characterization tests, the existence of the hierarchical pore structure can promote the mass transfer rate of the gas and increase the BET specific surface area of the catalyst, and simultaneously, a large amount of Cu+The species is the excellent hydrothermal stability and the water and sulfur resisting capacityConditions are provided.
The catalyst of the experiment has the NO concentration of 400-3The concentration is 400-2Volume concentration of 2-5% and N2As balance gas, the space velocity is 40,000--1And (4) carrying out a denitration reaction test under the condition. The Cu/SAPO-34 catalyst with the hierarchical pores of 4.1 wt.% is suitable for being applied under the conditions of low, medium and high speed, low, medium and high temperature (170-.
Comparative experiment: ion exchange method for preparing 3.8 wt% Cu/SAPO-34 denitration catalyst
Firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 3h, then adding 3.3mL of phosphoric acid, stirring for 3h, then adding 1.5g of white carbon black, stirring for 3h, then adding 7.0mL of triethylamine, stirring for 12h, and finally adding 2g of CaCO3Stirring for 8h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, putting the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at 200 ℃, washing the product for 4 times by using hydrochloric acid with the concentration of 0.5mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 7, and drying the product at 110 ℃ to obtain a sample;
thirdly, placing the obtained sample in a muffle furnace, heating to 550 ℃ at the heating rate of 8 ℃/min, treating for 5 hours in the muffle furnace at 550 ℃, and naturally cooling to room temperature.
Fourthly, exchanging the obtained 2g H-SAPO-34 carrier with 0.1mol/L ammonium nitrate solution for 1h at the temperature of 70-80 ℃. Repeating the above steps for 3 times, centrifuging with water for 5 times, and drying at 110 deg.C for 16h to obtain NH4+-SAPO-34。
2g of NH obtained4+Exchanging SAPO-34 with 2.5g of copper citrate at 80 ℃ for 12h, continuously dropwise adding ammonia water to accelerate the dissolution of the copper citrate, centrifuging with water for 5 times after the exchange is finished, and drying at 110 ℃ for 16 h.
Fifthly, placing the obtained sample in a muffle furnace, heating to 550 ℃ at the heating rate of 8 ℃/min, treating for 5 hours in the muffle furnace at 550 ℃, and naturally cooling to room temperature. Grinding, tabletting and granulating to obtain the 40-60-mesh Cu/SAPO-34 catalyst with 5.4 wt.% of hierarchical pores.
Sixthly, 1100ppm NH of the multi-stage pore Cu/SAPO-34 catalyst prepared by the ion exchange method at the NO concentration of 400-3The concentration is 400-2Volume concentration of 2-5% and N2As balance gas, H2The volume concentration of O is 3-12%, and the space velocity is 40,000.
TABLE 4 comparison of Cu/SAPO-34 activities obtained by different preparation methods
Although the multi-stage pore Cu/SAPO-34 prepared by the one-step method only shows the denitration performance similar to that of the ion exchange method, the Cu/SAPO-34 prepared by the one-step method omits the time of ammonium exchange, ion exchange and baking roasting by simplifying the synthesis process, and compared with the ion exchange method, the one-step synthesis process saves about 40 hours. (2 times of ammonium exchange +1 time of ion exchange +3 times of drying + multiple times of centrifugation +1 time of calcination)
Experiment four:
the multiwell 5.4 wt.% Cu/SAPO-34 catalyst process was carried out according to the following steps:
firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 2.5h, then adding 3.3mL of phosphoric acid, stirring for 2-3h, then adding 2.5g of white carbon black, stirring for 2.5h, then adding 7.0mL of triethylamine, stirring for 2.5h, adding 0.890g of copper citrate, stirring for 12h, and finally adding 2g of CaCO3Stirring for 4h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, putting the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at 185 ℃, washing the product for 3 times by using hydrochloric acid with the concentration of 0.35mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 6.5, and drying the product at 110 ℃ to obtain a sample;
and thirdly, grinding the sample, then placing the sample in a muffle furnace, heating the sample to 600 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 5 hours at the temperature of 600 ℃, cooling the sample to room temperature, and then grinding, tabletting and granulating the sample to obtain the 5.4 wt.% hierarchical pore Cu/SAPO-34 catalyst with the size of 40-60 meshes.
0.8 wt.% Cu/SAPO-34 catalyst, 2.6 wt.% Cu/SAPO-34 catalyst, 4.1 wt.% Cu/SAPO-34 catalyst, 5.4 wt.% Cu/SAPO-34 catalyst prepared in experiments one through four at 40,000h-1In space velocity conditions, as shown in Table 5, reaction conditions [ NO ]]＝[NH3]＝1000ppm，[O2]＝3％,GHSV＝40,000h-1。
TABLE 5 NO conversion of different catalysts
Claims (10)
1. The preparation method of the hierarchical pore Cu/SAPO-34 catalyst is characterized in that the hierarchical pore Cu/SAPO-34 catalyst is prepared according to the following steps:
firstly, adding 3.5g of pseudo-boehmite into 30mL of water, stirring for 2-3h, then adding 3.3mL of phosphoric acid, stirring for 2-3h, then adding 0.5-2.5g of silicon source, stirring for 2-3h, then adding 5-8mL of triethylamine, stirring for 2-3h, adding 0.223g-0.100g of copper citrate, stirring for 8-12h, and finally adding 1-2g of CaCO3Stirring for 4-8h to obtain sol;
secondly, transferring the sol into a 50mL hydrothermal kettle, placing the hydrothermal kettle into a high-temperature oven, heating the hydrothermal kettle for 48 hours at the temperature of 180 ℃ and 200 ℃, washing the product for 3 to 5 times by using hydrochloric acid with the concentration of 0.3 to 0.5mol/L after crystallization of the product is finished, washing the product by using distilled water until the pH value of the washing solution is 6.5 to 7, and then drying the product at the temperature of 110 ℃ to obtain a sample;
and thirdly, grinding the sample, then placing the sample in a muffle furnace, heating the sample to 600 ℃ at the heating rate of 1-10 ℃/min, keeping the temperature for 5 hours at the temperature of 600 ℃, cooling the sample to room temperature, and then grinding, tabletting and granulating the sample to obtain the 40-60-mesh hierarchical pore Cu/SAPO-34 catalyst.
2. The method for preparing the hierarchical pore Cu/SAPO-34 catalyst according to claim 1, wherein the silicon source in step one is silica.
3. The method for preparing a multi-stage pore Cu/SAPO-34 catalyst according to claim 1, wherein 1.5g of silicon source is added to the first step and stirred for 3 hours.
4. The method for preparing a hierarchical pore Cu/SAPO-34 catalyst according to claim 1, wherein 0.670 copper citrate is added and stirred for 12h in step one.
5. The method for preparing the multi-stage pore Cu/SAPO-34 catalyst according to claim 1, wherein the second step is carried out by heating at 190 ℃ for 48 h.
6. The method for preparing a multi-stage pore Cu/SAPO-34 catalyst according to claim 1, wherein the washing in the second step with hydrochloric acid having a concentration of 0.4mol/L is performed 4 times.
7. The method for preparing a hierarchical pore Cu/SAPO-34 catalyst according to claim 1, wherein the temperature is raised to 600 ℃ in the third step at a temperature raising rate of 2-9 ℃/min.
8. The method for preparing a hierarchical pore Cu/SAPO-34 catalyst according to claim 1, wherein the temperature is raised to 600 ℃ in step three at a temperature rise rate of 3-8 ℃/min.
9. The method for preparing a hierarchical pore Cu/SAPO-34 catalyst according to claim 1, wherein the temperature is raised to 600 ℃ in step three at a temperature rise rate of 4-7 ℃/min.
10. The method for preparing a hierarchical pore Cu/SAPO-34 catalyst according to claim 1, wherein the temperature is raised to 600 ℃ in step three at a temperature rise rate of 5 ℃/min.
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| CN111195527A (en) * | 2020-02-21 | 2020-05-26 | 中国科学院生态环境研究中心 | Cu-SAPO-34 molecular sieve catalyst, and preparation method and application thereof |
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