CN109529913B - Preparation method of Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing active coating - Google Patents
Preparation method of Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing active coating Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 83
- 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 82
- 239000011248 coating agent Substances 0.000 title claims abstract description 30
- 238000000576 coating method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 21
- 239000003546 flue gas Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 21
- 239000006255 coating slurry Substances 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 150000000703 Cerium Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 244000282866 Euchlaena mexicana Species 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 231100000572 poisoning Toxicity 0.000 abstract description 12
- 230000000607 poisoning effect Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 29
- 230000000694 effects Effects 0.000 description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 239000000779 smoke Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
-
- B01J35/394—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention relates to the technical field of denitration, and particularly relates to a preparation method of a Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing an active coating, which comprises the steps of preparing the SBA-15 mesoporous molecular sieve, preparing the Mn-Ce/SBA-15 mesoporous molecular sieve, preparing a catalyst precursor and preparing a catalyst finished product. The catalyst has the advantages of strong catalytic performance, high medium-low temperature denitration efficiency, wide active temperature window and H resistance2O poisoning and SO resistance2Strong poisoning performance and is not easy to be affected by SO in flue gas2Reducing catalyst life.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of denitration, and particularly relates to a preparation method of a Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing an active coating.
[ background of the invention ]
Nitrogen oxides (NOx) are one of the main pollutants of the atmospheric environment, and have great harm to human health and ecological environment. The NOx comes from flue gas generated by fuel combustion, wherein NO is taken as the main component and accounts for more than 90% of the total amount of the NOx. In the atmosphere, NO is oxidized again to NO2And NO2Under the condition of ultraviolet irradiation, the smoke reacts with CHx in the smoke to generate photochemical smoke, the toxicity of the photochemical smoke is 4-5 times that of NO, and the photochemical smoke has great harm to most organs of a human body and animals and plants. Currently, the denitration technology for realizing industrial application is mainly NH3Selective Catalytic Reduction (SCR) denitration technology for reducing agent, wherein the catalyst is the core of the SCR denitration technology, and the commercialized catalyst is V2O5+WO3(MoO3)/TiO2(anatase) as active component, the catalyst has an activity temperature window of 300-400 ℃ and H resistance below 300 DEG C2O-Performance and SO-resistance2The poisoning performance is not strong, and the flue gas is easy to be subjected to SO2The catalyst life is reduced and the catalyst is easily deactivated in a flue gas environment.
In the general case of the above-mentioned,H2there are two cases of the effect of O on the catalyst activity, one being H2O with NO and NH3Existence of competitive adsorption, H2O weakens the catalyst to NO and NH3Adsorption of (3). Due to the reduction of the available active sites, water vapor may lead to partial deactivation of the catalyst, even in the case of flue gases under dry conditions, the catalytic activity of which is affected by the H produced by the SCR reaction2The influence of O. When removing H2After O, the catalyst recovers activity and is reversibly deactivated. The other is a catalyst pair H2O is chemisorbed and decomposition to hydroxyl results in catalyst deactivation, removal of H2After O, the catalyst fails to recover its activity and is irreversibly deactivated.
SO2The influence on the catalyst activity is mainly due to the formation of sulfur-containing species on the catalyst surface, which species have an effect on the NH3The effect of SCR plays a dual role. On the one hand, sulfur-containing species can improve catalyst surface acidity, which helps to increase catalyst activity. For example, NH4HSO4The decomposition on the catalyst surface may be as NH3Adsorbed neo-acid sites, and the ammonium ions can react with NO to avoid deposition of excess ammonium sulfate salts. On the other hand, SO2And NH3Ammonium sulfate salts produced by the reaction may cover active sites on the catalyst surface, which is a major cause of low temperature catalyst deactivation.
[ summary of the invention ]
In view of the above, there is a need for a method for preparing a Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing an active coating, which has strong catalytic performance, high denitration efficiency at medium and low temperatures, wide active temperature window, and H resistance2O poisoning and SO resistance2Strong poisoning performance and is not easy to be affected by SO in flue gas2Reducing catalyst life.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing active coating comprises the following steps:
(1) and preparing the SBA-15 mesoporous molecular sieve: by nonionic surface activityTaking P123 as a structure directing agent and tetraethoxysilane as a silicon source according to the following steps of TEOS, P123, HCl and H2Feeding materials according to the molar ratio of 1:0.017:5.88:150, and preparing the material by a hydrothermal synthesis method;
(2) and preparation of the Mn-Ce/SBA-15 mesoporous molecular sieve: adding manganese salt, cerium salt, water and deionized water into a beaker, stirring to completely dissolve the manganese salt and the cerium salt, then adding the SBA-15 mesoporous molecular sieve in the step (1) into the beaker, and uniformly stirring; putting the beaker into a heat collection type constant temperature heating magnetic stirrer, heating and stirring the mixture in the beaker until the mixture is evaporated to dryness, drying, roasting and cooling the obtained sample, and grinding and screening out the 20-40-mesh Mn-Ce/SBA-15 mesoporous molecular sieve;
(3) and preparing a catalyst precursor: dipping the Mn-Ce/SBA-15 mesoporous molecular sieve in the step (2) in active coating slurry, taking out, blowing off residual liquid, drying and roasting to obtain a catalyst precursor loading an active coating;
(4) and preparing a finished catalyst product: the catalyst precursor in the step (3) is added into the reactor in a volume ratio of H2/N21:10-1:2, and performing reduction activation at 200-500 ℃; then the catalyst is sulfonated by chlorosulfonic acid to obtain the finished product of the catalyst.
In the invention, further, in the step (1), the specific preparation method of the SBA-15 mesoporous molecular sieve comprises the following steps:
firstly, P123, 37% by mass of HCl and H2Mixing and dissolving O, rapidly stirring at 40-45 deg.C for 3-3.5h, adding TEOS into the above mixed solution, and rapidly stirring at 40-45 deg.C for 12-13h to obtain milky white suspension; transferring the milky white suspension into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, standing for 20-24h at the temperature of 100 ℃ plus 110 ℃, washing filter residues by using deionized water after filtering to obtain white solid, drying the white solid for 12-48h at the temperature of 60-100 ℃, then heating to 550 ℃ at the heating rate of 1-5 ℃/min in a muffle furnace, preserving heat for 5-6h, and finally cooling to obtain powdery solid, namely the SBA-15 mesoporous molecular sieve.
In the invention, in the step (2), the weight ratio of the manganese salt, the cerium salt, the water, the deionized water and the SBA-15 mesoporous molecular sieve in the step (1) is 0.5-1:0.3-0.8:30-35:40-55: 1; wherein the manganese salt is manganese nitrate, and the cerium salt is cerous nitrate hexahydrate.
In the invention, further, in the step (2), the heating temperature is 60-80 ℃, the drying temperature is 80-85 ℃, the drying time is 12-14h, the roasting temperature is 300 ℃, and the roasting time is 4-5 h.
In the present invention, in the step (3), the weight ratio of the Mn-Ce/SBA-15 mesoporous molecular sieve to the active coating slurry is 1-3: 50-55.
In the invention, further, the preparation method of the active coating slurry comprises the following steps: firstly, weighing the components in a weight ratio of 1: 0.36-0.5:80-85:3-4:1-2 TiO2ZSM-5 molecular sieve, 0.1mol/L-0.3mol/L nitric acid solution, adhesive and surfactant for standby, and then the TiO is added2The ZSM-5 molecular sieve and the nitric acid solution are mixed evenly, then the adhesive is added and mixed evenly, then the surfactant is added and mixed for 100-120min, and the active coating slurry can be obtained.
In the invention, further, the binder is alumina sol, and the surfactant is fatty alcohol-polyoxyethylene ether.
In the invention, further, in the step (3), the immersion treatment time is 10-120min, preferably 20-60min, and the residual liquid is blown off by compressed air after being taken out; the drying temperature is 50-60 ℃, and the drying time is 3-12 h; the roasting temperature is 400-600 ℃, and the roasting time is 2-10 h.
The invention has the following beneficial effects:
1. in the invention, Mn and Ce are simultaneously loaded on the SBA-15 mesoporous molecular sieve, which is beneficial to increasing the acid sites of the weak acid sites of the SBA-15 mesoporous molecular sieve, and the increase of the acid sites is beneficial to promoting NH3Adsorption and activation on the surface of the SBA-15 mesoporous molecular sieve; in addition, because of strong interaction between Mn element and Ce element, the specific surface area of the SBA-15 mesoporous molecular sieve can be effectively increased, the dispersion degree of the surface of the SBA-15 mesoporous molecular sieve is improved, the degree of surface crystallization is reduced, the activity of the molecular sieve is greatly improved, the specific surface area and the pore volume loss of the molecular sieve in the calcining process can be reduced, and the molecular sieve is improvedThe amount of active oxygen on the surface of the sieve is further increased, and the molecular sieve pair NH is further increased3Thereby promoting the SCR reaction, inhibiting the generation of ammonium sulfate on the surface of the catalyst and realizing the SO resistance of the Mn-Ce/SBA-15 mesoporous molecular sieve2And (4) performance enhancement.
2. In the invention, the Ce salt can not only play a synergistic role with the SBA-15 mesoporous molecular sieve to improve the high-temperature activity of the molecular sieve, but also can effectively isolate Mn particles, so that the Mn salt is always in an amorphous state, and the low-temperature activity of the molecular sieve can be improved. In addition, the Mn-Ce/SBA-15 mesoporous molecular sieve is dipped in the active coating, so that the structure of the active coating can be effectively improved under the action of Ce salt, all components in the active coating are uniformly mixed, the interaction among all components in the active coating is enhanced, and the firmness between the active coating and the Mn-Ce/SBA-15 mesoporous molecular sieve is improved. Moreover, after the active coating is loaded on the Mn-Ce/SBA-15 mesoporous molecular sieve, the specific surface area of the Mn-Ce/SBA-15 mesoporous molecular sieve can be further increased, so that the surface energy is high, the adsorption capacity is strong, the diffusion resistance is small, the loading capacity and the dispersity of active components on the Mn-Ce/SBA-15 mesoporous molecular sieve are improved, the thermal stability is good, the reaction temperature window of the catalyst can be widened, and the anti-toxicity performance of the catalyst can be improved.
3. In the present invention, the catalyst precursor is used as H on the premise that the catalyst precursor has the characteristics2/N2Reduction activating, sulfonating with chlorosulfonic acid, and reacting in H2/N2Can make the catalyst have hydrophobic property, so that it can reduce H pair2Adsorption of O, further realizing H resistance of the catalyst2Enhancement of O performance; meanwhile, after sulfonation treatment, the catalyst has stronger acidity, so that better catalytic performance is shown, the NO removal rate of the catalyst can reach more than 90% in a temperature range of 80-600 ℃, and the NO removal rate can reach 98-100% in a temperature range of 100 plus materials and 360 ℃.
4. In conclusion, the Mn-Ce/SBA in the catalyst of the invention15 the mesoporous molecular sieve and the active coating play a synergistic role to form a catalyst precursor, and the catalyst precursor passes through H2/N2After the treatment and the sulfonation treatment, the catalytic performance of the catalyst is enhanced, the medium-low temperature denitration efficiency of the catalyst is improved, the activity temperature window of the catalyst is widened, and the catalyst is resistant to H2O poisoning and SO resistance2The poisoning performance is enhanced, SO that the catalyst is not easy to be affected by SO in flue gas2The life is reduced.
[ detailed description ] embodiments
The following examples may assist those skilled in the art in a more complete understanding of the present invention, but are not intended to limit the invention in any way.
Example 1
A preparation method of Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing active coating comprises the following steps:
(1) and preparing the SBA-15 mesoporous molecular sieve: the preparation method is characterized in that a nonionic surfactant P123 is used as a structure directing agent, tetraethoxysilane is used as a silicon source, and the preparation method is prepared by a hydrothermal synthesis method according to the molar ratio of TEOS to P123 to HCl to H2O to 1 to 0.017 to 5.88 to 150.
The specific preparation method of the SBA-15 mesoporous molecular sieve comprises the following steps:
firstly, mixing 4g of P123, 8.9g of HCl with the mass fraction of 37% and 108.9g of 108.9g H2O for dissolving, rapidly stirring for 3-3.5h at 40-45 ℃, adding 8.4g of TEOS into the mixed solution, and rapidly stirring for 12-13h at 40-45 ℃ to obtain milky suspension; transferring the milky white suspension into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, standing for 20-24h at the temperature of 100 ℃ plus 110 ℃, washing filter residues by using deionized water after filtering to obtain white solid, drying the white solid for 12-48h at the temperature of 60-100 ℃, then heating to 550 ℃ at the heating rate of 1-5 ℃/min in a muffle furnace, preserving heat for 5-6h, and finally cooling to obtain powdery solid, namely the SBA-15 mesoporous molecular sieve.
(2) And preparation of the Mn-Ce/SBA-15 mesoporous molecular sieve: adding 1.5g of manganese nitrate, 0.9g of cerous nitrate hexahydrate, 90g of water and 120g of deionized water into a beaker, stirring to completely dissolve the manganese nitrate and the cerous nitrate hexahydrate, then adding 3g of the SBA-15 mesoporous molecular sieve obtained in the step (1) into the beaker, and uniformly stirring; and then putting the beaker into a heat collection type constant temperature heating magnetic stirrer, heating the mixture in the beaker to 60 ℃, stirring until the mixture is evaporated to dryness, putting the obtained sample into a drying oven at 80 ℃ for drying for 12h, putting the sample into a muffle furnace at 300 ℃ for roasting for 4h, taking out the sample from the air for cooling, and grinding and screening the sample to obtain the 20-mesh Mn-Ce/SBA-15 mesoporous molecular sieve.
(3) And preparing a catalyst precursor: and (3) dipping 1g of the Mn-Ce/SBA-15 mesoporous molecular sieve obtained in the step (2) in 50g of active coating slurry for 10min, taking out, blowing off residual liquid by using compressed air, drying in a 60 ℃ drying oven for 3h, and roasting in a 400 ℃ muffle furnace for 2h to obtain the catalyst precursor loaded with the active coating.
The preparation method of the active coating slurry comprises the following steps: 3g of TiO21.08g of ZSM-5 molecular sieve and 240g of 0.1mol/L-0.3mol/L nitric acid solution are uniformly mixed, 9g of alumina sol is added and uniformly mixed, 3g of fatty alcohol-polyoxyethylene ether is added and mixed for 100min, and then the active coating slurry is obtained.
(4) And preparing a finished catalyst product: the catalyst precursor in the step (3) is added into the reactor in a volume ratio of H2/N21:10-1:2, and performing reduction activation at 200-500 ℃; then the catalyst is sulfonated by chlorosulfonic acid to obtain the finished product of the catalyst.
Example 2
A preparation method of Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing active coating comprises the following steps:
(1) and preparing the SBA-15 mesoporous molecular sieve: same as in example 1.
(2) And preparation of the Mn-Ce/SBA-15 mesoporous molecular sieve: adding 2.4g of manganese nitrate, 2.1g of cerous nitrate hexahydrate, 93g of water and 132g of deionized water into a beaker, stirring to completely dissolve the manganese nitrate and the cerous nitrate hexahydrate, then adding 3g of the SBA-15 mesoporous molecular sieve obtained in the step (1) into the beaker, and uniformly stirring; and then putting the beaker into a heat collection type constant temperature heating magnetic stirrer, heating the mixture in the beaker at 70 ℃, stirring until the mixture is evaporated to dryness, putting the obtained sample into a drying oven at 83 ℃ for drying for 13h, putting the sample into a muffle furnace at 300 ℃ for roasting for 4h, taking out the sample from the air for cooling, and grinding and screening the sample to obtain the 30-mesh Mn-Ce/SBA-15 mesoporous molecular sieve.
(3) And preparing a catalyst precursor: and (3) dipping 2g of the Mn-Ce/SBA-15 mesoporous molecular sieve obtained in the step (2) in 53g of active coating slurry for 50min, taking out, blowing off residual liquid by using compressed air, drying in a 55 ℃ oven for 6h, and roasting in a 500 ℃ muffle furnace for 6h to obtain the catalyst precursor loaded with the active coating.
The preparation method of the active coating slurry comprises the following steps: 3g of TiO2, 0.9g of ZSM-5 molecular sieve and 186g of nitric acid solution with the concentration of 0.1mol/L-0.3mol/L are uniformly mixed, then 12g of alumina sol is added and uniformly mixed, 6g of fatty alcohol-polyoxyethylene ether is added and mixed for 110min, and the active coating slurry is obtained.
(4) And preparing a finished catalyst product: same as in example 1.
Example 3
A preparation method of Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing active coating comprises the following steps:
(1) and preparing the SBA-15 mesoporous molecular sieve: same as in example 1.
(2) And preparation of the Mn-Ce/SBA-15 mesoporous molecular sieve: adding 3g of manganese nitrate, 2.4g of cerous nitrate hexahydrate, 105g of water and 165g of deionized water into a beaker, stirring to completely dissolve the manganese nitrate and the cerous nitrate hexahydrate, then adding 3g of the SBA-15 mesoporous molecular sieve obtained in the step (1) into the beaker, and uniformly stirring; and then putting the beaker into a heat collection type constant temperature heating magnetic stirrer, heating the mixture in the beaker at 80 ℃, stirring until the mixture is evaporated to dryness, putting the obtained sample into a drying oven at 85 ℃ for drying for 14h, putting the sample into a muffle furnace at 300 ℃ for roasting for 5h, taking out the sample from the air for cooling, and grinding and screening the sample to obtain the Mn-Ce/SBA-15 mesoporous molecular sieve with 40 meshes.
(3) And preparing a catalyst precursor: and (3) dipping 3g of the Mn-Ce/SBA-15 mesoporous molecular sieve obtained in the step (2) in 55g of active coating slurry for 120min, taking out, blowing off residual liquid by using compressed air, drying in a 60 ℃ drying oven for 12h, and roasting in a 600 ℃ muffle furnace for 10h to obtain the catalyst precursor loaded with the active coating.
The preparation method of the active coating slurry comprises the following steps: 3g of TiO21.5g of ZSM-5 molecular sieve and 255g of 0.1mol/L-0.3mol/L nitric acid solution are uniformly mixed, then 12g of alumina sol is added and uniformly mixed, 6g of fatty alcohol-polyoxyethylene ether is added and mixed for 130min, and the active coating slurry is obtained.
(4) And preparing a finished catalyst product: same as in example 1.
Comparative example 1
This comparative example differs from example 2 in that no cerium nitrate hexahydrate was added and an Mn/SBA-15 mesoporous molecular sieve catalyst containing an active coating was obtained.
Comparative example 2
This comparative example differs from example 2 in that the Mn-Ce/SBA-15 mesoporous molecular sieve was not impregnated in the active coating slurry, resulting in a Mn/SBA-15 mesoporous molecular sieve catalyst that did not contain an active coating.
Comparative example 3
This comparative example differs from example 2 in that the catalyst precursor was not added in a volume ratio of H2/N2Reducing and activating the mixed gas at the temperature of 200-500 ℃, and then sulfonating the mixed gas by using chlorosulfonic acid to obtain the Mn/SBA-15 mesoporous molecular sieve catalyst precursor containing the active coating.
Firstly, the catalytic performance of the catalyst synthesized by the invention on SCR of NO
And (3) carrying out activity test on the prepared catalyst on a catalyst activity evaluation device, wherein the test operation is as follows: the catalysts prepared in each example and comparative example are respectively filled in a fixed tubular reactor, and simulated flue gas is introduced, wherein NO and NH are contained in the simulated flue gas3Are all 1000ppm, 10% O2，10％H2O，N2The reaction space velocity is 50000h-1 and the temperature is 80-600 ℃ for equilibrium gas. The results are shown in Table 1.
TABLE 1 conversion of NO in the catalysts prepared in each of the examples and comparative examples at different temperatures
| Group of | 80℃ | 100℃ | 150℃ | 200℃ | 300℃ | 400℃ | 500℃ | 600℃ | 650℃ |
| Example 1 | 95 | 98 | 99 | 98 | 99 | 94 | 93 | 91 | 85 |
| Example 2 | 94 | 99 | 99 | 98 | 98 | 96 | 94 | 93 | 90 |
| Example 3 | 90 | 98 | 98 | 99 | 99 | 90 | 92 | 91 | 90 |
| Comparative example 1 | 83 | 83 | 90 | 97 | 90 | 84 | 60 | 52 | 48 |
| Comparative example 2 | 85 | 92 | 94 | 90 | 94 | 89 | 81 | 30 | 23 |
| Comparative example 3 | 85 | 92 | 90 | 91 | 91 | 83 | 86 | 77 | 68 |
As can be seen from the results in Table 1, the catalysts prepared in the examples of the present invention generally have better NO conversion rate of 98-100% in the range of 100-360 deg.C, while the comparative examples have lower NO conversion rate in the range of 80-400 deg.C than the examples, indicating that the present invention has excellent catalytic activity under low temperature conditions. In addition, the NO conversion rate of the catalyst of the invention reaches more than 90% within the range of 80-600 ℃, while the NO conversion rate of the catalyst of the comparative example is reduced in different degrees at high temperature, which shows that the activity temperature window of the catalyst is wider than that of the catalyst of the comparative example, and the catalyst of the invention has better catalytic performance than that of the catalyst of the comparative example.
Second, anti-poisoning ability test
And (3) performing an activity test on the prepared catalyst on a catalyst activity evaluation device to perform an anti-poisoning capability test on the catalyst, wherein the test operation is as follows: the catalysts prepared in each example and comparative example are respectively filled in a fixed tubular reactor with constant temperature (the test is based on 80 ℃), and then simulated smoke is introduced, wherein the smoke is NO and O2The volume fractions of (A) and (B) are respectively 0.2% and 12%, the ammonia-nitrogen ratio is 1:1, and CO is2Is 0.04%, SO2Is 0.06% by volume, H2The volume fraction of O is 14%, N2To balance the gas, the reaction is carried outThe speed is 50000 h-1. The results are shown in Table 2.
TABLE 2 NO conversion over time for the catalysts prepared in the examples and comparative examples
| Group of | 15min | 30min | 45min | 60min | 75min | 90min | 105min | 120min | 135min |
| Example 1 | 95 | 93 | 96 | 95 | 92 | 91 | 90 | 91 | 95 |
| Example 2 | 94 | 95 | 96 | 96 | 95 | 91 | 92 | 94 | 95 |
| Example 3 | 90 | 94 | 93 | 92 | 93 | 93 | 94 | 93 | 91 |
| Comparative example 1 | 83 | 83 | 81 | 72 | 60 | 54 | 45 | 37 | 18 |
| Comparative example 2 | 85 | 82 | 84 | 80 | 74 | 79 | 71 | 60 | 53 |
| Comparative example 3 | 85 | 82 | 80 | 81 | 81 | 73 | 76 | 77 | 68 |
From the results in table 2, it can be seen that the catalysts prepared in examples 1-3 still have good catalytic performance of NH3-SCR in the atmosphere containing H2O and SO2 at low temperature, SO that the conversion rate of NO tends to be stable and is above 90%, therefore, the catalysts prepared in examples 1-3 have good catalytic performance not only at low temperature, but also have strong resistance to poisoning by H2O and SO 2.
Comparative example 1 NO cerium nitrate hexahydrate was added, and therefore, the poisoning resistance of the resulting catalyst against H2O and SO2 was reduced, SO that the conversion rate of NO of the catalyst of comparative example 1 was rapidly decreased with time.
Comparative example 2 since the Mn-Ce/SBA-15 mesoporous molecular sieve was not impregnated in the active coating slurry, the catalyst of comparative example 2 also had reduced resistance to H2O, SO2 poisoning, but at a slower rate than comparative example 1, SO that the catalyst of comparative example 2 had a moderate rate of reduction in NO conversion over time.
Comparative example 3 since the catalyst precursor was not subjected to sulfonation with chlorosulfonic acid after reductive activation under a mixed gas at a volume ratio of H2/N2 of 1:10-1:2 and at a temperature of 200 ℃. 500 ℃, the catalyst of comparative example 3 had decreased H2O poisoning resistance, but retained SO2 poisoning resistance, SO that the conversion of NO by the catalyst of comparative example 3 decreased slowly with time.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. A preparation method of Mn-Ce/SBA-15 mesoporous molecular sieve catalyst containing active coating is characterized in that: the method comprises the following steps:
(1) and preparing the SBA-15 mesoporous molecular sieve: taking a nonionic surfactant P123 as a structure directing agent, taking tetraethoxysilane as a silicon source, and mixing the components according to the ratio of TEOS to P123 to HCl to H2Feeding materials according to the molar ratio of O =1:0.017:5.88:150, and preparing the material by a hydrothermal synthesis method;
(2) and preparation of the Mn-Ce/SBA-15 mesoporous molecular sieve: adding manganese salt, cerium salt, water and deionized water into a beaker, stirring to completely dissolve the manganese salt and the cerium salt, then adding the SBA-15 mesoporous molecular sieve in the step (1) into the beaker, and uniformly stirring; putting the beaker into a heat collection type constant temperature heating magnetic stirrer, heating and stirring the mixture in the beaker until the mixture is evaporated to dryness, drying, roasting and cooling the obtained sample, and grinding and screening out the 20-40-mesh Mn-Ce/SBA-15 mesoporous molecular sieve;
(3) and preparing a catalyst precursor: dipping the Mn-Ce/SBA-15 mesoporous molecular sieve in the step (2) in active coating slurry, taking out, blowing off residual liquid, drying and roasting to obtain a catalyst precursor loading an active coating;
(4) and preparing a finished catalyst product: the catalyst precursor in the step (3) is added into the reactor in a volume ratio of H2/N21:10-1:2, and performing reduction activation at 200-500 ℃; reuse of chlorosulfonic acidSulfonating the acid to obtain a catalyst finished product;
in the step (3), the weight ratio of the Mn-Ce/SBA-15 mesoporous molecular sieve to the active coating slurry is =1-3: 50-55;
the preparation method of the active coating slurry comprises the following steps: firstly, weighing the components in a weight ratio of 1: 0.36-0.5:80-85:3-4:1-2 TiO2ZSM-5 molecular sieve, 0.1mol/L-0.3mol/L nitric acid solution, adhesive and surfactant for standby, and then the TiO is added2Uniformly mixing the ZSM-5 molecular sieve and the nitric acid solution, then adding the binder to uniformly mix, then adding the surfactant to mix for 100-fold for 120min to obtain active coating slurry;
the binder is alumina sol, and the surfactant is fatty alcohol-polyoxyethylene ether.
2. The method of claim 1 for preparing a Mn-Ce/SBA-15 mesoporous molecular sieve catalyst comprising an active coating, wherein: in the step (1), the specific preparation method of the SBA-15 mesoporous molecular sieve comprises the following steps:
firstly, P123, 37% by mass of HCl and H2Mixing and dissolving O, rapidly stirring at 40-45 deg.C for 3-3.5h, adding TEOS into the mixed solution, and rapidly stirring at 40-45 deg.C for 12-13h to obtain milky white suspension; transferring the milky white suspension into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, standing for 20-24h at the temperature of 100 ℃ plus 110 ℃, washing filter residues by using deionized water after filtering to obtain white solid, drying the white solid for 12-48h at the temperature of 60-100 ℃, then heating to 550 ℃ at the heating rate of 1-5 ℃/min in a muffle furnace, preserving heat for 5-6h, and finally cooling to obtain powdery solid, namely the SBA-15 mesoporous molecular sieve.
3. The method of claim 1 for preparing a Mn-Ce/SBA-15 mesoporous molecular sieve catalyst comprising an active coating, wherein: in the step (2), the weight ratio of the manganese salt, the cerium salt, the water, the deionized water and the SBA-15 mesoporous molecular sieve in the step (1) is =0.5-1:0.3-0.8:30-35:40-55: 1; wherein the manganese salt is manganese nitrate, and the cerium salt is cerous nitrate hexahydrate.
4. The method of claim 1 for preparing a Mn-Ce/SBA-15 mesoporous molecular sieve catalyst comprising an active coating, wherein: in the step (2), the heating temperature is 60-80 ℃, the drying temperature is 80-85 ℃, the drying time is 12-14h, the roasting temperature is 300 ℃, and the roasting time is 4-5 h.
5. The method of claim 1 for preparing a Mn-Ce/SBA-15 mesoporous molecular sieve catalyst comprising an active coating, wherein: in the step (3), the dipping treatment time is 10-120min, and the residual liquid is blown away by compressed air after being taken out; the drying temperature is 50-60 ℃, and the drying time is 3-12 h; the roasting temperature is 400-600 ℃, and the roasting time is 2-10 h.
6. The catalyst prepared by the method of any one of claims 1 to 5 in NH3-application in SCR flue gas denitration, characterized in that: the process conditions are as follows: the temperature is 80-600 ℃, and the reaction space velocity is 4000--1The NOx concentration was 500-1500 ppm.
7. An Mn-Ce/SBA-15 mesoporous molecular sieve catalyst comprising an active coating prepared by the preparation method of any one of claims 1-5.
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