CN112844423A - High-sulfur-resistance metal sulfate denitration catalyst and preparation method thereof - Google Patents
High-sulfur-resistance metal sulfate denitration catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 234
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 96
- 239000002184 metal Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 98
- 239000011593 sulfur Substances 0.000 claims abstract description 98
- 238000000034 method Methods 0.000 claims abstract description 45
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000005470 impregnation Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 82
- 239000012018 catalyst precursor Substances 0.000 claims description 71
- 229910001868 water Inorganic materials 0.000 claims description 64
- 238000001354 calcination Methods 0.000 claims description 58
- 238000005303 weighing Methods 0.000 claims description 45
- 238000009210 therapy by ultrasound Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 20
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 238000007873 sieving Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 85
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 24
- 239000007789 gas Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002028 Biomass Substances 0.000 abstract description 5
- 238000004056 waste incineration Methods 0.000 abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 229
- 238000006243 chemical reaction Methods 0.000 description 151
- 239000012495 reaction gas Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 14
- 230000001681 protective effect Effects 0.000 description 13
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
Abstract
The invention discloses a metal sulfate denitration catalyst with high sulfur resistance and a preparation method thereof, and belongs to the field of preparation of thermal catalytic materials and atmospheric control. According to the method, 1-20 wt% of metal sulfate is anchored on a carrier by a rotary evaporation impregnation method, so that the metal sulfate is uniformly distributed on the carrier, and then the catalyst is obtained by drying and high-temperature calcination. The catalyst has the advantages of excellent SCR activity, super-strong sulfur resistance, better durability and circulation stability, simple and convenient preparation, easy obtainment and the like. The catalyst can be used for catalytic treatment of nitrogen oxides in tail gas generated by various fixed pollution sources such as coal-fired power plants, biomass power plants, waste incineration boilers and the like.
Description
Technical Field
The invention discloses a preparation method of a metal sulfate denitration catalyst with high sulfur resistance, and belongs to the field of preparation of thermal catalytic materials and atmospheric treatment. The method is used for catalytic treatment of nitrogen oxides in tail gas generated by various fixed pollution sources such as coal-fired power plants, biomass power plants, waste incineration boilers and the like.
Background
In the rapid development of modern economies, and in the accelerated progress of industrialization, the large consumption of fossil fuels results in the emission of a large amount of environmentally harmful gases. Wherein the nitrogen oxide is one of the main air pollutants at present, nitrogen oxide NOxWherein mainly comprises NO and NO2It can cause acid rain, photochemical smog and respiratory system diseases. Selective catalytic reduction of ammonia (NH)3SCR) is currently the most effective nitrogen oxide removal method, and has been widely used for removing NOx from stationary pollution sources such as coal-fired power plants, biomass power plants, waste incineration boilers and the like and mobile pollution sources such as motor vehicle exhaust aftertreatment and the like. V currently in commercial use at fixed sources2O5-WO3(MO3)/TiO2Both the catalyst and the Cu-CHA catalyst used commercially in mobile sources are subjected to SO in the exhaust gas2Thereby reducing the catalytic efficiency of the catalyst.
Although most of fossil fuels used at present are subjected to desulfurization treatment, and a desulfurization device is installed at the front section of a denitration device in actual working conditions, a small amount of SO still remains in tail gas2At lower temperatures, NH3SCR catalysts adsorb SO extremely easily2And SO is reacted with2By oxidation to SO3Then Ammonium Bisulfate (ABS) is formed on the surface of the catalyst to cover active sites and active sites of the sulfation catalyst so as to deactivate the catalyst, and the existence of the problems causes NH3The SCR catalyst is less efficient during actual use. In order to meet the current stringent standards for nitrogen oxide emissions, research and development of a denitration catalyst having high sulfur resistance and high activity is one of the current focuses. In the existing research on sulfur resistance of denitration catalyst, the main solution is to add a second metal element as a sacrificial site in the catalystThe introduction of the animal site can promote SO2Reacting with the sacrificial site, keeping the activity of the original active site, and keeping the catalyst still at higher SCR activity in a sulfur-containing atmosphere; can also prevent SO by coating a layer of sulfur-thinning shell on the surface of the catalyst2And contact with active species of the catalyst, thereby achieving the effect of improving the sulfur resistance. However, the introduction of the shell layer necessarily covers certain active sites, namely NO and O in the reaction gases2And NH3The mass transfer of (2) has a certain influence, so that the catalytic efficiency of the catalyst is reduced. How to keep the sulfur resistance stability of the catalyst for a long time without losing the efficiency of the catalyst and further improve the service life of the catalyst is still a problem to be solved at present. However, numerous studies have shown that metal sulfates are due to their unique sulfur phobicity and NH3SCR activity can be used as NH3Active component of SCR catalyst, so as to obtain NH with high activity and high sulphur resistance3-an SCR catalyst.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a high-sulfur-resistance metal sulfate denitration catalyst and a preparation method thereof.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a metal sulfate denitration catalyst with high sulfur resistance takes metal sulfate as an active component of the denitration catalyst and as sulfur-phobic particles, and the active component is evenly anchored on a carrier to form a composite denitration catalyst material with metal sulfate evenly loaded on the carrier.
Preferably, the metal sulfate is at least one of copper sulfate, iron sulfate and cerium sulfate.
Preferably, the carrier is at least one of titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, cerium oxide and molecular sieve.
The invention relates to a preparation method of a metal sulfate denitration catalyst with high sulfur resistance, which adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst and comprises the following steps:
a. weighing 0.02-0.4g of metal sulfate, placing the metal sulfate in a round-bottom flask, weighing 70ml of solvent by using a measuring cylinder, pouring the solvent into the round-bottom flask, placing the round-bottom flask in an ultrasonic machine, and performing ultrasonic treatment to uniformly disperse the solvent to obtain a metal sulfate solution;
b. weighing 2g of carrier, placing the carrier in a metal sulfate solution in a round-bottom flask, and carrying out ultrasonic treatment on the mixed solution again to form uniform suspension; putting the round-bottom flask on a rotary evaporator, and carrying out rotary evaporation in a water bath process at 40-60 ℃ to obtain a catalyst precursor;
c. putting the obtained catalyst precursor into a 60-100 ℃ oven, drying for 4-12h, fully grinding the dried catalyst precursor, and sieving by a 60-mesh sieve to obtain catalyst precursor powder;
d. placing the ground catalyst precursor powder into a tubular furnace for calcination, wherein the calcination conditions are controlled as follows: the initial temperature is not higher than 20 ℃, the temperature is raised to the target calcining temperature of 300-2And after the calcination is finished, naturally cooling to room temperature to obtain the metal sulfate denitration catalyst.
Preferably, in the step a, the metal sulfate is at least one of copper sulfate, iron sulfate and cerium sulfate.
Preferably, in the step a, the solvent is at least one of deionized water, ethanol and isopropanol.
Preferably, in the step a, 0.02 to 0.4g of metal sulfate is weighed and mixed with 70ml of solvent to prepare a metal sulfate solution.
Preferably, in the step b, the carrier is at least one of titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, cerium oxide and molecular sieve. Further preferably, the molecular sieve is at least one of SSZ-13, SAPO-34, ZSM-5.
Preferably, in the step d, the temperature is increased to the target calcining temperature at the temperature increasing rate of 2-10 ℃/min.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the denitration catalyst of the invention takes metal sulfate as an active component of the denitration catalyst, and evenly anchors the active component on a carrier by a rotary dipping method, thereby leading the catalyst to have excellent SCR activity, and simultaneously leading the metal sulfate to be difficult to adsorb SO due to the special sulfur-phobicity of the metal sulfate2And SO is not easily oxidized2Thereby better avoiding SO2And sulfate species are deposited on the surface of the catalyst, so that mass transfer and heat transfer in the SCR reaction process are not influenced, active components of the catalyst are not rapidly reduced due to the influence of sulfur poisoning, and the catalyst can also keep higher SCR activity in a sulfur-containing atmosphere;
2. the denitration catalyst has low cost of active metal sulfate, low requirement on synthesis equipment, excellent SCR activity and sulfur resistance, and can be used for catalytic treatment of nitrogen oxides in tail gas generated by various fixed pollution sources such as a coal-fired power plant, a biomass power plant, a waste incineration boiler and the like;
3. the catalyst has the advantages of excellent denitration activity, super-strong sulfur resistance, better durability and circulation stability, and simple and easy preparation; the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
FIG. 1 is a graph of the activity of the sulfate catalyst tested in example 11 of the present invention.
FIG. 2 is a graph of the sulfur resistance of the sulfate catalyst tested in example 11 of the present invention.
FIG. 3 is a graph of the activity of the sulfate catalyst tested in example 12 of the present invention.
FIG. 4 is a graph of the sulfur resistance of the sulfate catalyst tested in example 12 of the present invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
a. weighing 0.02g of copper sulfate, placing the copper sulfate in a 100ml round-bottom flask, weighing 70ml of deionized water by using a measuring cylinder, pouring the deionized water into the round-bottom flask, placing the round-bottom flask in an ultrasonic machine, and performing ultrasonic treatment to uniformly disperse the deionized water to obtain a metal sulfate solution;
b. weighing 2g of silicon oxide, placing the silicon oxide in a metal sulfate solution in a round-bottom flask, and carrying out ultrasonic treatment on the mixed solution again to form uniform suspension; placing the round-bottom flask on a rotary evaporator, and carrying out rotary evaporation in a water bath process at 40 ℃ to obtain a catalyst precursor;
c. putting the obtained catalyst precursor into a 60 ℃ oven, drying for 12h, fully grinding the dried catalyst precursor, and sieving by a 60-mesh sieve to obtain catalyst precursor powder;
d. placing the ground catalyst precursor powder into a tubular furnace for calcination, wherein the calcination conditions are controlled as follows: the initial temperature is 20 ℃, the temperature is increased to the target calcination temperature of 300 ℃ at the heating rate of 6 ℃/min, the heat is preserved and calcined for 5 hours, the protective atmosphere is air, and after the calcination, the temperature is naturally reduced to the room temperature, so that the metal sulfate denitration catalyst is obtained.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test is carried out, the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The reaction test temperature range is 90-510 deg.C, the catalyst has 300 deg.C reaction activity window (NOx conversion rate is higher than 90%) in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and loaded into an SCR (selective catalytic reduction) deviceAnd (3) carrying out a water-resistant sulfur-resistant activity test in a reaction test tube: the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The sulfur resistance test temperature was 280 ℃. Heating the catalytic reaction furnace to 280 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 24h (1-8h with 100ppm SO)2And 2% of H2Introducing 100ppm SO for 9-16h2And 1% of H2O, 17-24h, 100ppm of SO is introduced2And 2.5% H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 2:
this embodiment is substantially the same as embodiment 1, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.15g of copper sulfate, placing the copper sulfate into a 100ml round-bottom flask, weighing 70ml of ethanol by using a measuring cylinder, pouring the ethanol into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the copper sulfate, weighing 2g of silicon oxide, placing the silicon oxide into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 45 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in an oven at 80 ℃ for 6h, fully grinding the dried catalyst precursor and sieving the ground catalyst precursor with a 60-mesh sieve, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 350 ℃ at the heating rate of 3 ℃, and the mixture is subjected to heat preservation and calcination for 6 hours in the protective atmosphere of N2And naturally cooling to room temperature after calcination to obtain the catalyst.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), and 0.15g of catalyst is weighed and filled into an SCR test reaction tubeSCR Activity test, N2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction space velocity is 100000h-1The reaction test temperature range is 120-480 ℃, the catalyst has a 250 ℃ reaction activity window (NOx conversion rate is higher than 90%) in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.15g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of the reaction gas tested was 260ml/min, and the reaction space velocity was 100000h-1The sulfur resistance test temperature was 270 ℃. Heating the catalytic reaction furnace to 270 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 24h (1-8h with 50ppm SO)2And 1% of H2Introducing 100ppm SO for 9-16h2And 1% of H2O, introducing 150ppm SO for 17-24h2And 1% of H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 3:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of copper sulfate, placing the copper sulfate into a 100ml round-bottom flask, weighing 70ml of isopropanol by using a measuring cylinder, pouring the isopropanol into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the isopropanol, weighing 2g of zirconium oxide, placing the zirconium oxide into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a 50 ℃ water bath process to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 60 ℃ drying oven for 2h, and drying the catalyst precursorFully grinding the precursor of the catalyst, sieving the precursor by a 60-mesh sieve, and calcining the ground precursor of the catalyst in a tubular furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 400 ℃ at the temperature raising rate of 2 ℃, the mixture is subjected to heat preservation and calcination for 12 hours, and the protective atmosphere is N2And naturally cooling to room temperature after calcination to obtain the catalyst.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.2g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction space velocity is 75000h-1The reaction test temperature range is 150-450 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 200 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.2g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reaction gas tested was 260ml/min, and the reaction space velocity was 75000h-1The temperature for the sulfur resistance test was 300 ℃. Heating the catalytic reaction furnace to 300 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, NOx conversion was continuously measured for 16h (1-8h with 100ppm SO)2And 1% of H2Introducing 100ppm SO for 9-16h2And 1% of H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 4:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of copper sulfate into a 100ml round-bottom flask, weighing 70ml of deionized water by using a measuring cylinder, pouring the deionized water into the round-bottom flask, putting the round-bottom flask into an ultrasonic machine for ultrasonic treatment to uniformly disperse the copper sulfate, weighing 2g of SSZ-13 into a metal sulfate solution in the round-bottom flask, and performing ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 40 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 60 ℃ drying oven for 5h, fully grinding the dried catalyst precursor and passing through a 60-mesh screen, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 450 ℃ at the temperature raising rate of 5 ℃, the temperature is preserved and calcined for 10 hours, the protective atmosphere is air, and the temperature is naturally reduced to the room temperature after the calcination is finished, so that the catalyst is obtained.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.1g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction space velocity is 150000h-1The reaction test temperature range is 180-420 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 150 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.1g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reaction gas tested was 260ml/min, the reaction space velocity 150000h-1The sulfur resistance test temperature was 350 ℃. Heating the catalytic reaction furnace to 350 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 24h (1-8h with 100ppm SO)2And 5% of H2Introducing 300ppm SO for O, 9-16h2And 5% of H2O, 17-24h, and 500ppm of SO is introduced2And 5% of H2O), the test interval is still 1 h. The catalyst remained above 90% throughout the test intervalNOx conversion rate, so that the catalyst has excellent SCR activity and sulfur resistance.
Example 5:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of copper sulfate into a 100ml round-bottom flask, weighing 70ml of deionized water by using a measuring cylinder, pouring the deionized water into the round-bottom flask, putting the round-bottom flask into an ultrasonic machine for ultrasonic treatment to uniformly disperse the copper sulfate, weighing 2g of SSZ-13 into a metal sulfate solution in the round-bottom flask, and performing ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 40 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 75 ℃ drying oven for 10h, fully grinding the dried catalyst precursor and passing through a 60-mesh screen, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 500 ℃ at the temperature raising rate of 4 ℃, the temperature is preserved and calcined for 5 hours, the protective atmosphere is air, and the temperature is naturally reduced to the room temperature after the calcination is finished, so that the catalyst is obtained.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test is carried out, the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The reaction test temperature range is 90-540 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 300 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reaction gas tested was 260ml/min, the space velocity of the reaction50000h-1The sulfur resistance test temperature was 280 ℃. Heating the catalytic reaction furnace to 280 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 24h (1-8h with 100ppm SO)2And 2% of H2Introducing 200ppm SO for O, 9-16h2And 2% of H2O, introducing 300ppm of SO for 17-24h2And 2% of H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 6:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of ferric sulfate, placing the ferric sulfate into a 100ml round-bottom flask, weighing 70ml of ethanol by using a measuring cylinder, pouring the ethanol into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the ethanol, weighing 2g of cerium oxide, placing the cerium oxide into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 45 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in an oven at 80 ℃ for 10h, fully grinding the dried catalyst precursor and sieving the ground catalyst precursor with a 60-mesh sieve, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 550 ℃ at the temperature raising rate of 8 ℃, the temperature is preserved and calcined for 9 hours, the protective atmosphere is air, and the temperature is naturally reduced to the room temperature after the calcination is finished, so that the catalyst is obtained.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction airSpeed 50000h-1The reaction test temperature range is 210-570 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 200 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The sulfur resistance test temperature was 350 ℃. Heating the catalytic reaction furnace to 350 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, NOx conversion was continuously measured for 16h (1-8h with 100ppm SO)2And 5% of H2Introducing 300ppm SO for O, 9-16h2And 5% of H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 7:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.3g of ferric sulfate into a 100ml round-bottom flask, weighing 70ml of isopropanol by using a measuring cylinder, pouring into the round-bottom flask, putting the round-bottom flask into an ultrasonic machine, performing ultrasonic treatment to uniformly disperse the isopropanol, weighing 2g of SAPO-34 into a metal sulfate solution in the round-bottom flask, and performing ultrasonic treatment again to uniformly disperse the SAPO-34 into a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 60 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 75 ℃ drying oven for 5 hours, fully grinding the dried catalyst precursor and sieving the ground catalyst precursor with a 60-mesh sieve, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature was 20 ℃ at a ramp rate of 10 ℃Heating to 300 ℃ and calcining for 9h under the protection atmosphere of N2And naturally cooling to room temperature after calcination to obtain the catalyst.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.5g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction space velocity is 30000h-1The reaction test temperature range is 180-2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.5g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of the reaction gas tested is 260ml/min, and the reaction space velocity is 30000h-1The sulfur resistance test temperature was 250 ℃. Heating the catalytic reaction furnace to 250 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 24h (1-8h with 100ppm SO)2And 2.5% H2Introducing 300ppm SO for O, 9-16h2And 2.5% H2O, 17-24h, and 500ppm of SO is introduced2And 2.5% H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 8:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
0.2g of ferric sulfate is weighed and placed in a 100ml round-bottom flask, 70ml of isopropanol is removed by a measuring cylinder and poured into the round-bottom flask, the round-bottom flask is placed in an ultrasonic machine for ultrasonic treatment to be uniformly dispersed, 2g of ZSM-5 is weighed and placed in a metal sulfate solution in the round-bottom flask, and the solution is subjected to ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 55 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a drying oven at 100 ℃ for 6 hours, fully grinding the dried catalyst precursor and sieving the ground catalyst precursor with a 60-mesh sieve, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 450 ℃ at the temperature raising rate of 10 ℃, the temperature is preserved and calcined for 6 hours, the protective atmosphere is air, and the temperature is naturally reduced to the room temperature after the calcination is finished, so that the catalyst is obtained.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.2g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction space velocity is 100000h-1The reaction test temperature range is 180-2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.2g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of the reaction gas tested was 260ml/min, and the reaction space velocity was 100000h-1The sulfur resistance test temperature was 280 ℃. Heating the catalytic reaction furnace to 280 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 24h (1-8h with 100ppm SO)2And 5% of H2Introducing 200ppm SO for O, 9-16h2And 5% of H2O, introducing 300ppm of SO for 17-24h2And 5% of H2O,) the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 9:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of cerium sulfate, placing the cerium sulfate into a 100ml round-bottom flask, weighing 70ml of deionized water by using a measuring cylinder, pouring the deionized water into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the cerium sulfate, weighing 2g of cerium oxide, placing the cerium oxide into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 45 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 60 ℃ drying oven for 10h, fully grinding the dried catalyst precursor and passing through a 60-mesh screen, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 500 ℃ at the heating rate of 3 ℃, and the mixture is subjected to heat preservation and calcination for 7 hours in the protective atmosphere of N2And naturally cooling to room temperature after calcination to obtain the catalyst.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test is carried out, the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The reaction test temperature range is 210-420 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 150 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The sulfur resistance test temperature was 350 ℃. Heating the catalytic reaction furnace to 350 ℃,testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing for NOx conversion for 15h (1-8h with 40ppm SO)2And 5% of H2Introducing 80ppm SO for O, 9-15h2And 5% of H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 10:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of cerium sulfate, placing the cerium sulfate into a 100ml round-bottom flask, weighing 70ml of deionized water by using a measuring cylinder, pouring the deionized water into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the cerium sulfate, weighing 2g of titanium oxide, placing the titanium oxide into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a 50 ℃ water bath process to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 70 ℃ drying oven for 7h, fully grinding the dried catalyst precursor and sieving the ground catalyst precursor with a 60-mesh sieve, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is increased to 480 ℃ at the temperature increasing rate of 10 ℃, and the mixture is subjected to heat preservation and calcination for 6 hours in the protective atmosphere of N2And naturally cooling to room temperature after calcination to obtain the catalyst.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.6g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction space velocity is 25000h-1The reaction test temperature range is 180-510 ℃, and the catalyst has a reaction activity window of 250 ℃ in the test temperature range(NOx conversion higher than 90%), N throughout the test temperature interval2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.6g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of the reaction gas tested was 260ml/min, and the reaction space velocity was 25000h-1The sulfur resistance test temperature was 350 ℃. Heating the catalytic reaction furnace to 350 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, NOx conversion was continuously measured for 16h (1-8h with 40ppm SO)2And 5% of H2Introducing 50ppm SO for O, 9-16h2And 5% of H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
Example 11:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of copper sulfate, placing the copper sulfate into a 100ml round-bottom flask, weighing 70ml of deionized water by using a measuring cylinder, pouring the deionized water into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, performing ultrasonic treatment to uniformly disperse the deionized water, weighing 2g of SAPO-34, placing the SAPO-34 into a metal sulfate solution in the round-bottom flask, and performing ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 60 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in an oven at 80 ℃ for 5 hours, fully grinding the dried catalyst precursor and sieving the ground catalyst precursor with a 60-mesh sieve, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 500 ℃ at the temperature raising rate of 2 ℃, the temperature is preserved and calcined for 5 hours, the protective atmosphere is air, and the temperature is naturally reduced to the room temperature after the calcination is finished, so that the catalyst is obtained.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test is carried out, the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The reaction test temperature range is 120-480 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 200 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10ppm, see FIG. 1.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The temperature for the sulfur resistance test was 300 ℃. Heating the catalytic reaction furnace to 300 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, NOx conversion was continuously measured for 16h (1-8h with 100ppm SO)2And 2.5% H2Introducing 300ppm SO for O, 9-16h2And 2.5% H2O), the test interval is still 1 h. The catalyst still maintained a NOx conversion of more than 90% throughout the test interval and therefore the catalyst had excellent SCR activity and sulphur resistance, see figure 1.
Example 12:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.16g of copper sulfate, placing the copper sulfate into a 100ml round-bottom flask, weighing 70ml of deionized water by using a measuring cylinder, pouring the deionized water into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the copper sulfate, weighing 2g of titanium oxide, placing the titanium oxide into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 40 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 60 ℃ drying oven for 5h, fully grinding the dried catalyst precursor and passing through a 60-mesh screen, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 400 ℃ at the temperature raising rate of 2 ℃, the temperature is preserved and calcined for 5 hours, the protective atmosphere is air, and the temperature is naturally reduced to the room temperature after the calcination is finished, so that the catalyst is obtained.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test is carried out, the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The reaction test temperature range is 150-450 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 120 ℃ in the test temperature range, and N is in the whole test temperature range2O was produced in an amount of less than 10ppm, see FIG. 2.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.3g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reaction gas tested is 260ml/min, and the reaction space velocity is 50000h-1The sulfur resistance test temperature was 280 ℃. Heating the catalytic reaction furnace to 280 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 10h (1-10h with 100ppm SO)2And 5% of H2O), the test interval is still 1 h. The catalyst still maintained a NOx conversion of more than 90% throughout the test interval and therefore the catalyst had excellent SCR activity and sulphur resistance, see figure 2.
Example 13:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.2g of cerium sulfate, placing the cerium sulfate into a 100ml round-bottom flask, weighing 70ml of ethanol by using a measuring cylinder, pouring the ethanol into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the cerium sulfate, weighing 2g of aluminum oxide, placing the aluminum oxide into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 60 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 70 ℃ drying oven for 8h, fully grinding the dried catalyst precursor and passing through a 60-mesh screen, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 450 ℃ at the temperature raising rate of 5 ℃, the temperature is kept and calcined for 5 hours, and the protective atmosphere is N2And naturally cooling to room temperature after calcination to obtain the catalyst.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.2g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2The selectivity test is carried out, the total amount of the reaction gas is 260ml/min, and the reaction space velocity is 10000h-1The reaction test temperature range is 180-420 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 150 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.2g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of the reaction gas tested was 260ml/min, and the reaction space velocity was 100000h-1The sulfur resistance test temperature was 350 ℃. Heating the catalytic reaction furnace to 350 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, NOx conversion was continuously measured for 12h (1-2h with 100ppm SO)2And 5% of H2O), the test interval is still 1 h. The catalyst remains in the whole test intervalNOx conversion higher than 90% is maintained, and thus the catalyst has excellent SCR activity and sulfur resistance.
Example 14:
this embodiment is substantially the same as the previous embodiment, and is characterized in that:
a preparation method of a metal sulfate denitration catalyst with high sulfur resistance adopts a rotary evaporation impregnation method to prepare the metal sulfate denitration catalyst, and comprises the following steps:
weighing 0.4g of cerium sulfate, placing the cerium sulfate into a 100ml round-bottom flask, weighing 70ml of isopropanol by using a measuring cylinder, pouring the isopropanol into the round-bottom flask, placing the round-bottom flask into an ultrasonic machine, carrying out ultrasonic treatment to uniformly disperse the cerium sulfate, weighing 2g of ZSM-5, placing the ZSM-5 into a metal sulfate solution in the round-bottom flask, and carrying out ultrasonic treatment again to form a uniform suspension. Placing the round-bottom flask on a rotary evaporator, and performing rotary evaporation in a water bath process at 60 ℃ to obtain a catalyst precursor.
Drying the obtained catalyst precursor in a 60 ℃ drying oven for 10h, fully grinding the dried catalyst precursor and passing through a 60-mesh screen, and calcining the ground catalyst precursor in a tube furnace under the calcining conditions that: the initial temperature is 20 ℃, the temperature is raised to 600 ℃ at the temperature raising rate of 8 ℃, and the mixture is subjected to heat preservation and calcination for 3 hours in the protective atmosphere of N2And naturally cooling to room temperature after calcination to obtain the catalyst.
Experimental test analysis:
and (3) SCR activity test: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.1g of catalyst is weighed and filled into an SCR test reaction tube for SCR activity test, and N is2Selectivity test, total amount of reaction gas tested is 260ml/min, reaction space velocity is 150000h-1The reaction test temperature range is 210-420 ℃, the catalyst has a reaction activity window (NOx conversion rate is higher than 90%) of 100 ℃ in the test temperature range, and N is in the whole test temperature range2O is produced in an amount of less than 10 ppm.
Water-resistant and sulfur-resistant testing of the catalyst: the prepared catalyst is pressed into tablets and sieved by a screen (40-60 meshes), 0.1g of catalyst is weighed and loaded into an SCR test reaction tube for water resistance and sulfur resistance activity test: the total amount of reactive gas tested was260ml/min, reaction space velocity 150000h-1The sulfur resistance test temperature was 350 ℃. Heating the catalytic reaction furnace to 350 ℃, testing the NOx conversion rate of the catalyst, continuously testing the NOx conversion rate for 2 hours at intervals of 1 hour, and introducing SO after 2 hours2And steam, continuously testing NOx conversion for 8h (1-8h with 100ppm SO)2And 5% of H2O), the test interval is still 1 h. The catalyst still maintains a NOx conversion rate higher than 90% throughout the test interval, so the catalyst has excellent SCR activity and sulfur resistance.
In summary, the metal sulfates of the above examples are due to their unique sulfur repellency and NH properties3SCR activity can be used as NH3Active component of SCR catalyst, so as to obtain NH with high activity and high sulphur resistance3-an SCR catalyst. In the above embodiment, the metal sulfate is anchored on the carrier by a rotary evaporation impregnation method, so that the metal sulfate is uniformly distributed on the carrier, and then the catalyst is obtained by drying and high-temperature calcination. The catalyst of the embodiment has the advantages of excellent denitration activity, super-strong sulfur resistance, better durability and circulation stability, simple and convenient preparation, easy obtainment and the like. In a word, the catalyst of the embodiment has the advantages of excellent SCR activity, super-strong sulfur resistance, better durability and cycling stability, simple and easy preparation, and the like. The catalyst can be used for catalytic treatment of nitrogen oxides in tail gas generated by various fixed pollution sources such as coal-fired power plants, biomass power plants, waste incineration boilers and the like.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (10)
1. The utility model provides a metal sulfate denitration catalyst of high sulfur resistance which characterized in that: the metal sulfate is used as an active component of the denitration catalyst and is used as a sulfur-phobic mass point, and the active component is evenly anchored on the carrier to form the composite denitration catalyst material with the metal sulfate uniformly loaded on the carrier.
2. The high sulfur resistance metal sulfate denitration catalyst according to claim 1, characterized in that: the metal sulfate is at least one of copper sulfate, ferric sulfate and cerium sulfate.
3. The high sulfur resistance metal sulfate denitration catalyst according to claim 1, characterized in that: the carrier is at least one of titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, cerium oxide and molecular sieve.
4. A method for preparing the metal sulfate denitration catalyst with high sulfur resistance according to claim 1, which is characterized in that: the preparation method of the metal sulfate denitration catalyst by adopting a rotary evaporation impregnation method comprises the following steps:
a. weighing 0.02-0.4g of metal sulfate, placing the metal sulfate in a round-bottom flask, weighing 70ml of solvent by using a measuring cylinder, pouring the solvent into the round-bottom flask, placing the round-bottom flask in an ultrasonic machine, and performing ultrasonic treatment to uniformly disperse the solvent to obtain a metal sulfate solution;
b. weighing 2g of carrier, placing the carrier in a metal sulfate solution in a round-bottom flask, and carrying out ultrasonic treatment on the mixed solution again to form uniform suspension; putting the round-bottom flask on a rotary evaporator, and carrying out rotary evaporation in a water bath process at 40-60 ℃ to obtain a catalyst precursor;
c. putting the obtained catalyst precursor into a 60-100 ℃ oven, drying for 4-12h, fully grinding the dried catalyst precursor, and sieving by a 60-mesh sieve to obtain catalyst precursor powder;
d. placing the ground catalyst precursor powder into a tubular furnace for calcination, wherein the calcination conditions are controlled as follows: the initial temperature is not higher than 20 ℃, the temperature is raised to the target calcining temperature of 300-2At least one kind of air in the sintered junctionAnd after that, naturally cooling to room temperature to obtain the metal sulfate denitration catalyst.
5. The method for preparing a metal sulfate denitration catalyst with high sulfur resistance according to claim 4, wherein: in the step a, the metal sulfate is at least one of copper sulfate, ferric sulfate and cerium sulfate.
6. The method for preparing a metal sulfate denitration catalyst with high sulfur resistance according to claim 4, wherein in the step a, the solvent is at least one of deionized water, ethanol and isopropanol.
7. The method for preparing a metal sulfate denitration catalyst with high sulfur resistance as claimed in claim 4, wherein in the step a, 0.02-0.4g of metal sulfate is weighed and mixed with 70ml of solvent to prepare a metal sulfate solution.
8. The method for preparing a metal sulfate denitration catalyst with high sulfur resistance according to claim 4, wherein: in the step b, the carrier is at least one of titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, cerium oxide and molecular sieve.
9. The method for preparing a metal sulfate denitration catalyst with high sulfur resistance according to claim 8, wherein: the molecular sieve is at least one of SSZ-13, SAPO-34 and ZSM-5.
10. The method for preparing a metal sulfate denitration catalyst with high sulfur resistance according to claim 4, wherein: in the step d, the temperature is increased to the target calcining temperature at the temperature increasing rate of 2-10 ℃/min.
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