CN110813308A - Preparation method of low-pressure-drop denitration catalyst - Google Patents
Preparation method of low-pressure-drop denitration catalyst Download PDFInfo
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- CN110813308A CN110813308A CN201910833107.7A CN201910833107A CN110813308A CN 110813308 A CN110813308 A CN 110813308A CN 201910833107 A CN201910833107 A CN 201910833107A CN 110813308 A CN110813308 A CN 110813308A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 12
- 238000001238 wet grinding Methods 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 238000003801 milling Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 8
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
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- 239000002243 precursor Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
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- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 229910015189 FeOx Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910003320 CeOx Inorganic materials 0.000 description 1
- 229910016553 CuOx Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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Abstract
The invention provides a preparation method of a low-pressure-drop denitration catalyst, which comprises the following steps: preparing a raw material, namely a metal nitrate solution and an alkali solution, wherein the metal nitrate solution contains equal amount of iron and manganese, and the alkali solution consists of an ammonia solution, an ammonia mixture and a mixed solution of ammonium bicarbonate or only an ammonium bicarbonate solution; step two, preparing a powder catalyst; step three, coating a catalyst, including grinding the catalyst powder obtained in the step two, and grinding the powder by adopting a dry ring milling process; wet grinding the ground catalyst powder, and milling by adopting a wet die, wherein an additive is added in the wet grinding process; coated on a catalyst support comprising: cutting the whole material to prepare a substrate, washing the substrate, and coating the wet-milled catalyst on the washed substrate to form a wash coat; thereafter drying at room temperature; and placing the dried catalyst carrier in a roasting furnace for roasting to obtain the low-pressure-drop supported catalyst.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a low-pressure-drop denitration catalyst.
Background
Nitrogen oxides (NOx, x ═ 1,2) as major atmospheric pollutants are causing a range of environmental problems such as photochemical smog, acid rain, ozone depletion, and particulate contamination. It is well known that 90% of the nox emissions are from combustion, both stationary and mobile sources. In stationary source fuel combustion, nitrogen oxides are mainly derived from power stations, industrial heaters and thermal power plants.
NH3SCR denitration technology is considered to be the most effective and widely used technology for reducing nitrogen oxide emissions from stationary sources. The catalyst is the key of denitration by an ammonia method or a urea method. Currently, it is used industrially for NH3Industrial catalysts for SCR, mainly V on titanium dioxide2O5Catalyst, in WO3(MoO3)/TiO2As the catalyst, the vanadium-tungsten-titanium has higher temperature requirement, the optimal operation temperature is 350-400 ℃, and V can be obtained only in the temperature range2O5-WO3/TiO2High conversion of (b). Although vanadium catalysts have entered the power plant and diesel vehicle markets, they are SO-rich2Oxidation to SO3The activity is high, the activity and the selectivity are rapidly reduced above 550 ℃, and vanadium has toxicity to the ecological environment, so that the application of the vanadium catalyst still has some problems. Furthermore, the commercial V2O 5-WO 3/TiO2 catalyst must be installed upstream of the particle collector and flue gas desulfurization to meet the optimum operating temperature of 350 ℃ and 420 ℃. Therefore, researchers in academia and industry continue to develop new low temperature catalysts to facilitate catalysts capable of temperatures around and below 200 ℃. Thus, SCR deviceAfter the device can be arranged in an electric precipitation desulfurizer of a power plant, the nitrogen oxide can be effectively removed within a wider temperature range, thereby realizing the control of the nitrogen oxide. Because the desulfurization and dust removal device is arranged behind the denitration device, in the denitration process, substances such as sulfur dioxide, smoke dust and the like in the flue greatly reduce the denitration efficiency and stability of the vanadium-tungsten-titanium catalyst, if the denitration device is arranged behind the desulfurization and dust removal device, the problem can be solved, but the temperature of flue gas after desulfurization and dust removal is about 150 ℃, and the working temperature of the vanadium-tungsten-titanium catalyst cannot be reached, so the flue gas needs to be reheated, the energy consumption is increased, and the operation cost is increased.
Considering the flue gas composition and the ambient temperature to the (NH) in the flue gas4)2SO4、NH4NO3And N2Because of the influence of O generation, it is necessary to develop a low-temperature SCR catalyst having good activity, high selectivity, high stability, and a wide operating temperature range by using a novel carrier. Such a catalyst may be placed downstream of the electrostatic precipitator and even downstream of the desulfurizer, at temperatures below 200 degrees celsius. However, such low temperature catalysts have rarely been demonstrated for removing nitrogen oxides from power plant flue gases. Manganese oxide (MnO)2) Is the main active ingredient for the denitration of the ammonium nitrate-SCR method at low temperature. The techniques for preparing low temperature catalysts reported at present are extrusion (extrusion), hydrothermal and thermal decomposition, simple precipitation and coprecipitation, wet impregnation, ion exchange of support precursors and sol-gel. In most cases, V2O5 and a noble metal are used as key active ingredients of the denitration catalyst, thereby reducing cost effectiveness. Other problems with the above preparation techniques are due to the complexity of the scale-up process, some techniques can only be used for batch reactions (e.g. hydrothermal reactions), some can produce hazardous and unfavorable by-products (e.g. thermal decomposition using citric acid to produce harmful nitrogen oxide fumes, sol-gel methods require the use of hazardous and expensive solvents).
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing a low-pressure-drop denitration catalyst of a manganese and iron blended oxide MnOx/FeOx-based catalyst, which is non-toxic and low in cost, so that the obtained catalyst can show excellent catalytic activity in the temperature range of 100-200 ℃.
The invention aims to provide a preparation method of a low-pressure-drop denitration catalyst, which comprises the following steps:
preparing a raw material, wherein the raw material is a catalyst precursor and consists of two components, namely a metal nitrate solution and an alkali solution, the metal nitrate solution contains equal amount of iron and manganese, and the alkali solution consists of a mixed solution of an ammonia solution, an ammonia mixture and ammonium bicarbonate or only consists of an ammonium bicarbonate solution;
step two, preparing a powder catalyst;
and step three, coating a catalyst.
Preferably, the metal nitrate solution further contains deionized water as a metal nitrate additive.
Preferably, the second step includes:
step 21, pumping the prepared precursor into a high-power ultrasonic reactor with the power of 500 watts and the frequency of 20 kilohertz at the flow rate of 50ml/s to 200ml/s, and forming liquid into a slurry state when the precursor is applied to a precursor in a continuous-flow stainless steel shell reaction tank;
step 22, washing the collected slurry in a centrifuge or a rotary dryer for three times by using water or once by using acetone to form a precipitate, standing for 5 hours before washing, and discharging waste liquid after washing in the washing process;
step 23, further drying the formed precipitate at room temperature for more than 24 hours, and then coarsely grinding into broken blocks;
step 24, placing the semi-finished product which is coarsely ground into the crushed blocks in a roasting furnace for roasting, and roasting the semi-finished product catalyst in a programmable furnace at the temperature rise rate of 10 ℃/min for 3 hours at 500 ℃;
and step 25, grinding the particle size of the calcined catalyst by a ring mill for about 10 minutes to obtain a particle size with the particle size of submicron <2 μm, and finally forming the powdery catalyst.
Preferably, the third step includes:
step 31, grinding the catalyst powder obtained in the step two;
step 32, wet grinding the ground catalyst powder, wherein wet grinding adopts wet die milling, and an additive is added in the wet grinding process;
step 33, coating on the catalyst carrier;
step 34, drying the catalyst carrier coated with the catalyst at room temperature;
and step 35, placing the dried catalyst carrier in a roasting furnace for roasting to obtain the low pressure drop load roasting monolithic catalyst.
Preferably, the step 31 includes performing powder grinding by a dry ring milling process, and the adopted equipment is an end mill grinder with power of AC220V/180W, and the diameter of the milling cutter is phi 3-phi 13.
Preferably, the additive of step 32 is PTFE.
Preferably, said step 33 comprises: the monolith is cut to prepare a substrate, the substrate is then washed, and a wet-milled catalyst is coated on the washed substrate to form a washcoat.
Preferably, the catalyst support of step 33 is a honeycomb ceramic.
The invention has the beneficial effects that:
(1) iron oxide and manganese oxide based, non-toxic, relatively inexpensive because they can be supplied in large quantities.
(2) Since the manufacturing process can be semi-continuous to fully continuous, it is easy to mass produce.
(3) In the production process of the catalyst, more effective low-temperature denitration catalyst performances can be obtained due to the enhanced reactant dispersibility and the shearing action of high-power ultrasound on catalyst particles.
(4) The catalyst is loaded on the honeycomb ceramic carrier, has the advantage of low pressure drop, and has no influence on the upstream and downstream processes.
Drawings
FIG. 1 is a flow diagram of a method of making a catalyst according to an embodiment of the invention;
FIG. 2 is a flow chart of a method of performing catalyst coating in accordance with an embodiment of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention is provided with reference to the accompanying drawings, but the present invention is not limited thereto.
The metal oxide catalyst has high low-temperature denitration spark and low price, and transition metal oxides such as MnOx, CuOx, FeOx, CeOx, ZrOx and the like have good low-temperature denitration performance. Metal oxide catalysts are subdivided into monometallic oxide catalysts and corresponding metal oxide catalysts. The low-temperature denitration performance of the single metal oxide catalyst is general and is unstable at high temperature, and the composite oxide has a determined composition and structure, and various metal ions in the structure can be adjusted. The oxides of Fe and Mn show better catalytic performance under the condition of low temperature, and the ammonia selective denitration reaction mechanism is as follows: the surface of the metal oxide catalyst is provided with a plurality of active sites, NO is firstly adsorbed on the active sites and then decomposed into nitrogen and oxygen atoms, and finally nitrogen and oxygen are formed and desorbed to release the active sites.
Referring to fig. 1, the method for manufacturing the low pressure drop denitration catalyst of the embodiment includes three steps of the flow chart of fig. 1:
preparing a raw material, wherein the raw material is a catalyst precursor and consists of a metal nitrate solution and an alkali solution, the metal nitrate solution can contain equal amount of iron and manganese, and the alkali solution consists of an ammonia solution, an ammonia mixture and an ammonium bicarbonate mixed solution or only consists of an ammonium bicarbonate solution; in this example, the ammonia solution is ammonia water. The metal nitrate solution also contains an additive, and in this embodiment, the additive is deionized water.
Step two, preparing the powder catalyst, comprising:
step 21, pumping the prepared precursor into a high-power ultrasonic reactor with the power of 500 watts and 20 kilohertz at the flow rate of 50ml/s to 200ml/s, wherein when the high-power ultrasonic reactor is applied to the precursor in a continuous flow reaction tank (stainless steel shell), the low-frequency and high-power ultrasonic waves can generate strong cavitation, the cavitation effect can greatly enhance the dispersion and uniform reaction and remove liquid, so that the processing consistency is improved, and the slurry state is formed, and the current setting can process the precursor with the power of 250 plus 2000 ml/min;
step 22, washing the collected slurry in a centrifuge or a rotary dryer for three times by using water or once by using acetone to form a precipitate, standing for 5 hours before washing, and discharging waste liquid after washing in the washing process;
step 23, further drying the formed precipitate at room temperature for more than 24 hours, and then coarsely grinding into broken blocks;
step 24, placing the semi-finished product which is coarsely ground into the crushed blocks in a roasting furnace for roasting, and roasting the semi-finished product catalyst in a programmable furnace at the temperature rise rate of 10 ℃/min for 3 hours at 500 ℃;
and step 25, grinding the particle size of the calcined catalyst by a ring mill for about 10 minutes to obtain a particle size with the particle size of submicron <2 μm, and finally forming the powdery catalyst.
Referring to fig. 2, step three, catalyst coating is performed, including:
step 31, grinding the catalyst powder obtained in the step two, wherein a dry ring milling process is adopted for grinding the powder, the adopted equipment is that an end mill grinder is a grinder with the power of AC220V/180W, and the diameter of a milling cutter is phi 3-phi 13;
step 32, wet grinding the ground catalyst powder, wherein wet grinding is performed by wet die milling, an additive is added during the wet grinding process, the additive in this embodiment is PTFE, and of course, other additives which are helpful for wet grinding and improve the performance of the catalyst can be added by those skilled in the art according to the needs;
step 33, coating is performed on the catalyst carrier, which is honeycomb ceramic, although other carriers can be selected by those skilled in the art as needed. Other vectors include:
1. molecular sieve catalyst: the molecular sieve is used as a catalyst carrier due to the unique pore channel structure, the large specific surface area and the abundant surface acid sites, the large specific surface agent can enable active components to be more uniformly distributed on the carrier, NH3 adsorption and activation are promoted, and the molecular sieve is applied to the aspect of denitration catalysts due to the characteristics of high stability, wide temperature window and the like. The denitration efficiency of the molecular sieve catalyst loading bimetallic Fe and Mn on the SBA-15 type molecular sieve is superior to that of single metal, the dispersion of Mn element on the surface of the molecular sieve is promoted due to the introduction of Fe element, and the Mn element increases acid sites on the surface of the molecular sieve.
2. Activated carbon: the activated carbon is widely used as a denitration catalyst carrier due to its huge specific surface area, strong adsorption performance and chemical stability. The nitric acid is used for pretreating the activated carbon to increase the acid sites of the activated carbon, so that the catalytic performance of the catalyst is further improved.
3. Titanium dioxide: the titanium dioxide of the titanium removal ore type is higher than a surface agent, sulfate generated in the presence of sulfur dioxide is not easy to deposit on the surface of the titanium dioxide, so that active ingredients of the catalyst are protected from being covered, the sulfur resistance of the catalyst is enhanced, and the transition metal oxide is loaded on a sulfur dioxide carrier to research the catalytic activity of the catalyst, so that the manganese oxide-loaded catalyst has the best low-temperature denitration effect, and Mn is loaded on the titanium dioxide carrier through an impregnation method.
Step 34, drying the catalyst carrier coated with the catalyst at room temperature;
and step 35, placing the dried catalyst carrier in a roasting furnace for roasting to obtain the low-pressure-drop supported catalyst.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the embodiments are only used to help understanding the principles of the embodiments of the present invention; meanwhile, the detailed description and the application scope of the embodiments according to the present invention may be changed by those skilled in the art, and in summary, the present disclosure should not be construed as limiting the present invention.
Claims (8)
1. A method for preparing a low-pressure-drop denitration catalyst is characterized by comprising the following steps of:
preparing a raw material, wherein the raw material is a catalyst precursor and consists of two components, namely a metal nitrate solution and an alkali solution, the metal nitrate solution contains equal amount of iron and manganese, and the alkali solution consists of a mixed solution of an ammonia solution, an ammonia mixture and ammonium bicarbonate or only consists of an ammonium bicarbonate solution;
step two, preparing a powder catalyst;
and step three, coating a catalyst.
2. The method of claim 1, wherein the method comprises the steps of: the metal nitrate solution also contains deionized water as a metal nitrate additive.
3. The method of claim 1, wherein the method comprises the steps of: the second step comprises the following steps:
step 21, pumping the prepared precursor into a high-power ultrasonic reactor with the power of 500 watts and the frequency of 20 kilohertz at the flow rate of 50ml/s to 200ml/s, and forming liquid into a slurry state when the precursor is applied to a precursor in a continuous-flow stainless steel shell reaction tank;
step 22, washing the collected slurry in a centrifuge or a rotary dryer for three times by using water or once by using acetone to form a precipitate, standing for 5 hours before washing, and discharging waste liquid after washing in the washing process;
step 23, further drying the formed precipitate at room temperature for more than 24 hours, and then coarsely grinding into broken blocks;
step 24, placing the semi-finished product which is coarsely ground into the crushed blocks in a roasting furnace for roasting, and roasting the semi-finished product catalyst in a programmable furnace at the temperature rise rate of 10 ℃/min for 3 hours at 500 ℃;
and step 25, grinding the particle size of the calcined catalyst by a ring mill for about 10 minutes to obtain a particle size with the particle size of submicron <2 μm, and finally forming the powdery catalyst.
4. The method of claim 1, wherein the method comprises the steps of: the third step comprises:
step 31, grinding the catalyst powder obtained in the step two;
step 32, wet grinding the ground catalyst powder, wherein wet grinding adopts wet die milling, and an additive is added in the wet grinding process;
step 33, coating on the catalyst carrier;
step 34, drying the catalyst carrier coated with the catalyst at room temperature;
and step 35, placing the dried catalyst carrier in a roasting furnace for roasting to obtain the low pressure drop load roasting monolithic catalyst.
5. The method of claim 4, wherein the catalyst is prepared by the following steps: the step 31 comprises the step of grinding the powder by adopting a dry ring milling process, wherein the adopted equipment is that an end mill grinder is a grinder with the power of AC220V/180W, and the diameter of a milling cutter is phi 3-phi 13.
6. The method of claim 4, wherein the catalyst is prepared by the following steps: the additive of step 32 is PTFE.
7. The method of claim 4, wherein the catalyst is prepared by the following steps: the step 33 includes: the monolith is cut to prepare a substrate, the substrate is then washed, and a wet-milled catalyst is coated on the washed substrate to form a washcoat.
8. The method of claim 4, wherein the catalyst is prepared by the following steps: the catalyst support of step 33 is a honeycomb ceramic.
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