CN112473689A - Preparation method of nitrate type ultralow-temperature denitration granular catalyst - Google Patents
Preparation method of nitrate type ultralow-temperature denitration granular catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 46
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 43
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 239000000314 lubricant Substances 0.000 claims abstract description 39
- 239000003755 preservative agent Substances 0.000 claims abstract description 39
- 230000002335 preservative effect Effects 0.000 claims abstract description 39
- 239000011230 binding agent Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 30
- 210000001161 mammalian embryo Anatomy 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 21
- 238000005303 weighing Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 15
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- 240000008415 Lactuca sativa Species 0.000 claims description 6
- 229920001131 Pulp (paper) Polymers 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003311 flocculating effect Effects 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000019359 magnesium stearate Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 235000012045 salad Nutrition 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 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 5
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 229920006184 cellulose methylcellulose Polymers 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000779 smoke Substances 0.000 abstract description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003002 pH adjusting agent Substances 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 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
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002912 waste gas 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
-
- 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
- B01D53/90—Injecting reactants
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention relates to the technical field of denitration catalysts, and discloses a preparation method of a nitrate type ultralow-temperature denitration granular catalyst, which comprises the following steps: s1, mixing materials: weighing a carrier, a release agent, a preservative, a lubricant, a metal nitrate, a pH regulator, a structural assistant, a binder and the like, sequentially adding the weighed carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant, the binder and the like into a mud mixer, and mixing and kneading for a certain time to obtain mud; s2, pre-squeezing and aging: putting the obtained pug into a pre-extruder to obtain pug sections, and then sealing, boxing and aging; s3, forming, namely feeding the aged pug into an extruder to obtain a wet blank of the granular catalyst; s4, drying: flatly paving the wet embryo in a sieve tray, and putting the sieve tray into a drying chamber for drying for a certain time to obtain a catalyst dry embryo; s5, calcining: and (3) putting the catalyst dry blank into a calcining furnace to calcine in an inert atmosphere, gradually decomposing the metal nitrate into active components in the form of oxides, and cooling to room temperature after the calcination is finished to obtain a finished product. The catalyst prepared by the invention is added with a certain amount of metal nitrate high-temperature decomposed oxides as active components and some auxiliary agents, the sources of all raw materials are wide, the cost is low, the durability of the granular catalyst is high, the pressure drop of smoke passing through is low, and the denitration efficiency can reach more than 85% at the ultralow temperature of 150 ℃.
Description
Technical Field
The invention relates to the technical field of denitration catalysts and discloses a preparation method of a nitrate type ultralow-temperature denitration granular catalyst.
Background
With the rapid development of society, factories such as coal-fired thermal power plants, cement plants, glass plants and the like in various regions stand, and a large amount of nitrogen oxides NOx are generated while great convenience is brought to human life. NOx mainly comprises NO and NO2、N2O、N2O3、N2O4And N2O5The environment-friendly type organic fertilizer is one of main atmospheric pollutants, is easy to cause a series of environmental problems such as photochemical smog, water eutrophication and the like, and has strong harmfulness to ecological development balance. With the improvement of environmental awareness of people, the emission standard of NOx is becoming stricter, but data show that the annual emission of NOx still has a rapid growth trend, and research on the denitration technology for removing nitrogen oxides in industrial waste gas is still not slow.
At present, the NOx emission control technology mostly adopts a Selective Catalytic Reduction (SCR) technology to treat fixed source flue gas, the core of the technology is a catalyst which is classified according to a proper flue gas reaction temperature window of a catalyst filled in a reactor and generally can be divided into a high-temperature region of 450-600 ℃ and above, a medium-temperature region of 320-450 ℃, a low-temperature region of 170-300 ℃ and an ultra-low-temperature region below 170 ℃, the development of the high-temperature SCR technology is mature in the past decades, and the development of the low-temperature SCR technology has made certain breakthrough in recent years. The most mature commercial denitration catalyst is V2O5-WO3(MoO3)/TiO2Catalyst of the formula V2O5As the main active ingredient, WO3Or MoO3As a co-agent, anatase type TiO2The vanadium-containing catalyst is a carrier, the content of vanadium oxide is 0-3.5 wt%, the applied temperature window is more than 220-420 ℃, and a very good effect is achieved in various flue gas engineering treatments, but the catalyst is high in cost and energy consumption, and is easy to cause secondary pollution to the environment, so that an economical, green and efficient ultralow-temperature SCR denitration technology is urgently needed to be developed.
Chinese patent document No. 201010513687.0 discloses a catalyst for removing NOx and a preparation method thereof, which is characterized in that 0.05-3 wt% of vanadium pentoxide (V) is adopted2O5) As an active component, TiO2、WO3And SiO2The denitration catalyst is prepared by taking the composite titanium dioxide as a carrier and other auxiliary agents such as glass fiber and the like, and waste gas, waste liquid and waste solids generated in the preparation process are recycled, so that the pollution problem in the production process of the catalyst is reduced, but V is used2O5The metal oxides are high in price, high in leaching toxicity and great in environmental hazard, so that the research of more economical and green high-efficiency non-vanadium catalysts is necessary.
Chinese patent application No. 201910417113.4 discloses a denitration and VOC-removal catalyst, a preparation method and a regeneration method, which is characterized in that the catalyst comprises a molybdenum compound, a palladium simple substance product, a lanthanum compound and a cerium compound as active components, and attapulgite as a carrier to prepare the catalyst, but the technique is to impregnate and load the active components on a ceramic honeycomb catalyst by a coating method, so that the prepared catalyst has the advantages of less actual active substances, small specific surface area, high pressure drop in actual flue gas operation, easy abrasion, and short service life and frequent replacement.
At present, the optimum active temperature range of the mainstream V-based honeycomb denitration catalyst is 320-500 ℃, the low-temperature activity is not obvious, the ultralow temperature below 170 ℃ is difficult to effectively exert, and the V is high in cost and high in toxicity. In view of the above circumstances, it is urgently needed to develop a new SCR denitration catalyst, which has a better denitration effect and high durability under an ultralow temperature condition, has a low pressure drop for flue gas to pass through, has a wide raw material source and low cost, and is suitable for industrial production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a nitrate type ultralow-temperature denitration granular catalyst, which is prepared by adopting an oxide decomposed at high temperature of metal nitrate as an active component, titanium dioxide or a molecular sieve as a carrier and adding a release agent, a preservative, a lubricant, a pH regulator, a structural assistant, a binder and the like, so that the ultralow-temperature denitration granular catalyst has better denitration effect and high durability under the ultralow-temperature condition, the pressure drop of smoke passing through is low, the sources of all raw materials are wide, the cost is low, and the method is suitable for industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a low-temperature SCR honeycomb type denitration catalyst, which comprises the following steps:
s1, mixing materials: weighing a carrier, a release agent, a preservative, a lubricant, a metal nitrate, a pH regulator, a structural assistant, a binder and the like, sequentially adding the weighed carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant, the binder and the like into a mud mixer, and mixing and kneading for a certain time to obtain mud;
s2, pre-squeezing and aging: putting the obtained pug into a pre-extruder to obtain pug sections, and then sealing, boxing and aging;
s3, forming, namely feeding the aged pug into an extruder to obtain a wet blank of the granular catalyst;
s4, drying: flatly paving the wet embryo in a sieve tray, and putting the sieve tray into a drying chamber for drying for a certain time to obtain a catalyst dry embryo;
s5, calcining: and (3) putting the catalyst dry blank into a calcining furnace to calcine in an inert atmosphere, gradually decomposing the metal nitrate into active components in the form of oxides, and cooling to room temperature after the calcination is finished to obtain a finished product.
Preferably, the mass ratio of the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH adjuster, the structural assistant and the binder in the step S1 is 100: 2-4: 2-4: 5-10: 10-20: 2-6: 5-8: 0 to 2;
the carrier is anatase titanium dioxide or a molecular sieve;
the release agent is stearic acid and magnesium stearate;
the preservative is lactic acid;
the lubricant is glycerol and salad oil;
the metal nitrate is selected from one or more of nitrates of Mn, Ce, Cu, Sn, Cr, Fe, Co and Zr, and the active component decomposed by corresponding calcination is MnO2、CeO2、CuO、SnO2、Cr2O3、Fe2O3、Co2O3、ZrO2；
The pH regulator is ammonia water and monoethanolamine;
the structural auxiliary agent is glass fiber and paper pulp;
the binder is sodium carboxymethyl cellulose (CMC) and polyethylene oxide (PEO);
preferably, the step S1 specifically includes the following steps:
s6, preparing an active solution, adding excessive deionized water to dissolve the metal nitrate component to obtain a precursor solution, and adding a pH regulator to regulate the pH to 6-8 to obtain the active solution;
and S7, adding a carrier, a release agent, a preservative, a lubricant and the active solution into a mud mixer, stirring for the first time, adding a structural auxiliary agent after uniformly mixing, stirring for the second time, adding a binder after uniformly mixing, stirring for the third time, opening a steam valve, stirring for the fourth time after uniformly mixing, and obtaining the mud material until the water content is reduced to 20-28 wt%.
Preferably, in the step S6,
the pH regulator can be added at intervals of 5min for 6-10 times, so that the active solution is prevented from flocculating due to too fast addition;
preferably, in the step S7,
during the first stirring, the stirring time is 35-60 min, and the stirring temperature is increased to 75-90 ℃;
during the second stirring, the stirring time is 35-60 min;
during the third stirring, opening a steam valve, reducing the stirring temperature to below 60 ℃, and stirring for 30-60 min; and during the fourth stirring, testing the water content of the pug by experience or sampling by a moisture meter until the water content of the pug is reduced to 20-28 wt%.
Preferably, the staling time in the step S2 is 2-4 days and is not more than 14 days;
preferably, the granular catalyst in step S3 is a cloverleaf-shaped, cylindrical or the like catalyst;
preferably, the specification of the granular catalyst in the step S3 is that the diameter of the circumscribed circle of the cross section is 1.5-3 mm, and the length is 6-30 mm;
preferably, the wet embryo is tiled on a sieve tray in the step S4, wherein the height of the sieve tray is not more than 10 cm;
preferably, in the drying process in the step S4, the temperature is increased from 30 ℃ to 60 ℃ at a temperature increase rate of 5-10 ℃/day, and then is increased from 60 ℃ to 80 ℃ at a temperature increase rate of 5-10 ℃/12 h;
preferably, in the calcining process of the rotary furnace in the step S5, the temperature rise rate is 5-10 ℃/12h, the temperature is 80-150 ℃, the calcining time is 3-7 days, the temperature is raised to 550 ℃ at the temperature rise rate of 60-100 ℃/2h, and the calcining time is 8-14 h.
Preferably, the inert gas in the step S5 is N2。
The denitration efficiency of the ultralow-temperature denitration granular catalyst obtained by the preparation method of the nitrate ultralow-temperature denitration granular catalyst is over 85 percent at 150 ℃.
The invention has the beneficial effects that:
1. according to the preparation method of the nitrate type ultralow-temperature denitration granular catalyst, oxides decomposed at high temperature of metal nitrates are used as active components, titanium dioxide or molecular sieve is used as a carrier, and a release agent, a preservative, a lubricant, a pH regulator, a structural assistant, a binder and the like are added to prepare the ultralow-temperature denitration granular catalyst, so that the ultralow-temperature denitration granular catalyst has a good denitration effect under an ultralow-temperature condition, is wide in raw material source and low in cost, and is suitable for industrial production.
2. According to the preparation method of the nitrate type ultralow-temperature denitration granular catalyst, the oxide decomposed at high temperature of metal nitrate is used as an active component and some auxiliary agents, the granular catalyst is formed by extrusion molding, the specific surface area is large, the pressure for passing flue gas is reduced, the durability is high, and secondary pollution to the environment is not easily caused.
3. The preparation method of the nitrate type ultralow-temperature denitration granular catalyst adopts the sectional stepped drying and calcining mechanism under the protection of inert atmosphere, effectively solves the problems of long production cycle, easy ignition, easy cracking and burning and the like of the nitrate type molded low-temperature catalyst, reduces the manual strength and energy consumption, and improves the yield.
Drawings
Other features, objects and advantages of the invention will appear more clearly on a reading of the detailed description of the embodiments of the invention, with reference to the following drawings, which are given as a few examples and are not intended to limit the invention in any way:
FIG. 1 is a process flow diagram of a preparation method of nitrate-based ultra-low temperature denitration granular catalyst of the invention;
FIG. 2 is a schematic cross-sectional view of a clover-shaped catalyst of the nitrate-based ultra-low temperature denitration granular catalyst of the present invention;
wherein:
is the diameter of the circumscribed circle of the clover cross section.
FIG. 3 is a schematic diagram showing the weight change of the nitrate-based ultra-low temperature denitration granular catalyst blank during the drying and calcining stage of the present invention.
Detailed Description
As shown in fig. 1, the preparation method of the nitrate-based ultra-low temperature denitration granular catalyst provided by the invention comprises the following steps:
s1, mixing materials: weighing a carrier, a release agent, a preservative, a lubricant, a metal nitrate, a pH regulator, a structural assistant, a binder and the like, sequentially adding the weighed carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant, the binder and the like into a mud mixer, and mixing and kneading for a certain time to obtain mud;
wherein the mass ratio of the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant and the binder is 100: 2-4: 2-4: 5-10: 10-20: 2-6: 5-8: 0 to 2; the carrier is anatase titanium dioxide or a molecular sieve, and has stronger alkali metal poisoning resistance; the release agent is stearic acid and magnesium stearate, which is beneficial to kneading pug; the preservative is lactic acid; the lubricant is glycerol and salad oil, which is beneficial to extrusion molding of the catalyst; the metal nitrate is selected from one or more of nitrates of Mn, Ce, Cu, Sn, Cr, Fe, Co and Zr, and the active component decomposed by calcination is MnO2、CeO2、CuO、SnO2、Cr2O3、Fe2O3、Co2O3、ZrO2(ii) a The pH regulator is ammonia water and monoethanolamine; the structural auxiliary agent is glass fiber and paper pulp, so that the mechanical strength of the catalyst is improved; the binder is sodium carboxymethyl cellulose CMC and polyethylene oxide PEO, which improves the plasticity of the pug.
The concrete operation is as follows when mixing materials:
s6, preparing an active solution, weighing corresponding metal nitrate according to a metal molar ratio of one of the formulas and the mass ratio according to a high-efficiency catalyst formula obtained through experimental verification, adding excessive deionized water to dissolve the metal nitrate component to obtain a precursor solution, adding a pH regulator to regulate the pH to 6-8 to obtain the active solution, and paying attention to the fact that the pH regulator can be added at intervals of 5min for 6-10 times to prevent the active solution from flocculating due to too fast addition;
s7, weighing the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant and the binder according to the mass ratio, adding the carrier, the release agent, the preservative, the lubricant and the active solution into a mud mixer for first stirring, gradually raising the temperature of the mixer to 75-90 ℃ in the stirring process, and stirring for 35-60 min; after uniformly mixing, adding a structural auxiliary agent for secondary stirring, and stirring for 35-60 min; after uniformly mixing, adding a binder for stirring for the third time, opening a steam valve, gradually reducing the stirring temperature in a machine to be below 60 ℃, and stirring for 30-60 min; and (3) uniformly mixing, stirring for the fourth time, and sampling according to experience or a moisture meter to test the water content of the pug until the water content is reduced to 20-28 wt% to obtain the pug.
S2, pre-squeezing and aging: putting the obtained pug into a pre-extruder to obtain pug sections, and then sealing, boxing and aging;
the pre-squeezing and staling operation is as follows: putting the pug into a pre-extruder to obtain relatively uniform cuboid brick-shaped pug sections, wherein the specifications of the pug sections are generally selected as the standards suitable for feeding and discharging of the extruder, then boxing the pug sections and sealing the pug sections in a ageing room at 25 +/-2 ℃ for ageing, wherein the optimal ageing time is 2-4 days, at the moment, all substances in the pug are combined and distributed more uniformly and do not exceed 14 days at most, otherwise, the pug can be hardened and even cracked due to the loss of a large amount of water;
s3, forming, namely feeding the aged pug into an extruder to obtain a wet blank of the granular catalyst, and selecting different dies according to engineering requirements, wherein the granular catalyst can be clover-shaped, cylindrical and the like, and is characterized in that the diameter of a circumscribed circle of the cross section is 1.5-3 mm, the length is 6-30 mm, and the performance of the catalyst in the specification range is optimal;
s4, drying: flatly paving the wet embryo in a sieve tray, and putting the sieve tray into a drying chamber for drying for a certain time to obtain a catalyst dry embryo;
the wet blank is paved on a sieve tray, the height of the sieve tray is not more than 10cm, the drying efficiency and the yield of the catalyst are improved, in the drying process, the temperature is increased from 30 ℃ to 60 ℃ at the temperature increasing rate of 5-10 ℃/day, and then is increased from 60 ℃ to 80 ℃ at the temperature increasing rate of 5-10 ℃/12 h. With the gradual rise of the temperature, the moisture in the catalyst wet blank is gradually and uniformly volatilized outwards, so that the self weight is gradually reduced, and the catalyst dry blank with the moisture content of 1-4 wt% is obtained.
S5, calcining: and (3) putting the catalyst dry blank into a calcining furnace to calcine in an inert atmosphere, gradually decomposing the metal nitrate into active components in the form of oxides, and cooling to room temperature after the calcination is finished to obtain a finished product.
In the calcining process of the calcining furnace, the temperature rise rate is 5-10 ℃/12h, the temperature is 80-150 ℃, the calcining time is 3-7 days, the temperature is raised to 550 ℃ at the temperature rise rate of 60-100 ℃/2h, the calcining time is 8-14 h, and the inert gas is N2. During the calcination process, the catalyst blank is subjected to a series of physical-chemical changes, the raw materials such as the release agent, the preservative, the lubricant and the like in the blank are completely burnt, the metal nitrate is gradually decomposed into corresponding oxides, and only the carrier, the structural assistant and the corresponding metal oxides are left in the finished catalyst. The catalyst prepared by the method has good performance, and the content of water vapor is 10 percent (volume ratio), SO2The concentration is 30mg/Nm3The space velocity is 5000h-1And the denitration efficiency reaches over 85 percent under the condition of the temperature of 150 ℃.
The preparation method of the nitrate-based ultra-low temperature denitration granular catalyst of the present invention will be further described with reference to specific examples.
Example 1
In this example, the mass ratio of the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH adjuster, the structural assistant, and the binder is 100: 2: 2: 6: 13: 5: 7: 1.85; the carrier is anatase titanium dioxide, the release agent is stearic acid and magnesium stearate, the preservative is lactic acid, the lubricant is glycerol and salad oil, and the metal nitrate is Mn (NO)3)2·2H2O、Ce(NO3)3·6H2O、Cu(NO3)2·9H2O and Zr (NO)3)4·5H2O, MnO being an active component decomposed by calcination2、CeO2、CuO、ZrO2And verifying the formula of the obtained high-efficiency catalyst according to experiments, wherein the molar ratio of Mn: ce: cu: zr 1: 1.5: 0.4: 0.2, and the pH regulator is ammonia water and monoethanolamine; the structural auxiliary agent is glass fiber and paper pulp, and the binder is sodium carboxymethyl cellulose CMC and polyethylene oxide PEO.
S1, mixing materials: weighing a carrier, a release agent, a preservative, a lubricant, a metal nitrate, a pH regulator, a structural assistant, a binder and the like, sequentially adding the weighed carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant, the binder and the like into a mud mixer, and mixing and kneading for a certain time to obtain mud;
the concrete operation is as follows when mixing materials:
s6, preparing an active solution, and weighing Mn (NO)3)2·2H2O、Ce(NO3)3·6H2O、Cu(NO3)2·9H2O and Zr (NO)3)4·5H2Adding excessive deionized water to dissolve to obtain a precursor solution, adding a pH regulator to regulate the pH to 7 to obtain an active solution, and adding the pH regulator 8 times at intervals of 5min to prevent the active solution from flocculating due to too fast addition;
s7, weighing the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant and the binder according to the formula, adding the carrier, the release agent, the preservative, the lubricant and the active solution into a mud mixer for first stirring, gradually raising the temperature of the mixer to 85 ℃ in the stirring process, and stirring for 45 min; after uniformly mixing, adding the structural assistant for secondary stirring, and stirring for 50 min; mixing, adding binder, stirring for the third time, opening steam valve, gradually lowering the stirring temperature in the machine to below 60 deg.C, and stirring for 50 min; and (4) stirring for the fourth time after uniformly mixing, and testing the water content of the pug by sampling according to experience or a moisture meter until the water content is reduced to 26 wt% to obtain the pug.
S2, pre-squeezing and aging: putting the mud into a pre-extruder to obtain uniform cuboid brick-shaped mud sections, wherein the specification of the mud sections is generally selected as the standard of the extruder suitable for feeding and discharging, and then boxing the mud sections and sealing in a ageing room at 25 +/-2 ℃ for ageing for 3 days.
And S3, forming, namely feeding the aged pug into an extruder to obtain the clover-shaped catalyst with the cross section circumscribed circle diameter of 2mm and the length of 8 mm.
S4, drying: and flatly paving the wet embryo in a sieve tray, putting the sieve tray into a drying chamber, drying for a certain time to obtain a catalyst dry embryo, flatly paving the wet embryo on the sieve tray with the height of 8cm, and in the drying process, raising the temperature from 30 ℃ to 60 ℃ at the temperature raising rate of 5 ℃/day, wherein the water content of a catalyst embryo body is 12 wt%, and then raising the temperature from 60 ℃ to 80 ℃ at the temperature raising rate of 5 ℃/12h to obtain the catalyst dry embryo with the water content of 2 wt%.
S5, calcining: putting the catalyst dry blank into a calcining furnace in N2Calcining in the atmosphere, wherein the heating rate is 7 ℃/12h, the temperature is 80-150 ℃, the calcining time is 5 days, the temperature is increased to 550 ℃ at the heating rate of 80 ℃/2h, the calcining time is 10h, and the finished product is obtained after the calcining is finished and the temperature is reduced to the room temperature. Only the rest titanium dioxide as carrier, glass fiber as structural assistant and MnO2、CeO2、CuO、ZrO2。
The particulate catalyst obtained in this example had a water vapor content of 10% (by volume), SO2The concentration is 30mg/Nm3The space velocity is 5000h-1And the denitration efficiency reaches 88.5% under the condition that the temperature is 150 ℃.
Example 2
In this example, the mass ratio of the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH adjuster, the structural assistant, and the binder is 100: 2: 2: 5: 10: 6: 7: 1.70; the carrier is anatase titanium dioxide, the release agent is stearic acid and magnesium stearate, the preservative is lactic acid, the lubricant is glycerol and salad oil, and the metal nitrate is Mn (NO)3)2·2H2O、Ce(NO3)3·6H2O、Cu(NO3)2·9H2O and Zr (NO)3)4·5H2O, MnO being an active component decomposed by calcination2、CeO2、CuO、ZrO2And verifying the formula of the obtained high-efficiency catalyst according to experiments, wherein the molar ratio of Mn: ce: cu: zr 1: 1.5: 0.4: 0.2, and the pH regulator is ammonia water and monoethanolamine; the structural auxiliary agent is glass fiber and paper pulp, and the binder is sodium carboxymethyl cellulose CMC and polyethylene oxide PEO.
S1, mixing materials: weighing a carrier, a release agent, a preservative, a lubricant, a metal nitrate, a pH regulator, a structural assistant, a binder and the like, sequentially adding the weighed carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant, the binder and the like into a mud mixer, and mixing and kneading for a certain time to obtain mud;
the concrete operation is as follows when mixing materials:
s6, preparing an active solution, and weighing Mn (NO)3)2·2H2O、Ce(NO3)3·6H2O、Cu(NO3)2·9H2O and Zr (NO)3)4·5H2Adding excessive deionized water to dissolve to obtain a precursor solution, adding a pH regulator to regulate the pH to 7 to obtain an active solution, and adding the pH regulator at intervals of 5min for 6 times to prevent the active solution from flocculating due to too fast addition;
s7, weighing the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant and the binder according to the formula, adding the carrier, the release agent, the preservative, the lubricant and the active solution into a mud mixer for primary stirring, gradually raising the temperature of the mixer to 80 ℃ in the stirring process, and stirring for 35 min; after uniformly mixing, adding the structural assistant for secondary stirring for 45 min; mixing, adding binder, stirring for the third time, opening steam valve, gradually lowering the stirring temperature in the machine to below 60 deg.C, and stirring for 45 min; and (4) stirring for the fourth time after uniformly mixing, and testing the water content of the pug by sampling according to experience or a moisture meter until the water content is reduced to 24 wt% to obtain the pug.
S2, pre-squeezing and aging: putting the mud into a pre-extruder to obtain uniform cuboid brick-shaped mud sections, wherein the specification of the mud sections is generally selected to be the standard of the extruder suitable for feeding and discharging, and then boxing the mud sections and sealing in a ageing room at 25 +/-2 ℃ for ageing for 2.5 days.
And S3, forming, namely feeding the aged pug into an extruder to obtain a clover-shaped catalyst with the cross section circumscribed circle diameter of 2mm and the length of 10 mm.
S4, drying: and flatly paving the wet embryo in a sieve tray, putting the sieve tray into a drying chamber, drying for a certain time to obtain a catalyst dry embryo, flatly paving the wet embryo in the sieve tray with the height of 10cm, and in the drying process, raising the temperature from 30 ℃ to 60 ℃ at the temperature raising rate of 5 ℃/day, wherein the water content of a catalyst embryo body is 10 wt%, and then raising the temperature from 60 ℃ to 80 ℃ at the temperature raising rate of 10 ℃/12h to obtain the catalyst dry embryo with the water content of 1 wt%.
S5, calcining: putting the catalyst dry blank intoCalcining furnace in N2Calcining in the atmosphere at the temperature rising rate of 10 ℃/12h, the temperature of 80-150 ℃ and the calcining time of 3.5 days, then heating the temperature to 550 ℃ at the temperature rising rate of 80 ℃/2h and the calcining time of 10h, and cooling to the room temperature after the calcining is finished to obtain the finished product. Only the rest titanium dioxide as carrier, glass fiber as structural assistant and MnO2、CeO2、CuO、ZrO2。
The particulate catalyst obtained in this example had a water vapor content of 10% (by volume) and a SO2 concentration of 30mg/Nm3The space velocity is 5000h-1And the denitration efficiency reaches 86.8% under the condition that the temperature is 150 ℃.
Example 3
In this example, the mass ratio of the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH adjuster, the structural assistant, and the binder is 100: 3: 3: 6: 20: 6: 8: 2; the carrier is anatase titanium dioxide, the release agent is stearic acid and magnesium stearate, the preservative is lactic acid, the lubricant is glycerol and salad oil, and the metal nitrate is Mn (NO)3)2·2H2O、Ce(NO3)3·6H2O、Cu(NO3)2·9H2O and Zr (NO)3)4·5H2O, MnO being an active component decomposed by calcination2、CeO2、CuO、ZrO2And verifying the formula of the obtained high-efficiency catalyst according to experiments, wherein the molar ratio of Mn: ce: cu: zr 1: 1.5: 0.4: 0.2, and the pH regulator is ammonia water and monoethanolamine; the structural auxiliary agent is glass fiber and paper pulp, and the binder is sodium carboxymethyl cellulose CMC and polyethylene oxide PEO.
S1, mixing materials: weighing a carrier, a release agent, a preservative, a lubricant, a metal nitrate, a pH regulator, a structural assistant, a binder and the like, sequentially adding the weighed carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant, the binder and the like into a mud mixer, and mixing and kneading for a certain time to obtain mud;
the concrete operation is as follows when mixing materials:
s6, preparing an active solution, and weighing Mn (NO)3)2·2H2O、Ce(NO3)3·6H2O、Cu(NO3)2·9H2O and Zr (NO)3)4·5H2Adding excessive deionized water to dissolve to obtain a precursor solution, adding a pH regulator to regulate the pH to 7 to obtain an active solution, and adding the pH regulator 10 times at intervals of 5min to prevent the active solution from flocculating due to too fast addition;
s7, weighing the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant and the binder according to the formula, adding the carrier, the release agent, the preservative, the lubricant and the active solution into a mud mixer for first stirring, gradually raising the temperature of the mixer to 90 ℃ in the stirring process, and stirring for 50 min; after uniformly mixing, adding the structural assistant for secondary stirring for 60 min; mixing, adding binder, stirring for the third time, opening steam valve, gradually lowering the stirring temperature in the machine to below 60 deg.C, and stirring for 60 min; and (4) stirring for the fourth time after uniformly mixing, and testing the water content of the pug by sampling according to experience or a moisture meter until the water content is reduced to 26 wt% to obtain the pug.
S2, pre-squeezing and aging: putting the mud into a pre-extruder to obtain uniform cuboid brick-shaped mud sections, wherein the specification of the mud sections is generally selected as the standard of the extruder suitable for feeding and discharging, and then boxing the mud sections and sealing in a ageing room at 25 +/-2 ℃ for ageing for 4 days.
And S3, forming, namely feeding the aged pug into an extruder to obtain the clover-shaped catalyst with the cross section circumscribed circle diameter of 3mm and the length of 20 mm.
S4, drying: and flatly paving the wet embryo in a sieve tray, putting the sieve tray into a drying chamber, drying for a certain time to obtain a catalyst dry embryo, flatly paving the wet embryo in the sieve tray with the height of 5cm, and in the drying process, raising the temperature from 30 ℃ to 60 ℃ at the temperature raising rate of 5 ℃/day, wherein the water content of a catalyst embryo body is 14 wt%, and then raising the temperature from 60 ℃ to 80 ℃ at the temperature raising rate of 5 ℃/12h to obtain the catalyst dry embryo with the water content of 3 wt%.
S5, calcining: putting the catalyst dry blank into a calcining furnace in N2Calcining in atmosphere at a temperature rise rate of 5 deg.C/12 h, 80-150 deg.C for 7 days, and at a temperature rise rate of 60 deg.C/2 h to 550 deg.C for 14hAnd cooling to room temperature after calcination to obtain the finished product. Only the rest titanium dioxide as carrier, glass fiber as structural assistant and MnO2、CeO2、CuO、ZrO2。
The particulate catalyst obtained in this example had a water vapor content of 10% (by volume), SO2The concentration is 30mg/Nm3The space velocity is 5000h-1And the denitration efficiency reaches 85.8% under the condition that the temperature is 150 ℃.
Claims (10)
1. A preparation method of nitrate type ultra-low temperature denitration granular catalyst is characterized by comprising the following steps:
s1, mixing materials: weighing a carrier, a release agent, a preservative, a lubricant, a metal nitrate, a pH regulator, a structural assistant, a binder and the like, sequentially adding the weighed carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant, the binder and the like into a mud mixer, and mixing and kneading for a certain time to obtain mud;
s2, pre-squeezing and aging: putting the obtained pug into a pre-extruder to obtain pug sections, and then sealing, boxing and aging;
s3, forming, namely feeding the aged pug into an extruder to obtain a wet blank of the granular catalyst;
s4, drying: flatly paving the wet embryo in a sieve tray, and putting the sieve tray into a drying chamber for drying for a certain time to obtain a catalyst dry embryo;
s5, calcining: and (3) putting the catalyst dry blank into a calcining furnace to calcine in an inert atmosphere, gradually decomposing the metal nitrate into active components in the form of oxides, and cooling to room temperature after the calcination is finished to obtain a finished product.
2. The method for preparing nitrate-based ultra-low temperature denitration granular catalyst according to claim 1, wherein the mass ratio of the carrier, the release agent, the preservative, the lubricant, the metal nitrate, the pH regulator, the structural assistant and the binder in S1 is 100: 2-4: 2-4: 5-10: 10-20: 2-6: 5-8: 0 to 2;
the carrier is anatase titanium dioxide or a molecular sieve;
the release agent is stearic acid and magnesium stearate;
the preservative is lactic acid;
the lubricant is glycerol and salad oil;
the metal nitrate is selected from one or more of nitrates of Mn, Ce, Cu, Sn, Cr, Fe, Co and Zr, and the active component decomposed by corresponding calcination is MnO2、CeO2、CuO、SnO2、Cr2O3、Fe2O3、Co2O3、ZrO2；
The pH regulator is ammonia water and monoethanolamine;
the structural auxiliary agent is glass fiber and paper pulp;
the binder is sodium carboxymethyl cellulose CMC and polyethylene oxide PEO.
3. The method for preparing nitrate-based ultra-low temperature denitration granular catalyst according to claim 1, wherein the S1 specifically comprises the following steps:
s6, preparing an active solution, adding excessive deionized water to dissolve the metal nitrate component to obtain a precursor solution, and adding a pH regulator to regulate the pH to 6-8 to obtain the active solution;
and S7, adding a carrier, a release agent, a preservative, a lubricant and the active solution into a mud mixer, stirring for the first time, adding a structural auxiliary agent after uniformly mixing, stirring for the second time, adding a binder after uniformly mixing, stirring for the third time, opening a steam valve, stirring for the fourth time after uniformly mixing, and obtaining the mud material until the water content is reduced to 20-28 wt%.
Preferably, in the step S6,
the pH regulator can be added at intervals of 5min for 6-10 times, so that the active solution is prevented from flocculating due to too fast addition;
preferably, in the step S7,
during the first stirring, the stirring time is 35-60 min, and the stirring temperature is increased to 75-90 ℃;
during the second stirring, the stirring time is 35-60 min;
during the third stirring, opening a steam valve, reducing the stirring temperature to below 60 ℃, and stirring for 30-60 min; and during the fourth stirring, testing the water content of the pug by experience or sampling by a moisture meter until the water content of the pug is reduced to 20-28 wt%.
4. The method for preparing a nitrate-based ultra-low temperature denitration granular catalyst according to claim 1, wherein the aging time in S2 is 2-4 days, not more than 14 days.
5. The method for preparing a nitrate-based ultra-low temperature denitration granular catalyst according to claim 1, wherein the granular catalyst in the S3 is a cloverleaf-shaped or cylindrical catalyst.
6. The method according to claim 1, wherein the granular catalyst is characterized in that the diameter of the circumscribed circle of the cross section is 1.5-3 mm, and the length of the catalyst is 6-30 mm in S3.
7. The method of claim 1, wherein the wet embryo is laid on a sieve tray at a height of not more than 10cm in S4.
8. The method of claim 1, wherein in the drying step of S4, the temperature is increased from 30 ℃ to 60 ℃ at a rate of 5-10 ℃/day, and then increased from 60 ℃ to 80 ℃ at a rate of 5-10 ℃/12 h.
9. The process flow of the nitrate low-temperature SCR honeycomb type denitration catalyst as claimed in claim 1, wherein in the rotary furnace calcination process in S5, the temperature rise rate is 5-10 ℃/12h, the temperature is 80-150 ℃, the calcination time is 3-7 days, the temperature is raised to 550 ℃ at the temperature rise rate of 60-100 ℃/2h, and the calcination time is 8-14 h.
10. The process flow of claim 1, wherein the inert gas in S5 is N2、CO2Or argon, etc.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113398952A (en) * | 2021-06-21 | 2021-09-17 | 山东熔石科技有限公司 | Flue gas wide-temperature SCR denitration catalyst and production process thereof |
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Address after: 214000 Zhuhai Road, huankeyuan, Yixing, Wuxi, Jiangsu Applicant after: Jiangsu xinzhongjin Low Carbon Technology Co.,Ltd. Address before: 214200 huankeyuan Zhuhai Road, Yixing City, Wuxi City, Jiangsu Province Applicant before: JIANGSU XINZHONGJIN ENVIRONMENTAL PROTECTION TECHNOLOGY CO.,LTD. |
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Application publication date: 20210312 |