CN115318302A - For NH 3 Denitration catalyst for denitration of SCR flue gas and preparation method thereof - Google Patents
For NH 3 Denitration catalyst for denitration of SCR flue gas and preparation method thereof Download PDFInfo
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- CN115318302A CN115318302A CN202210955810.7A CN202210955810A CN115318302A CN 115318302 A CN115318302 A CN 115318302A CN 202210955810 A CN202210955810 A CN 202210955810A CN 115318302 A CN115318302 A CN 115318302A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003546 flue gas Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 43
- 238000001354 calcination Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000007598 dipping method Methods 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- -1 iron ions Chemical class 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001437 manganese ion Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000012018 catalyst precursor Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 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
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- 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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- 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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0234—Impregnation and coating simultaneously
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- B01D2251/2062—Ammonia
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Abstract
The invention relates to a method for preparing NH 3 A denitration catalyst for SCR flue gas denitration and a preparation method thereof. Is used forNH 3 The preparation method of the denitration catalyst for SCR flue gas denitration comprises the following steps: (1) Dipping the mullite carrier in a pretreatment solution, and drying to obtain a pretreated carrier; (2) Dipping the pretreated carrier in a precursor solution containing ferric salt and manganese salt for treatment to obtain a precursor-coated carrier; (3) Drying the carrier coated with the precursor, and calcining to obtain the carrier for NH 3 -a denitration catalyst for SCR flue gas denitration. One of the invention is used for NH 3 The denitration catalyst for SCR flue gas denitration and the preparation method thereof, and the prepared catalyst has excellent low-temperature denitration performance, high load capacity, firm combination of the coating and the carrier, low cost and easy realization of industrialization.
Description
Technical Field
The invention belongs to NH 3 -SCR flue gas denitration technical field, in particular to a method for NH 3 A denitration catalyst for SCR flue gas denitration and a preparation method thereof.
Background
In recent years, due to the excessive exploitation and use of coal, oil and natural gas, haze frequently appears, and the life quality of people is seriously influenced. Haze is however caused by dust, sulphur dioxide and nitrogen oxides. At present, industrial dust and sulfur dioxide are well controlled, but nitrogen oxide treatment remains a challenge. Nitrogen oxides are the main components of air pollution, and the common nitrogen oxides mainly comprise nitrous oxide, nitric Oxide (NO) and nitrogen dioxide (NO) 2 ) Excessive emission of nitrogen oxides not only causes serious harm to the environment and causes damage to animals, plants, buildings due to acid rain, but also reduces visibility of air, seriously affects travel safety of people and destroys the ozone layer, however, when the content of nitrogen oxides in the air is too high, the nitrogen oxides can harm immune systems, respiratory systems, cardiovascular and cerebrovascular systems and the like of human bodies, and when the content of nitrogen oxides in the air is serious, the human bodies can be killed. However, at present, the selective catalytic reduction method is the most effective method for removing nitrogen oxides, NH 3 SCR is now the most widely used and widely used method for removing nitrogen oxides.
The existing preparation methods of the monolithic catalyst applied to the denitration of factory flue gas mainly comprise two methods, namely preparing a honeycomb monolithic denitration catalyst by loading active components on the surface of a cordierite carrier, and preparing the honeycomb monolithic denitration catalyst by adopting an extrusion molding method. When the monolithic denitration catalyst is prepared by adopting a method of loading the active component on the surface of the cordierite carrier, the active component has poor adhesion and is easy to fall off, and the denitration efficiency is reduced. By adopting the extrusion molding method, the amount of the required active components is too much, the production cost is high, the honeycomb monolithic catalyst is easy to crack during calcination, the honeycomb monolithic catalyst is difficult to prepare and has high cost, and the catalyst cannot achieve higher low-temperature denitration efficiency.
In view of the above, the present invention provides a new NH catalyst 3 The denitration catalyst for SCR flue gas denitration and the preparation method thereof have the advantages of good low-temperature denitration performance, strong adhesion and low cost.
Disclosure of Invention
The invention aims to provide a method for NH 3 The preparation method of the denitration catalyst for SCR flue gas denitration can improve the loading capacity of the active component, so that the coating and the carrier are firmly combined, and the preparation method has the advantages of simple process flow and low cost.
In order to realize the purpose, the adopted technical scheme is as follows:
for NH 3 The preparation method of the denitration catalyst for SCR flue gas denitration comprises the following steps:
(1) Dipping the mullite carrier in a pretreatment solution, and drying to obtain a pretreated carrier;
(2) Dipping the pretreated carrier in a precursor solution containing ferric salt and manganese salt for treatment to obtain a precursor-coated carrier;
(3) Drying the carrier coated with the precursor, and calcining to obtain the carrier for NH 3 -a denitration catalyst for SCR flue gas denitration.
Further, in the step (1), the mullite carrier is a honeycomb-shaped mullite carrier;
the pretreatment solution is dilute hydrochloric acid with the concentration of 0.58mol/L;
the dipping time is 10-14h.
Further, in the step (2), the manganese salt is at least one of manganese sulfate, manganese acetate, manganese carbonate and manganese nitrate; the iron salt is at least one of ferric nitrate, ferric chloride and ferric sulfate.
Further, in the step (2), the molar ratio of iron ions to manganese ions in the precursor solution is 1.
Still further, in the step (2), the molar ratio of iron ions to manganese ions in the precursor solution is 1.
Further, in the step (3), the drying temperature is 100-120 ℃, and the drying time is 6-10h;
the calcining temperature is 450-550 ℃, and the time is 2.5-3.5h.
Further, in the step (3), the calcining temperature is 500 ℃ and the time is 3 hours.
It is another object of the present invention to provide a method for NH 3 The denitration catalyst for SCR flue gas denitration is prepared by the preparation method, and has the advantages of good low-temperature denitration performance, strong adhesion and low cost.
Furthermore, the loading amount of the active component in the denitration catalyst on the mullite carrier is 17-40%.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation process has the advantages of simple flow, low cost and easy realization of industrialization.
2. The denitration catalyst prepared by the preparation method has high loading rate of the active components of the catalyst on the carrier, the mass of the denitration catalyst is 110-130% of that of the pretreated mullite carrier, and the coating can be firmly combined with the carrier.
3. The catalyst prepared by the method has the advantages of nitrogen oxide conversion rate of more than 80% at 150-250 ℃, high denitration activity and suitability for denitration under the low-temperature condition.
Drawings
FIG. 1 is a graph of the performance of a catalyst for denitration; wherein the solution is the catalyst prepared in example 1, the precursor represents the catalyst prepared in example 2, and the powder represents the catalyst prepared in example 3.
Detailed Description
For further elucidation of the invention 3 The denitration catalyst for denitration of SCR flue gas and the preparation method thereof, which achieve the intended purpose of the invention, are described below with reference to the preferred embodiments 3 The specific embodiment, structure, characteristics and efficacy of the denitration catalyst for SCR flue gas denitration are described in detail later. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The following will describe a process for NH according to the invention with reference to specific examples 3 The denitration catalyst for SCR flue gas denitration and the preparation method thereof are further described in detail:
in order to enable the denitration catalyst to have higher denitration activity under the low-temperature condition, so that the denitration catalyst is more suitable for industrial application, the technical scheme is as follows:
for NH 3 The preparation method of the denitration catalyst for SCR flue gas denitration comprises the following steps:
(1) Dipping the mullite carrier in a pretreatment solution, and drying to obtain a pretreated carrier;
(2) Dipping the pretreated carrier in a precursor solution containing ferric salt and manganese salt for treatment to obtain a precursor-coated carrier;
(3) Drying the carrier coated with the precursor, and calcining to obtain the carrier for NH 3 -a denitration catalyst for SCR flue gas denitration.
Preferably, in the step (1), the mullite carrier is a honeycomb-shaped mullite carrier;
the pretreatment solution is at least one of dilute hydrochloric acid and dilute sulfuric acid;
the dipping time is 10-14h.
The loading of the active component in the catalyst can be increased by acid treatment of the support. And (3) determining the loading comparison of the mullite after the acid treatment by adopting a single-factor comparison method, wherein after the acid treatment, the mullite loading rate is 16.8-37.9%, and the mullite loading rate is 6.4-11.5% after the soaking treatment is carried out by adopting clear water.
Preferably, in the step (2), the manganese salt is at least one of manganese sulfate, manganese acetate, manganese carbonate and manganese nitrate; the ferric salt is at least one of ferric nitrate, ferric chloride and ferric sulfate.
The active components in the catalyst are manganese oxide and iron oxide. The oxide of manganese being MnO 2 、Mn 2 O 3 And Mn 3 O 4 At least one of, the iron oxide is Fe 3 O 4 Or Fe 2 O 3 。
Preferably, in the step (2), the molar ratio of iron ions to manganese ions in the precursor solution is 1.
Further preferably, in the step (2), the molar ratio of the iron ions to the manganese ions in the precursor solution is 1.
Preferably, in the step (3), the drying temperature is 100-120 ℃, and the drying time is 6-10h;
the calcining temperature is 450-550 ℃ and the time is 2.5-3.5h.
Further preferably, in the step (3), the calcination temperature is 500 ℃ and the calcination time is 3 hours.
It is a further object of the invention to provide a process for NH 3 The denitration catalyst for SCR flue gas denitration is prepared by the preparation method, and has the advantages of good low-temperature denitration performance, strong adhesion and low cost.
Preferably, the loading amount of the active component in the denitration catalyst on the mullite carrier is 17-40%.
Example 1.
The specific operation steps are as follows:
(1) 245.088gMn (CH) 3 COO) 2 ·4H 2 O，40.4gFe(NO 3 ) 3 ·9H 2 And adding O into 600ml of water, and stirring the mixture by a tilting stirring pot until the O is dissolved to obtain a uniform catalyst precursor solution.
(2) Soaking the honeycomb-shaped mullite carrier in a pretreatment solution (0.58 mol/L dilute hydrochloric acid solution) for 12 hours, washing away surface residues with clear water, placing in an oven, and drying at 100 ℃ for later use.
(3) And putting the dried mullite carrier into a mold of 20cm-20cm, pouring the catalyst precursor solution into the mold, and soaking for 6 hours by a soaking method to directly coat the precursor on the honeycomb mullite carrier.
(4) And drying the coated honeycomb mullite carrier in an oven at the drying temperature of 100 ℃ for 10 hours.
And then, calcining in a muffle furnace, raising the temperature to the calcining temperature at the speed of 5 ℃/min, wherein the calcining temperature is 500 ℃, and the calcining time is 3h, so as to obtain the honeycomb integral type low-temperature denitration catalyst.
The mass of the mullite is weighed before and after coating, and the weight of the mullite is increased by 26 percent after coating.
Example 2.
The specific operation steps are as follows:
(1) 245.088gMn (CH) 3 COO) 2 ·4H 2 O and 40.4gFe (NO) 3 ) 3 ·9H 2 And adding O into 600ml of water, and stirring the mixture by a tilting stirring pot until the O is dissolved to obtain a uniform catalyst precursor solution.
And (3) putting the precursor solution into an oven, drying for 10h at 100 ℃, and drying to form a precursor for later use.
(2) Soaking the honeycomb mullite carrier in a pretreatment solution (0.58 mol/L dilute hydrochloric acid solution) for 12 hours, washing away surface residues with clear water, placing in a drying oven, and drying at 100 ℃ for later use.
(3) Placing the mullite honeycomb carrier into a mold of 20cm;
adding 300ml of water into 60g of the precursor, stirring and dissolving the mixture into precursor liquid, pouring the precursor liquid into a mould, and directly dipping the catalyst precursor liquid for 6 hours by a direct dipping method to directly coat the precursor on the honeycomb mullite carrier.
(4) And drying the coated honeycomb mullite carrier in an oven at the drying temperature of 100 ℃ for 10 hours.
And then, calcining in a muffle furnace, raising the temperature to the calcining temperature at the speed of 5 ℃/min, wherein the calcining temperature is 500 ℃, and the calcining time is 3h, so as to obtain the honeycomb monolithic denitration catalyst.
The mass of the mullite is weighed before and after coating, and the weight of the mullite is increased by 24 percent after coating.
Example 3.
The specific operation steps are as follows:
(1) 245.088gMn (CH) 3 COO) 2 ·4H 2 O and 40.4gFe (NO) 3 ) 3 ·9H 2 And adding O into 600ml of water, and stirring the mixture by a tilting stirring pot until the O is dissolved to obtain a uniform catalyst precursor solution.
(2) And (3) putting the obtained precursor solution into an oven, drying for 10h at 100 ℃, and drying to form a precursor.
(3) And calcining the obtained precursor in a muffle furnace, and heating to the calcining temperature at the speed of 5 ℃/min, wherein the calcining temperature is 500 ℃, and the calcining time is 3 hours, so as to obtain the powder catalyst.
(4) Soaking the honeycomb mullite carrier in a pretreatment solution (0.58 mol/L dilute hydrochloric acid solution) for 12 hours, washing away surface residues with clear water, placing in a drying oven, and drying at 100 ℃ for later use.
(5) Putting the dried mullite carrier into a mold of 20cm to 20cm;
adding 300ml of water into 30g of powder catalyst, uniformly stirring, pouring into a mould, and soaking the prepared powder suspension for 6 hours by a direct impregnation method to directly coat the active component on the honeycomb mullite carrier.
(6) And drying the coated honeycomb mullite carrier in an oven at the drying temperature of 100 ℃ for 10 hours.
And then, calcining in a muffle furnace, raising the temperature to the calcining temperature at the speed of 5 ℃/min, wherein the calcining temperature is 500 ℃, and the calcining time is 3h, so as to obtain the honeycomb monolithic denitration catalyst.
The mass of the mullite before and after coating is weighed, and the weight gain of the mullite after coating is 21 percent.
The catalysts prepared in examples 1 to3 were used for low-temperature denitration reaction.
Catalyst performance test conditions: the activity experiment was carried out on a simulated flue gas fixed bed with an ammonia-to-nitrogen ratio of 1,o 2 The concentration is 6% (V/V), GHSV (gas space velocity per hour) =3000h -1 The flue gas of (1) is passed through a temperature programming reaction device from room temperature to 500 ℃, a detection device with 50 ℃ at each temperature point is a flue gas analyzer (Testo 350) to detect denitration performance at different temperatures at each temperature point, the continuous measurement time at each temperature point is 120min, and the average value is obtained, and the result is shown in figure 1. The NO conversion, i.e., the denitration rate, was calculated according to formula 1.
NO conversion = [ (NO) in -NO out )/NO in ]×100
As can be seen from fig. 1, the comparison of the examples shows that the denitration catalyst prepared by directly impregnating the precursor solution of the present invention has high denitration catalytic activity at low temperature, and the preparation process is simple, so that compared with other two preparation methods, the preparation method not only saves the preparation process, but also has the advantages of low cost and high denitration performance, thereby being more easily industrialized.
Example 4.
The specific operation steps are as follows:
(1) 166.10g of MnSO 4 And 16.22g FeCl 3 Adding the mixture into 600ml of water, and stirring the mixture by a tilting stirring pot until the mixture is dissolved to obtain a uniform catalyst precursor solution.
(2) Soaking the honeycomb mullite carrier in a pretreatment solution (0.58 mol/L dilute hydrochloric acid solution) for 10 hours, washing away surface residues with clear water, placing in a drying oven, and drying at 100 ℃ for later use.
(3) And (3) putting the dried mullite carrier into a mold of 20cm-20cm, pouring the catalyst precursor solution into the mold, and impregnating for 6 hours by an impregnation method to directly coat the precursor on the honeycomb mullite carrier.
(4) And drying the coated honeycomb mullite carrier in an oven at the drying temperature of 120 ℃ for 6 hours.
And then calcining in a muffle furnace, and heating to the calcining temperature at the speed of 5 ℃/min, wherein the calcining temperature is 550 ℃, and the calcining time is 2.5h, so as to obtain the honeycomb integral type low-temperature denitration catalyst.
Example 5.
The specific operation steps are as follows:
(1) Mixing 89.474gMn (NO) 3 ) 2 、45.98gMnCO 3 And 19.99gFe 2 (SO 4 ) 3 Adding the mixture into 1000ml of water, and stirring the mixture by a tilting stirring pot until the mixture is dissolved to obtain a uniform catalyst precursor solution.
(2) Soaking the honeycomb mullite carrier in a pretreatment solution (0.58 mol/L dilute hydrochloric acid solution) for 14h, washing away surface residues with clear water, placing in an oven, and drying at 100 ℃ for later use.
(3) And (3) putting the dried mullite carrier into a mold of 20cm-20cm, pouring the catalyst precursor solution into the mold, and impregnating for 6 hours by an impregnation method to directly coat the precursor on the honeycomb mullite carrier.
(4) And drying the coated honeycomb mullite carrier in an oven at the drying temperature of 110 ℃ for 5 hours.
And then, calcining in a muffle furnace, raising the temperature to the calcining temperature at the speed of 5 ℃/min, wherein the calcining temperature is 450 ℃, and the calcining time is 3.5h, so as to obtain the honeycomb integral type low-temperature denitration catalyst.
While the embodiments of the present invention have been described in connection with the preferred embodiments, it will be understood that they are not intended to limit the embodiments of the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the embodiments of the invention as defined by the appended claims.
Claims (10)
1. For NH 3 The preparation method of the denitration catalyst for SCR flue gas denitration is characterized by comprising the following steps of:
(1) Dipping the mullite carrier in a pretreatment solution, and drying to obtain a pretreated carrier;
(2) Dipping the pretreated carrier in a precursor solution containing ferric salt and manganese salt for treatment to obtain a precursor-coated carrier;
(3) Drying the carrier coated with the precursor, and calcining to obtain the carrier for NH 3 -a denitration catalyst for SCR flue gas denitration.
2. The production method according to claim 1,
in the step (1), the mullite carrier is a honeycomb-shaped mullite carrier;
the pretreatment solution is dilute hydrochloric acid;
the dipping time is 10-14h.
3. The production method according to claim 1,
in the step (2), the manganese salt is at least one of manganese sulfate, manganese acetate, manganese carbonate and manganese nitrate; the ferric salt is at least one of ferric nitrate, ferric chloride and ferric sulfate.
4. The production method according to claim 1,
in the step (2), the molar ratio of iron ions to manganese ions in the precursor solution is 1.
5. The method according to claim 4,
in the step (2), the molar ratio of iron ions to manganese ions in the precursor solution is 1.
6. The method according to claim 5,
in the step (2), the concentration of the manganese salt is 0.9-1.84mol/L.
7. The production method according to claim 1,
in the step (3), the drying temperature is 100-120 ℃, and the drying time is 6-10h;
the calcining temperature is 450-550 ℃ and the time is 2.5-3.5h.
8. The method of claim 7,
in the step (3), the calcining temperature is 500 ℃ and the time is 3h.
9. For NH 3 -a denitration catalyst for denitration of SCR flue gas, characterized in that the denitration catalyst is prepared by the preparation method according to any one of claims 1 to 8.
10. The denitration catalyst according to claim 9,
the loading amount of the active component in the denitration catalyst on the mullite carrier is 17-40%.
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| US20060029535A1 (en) * | 2004-07-27 | 2006-02-09 | Ott Kevin C | Catalyst and method for reduction of nitrogen oxides |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060029535A1 (en) * | 2004-07-27 | 2006-02-09 | Ott Kevin C | Catalyst and method for reduction of nitrogen oxides |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
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