CN113499783A - Preparation method of ultralow-temperature SCR denitration catalyst - Google Patents
Preparation method of ultralow-temperature SCR denitration catalyst Download PDFInfo
- Publication number
- CN113499783A CN113499783A CN202110837329.3A CN202110837329A CN113499783A CN 113499783 A CN113499783 A CN 113499783A CN 202110837329 A CN202110837329 A CN 202110837329A CN 113499783 A CN113499783 A CN 113499783A
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- tio
- temperature
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 22
- 238000001125 extrusion Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 2
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 2
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 18
- 238000011068 loading method Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052721 tungsten Inorganic materials 0.000 abstract description 2
- 239000010937 tungsten Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 239000003546 flue gas Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts for removing nitrogen oxides in industrial or motor vehicle exhaust pollutants by selective catalytic reduction, and particularly discloses a preparation method of an ultralow-temperature SCR denitration catalyst. The method comprises the steps of firstly taking water or urea as a precipitator, loading tungsten on titanium dioxide by adopting a precipitation method, then taking sodium carbonate as the precipitator, and loading one or more of Mn, Ce, Co, Fe and Mo on W-TiO by adopting the precipitation method2And loading V by using an impregnation method, and finally adding a plasticizer, an adhesive, a lubricant and the like to prepare the finished catalyst. The invention strictly controls one or more metals of Mn, Ce, Co, Fe, Mo and the like in V-W/TiO2Preparation method of catalyst in proportionThe method not only enhances the stability of the catalyst, but also greatly improves the low-temperature denitration activity of the catalyst, and has the NOx conversion rate of 98 percent within the range of 100-150 ℃.
Description
Technical Field
The invention relates to the field of catalysts for removing nitrogen oxides in industrial or motor vehicle exhaust pollutants by selective catalytic reduction, in particular to a preparation method of an ultralow-temperature SCR denitration catalyst.
Background
With the continuous development of economy in China, the requirements of the quality of life of the nation are continuously improved, the pressure brought by environmental pollution is increased day by day, and the treatment level of nitrogen oxide is closely related to the quality of the atmospheric environment in China as one of the main pollutants of the current atmospheric pollution. The coal-fired power plant is used as a main pollution source for concentrated emission of nitrogen oxides, emission reduction of the nitrogen oxides in the emitted flue gas becomes an important target for treatment at present, flue gas denitrification also becomes a necessary environment-friendly facility for the coal-fired power plant, and the facility usually adopts NH3Denitration by SCR (Selective catalytic reduction of Ammonia) denitration technology, the principle of which is NH3Or urea is used as a reducing agent to react NO under the action of a catalystxReduction to N2And the high-efficiency removal of nitrogen oxides in the flue gas is realized.
For low-temperature flue gas in industries such as coking, sintering and the like, the flue gas temperature is generally 110-3The optimum reaction temperature of the catalyst needs to be about 350 ℃, and in order to solve the current situation of poor denitration efficiency at low temperature, measures such as heating the flue gas to 180-200 ℃, increasing the ammonia injection amount, increasing the content of V in the catalyst and the like are generally adopted, but the methods have various defects such as increased denitration cost, increased ammonia escape and the like, and are difficult to meet the requirements of flue gas emission standards. Therefore, it is necessary to develop a catalyst with high denitration efficiency under ultralow temperature (less than or equal to 150 ℃).
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides the preparation method of the ultralow-temperature SCR denitration catalyst with simple process, strong stability and high activity.
The invention is realized by the following technical scheme:
a preparation method of an ultralow-temperature SCR denitration catalyst comprises the following steps:
(1) adding the W precursor solution into water, mixing uniformly, and then adding TiO2Mixing the powders, slowly adding ammonia water or urea as precipitant, and filtering the solid precipitate with deionized water to obtain W-TiO2A solution;
(2) adding one or more precursor solutions of Mn, Ce, Co, Fe and Mo into W-TiO2Fully stirring in the solution;
(3) slowly adding sodium carbonate into the solution obtained in the step (2), continuously stirring for 3 hours to obtain a precipitate, filtering the precipitate, and washing the precipitate for 3-6 times by using warm distilled water to obtain a sample;
(4) adding the V precursor solution into a sample, adding distilled water, and uniformly stirring to obtain a catalyst solution;
(5) stirring and heating the catalyst solution, adding a plasticizer, an adhesive and a lubricant, kneading, ageing, extruding and molding, drying and calcining to obtain the finished catalyst.
The method comprises the steps of firstly taking water or urea as a precipitator, loading tungsten on titanium dioxide by adopting a precipitation method, then taking sodium carbonate as the precipitator, and loading one or more of Mn, Ce, Co, Fe and Mo on W-TiO by adopting the precipitation method2And loading V by using an impregnation method, finally adding a plasticizer, an adhesive, a lubricant and the like, and preparing to obtain a finished catalyst, wherein preparation parameters such as temperature, time and the like are strictly controlled in the preparation process.
The more preferable technical scheme of the invention is as follows:
in the step (1), the W precursor solution is ammonium metatungstate or ammonium paratungstate solution, W-TiO2The mass concentration of W in the solution is 0.5-10%.
Further preferably, when ammonia or urea is added as a precipitant, the pH of the solution is maintained at 7 to 9.
In the step (2), one or more precursor solutions of Mn, Ce, Co, Fe and Mo are one or more of nitrate, acetate, phosphate and sulfate solutions, and the mass of metal in the precursor solution accounts for W-TiO20.5-10% of the mass.
In the step (3), the pH value of the solution is kept between 7 and 9 after sodium carbonate is added.
In the step (4), the V precursor is dissolvedThe solution is a solution of vitriol, vanadyl sulfate, ammonium metavanadate, vanadium nitrate or vanadium oxalate, wherein the mass of V accounts for TiO21-15% of the mass.
In the step (5), the plasticizer is one or more of kaolin, diatomite, montmorillonite and glass fiber, the binder is one or more of alumina sol, silica sol, polyethylene glycol, hydroxymethyl cellulose and starch, and the lubricant is one or two of stearic acid and glycerol.
Further preferably, kneading is to keep stirring the mixture at 20-50 ℃ for 5-60min at each step of the kneader to obtain wet dough; aging the kneaded pug for 5-36h at 20-50 ℃, then putting the aged pug into a pug mill for extrusion molding, wherein the extrusion pressure is 0.5-20MPa, the extrusion temperature is 20-50 ℃, and the extrusion shape is honeycomb type.
More preferably, the extrusion molded blank is dried for 10-36h at 90-160 ℃, and the dried catalyst is calcined in a calcining furnace in sections, wherein in the temperature section of 100-300 ℃, the heating rate is 5-35 ℃/h, and the heat preservation time is 5-20 h; in the temperature range of 300-600 ℃, the heating rate is 5-35 ℃/h, and the heat preservation time is 10-24 h; finally, in the cooling section, the cooling rate is 20-60 ℃/h, and the temperature is reduced to be below 100 ℃.
The invention strictly controls one or more metals of Mn, Ce, Co, Fe, Mo and the like in V-W/TiO2The preparation method parameters such as the content, the proportion and the like of the catalyst not only enhance the stability of the catalyst, but also greatly improve the low-temperature denitration activity of the catalyst, and the NOx conversion rate is up to 98 percent in the range of 100-150 ℃.
Drawings
The invention will be further described with reference to the accompanying drawings.
Fig. 1 is a graph showing denitration efficiency of the denitration catalysts obtained in example 1 and example 2 at different temperatures.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
an ultra-low temperature SCR denitration catalyst and a preparation method thereof comprise the following steps:
(1) adding ammonium metatungstate into water, mixing thoroughly, adding TiO2Adding ammonia water as precipitant slowly to maintain pH value of the solution at 7-9. Obtaining precipitate, filtering the solid precipitate with deionized water for 3-5 times to obtain W-TiO2Wherein the mass fraction of W is 3%;
(2) adding three precursors of Mn, Ce, Co and the like into the W-TiO prepared in the step (1)2Fully stirring the solution, wherein the mass fraction of metals such as Mn, Ce, Co and the like is 5%, and the mass fraction of Mn: ce: the molar ratio of Co is 1: 1: 1.2;
(3) mixing Na2CO3Slowly adding into the solution prepared in the step (2), maintaining the pH value of the solution at 7-9, continuously stirring for 3 hours to obtain precipitate, filtering the precipitate, washing with warm distilled water (45 ℃) for 3-6 times, and thoroughly removing impurities;
(4) adding ammonium metavanadate into the sample prepared in the step (3), adding distilled water, and fully stirring to uniformly disperse the ammonium metavanadate, wherein the mass fraction of V is 1%;
(5) continuously stirring and heating the catalyst prepared in the step (4), adding diatomite, kaolin, hydroxymethyl cellulose, starch, glycerol and the like, fully stirring, and preparing a finished product catalyst through the processes of kneading → ageing → extrusion molding → drying → calcining and the like;
the kneading is to keep stirring the mixed materials in the step of mixing materials at the temperature of 30-40 ℃ for 15-20min at the interval of each step of the kneader to obtain wet material masses;
the ageing is to age the kneaded pug for 24 hours at the temperature of 40-45 ℃, and finally, the aged pug is put into a forming machine for extrusion forming;
the extrusion molding is to extrude the aged and rotten mixed material in a pugmill, wherein the extrusion pressure is 5-6Mpa, the extrusion temperature is 30-35 ℃, and the extrusion shape is honeycomb type;
the drying is to dry the extruded and molded blank at the temperature of 100-110 ℃, and the drying time is 24 h;
the calcination is to calcine the dried catalyst in a calcination furnace in a segmented manner, wherein the heating rate of a 300 ℃ temperature section with 100 ℃ plus materials is 10 ℃/h, the heat preservation time is 15h, the heating rate of a 600 ℃ temperature section with 300 ℃ plus materials is 7 ℃/h, the heat preservation time is 20h, the cooling rate of a final cooling section is 30 ℃/h, and the temperature is reduced to be below 100 ℃, so that the ultralow-temperature denitration catalyst is prepared.
Example 2:
a preparation method of an ultralow-temperature SCR denitration catalyst comprises the following steps:
(1) adding ammonium metatungstate into water, mixing thoroughly, adding TiO2Adding ammonia water as precipitant slowly to maintain pH value of the solution at 7-9. Obtaining precipitate, filtering the solid precipitate with deionized water for 3-5 times to obtain W-TiO2Wherein the mass fraction of W is 2.5%;
(2) adding three precursors of Mn, Ce, Co and the like into the W-TiO prepared in the step (1)2Fully stirring the solution, wherein the mass fraction of metals such as Mn, Ce, Co and the like is 5%, and the mass fraction of Mn: ce: the molar ratio of Co is 1: 0.8: 0.8;
(3) mixing Na2CO3Slowly adding into the solution prepared in the step (2), maintaining the pH value of the solution at 7.5-8.5, continuously stirring for 6 hours to obtain precipitate, filtering the precipitate, washing with warm distilled water (30 ℃) for 3-6 times, and thoroughly removing impurities;
(4) adding ammonium metavanadate into the sample prepared in the step (3), adding distilled water, and fully stirring to uniformly disperse the ammonium metavanadate, wherein the mass fraction of V is 1.2%;
(5) continuously stirring and heating the catalyst prepared in the step (4), adding glass cellulose, kaolin, hydroxymethyl cellulose, glycerol, stearic acid and the like, fully stirring, and preparing a finished product catalyst through the processes of kneading → ageing → extrusion molding → drying → calcining and the like;
the kneading is to keep stirring the mixed materials in the step of mixing materials at the temperature of 30-40 ℃ for 15-20min at the interval of each step of the kneader to obtain wet material masses;
the ageing is to age the kneaded pug for 20 hours at the temperature of 40-45 ℃, and finally, the aged pug is put into a forming machine for extrusion forming;
the extrusion molding is to extrude the aged and rotten mixed material in a pugmill, wherein the extrusion pressure is 3-5Mpa, the extrusion temperature is 30-35 ℃, and the extrusion shape is honeycomb type;
the drying is to dry the extruded and molded blank at the temperature of 100-110 ℃, and the drying time is 24 h;
the calcination is to calcine the dried catalyst in a calcination furnace in a segmented manner, wherein the heating rate of a 300 ℃ temperature section with 100 ℃ plus materials is 10 ℃/h, the heat preservation time is 15h, the heating rate of a 600 ℃ temperature section with 300 ℃ plus materials is 7 ℃/h, the heat preservation time is 20h, the cooling rate of a final cooling section is 25 ℃/h, and the temperature is reduced to be below 100 ℃, so that the ultralow-temperature denitration catalyst is prepared.
The performance of the denitration catalyst is evaluated under the condition of adopting simulated flue gas, and NH is used3As a reducing agent, the reaction conditions are as follows: NO 500ppm, O2The volume fraction is 5 percent, the ammonia-nitrogen ratio is 1.05:1, N2For balancing gas, the space velocity is 10,000h-1The denitration efficiency of examples 1 and 2 is shown in the attached figure 1 within the reaction temperature range of 100-200 ℃.
In the above embodiments, the best mode of the present invention has been described, and it is apparent that many changes can be made under the inventive concept of the present invention. It should be noted here that any changes made under the inventive concept of the present invention shall fall within the protective scope of the present invention.
Claims (9)
1. A preparation method of an ultralow-temperature SCR denitration catalyst is characterized by comprising the following steps: (1) adding the W precursor solution into water, mixing uniformly, and then adding TiO2Mixing the powders, slowly adding ammonia water or urea as precipitant, and filtering the solid precipitate with deionized water to obtain W-TiO2A solution; (2) adding one or more precursor solutions of Mn, Ce, Co, Fe and Mo into W-TiO2Fully stirring in the solution; (3) slowly adding sodium carbonate into the solution obtained in the step (2), continuously stirring for 3 hours to obtain a precipitate, filtering the obtained precipitate, and steaming at a warm temperatureWashing with distilled water for 3-6 times to obtain a sample; (4) adding the V precursor solution into a sample, adding distilled water, and uniformly stirring to obtain a catalyst solution; (5) stirring and heating the catalyst solution, adding a plasticizer, an adhesive and a lubricant, kneading, ageing, extruding and molding, drying and calcining to obtain the finished catalyst.
2. The method of claim 1, wherein: in the step (1), the W precursor solution is ammonium metatungstate or ammonium paratungstate solution, W-TiO2The mass concentration of W in the solution is 0.5-10%.
3. The method of claim 1, wherein: in the step (1), when ammonia water or urea is added as a precipitator, the pH value of the solution is kept between 7 and 9.
4. The method of claim 1, wherein: in the step (2), one or more precursor solutions of Mn, Ce, Co, Fe and Mo are one or more of nitrate, acetate, phosphate and sulfate solutions, and the mass of metal in the precursor solution accounts for W-TiO20.5-10% of the mass.
5. The method of claim 1, wherein: in the step (3), the pH value of the solution is kept between 7 and 9 after sodium carbonate is added.
6. The method of claim 1, wherein: in the step (4), the V precursor solution is a solution of vitriol, vanadyl sulfate, ammonium metavanadate, vanadium nitrate or vanadium oxalate, wherein the mass of V accounts for TiO21-15% of the mass.
7. The method of claim 1, wherein: in the step (5), the plasticizer is one or more of kaolin, diatomite, montmorillonite and glass fiber, the binder is one or more of alumina sol, silica sol, polyethylene glycol, hydroxymethyl cellulose and starch, and the lubricant is one or two of stearic acid and glycerol.
8. The method of claim 1, wherein: in the step (5), kneading is to keep stirring the mixed materials at the temperature of 20-50 ℃ for 5-60min at the interval of each step of the kneader to obtain wet material masses; aging the kneaded pug for 5-36h at 20-50 ℃, then putting the aged pug into a pug mill for extrusion molding, wherein the extrusion pressure is 0.5-20MPa, the extrusion temperature is 20-50 ℃, and the extrusion shape is honeycomb type.
9. The method of claim 1 or 8, wherein: in the step (5), drying the extruded and molded blank at 90-160 ℃ for 10-36h, and calcining the dried catalyst in a calcining furnace in sections, wherein in the temperature range of 100-300 ℃, the heating rate is 5-35 ℃/h, and the heat preservation time is 5-20 h; in the temperature range of 300-600 ℃, the heating rate is 5-35 ℃/h, and the heat preservation time is 10-24 h; finally, in the cooling section, the cooling rate is 20-60 ℃/h, and the temperature is reduced to be below 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110837329.3A CN113499783A (en) | 2021-07-23 | 2021-07-23 | Preparation method of ultralow-temperature SCR denitration catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110837329.3A CN113499783A (en) | 2021-07-23 | 2021-07-23 | Preparation method of ultralow-temperature SCR denitration catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113499783A true CN113499783A (en) | 2021-10-15 |
Family
ID=78014405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110837329.3A Withdrawn CN113499783A (en) | 2021-07-23 | 2021-07-23 | Preparation method of ultralow-temperature SCR denitration catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113499783A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403485A (en) * | 2020-11-19 | 2021-02-26 | 高化学（江苏）化工新材料有限责任公司 | V/Cu/B/W-TiO2-ZrO2Production method of composite low-temperature denitration catalyst |
| CN115463653A (en) * | 2022-11-14 | 2022-12-13 | 国能龙源环保有限公司 | Method for preparing denitration catalyst by utilizing waste wind power blades and application |
-
2021
- 2021-07-23 CN CN202110837329.3A patent/CN113499783A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403485A (en) * | 2020-11-19 | 2021-02-26 | 高化学（江苏）化工新材料有限责任公司 | V/Cu/B/W-TiO2-ZrO2Production method of composite low-temperature denitration catalyst |
| CN115463653A (en) * | 2022-11-14 | 2022-12-13 | 国能龙源环保有限公司 | Method for preparing denitration catalyst by utilizing waste wind power blades and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101428212B (en) | Selective catalysis reduction denitrate catalyst for composite carrier flue gas and preparation method thereof | |
| CN113499783A (en) | Preparation method of ultralow-temperature SCR denitration catalyst | |
| CN113289609B (en) | High-wear-resistance wide-temperature denitration catalyst and preparation method and application thereof | |
| CN108772057B (en) | Low-temperature SCR manganese oxide catalyst and preparation method and application thereof | |
| CN112403485A (en) | V/Cu/B/W-TiO2-ZrO2Production method of composite low-temperature denitration catalyst | |
| CN109225248A (en) | Cellular low-temperature denitration catalyst and its preparation process | |
| CN112657552B (en) | Vanadium phosphorus oxygen low-temperature denitration catalyst and molding preparation method thereof | |
| CN104415781A (en) | Ship diesel engine gas exhaust denitration catalyst preparation method | |
| CN106268773A (en) | A kind of thin-walled wide active temperature windows denitrating catalyst and preparation method thereof | |
| CN109967069A (en) | A kind of low-temperature SCR catalyst and preparation method thereof for cement kiln flue gas denitration | |
| CN114210320A (en) | Heterogeneous diatom low-temperature sulfur-resistant SCR catalyst and preparation method thereof | |
| CN103657632A (en) | Alkali liquor treated integral chrome oxide catalyst, preparation method and application | |
| CN110882691B (en) | Cordierite supported medium-temperature denitration catalyst and preparation method thereof | |
| CN114011400A (en) | Preparation method of acid system waste incineration SCR denitration catalyst and prepared denitration catalyst | |
| CN113289651B (en) | Low SO 2 Oxidation rate denitration catalyst, preparation method and application thereof | |
| CN112973766B (en) | Preparation method of ammonium bisulfate-resistant flat-plate denitration catalyst and catalyst obtained by preparation method | |
| CN104415777A (en) | Active powder preparation method | |
| CN105879869A (en) | Catalyst used for hydrogen selective reduction of nitric oxide as well as preparation method and application thereof | |
| CN110694640B (en) | Water-resistant sulfur-resistant denitration catalyst and preparation method thereof | |
| CN106902807A (en) | A kind of particle type low-temperature SCR catalyst and preparation method thereof | |
| CN112206766A (en) | Honeycomb SCR denitration catalyst with high temperature of 550 ℃ and preparation method thereof | |
| CN105536771A (en) | Honeycomb-shaped catalyst for denitrating tail gas of diesel engine and preparing method | |
| CN108126692A (en) | Good automobile-used extruded type SCR denitration of a kind of low temperature active and preparation method thereof | |
| KR102558168B1 (en) | Catalyst for ammonia oxidation, and method for producing the same | |
| CN106492783A (en) | A kind of glass furnace fume SCR denitration and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211015 |
|
| WW01 | Invention patent application withdrawn after publication |