CN111729667A - Rare earth SCR catalyst and preparation method thereof - Google Patents
Rare earth SCR catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 55
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011259 mixed solution Substances 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 18
- 239000010937 tungsten Substances 0.000 claims abstract description 18
- 238000001694 spray drying Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010926 purge Methods 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
- 238000005303 weighing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 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 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010099 solid forming Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
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- B01J35/613—10-100 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The invention discloses a rare earth SCR catalyst and a preparation method thereof. The preparation method comprises the following steps: (1) forming a first mixed solution by a cerium source and a tungsten source, and mixing a rare earth element source, an auxiliary active element source and the first mixed solution to form a second mixed solution; (2) preparing an intermediate metatitanic acid slurry of anatase titanium dioxide by adopting a sulfuric acid method to form a first slurry; (3) adding the second mixed solution into the first slurry to form a second slurry; dispersing the second slurry to obtain third slurry; (4) carrying out centrifugal spray drying on the third slurry to obtain dry powder; wherein the rotation speed of centrifugal spray drying is 12000-18000 rpm, the air inlet temperature is 150-280 ℃, and the air outlet temperature is 90-98 ℃; (5) and roasting the dried powder to obtain the rare earth SCR catalyst. The method is convenient for controlling the granularity of the rare earth SCR catalyst, and the obtained catalyst has a solid spherical appearance, good dispersibility, moderate granularity and good granularity uniformity.
Description
Technical Field
The invention relates to a rare earth SCR catalyst and a preparation method thereof.
Background
The holding capacity of motor vehicles is increasing continuously, so that NOxThe exhaust emission is continuously increased, and the atmospheric pollution is continuously aggravated. Selective catalytic reduction method (Selective catalyst)tic Reduction, SCR) refers to the utilization of a reducing agent (e.g., NH) under the action of a catalyst3Liquid ammonia, urea, etc.) selectively react with NO in motor vehicle exhaustxReacting to generate nontoxic and pollution-free N2And H2And O. SCR technology for NO in motor vehicle exhaustxThe control effect is very obvious.
CN103464142B discloses a preparation method of a catalyst for ammonia selective catalytic reduction removal of nitrogen oxides. Which comprises the following steps: dissolving cerous nitrate, ammonium metatungstate and zirconium dioxide in water to obtain a mixed solution; mixing industrial grade anatase type TiO2Dipping the mixture into the mixed solution, then adding urea, heating the mixed solution after the urea is dissolved, keeping the temperature and stirring the mixture until the mixture is in a viscous solid state, drying and roasting the mixture to obtain the catalyst. The method needs organic solvent such as urea, and the particle size of the catalyst is not easy to control.
CN105107414B discloses a preparation method of a honeycomb-shaped non-vanadium denitration molded catalyst. The method comprises the steps of forming catalyst powder and forming auxiliaries, wherein the catalyst powder comprises titanium dioxide and auxiliaries, the auxiliaries are any four or more of copper oxide, zirconium oxide, molybdenum oxide, iron oxide, nickel oxide, cobalt oxide, tungsten oxide or cerium oxide, the raw materials are subjected to a coprecipitation method to prepare the catalyst powder, then the catalyst powder and a solid forming agent are subjected to dry mixing, wet mixing, mulling and ageing to obtain a blank, the blank is extruded and formed into a honeycomb shape, and the honeycomb-shaped non-vanadium denitration forming catalyst is obtained by drying and calcining the honeycomb-shaped blank. The method needs a large amount of forming auxiliary agents, increases the cost, and causes cracking of a catalyst dry blank in drying and calcining. The method firstly adopts a coprecipitation method to prepare powder, and then obtains the catalyst through extrusion molding, and the preparation method is complex.
CN101757907A discloses a preparation method of tungsten-containing titanium dioxide powder of a honeycomb SCR denitration catalyst. Preparing metatitanic acid as an intermediate for preparing anatase titanium dioxide by a sulfuric acid method into slurry A, dissolving tungsten in deionized water to prepare solution B, metering the solution B, adding into the slurry A, and adjusting pH to 8 with ammonia waterAnd spray drying and calcining to obtain the titanium-tungsten composite denitration powder. CN103172030B discloses a preparation method of oxide powder. Dissolving soluble titanate in water to obtain solution containing metal ions; adding ammonia water to adjust the pH value of the solution A to 5.5-9, and precipitating metal ions to obtain a precipitate B; washing the precipitate B to obtain a filter cake C, placing the filter cake C into an aqueous solution containing soluble tungsten salt, adding ammonia water to adjust the pH to 5.5-9, stirring to uniformly disperse the filter cake C, placing and aging to obtain a slurry D, spray-drying the slurry D, and calcining to obtain the WO with a porous hollow microsphere structure3-TiO2A composite oxide catalyst. The methods adopt pressure spray drying, the produced catalyst is a porous hollow structure, and the methods do not disclose how to modify the catalyst by using rare earth elements.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a rare earth SCR catalyst, which facilitates controlling the particle size of the rare earth SCR catalyst, and the obtained catalyst has a solid spherical appearance, good dispersibility, moderate particle size, and good particle size uniformity. Furthermore, the rare earth SCR catalyst obtained by the method has higher specific surface area and acid amount. Furthermore, the rare earth SCR catalyst obtained by the method has good denitration performance within the range of 350-450 ℃.
Another object of the present invention is to provide a rare earth SCR catalyst.
In one aspect, the invention provides a preparation method of a rare earth SCR catalyst, which comprises the following steps:
(1) forming a first mixed solution by a cerium source and a tungsten source with the molar ratio of the cerium element to the tungsten element being (1-2.5): 1, and mixing a rare earth element source, an auxiliary active element source and the first mixed solution to form a second mixed solution; wherein the pH of the first mixed solution is 0.5-3, the rare earth elements are selected from one or more of La, Pr, Nd, Sm and Gd, and the auxiliary active elements are selected from one or more of Zr, Co, Mo, Cu, Fe, Ni and Mn;
(2) preparing an intermediate metatitanic acid slurry of anatase titanium dioxide by adopting a sulfuric acid method to form a first slurry;
(3) adding the second mixed solution into the first slurry to form a second slurry; dispersing the second slurry to obtain third slurry; wherein the solid content of the second slurry is 10-60 wt%;
(4) carrying out centrifugal spray drying on the third slurry to obtain dry powder; wherein the rotation speed of centrifugal spray drying is 12000-18000 rpm, the air inlet temperature is 150-280 ℃, and the air outlet temperature is 90-98 ℃;
(5) and roasting the dried powder to obtain the rare earth SCR catalyst.
According to the preparation method of the present invention, preferably, the first mixed solution is formed by mixing cerium carbonate, ammonium metatungstate and nitric acid; wherein the mass ratio of cerium carbonate to ammonium metatungstate is 1-2.2: 1.
According to the preparation method, preferably, the cerium carbonate, the ammonium metatungstate and the nitric acid are mixed under the condition of stirring, the stirring speed is 300-1500 rpm, the concentration of the nitric acid is 5-20 wt%, and the mass ratio of the nitric acid to the ammonium metatungstate is (3-10): 1.
According to the preparation method of the invention, preferably, the rare earth element source, the auxiliary active element source and the first mixed solution are mixed under the condition of stirring, the stirring speed is 300-1500 rpm, and the mixing time is 0.5-3 h.
According to the preparation method of the invention, the molar ratio of the rare earth element to the auxiliary active element to the tungsten element in the step (1) is preferably (0.05-0.3): 0.01-0.2): 1.
According to the preparation method, the first slurry is preferably obtained by reacting a sulfuric acid solution and titanium dioxide under the condition of pH value of 1-4, wherein the concentration of the sulfuric acid solution is 10-20 wt%, and the mass ratio of the sulfuric acid solution to the titanium dioxide is (2.5-5): 1.
According to the preparation method of the invention, preferably, the sulfuric acid solution and the titanium dioxide react under the condition of stirring, the stirring speed is 500-2500 rpm, and the reaction time is 0.5-3 h.
According to the preparation method of the present invention, preferably, the rare earth element is La, and the auxiliary active element is Zr.
According to the preparation method of the invention, preferably, in the step (3), the dispersion is carried out for 0.5-3 h under the conditions that the temperature is 10-55 ℃, the pH is 0.5-2, and the stirring speed is 800-2500 rpm;
in the step (5), the roasting temperature is 400-800 ℃, and the roasting time is 0.5-4 h.
In another aspect, the invention provides a rare earth SCR catalyst prepared by the preparation method.
The invention adopts cerium source and tungsten source with specific proportion to match with centrifugal spray drying technology, thereby obtaining the rare earth SCR catalyst with good dispersibility and solid spherical appearance, and the catalyst has moderate granularity and good uniformity. Furthermore, the rare earth SCR catalyst obtained by the method has higher specific surface area and acid amount. Furthermore, the rare earth SCR catalyst obtained by the method has good denitration performance within the range of 350-450 ℃.
Drawings
FIG. 1 is a scanning electron microscope image of the rare earth SCR catalyst prepared in example 1 of the present invention.
FIG. 2 is a scanning electron microscope image of the rare earth SCR catalyst prepared in example 2 of the present invention.
FIG. 3 is a scanning electron microscope image of the rare earth SCR catalyst prepared in example 3 of the present invention.
Fig. 4 is a scanning electron microscope image of the rare earth SCR catalyst prepared in comparative example 1 of the present invention.
FIG. 5 is a graph showing the catalytic performance of the rare earth SCR catalysts prepared in examples 1 to 3 of the present invention and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
"specific surface area" refers to the total area per unit mass of material.
"acid amount" refers to the number of millimoles of acid sites per unit mass of catalyst.
The preparation method of the rare earth SCR catalyst comprises the following steps: (1) preparing an active component solution; (2) preparing matrix slurry; (3) preparing mixed slurry; (4) a step of centrifugal spray drying; (5) and (5) roasting. As described in detail below.
< preparation of active ingredient solution >
Forming a first mixed solution by a cerium source and a tungsten source with the molar ratio of the cerium element to the tungsten element being (1-2.5): 1, and mixing a rare earth element source, an auxiliary active element source and the first mixed solution to form a second mixed solution; the pH value of the first mixed solution is 0.5-3, the rare earth elements are selected from one or more of La, Pr, Nd, Sm and Gd, and the auxiliary active elements are selected from one or more of Zr, Co, Mo, Cu, Fe, Ni and Mn.
The molar ratio of cerium to tungsten in the first mixed solution is (1-2.5): 1; preferably (1.5-2.5) 1; more preferably (1.8-2.3): 1. Thus, a catalyst having a solid spherical morphology with good dispersibility can be obtained.
In the present invention, the cerium source may be one or more of carbonate of cerium, sulfate of cerium, nitrate of cerium, and acetate of cerium. The tungsten source may be one or more of ammonium metatungstate or ammonium paratungstate. According to one embodiment of the present invention, the first mixed solution is formed by mixing cerium carbonate, ammonium metatungstate, and nitric acid. The mass ratio of cerium carbonate to ammonium metatungstate is 1-2.2: 1; preferably 1.5-2.2: 1; more preferably 1.8 to 2.2: 1. According to one embodiment of the present invention, the mass ratio of cerium carbonate to ammonium metatungstate is 2: 1. The concentration of the nitric acid can be 5-20 wt%; preferably 6 to 16 wt%; more preferably 10 to 16 wt%. The mass ratio of the nitric acid to the ammonium metatungstate is (3-10) to 1; preferably (6-10) 1; more preferably (6-8): 1. The first mixed solution may be formed under stirring. The stirring speed can be 300-1500 rpm; preferably 400-1000 rpm; more preferably 400 to 800 rpm. Thus, a catalyst having a solid spherical morphology with good dispersibility can be obtained.
The pH value of the first mixed solution is 0.5-3; preferably 0.5-2; more preferably 0.5 to 1.5. This contributes to obtaining a catalyst having a solid spherical morphology with good dispersibility.
The rare earth elements are selected from one or more of La, Pr, Nd, Sm and Gd; preferably, selected from one or more of La, Pr; more preferably, La. The auxiliary active elements are selected from one or more of Zr, Co, Mo, Cu, Fe, Ni and Mn; preferably, one or more selected from Zr, Co, Mo and Cu; more preferably, it is Zr. This can improve the catalytic activity. The rare earth element source may be selected from one or more of oxides, carbonates, sulfates, nitrates, acetates of rare earth elements. The source of the co-active element may be selected from one or more of an oxide, carbonate, sulphate, nitrate, acetate of the co-active element.
In the invention, the molar ratio of the rare earth element, the auxiliary active element and the tungsten element can be (0.05-0.3): 0.01-0.2): 1. Preferably, the molar ratio of the rare earth element to the tungsten element is (0.05-0.2): 1; more preferably (0.08 to 0.15): 1. Preferably, the molar ratio of the auxiliary active element to the tungsten element is (0.01-0.1): 1; more preferably (0.03 to 0.08): 1. This can improve the catalytic activity.
And mixing the rare earth element source, the auxiliary active element source and the first mixed solution under the condition of stirring. The stirring speed can be 300-1500 rpm; preferably 400-1000 rpm; more preferably 400 to 800 rpm. The mixing time can be 0.5-3 h; preferably 0.5-2 h; more preferably 1 to 1.5 hours.
< preparation of matrix slurry >
A sulfuric acid method is adopted to prepare an intermediate metatitanic acid slurry of anatase titanium dioxide to form a first slurry. Specifically, the first slurry can be obtained by reacting a sulfuric acid solution with titanium dioxide under the condition that the pH value is 1-4.
The concentration of the sulfuric acid solution can be 10-20 wt%; preferably 12-18 wt%; more preferably 15 to 18 wt%. The mass ratio of the sulfuric acid solution to the titanium dioxide can be (2.5-5) to 1; preferably (2.5-4) 1; more preferably (3-4): 1. Thus, the catalyst with moderate granularity, large comparative area and rich acid sites can be obtained, and the catalytic activity can be improved.
The reaction of the sulfuric acid solution and the titanium dioxide is carried out under the condition that the pH value is 1-4; preferably, the pH is 1-3; more preferably, the pH is 1.5 to 2.5. This helps to obtain a catalyst with moderate particle size, large comparative area and rich acid sites.
The sulfuric acid solution and titanium dioxide may be reacted with stirring. The stirring speed is 500-2500 rpm; preferably 500-2000 rpm; more preferably 800 to 1500 rpm. The reaction time can be 0.5-3 h; preferably 0.5-2 h; more preferably 1 to 1.5 hours.
< preparation of Mixed slurry >
Adding the second mixed solution into the first slurry to form a second slurry; dispersing the second slurry to obtain third slurry; wherein the solid content of the second slurry is 10-60 wt%.
The solid content of the second slurry in the invention can be 10-60 wt%; preferably 20 to 50 wt%; more preferably 30 to 40 wt%. Thus, the catalyst with moderate granularity, large specific surface area and rich acid sites can be obtained, and the catalytic activity can be improved.
The dispersion can be carried out at a temperature of 10-55 ℃; preferably, the temperature is 10-50 ℃; more preferably, the temperature is 20 to 30 ℃. The dispersion can be carried out under the condition that the pH value is 0.5-2; preferably, the pH is 1-2; more preferably pH is 1 to 1.5. Thus, the catalyst with moderate granularity, large specific surface area and rich acid sites can be obtained, and the catalytic activity can be improved. The dispersion can be carried out under stirring, and the stirring speed can be 800-2500 rpm; preferably 800-2000 rpm; more preferably 1000 to 1500 rpm. The dispersing time can be 0.5-3 h; preferably 0.5-2 h; more preferably 0.5 to 1.5 hours.
< step of centrifugal spray drying >
Carrying out centrifugal spray drying on the third slurry to obtain dry powder; wherein the rotation speed of centrifugal spray drying is 12000-18000 rpm, the air inlet temperature is 150-280 ℃, and the air outlet temperature is 90-98 ℃.
The centrifugal spray-drying may be carried out in a centrifugal spray-dryer. The rotating speed of the centrifugal spray dryer can be 12000-18000 rpm; preferably 14000 to 17000 rpm; more preferably 15000 to 16000 rpm. The air inlet temperature can be 150-280 ℃; preferably 150-200 ℃; more preferably 150 to 170 ℃. The air outlet temperature can be 90-98 ℃; preferably 92 to 94 ℃. Thus, the catalyst with moderate granularity, large comparative area and rich acid sites can be obtained, and the catalytic activity can be improved.
< step of calcination >
And roasting the dried powder to obtain the rare earth SCR catalyst.
The roasting temperature can be 400-800 ℃; preferably 400-700 ℃; more preferably 500 to 600 ℃. The roasting time can be 0.5-4 h; preferably 1-4 h; more preferably 3 to 4 hours.
The rare earth SCR catalyst is prepared by the method, has a solid spherical shape with good dispersity, and D5014 to 18 μm, and a specific surface area of 65 to 77m2The acid amount is 0.6 to 0.8 mmol/g.
Examples 1 to 3
(1) Mixing 150g of nitric acid (with a concentration of 14.3 wt%), 45g of cerium carbonate and 22.5g of ammonium metatungstate at a rotation speed of 600rpm, and adjusting the pH to 1 to form a first mixed solution; 5g of lanthanum nitrate and 2g of zirconium nitrate were stirred with the first mixed solution at a rotation speed of 600rpm for 1 hour to form a second mixed solution.
(2) Titanium dioxide was slowly added to a sulfuric acid solution (16.8 wt% concentration), the pH was adjusted to 2, and the mixture was stirred at 1200rpm for 1h to form a first slurry.
(3) And slowly adding the second mixed solution into the first slurry to form second slurry, and dispersing the second slurry for 1h under the conditions of certain reaction temperature, pH of 1.5 and stirring speed of 1300rpm to obtain third slurry.
(4) And carrying out centrifugal spray drying on the third slurry under the conditions of a certain rotating speed, air inlet temperature and air outlet temperature to obtain dry powder.
(5) And roasting the dried powder for 3h at 550 ℃ to obtain the rare earth SCR catalyst.
Specific process parameters are shown in table 1.
TABLE 1
Comparative example 1
(1) Mixing 160g of nitric acid (with a concentration of 25 wt%), 80g of cerium carbonate and 30g of ammonium metatungstate at a rotation speed of 800rpm, and adjusting the pH to 1 to form a first mixed solution; 10g of lanthanum nitrate and 5g of zirconium nitrate were stirred with the first mixed solution at a rotation speed of 800rpm for 0.5h to form a second mixed solution.
(2) 780g of titanium dioxide was slowly added to 5000g of a sulfuric acid solution (concentration of 5 wt%), pH was adjusted to 3, and the mixture was stirred at 1200rpm for 1 hour to form a first slurry.
(3) Slowly adding the second mixed solution into the first slurry to form a second slurry, wherein the solid content of the second slurry is 35 wt%; the second slurry was dispersed at 60 ℃ at pH 3.5 and a stirring speed of 1300rpm for 1 hour to obtain a third slurry.
(4) And (3) carrying out centrifugal spray drying on the third slurry under the conditions that the rotating speed is 300rpm, the air inlet temperature is 140 ℃ and the air outlet temperature is 80 ℃ to obtain dry powder.
(5) And roasting the dried powder for 3 hours at the temperature of 550 ℃ to obtain the catalyst.
Examples of the experiments
The testing method of the granularity is as follows: and testing by adopting a laser particle size method. Weighing 200mg of sample, dispersing in ultrapure water for 10min, slowly dropping the dispersed slurry into a laser particle size analyzer detector, and recording data after the equipment value is stable.
Specific surface area test method: the test was carried out by the BET method. The specific surface area of the catalyst is tested by a Mike 2020HD88 specific surface area meter, and the degassing temperature is 105 ℃ and the degassing time is 2 h. Repeat three times, take the average.
Method for testing acid amount: the test was carried out using Temperature Programmed Desorption (TPD). Weighing 120mg of sample, placing the sample in a U-shaped quartz tube, carrying out drying pretreatment by carrying out temperature programming from room temperature to 300 ℃ at the temperature rise speed of 10 ℃/min, purging for 2h by He gas flow (the flow rate is 50mL/min), then cooling to 50 ℃, and introducing NH3NH with a volume fraction of 10%3Mixture of/HeMixing gas (flow rate is 50mL/min) for 1h to saturation, switching He gas flow (flow rate is 50mL/min) to purge for 1h, raising the temperature to 700 ℃ at a heating rate of 10 ℃/min under He atmosphere for desorption, and detecting the desorbed gas by TCD.
The method for testing the denitration performance comprises the following steps: the reaction gas composition (volume ratio): 500ppm NO, 500ppm NH3，12％O2，10％H2O，CO28％，CO 800ppm，C3H680ppm(C3)，N2For the equilibrium gas, the space velocity (GHSV) was 250000 h-1. The gas detection system is a flue gas analyzer. The catalyst is 40-60 mesh particles. The results are shown in FIG. 5.
TABLE 2
As can be seen from Table 2, in a solution environment, the rare earth SCR catalyst with a solid spherical morphology can be obtained according to the proportion of the cerium element to the tungsten element.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the rare earth SCR catalyst is characterized by comprising the following steps:
(1) forming a first mixed solution by a cerium source and a tungsten source with the molar ratio of the cerium element to the tungsten element being (1-2.5): 1, and mixing a rare earth element source, an auxiliary active element source and the first mixed solution to form a second mixed solution; wherein the pH of the first mixed solution is 0.5-3, the rare earth elements are selected from one or more of La, Pr, Nd, Sm and Gd, and the auxiliary active elements are selected from one or more of Zr, Co, Mo, Cu, Fe, Ni and Mn;
(2) preparing an intermediate metatitanic acid slurry of anatase titanium dioxide by adopting a sulfuric acid method to form a first slurry;
(3) adding the second mixed solution into the first slurry to form a second slurry; dispersing the second slurry to obtain third slurry; wherein the solid content of the second slurry is 10-60 wt%;
(4) carrying out centrifugal spray drying on the third slurry to obtain dry powder; wherein the rotation speed of centrifugal spray drying is 12000-18000 rpm, the air inlet temperature is 150-280 ℃, and the air outlet temperature is 90-98 ℃;
(5) and roasting the dried powder to obtain the rare earth SCR catalyst.
2. The method according to claim 1, wherein the first mixed solution is formed by mixing cerium carbonate, ammonium metatungstate and nitric acid; wherein the mass ratio of cerium carbonate to ammonium metatungstate is 1-2.2: 1.
3. The preparation method according to claim 2, wherein the cerium carbonate, the ammonium metatungstate and the nitric acid are mixed under stirring conditions, the stirring speed is 300-1500 rpm, the concentration of the nitric acid is 5-20 wt%, and the mass ratio of the nitric acid to the ammonium metatungstate is (3-10): 1.
4. The preparation method according to claim 1, wherein the rare earth element source, the auxiliary active element source and the first mixed solution are mixed under stirring at a rotation speed of 300-1500 rpm for 0.5-3 h.
5. The method according to claim 1, wherein the molar ratio of the rare earth element, the auxiliary active element and the tungsten element in the step (1) is (0.05-0.3): (0.01-0.2): 1.
6. The preparation method according to claim 1, wherein the first slurry is obtained by reacting a sulfuric acid solution with titanium dioxide at a pH of 1 to 4, wherein the concentration of the sulfuric acid solution is 10 to 20 wt%, and the mass ratio of the sulfuric acid solution to the titanium dioxide is (2.5 to 5): 1.
7. The preparation method according to claim 6, wherein the sulfuric acid solution and the titanium dioxide are reacted under stirring, wherein the stirring speed is 500-2500 rpm, and the reaction time is 0.5-3 h.
8. The production method according to claim 1, wherein the rare earth element is La and the co-active element is Zr.
9. The preparation method according to any one of claims 1 to 8, wherein in the step (3), the dispersion is carried out by stirring for 0.5 to 3 hours at a temperature of 10 to 55 ℃, a pH of 0.5 to 2 and a stirring speed of 800 to 2500 rpm;
in the step (5), the roasting temperature is 400-800 ℃, and the roasting time is 0.5-4 h.
10. A rare earth SCR catalyst, characterized by being prepared by the preparation method of any one of claims 1 to 9.
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