CN113522267A - Tin-cerium-titanium composite oxide catalyst and preparation method and application thereof - Google Patents
Tin-cerium-titanium composite oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN113522267A CN113522267A CN202110991721.3A CN202110991721A CN113522267A CN 113522267 A CN113522267 A CN 113522267A CN 202110991721 A CN202110991721 A CN 202110991721A CN 113522267 A CN113522267 A CN 113522267A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- NLZUAORSIFBQDX-UHFFFAOYSA-N [Sn].[Ce].[Ti] Chemical compound [Sn].[Ce].[Ti] NLZUAORSIFBQDX-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002077 nanosphere Substances 0.000 claims abstract description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 6
- 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 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000011807 nanoball Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 10
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- 229910021642 ultra pure water Inorganic materials 0.000 description 12
- 239000012498 ultrapure water Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RJIWZDNTCBHXAL-UHFFFAOYSA-N nitroxoline Chemical compound C1=CN=C2C(O)=CC=C([N+]([O-])=O)C2=C1 RJIWZDNTCBHXAL-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/615—
-
- B01J35/647—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention belongs to the field of catalysts, and particularly relates to a tin-cerium-titanium composite oxide catalyst, and a preparation method and application thereof. The preparation method of the tin-cerium-titanium composite oxide catalyst provided by the invention comprises the following steps: (1) preparing carbon nanospheres; (2) and preparing the tin-cerium-titanium composite oxide catalyst. The tin-cerium-titanium composite oxide catalyst prepared by the method has higher specific surface area and high thermal stability, and has anatase type TiO2And SnO2、CeO2Effectively makes up for the advantages of anatase type TiO2Is at the deficiency ofNH3The catalyst shows excellent catalytic performance and water and sulfur resistance in SCR catalysis.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a tin-cerium-titanium composite oxide catalyst and a preparation method and application thereof.
Background
The rapid development of industry requires huge energy consumption, and under the energy structure mainly based on coal in China, the flue gas discharged by coal combustion causes serious pollution to the environment, wherein Nitrogen Oxide (NO) is used as the fuelx) The environmental pollution is serious, and the treatment is not slow. In NOxIn emission control technology, with NH3Selective catalytic reduction of NO for a reductantxTechnique (i.e. NH)3SCR technology), which is the most effective method for flue gas denitration in coal-fired power plants.
Currently, industrially applied NH3SCR catalyst is predominantly V2O5-WO3(MoO3)/TiO2The catalyst has the characteristics that the NOx removal efficiency in a coal-fired boiler power station is more than 80%, and the catalyst has good sulfur resistance, and the working temperature is 280-420 ℃. However, the anatase type TiO in the catalyst2The carrier also has some problems in the using process, such as poor mechanical strength, small specific surface area and easy crystallization at high temperature into rutile TiO2And the like. In TiO2In which other oxides are incorporated, is modified TiO2An efficient method of carrier performance. For example Kobayashi M2O5/TiO2-SiO2Catalyst, discovery of SiO2The addition of the catalyst greatly improves the specific surface area of the carrier and the dispersion degree of vanadium species, thereby improving the thermal stability, surface acidity and denitration activity of the catalyst; liyuntao et al in TiO2Adding Al to the carrier2O3The overall mechanical properties of the catalyst are improved. In the presence of TiO2Of the modified numerous oxides, SnO2And CeO2Not only can improve TiO2The specific surface area and the mechanical strength of the catalyst can also greatly improve the redox performance and the thermal stability of the catalyst, thereby improving the denitration performance of the catalyst.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a tin-cerium-titanium composite oxide catalyst, a preparation method and a use thereof, which are used for solving the problem of poor mechanical strength in the prior artHas small specific surface area and is easy to be transformed into rutile TiO at high temperature2And the like.
In order to achieve the above object or other objects, the present invention is achieved by the following aspects.
A preparation method of a tin-cerium-titanium composite oxide catalyst comprises the following steps:
(1) preparing carbon nanospheres; (2) and preparing the tin-cerium-titanium composite oxide catalyst.
Specifically, the method comprises the following steps:
(1) preparation of carbon nanospheres:
dissolving glucose in a solvent, stirring and dissolving at room temperature, transferring to a reaction kettle for reaction, cooling after the reaction is finished, and drying after treatment to obtain carbon nanospheres;
(2) preparation of tin-cerium-titanium composite oxide catalyst:
adding carbon nanospheres into a solvent, adding tin chloride, cerium nitrate and titanium sulfate, stirring, adjusting pH, heating and stirring, and post-treating to obtain tin-cerium-titanium composite oxide catalysts with different tin contents, wherein the catalysts are marked as Snx-Ce-Ti-C, wherein x ═ 0.01, 0.03, 0.05, 0.07, 0.010, represents SnO2/(SnO2+CeO2+TiO2) Mole percent of (c).
Further, the solvent is ultrapure water.
Further, the mass-to-volume ratio of glucose to the solvent in the step (1) is as follows: (9-12): (150-200), i.e., the volume of solvent added per (9-12) g of glucose is (150-200) mL.
Further, in the step (1), the glucose is completely dissolved, and the solution is stirred at room temperature for 10-30 min.
Further, the reaction temperature in the reaction kettle in the step (1) is 160-200 ℃, and the reaction time is 8-12 h.
Further, after the reaction is finished, cooling is carried out, and the treatment after cooling comprises the following steps: respectively carrying out centrifugal washing by using ultrapure water and ethanol, adding the obtained solid into the ethanol for ultrasonic dispersion, wherein the ultrasonic dispersion time is 0.5-1h, and the ultrasonic power is 120-180W.
Further, in the step (1), the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
Further, the mass ratio of the tin chloride, the cerium nitrate, the titanium sulfate and the carbon nanospheres in the step (2) is (0.02-0.3): (0.23-0.25): (2.43-2.50): (0.08-0.09);
the mass-volume ratio of the carbon nanospheres to the solvent is as follows: (0.08-0.09): (250-300), that is, the volume of the solvent added per (0.08-0.09) g of the carbon nanoball is (250-300) mL.
Preferably, after adding tin chloride, cerium nitrate and titanium sulfate, stirring is carried out for 0.5-1h in order to uniformly mix the reactants.
Preferably, strong ammonia water is adopted for pH adjustment, specifically, strong ammonia water is added dropwise to adjust the pH to 9-11.
Further, in the step (2), the heating and stirring temperature is 80-90 ℃ and the time is 3-5 h.
Further, the post-processing in the step (2) comprises: aging, suction filtration, washing, drying and roasting.
Preferably, the aging time is 24-32 h. The washing is carried out 3-5 times by adopting ultrapure water. The drying temperature is 80-100 ℃, and the drying time is 12-16 h.
Preferably, during the roasting, the temperature is programmed to 500-550 ℃ at the temperature rising speed of 1-3 ℃/min for roasting for 4.5-5.5 h.
The specific surface area of the tin-cerium-titanium composite oxide catalyst prepared by the method is 110-120m2The particle size is 8-10nm, the particles are piled up into vermicular mesopores, and the pore diameter is 5-7.5 nm.
The invention also provides application of the tin-cerium-titanium composite oxide catalyst in the field of flue gas denitration.
The tin-cerium-titanium composite oxide catalyst prepared by the method has higher specific surface area and high thermal stability, and has anatase type TiO2And SnO2、CeO2Effectively makes up for the advantages of anatase type TiO2In NH3The catalyst shows excellent catalytic performance and water and sulfur resistance in SCR catalysis. The method has the advantages of cheap and easily-obtained raw materials, simple and rapid operation, and low energy consumptionSmall size, no special requirement on equipment and little additional environmental pollution, so that the method has potential application prospect in the field of flue gas denitration of coal-fired power plants.
Drawings
Fig. 1 is a TEM spectrum of tin-cerium-titanium composite oxide catalysts prepared in examples 1 to 5, and carbon nanoball prepared in comparative example 1;
fig. 2 is an XRD spectrum of the tin-cerium-titanium composite oxide catalysts prepared in examples 1 to 5;
FIG. 3 shows NH of Sn-Ce-Ti composite oxide catalysts prepared in examples 1 to 53SCR reaction performance results, in which (a) is the NO conversion result of the Sn-Ce-Ti composite oxide catalyst and (b) is the N of the Sn-Ce-Ti composite oxide catalyst2And (4) selective results.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
Example 1
Preparation of carbon nanosphere template
9g of glucose was dissolved in 150mL of ultrapure water, and the solution was sufficiently dissolved by magnetic stirring at room temperature for 10 min. Pouring the solution into a reaction kettle, preserving the temperature for 10 hours in an oven at 180 ℃, cooling, and then centrifugally washing the obtained sample by respectively using ultrapure water and ethanol. And adding trace ethanol into the solid obtained by centrifugation, performing ultrasonic dispersion, drying the solid on a watch glass at 60 ℃ for 12 hours, and cooling to obtain the carbon nanospheres.
Sn0.01Preparation of-Ce-Ti-C catalyst
Adding 0.083g of carbon nanospheres into 250mL of ultrapure water, carrying out ultrasonic treatment for 20min, then adding 0.021g of tin chloride, 0.23g of cerium nitrate and 2.43g of titanium sulfate, carrying out magnetic stirring at room temperature for 30min to uniformly mix, then dropwise adding concentrated ammonia water, adjusting the pH value to 10, carrying out magnetic stirring in a 90 ℃ water bath for 3h to completely precipitate, aging for 24h, carrying out suction filtration, washing, drying a filter cake at 80 ℃ for 12h, grinding uniformly, carrying out temperature rise at a speed of 3 ℃/min in a muffle furnace under an oxygen atmosphere, carrying out temperature programmed temperature rise to 550 ℃, roasting for 5h, and obtaining the Sn0.01-a Ce-Ti-C catalyst.
Example 2
Sn0.03Preparation of-Ce-Ti-C catalyst
Preparing carbon nanoball by the method of example 1, adding 0.084g of carbon nanoball into 250mL of ultrapure water, performing ultrasonic treatment for 20min, then adding 0.065g of tin chloride, 0.23g of cerium nitrate and 2.43g of titanium sulfate, performing magnetic stirring for 30min at room temperature to uniformly mix the carbon nanoball, then dropwise adding concentrated ammonia water, adjusting pH value to 10, performing magnetic stirring for 3h in a 90 ℃ water bath to completely precipitate the tin nanoball, aging for 24h, performing suction filtration, washing, drying a filter cake for 12h at 80 ℃, uniformly grinding, performing temperature programming to 550 ℃ at a heating rate of 3 ℃/min in an oxygen atmosphere of a muffle furnace, and roasting for 5h to obtain Sn0.03-a Ce-Ti-C catalyst.
Example 3
Sn0.05Preparation of-Ce-Ti-C catalyst
By using a blockThe preparation method of the embodiment 1 is to prepare the carbon nanospheres, 0.085g of the carbon nanospheres are added into 250mL of ultrapure water, the mixture is subjected to ultrasonic treatment for 20min, then 0.11g of tin chloride, 0.23g of cerium nitrate and 2.43g of titanium sulfate are added, the mixture is uniformly mixed by magnetic stirring at room temperature for 30min, then concentrated ammonia water is dropwise added, the pH value is adjusted to 10, the mixture is subjected to magnetic stirring in a 90 ℃ water bath for 3h to completely precipitate, the mixture is aged for 24h, subjected to suction filtration and washing, a filter cake is dried for 12h at 80 ℃, uniformly ground, and is roasted for 5h at the temperature rising speed of 3 ℃/min in a muffle furnace under the oxygen atmosphere, and the temperature is programmed to 550 ℃, so that the Sn is obtained0.05-a Ce-Ti-C catalyst.
Example 4
Sn0.07Preparation of-Ce-Ti-C catalyst
Preparing carbon nanoball by the method of example 1, adding 0.086g of carbon nanoball into 250mL of ultrapure water, performing ultrasonic treatment for 20min, then adding 0.16g of tin chloride, 0.23g of cerium nitrate and 2.43g of titanium sulfate, performing magnetic stirring for 30min at room temperature to uniformly mix the carbon nanoball, then dropwise adding concentrated ammonia water, adjusting pH value to 10, performing magnetic stirring for 3h in a 90 ℃ water bath to completely precipitate the tin nanoball, aging for 24h, performing suction filtration, washing, drying a filter cake for 12h at 80 ℃, uniformly grinding, performing temperature programming to 550 ℃ at a heating rate of 3 ℃/min under the oxygen atmosphere in a muffle furnace, and roasting for 5h to obtain Sn0.07-a Ce-Ti-C catalyst.
Example 5
Sn0.10Preparation of-Ce-Ti-C catalyst
Preparing carbon nanoball by the method of example 1, adding 0.088g of carbon nanoball into 250mL of ultrapure water, performing ultrasonic treatment for 20min, then adding 0.23g of tin chloride, 0.23g of cerium nitrate and 2.43g of titanium sulfate, performing magnetic stirring for 30min at room temperature to uniformly mix the carbon nanoball, then dropwise adding concentrated ammonia water, adjusting pH value to 10, performing magnetic stirring for 3h in a 90 ℃ water bath to completely precipitate the tin nanoball, aging for 24h, performing suction filtration, washing, drying a filter cake for 12h at 80 ℃, uniformly grinding, performing temperature programming to 550 ℃ at a heating rate of 3 ℃/min under the oxygen atmosphere in a muffle furnace, and roasting for 5h to obtain Sn0.10-a Ce-Ti-C catalyst.
Comparative example 1
Preparation of carbon nanosphere template
9g of glucose was dissolved in 150mL of ultrapure water, and the solution was sufficiently dissolved by magnetic stirring at room temperature for 10 min. Pouring the solution into a reaction kettle, preserving the temperature for 10 hours in an oven at 180 ℃, cooling, and then centrifugally washing the obtained sample by respectively using ultrapure water and ethanol. And adding trace ethanol into the solid obtained by centrifugation, performing ultrasonic dispersion, drying the solid on a watch glass at 60 ℃ for 12 hours, and cooling to obtain the carbon nanospheres. The TEM measurement results are shown in FIG. 1.
Performance testing
1. The tin-cerium-titanium composite oxide catalysts prepared in examples 1 to 5 were respectively subjected to nitrogen adsorption and desorption characterization, and the specific surface area of the catalyst was measured by a method of Brunauer-Emmett-teller (bet) at 77K using a Micromeritics ASAP-2020 analyzer, and the pore size distribution method of the catalyst was calculated by Barrett-Joyner-halenda (bjh). As shown in Table 1, it can be seen that the specific surface area of the composite oxide catalyst of Sn-Ce-Ti prepared by the example of the present invention is 110-120m2(ii)/g, the average pore diameter is 5-7.5 nm.
Table 1 shows the results of specific surface area, average pore diameter and particle size of the tin-cerium-titanium composite oxide catalysts prepared in examples 1 to 5
2. The tin-cerium-titanium composite oxide catalysts prepared in examples 1 to 5 and the carbon nanoball prepared in comparative example 1 were respectively subjected to TEM test (test on a Tecnai G2F 20 high resolution transmission electron microscope, operating voltage was 200 kV). As shown in FIG. 1, it can be seen that the carbon nanoball has good dispersibility, exhibits excellent spherical morphology, and has an average size of about 100 nm; the size of the tin-cerium-titanium composite oxide catalyst particles is uniform, and the particles are stacked into vermicular mesopores.
3. The tin-cerium-titanium composite oxide catalysts prepared in examples 1 to 5 were respectively subjected to XRD tests (tests were carried out on a diffractometer type D8-focus manufactured by brueck AXS ltd, germany, with a radiation source of CuK α (λ ═ 0.154nm), operating voltages and operating currents of 40kV and 35mA, respectively,the scanning speed was 0.04s step-1) As shown in FIG. 2, Sn is observed4+、Ce4+Can be well doped with anatase type TiO2The crystal lattice of (1). The particle size was calculated by the scherrer equation, and the results are shown in table 1, from which it can be seen that the tin-cerium-titanium composite oxide catalyst prepared in the examples of the present invention had a particle size of 8 to 10 nm.
4. The tin-cerium-titanium composite oxide catalysts prepared in examples 1 to 5 were subjected to NH3-SCR reaction performance test, during which the simulated flue gas composition is: 500ppm NO/N2、500ppm NH3/N2、5％O2/N2The total flow rate of gas is 100mL min-1After reaction NH3And N2The concentration of O is collected by Fourier infrared spectrometer, NOx(NO、NO2) Is formed by NOxAnd (5) collecting by an analyzer. The results are shown in FIG. 3, in which (a) shows the results of NO conversion in the Sn-Ce-Ti composite oxide catalyst and (b) shows the results of N conversion in the Sn-Ce-Ti composite oxide catalyst2And (4) selective results. As can be seen from the figure, the tin-cerium-titanium composite oxide catalyst has a wider temperature operation window and higher denitration performance, and has higher NO within the temperature range of 250-475 DEG CxThe conversion rate is higher N within the temperature range of 200-550 DEG C2And (4) selectivity.
In conclusion, the tin-cerium-titanium composite oxide catalyst prepared by the invention has higher specific surface area and high thermal stability, and has anatase type TiO2And SnO2、CeO2Effectively makes up for the advantages of anatase type TiO2In NH3The catalyst shows excellent catalytic performance and water and sulfur resistance in SCR catalysis.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the tin-cerium-titanium composite oxide catalyst is characterized by comprising the following steps of:
(1) preparing carbon nanospheres; (2) and preparing the tin-cerium-titanium composite oxide catalyst.
2. The method of claim 1, comprising the steps of:
(1) preparation of carbon nanospheres:
dissolving glucose in a solvent, stirring and dissolving at room temperature, transferring to a reaction kettle for reaction, cooling after the reaction is finished, and drying after treatment to obtain carbon nanospheres;
(2) preparation of tin-cerium-titanium composite oxide catalyst:
adding carbon nanospheres into a solvent, adding tin chloride, cerium nitrate and titanium sulfate, stirring, adjusting pH, heating and stirring, and post-treating to obtain tin-cerium-titanium composite oxide catalysts with different tin contents, wherein the catalysts are marked as Snx-Ce-Ti-C, wherein x ═ 0.01, 0.03, 0.05, 0.07, 0.010, represents SnO2/(SnO2+CeO2+TiO2) Mole percent of (c).
3. The method according to claim 1, wherein the mass-to-volume ratio of glucose to the solvent in step (1) is: (9-12): (150-200), i.e., the volume of solvent added per (9-12) g of glucose is (150-200) mL.
4. The method as claimed in claim 1, wherein the reaction temperature in the reaction kettle in the step (1) is 160-200 ℃ and the reaction time is 8-12 h.
5. The preparation method according to claim 1, wherein the mass ratio of the tin chloride, the cerium nitrate, the titanium sulfate and the carbon nanoball in the step (2) is (0.02-0.3): (0.23-0.25): (2.43-2.50): (0.08-0.09);
the mass-volume ratio of the carbon nanospheres to the solvent is as follows: (0.08-0.09): (250-300), that is, the volume of the solvent added per (0.08-0.09) g of the carbon nanoball is (250-300) mL.
6. The method according to claim 1, wherein in the step (2), the post-treatment comprises: aging, suction filtration, washing, drying and roasting.
7. The method of claim 6, wherein the aging time is from 24 to 32 hours.
8. The method as claimed in claim 6, wherein the temperature is raised to 500-550 ℃ at a rate of 1-3 ℃/min for 4.5-5.5 h.
9. The tin-cerium-titanium composite oxide catalyst prepared by the preparation method as described in any one of claims 1 to 8, wherein the specific surface area of the catalyst is 110-120m2The particle size is 8-10nm, the particles are piled up into vermicular mesopores, and the pore diameter is 5-7.5 nm.
10. The use of the tin-cerium-titanium composite oxide catalyst prepared by the method of any one of claims 1 to 9 in the field of flue gas denitration.
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| CN103736479A (en) * | 2014-01-02 | 2014-04-23 | 南京大学 | Cerium titanium tin composite oxide catalyst for fume denitration and preparation method thereof |
| CN108906074A (en) * | 2018-07-18 | 2018-11-30 | 江苏新沃催化剂有限公司 | It is a kind of using carbon ball as low-temperature SCR catalyst of template and preparation method thereof |
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