CN116510738A - Catalyst, preparation method and application thereof - Google Patents
Catalyst, preparation method and application thereof Download PDFInfo
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- CN116510738A CN116510738A CN202310546285.8A CN202310546285A CN116510738A CN 116510738 A CN116510738 A CN 116510738A CN 202310546285 A CN202310546285 A CN 202310546285A CN 116510738 A CN116510738 A CN 116510738A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 182
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 90
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 56
- 230000002195 synergetic effect Effects 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 38
- 239000005457 ice water Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003546 flue gas Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical group [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 8
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 26
- 230000003647 oxidation Effects 0.000 abstract description 25
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 27
- 239000010936 titanium Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 230000010718 Oxidation Activity Effects 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 9
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 239000012716 precipitator Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 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 4
- 150000003841 chloride salts Chemical class 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- -1 inorganic acid salts Chemical class 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
- 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
- B01J23/835—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 germanium, tin or lead
-
- 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
- B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
- B01D53/8646—Simultaneous elimination of the components
- B01D53/865—Simultaneous elimination of the components 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
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- 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)
- Catalysts (AREA)
Abstract
The invention provides a catalyst, a preparation method and application thereof. The catalyst comprises: a catalyst carrier, and an active component supported on the surface and/or inside of the catalyst carrier; wherein the content of the active component is 1-10% and the content of the catalyst carrier is 90-99% based on the total mass of the catalyst. The catalyst of the invention can realize the synergistic removal of nitrogen oxides and carbon monoxide. The catalyst can realize the removal of nitrogen oxides and the in-situ decoupling separation of carbon monoxide oxidation, wherein the active component is used for removing the nitrogen oxides, and the catalyst carrier is used for the oxidation of the carbon monoxide.
Description
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, and belongs to the field of catalysts.
Background
Nitrogen Oxides (NO) x ) Is one of main pollutants discharged by industrial flue gas, and also forms dust haze, ozone and other atmospheric pollutantsImportant precursors of the material; meanwhile, the energy structure taking coal as the main fuel in China also leads to the emission of a large amount of carbon monoxide (carbon monoxide) from industrial flue gas, and the carbon monoxide has biotoxicity and durability in the environment and has great damage to human health and ecological environment. Thus, control of NO in flue gas x And carbon monoxide emission are important works for improving the air quality of China.
Currently, ammonia selective catalytic reduction (NH 3 -SCR) denitration is to reduce NO in industrial flue gas x One of the most efficient techniques is discharged. The core of this technology is a nitrogen oxide removal catalyst, of which the most widely used SCR catalyst in industry is V 2 O 5 -WO 3 /TiO 2 A catalyst. V (V) 2 O 5 -WO 3 /TiO 2 The catalyst can effectively control NO in a temperature window of 300-450 DEG C x And (5) discharging. Catalytic oxidation is the most effective technique for controlling carbon monoxide emissions, and the carbon monoxide oxidation catalysts most widely used in industry today are noble metal catalysts such as Pt/CeO 2 And Pt/TiO 2 Etc.
The simultaneous removal of multiple contaminants using one reactor or one catalyst is the most economical atmospheric pollution control technology. For NO in flue gas x And carbon monoxide, if the SCR reactor is used for simultaneously removing NO in flue gas x And carbon monoxide, the floor area, the catalyst and the energy consumption required by pollution control can be reduced, and the cost of controlling industrial flue gas pollutants can be effectively reduced. However, SCR catalyst V for industrial use 2 O 5 -WO 3 /TiO 2 There is substantially no carbon monoxide oxidation activity in the operating temperature window and carbon monoxide oxidation catalysts (noble metal catalysts) used industrially will preferentially drive the reductant NH 3 Oxidation to N 2 O and NO, exhibit very poor SCR activity. Therefore, the development of a high-efficiency catalyst is a key for realizing flue gas denitration and carbon monoxide oxidation.
The denitration and co-oxidation carbon monoxide catalyst must have the following conditions: (1) simultaneously has excellent SCR activity and carbon monoxide oxidation activity; (2) the SCR reaction temperature window is matched with the carbon monoxide oxidation temperature window; (3) certain water-resistant and sulfur-resistant stability. However, no catalysts capable of satisfying these requirements at the same time have been reported in the literature.
Therefore, research on a catalyst capable of co-oxidizing carbon monoxide while denitrating is an urgent technical problem to be solved.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems existing in the prior art, the invention firstly provides a catalyst. The catalyst of the invention can realize the synergistic removal of nitrogen oxides and carbon monoxide. The catalyst can realize the removal of nitrogen oxides and the in-situ decoupling separation of carbon monoxide oxidation, wherein the active component is used for removing the nitrogen oxides, and the catalyst carrier is used for the oxidation of the carbon monoxide.
Furthermore, the invention also provides a preparation method of the catalyst, which is simple and easy to implement, raw materials are easy to obtain, and the catalyst is suitable for mass production.
Solution for solving the problem
[1] A catalyst, the catalyst comprising:
a catalyst support, and, in addition,
an active component supported on the surface and/or inside of the catalyst carrier; wherein the content of the active component is 1-10% and the content of the catalyst carrier is 90-99% based on the total mass of the catalyst.
[2] The catalyst according to the above [1], wherein the catalyst support comprises a solid solution oxide containing a tin atom, a titanium atom, a boron atom and optionally a praseodymium atom; preferably, the molar amount of the tin atoms is 10% to 50%, the molar amount of the titanium atoms is 10% to 90%, the molar amount of the boron atoms is 1% to 10%, and the molar amount of the praseodymium atoms is 0% to 5% based on 100% of the total molar amount of the catalyst.
[3] The catalyst according to the above [2], wherein the molar amount of the titanium atom in the catalyst carrier is equal to or larger than the sum of the molar amounts of the tin atom, the boron atom and the praseodymium atom, if any.
[4] The catalyst according to any one of the above [1] to [3], wherein the active component comprises cerium oxide, iron oxide and optionally nickel oxide; preferably, the content of the cerium oxide is 1 to 10%, the content of the iron oxide is 1 to 3%, and the content of the nickel oxide is 0 to 3% based on 100% of the total mass of the catalyst.
[5] The catalyst according to the above [4], wherein the content of the cerium oxide is larger than the content of the iron oxide by mass.
[6] A method for producing a catalyst according to any one of the above [1] to [5], which comprises a step of supporting an active component on the surface and/or inside of the catalyst carrier.
[7] The production method according to the above [6], wherein the production method comprises the steps of:
step 1) preparing the catalyst carrier by using an ice bath coprecipitation method;
and 2) loading the active components on the surface and/or the inside of the catalyst carrier by using an impregnation method to obtain the catalyst.
[8] The production method according to the above [7], wherein the production step of the catalyst carrier comprises:
mixing precursors of the catalyst carrier under the condition of ice-water bath to obtain a precursor mixture;
dissolving a precipitant in a first solvent under the condition of ice-water bath to obtain a first solution;
mixing the precursor mixture with the first solution to obtain a precipitate;
and drying and roasting the precipitate to obtain the catalyst carrier.
[9] The production method according to the above [7] or [8], wherein the precursor of the active component is dissolved in a second solvent to obtain a second solution;
placing the catalyst carrier in the second solution and condensing and refluxing under the condition of oil bath to obtain an impregnation product;
and drying and roasting the impregnated product to obtain the catalyst carrier.
[10] The use of the catalyst according to any one of [1] to [5] above for the synergistic removal of nitrogen oxides and carbon monoxide in industrial flue gas.
ADVANTAGEOUS EFFECTS OF INVENTION
The catalyst of the invention can realize the synergistic removal of nitrogen oxides and carbon monoxide. The catalyst can realize the removal of nitrogen oxides and the in-situ decoupling separation of carbon monoxide oxidation, wherein the active component is used for removing the nitrogen oxides, and the catalyst carrier is used for the oxidation of the carbon monoxide.
The preparation method of the catalyst is simple and feasible, raw materials are easy to obtain, and the catalyst is suitable for mass production.
Drawings
FIG. 1 shows catalyst support Sn of example 2 0.48 Ti 0.5 B 0.01 Na 0.01 Pr 0.01 O 2 Schematic diagram of denitration activity and carbon monoxide oxidation activity;
FIG. 2 shows catalyst Ce of example 2 0.05 Fe 0.01 /Sn 0.48 Ti 0.5 B 0.01 Na 0.01 Pr 0.01 O 2 Schematic diagram of denitration activity and carbon monoxide oxidation activity;
FIG. 3 shows catalyst Ce of example 3 0.07 Fe 0.02 Ni 0.01 /Sn 0.4 Ti 0.6 B 0.02 O 2 Schematic diagram of denitration activity and carbon monoxide oxidation activity;
FIG. 4 shows catalysts and TiO according to examples 4 to 6 of the invention 2 Is an X-ray diffraction pattern of (2).
Detailed Description
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
< first aspect >
A first aspect of the present invention provides a catalyst comprising:
a catalyst support, and, in addition,
an active component supported on the surface and/or inside of the catalyst carrier; wherein the content of the active component is 1 to 10% by weight based on the total mass of the catalyst, for example: 2%, 4%, 6%, 8%, etc.; the catalyst carrier is contained in an amount of 90 to 99%, for example: 92%, 94%, 96%, 98%, etc. When the content of the active component is 1-10%, the content of the catalyst carrier is 90-99%, the denitration rate is 80-95%, and the oxidation activity of CO is 70-95%.
The catalyst of the invention can realize the synergistic removal of nitrogen oxides and carbon monoxide. Specifically, in the invention, the catalyst can realize the removal of nitrogen oxides and the in-situ decoupling separation of carbon monoxide oxidation, wherein the active components are mainly used for removing the nitrogen oxides, and the catalyst carrier is mainly used for the oxidation of the carbon monoxide.
Catalyst carrier
In the present invention, the catalyst support is mainly used for oxidation of carbon monoxide.
In some specific embodiments the catalyst support may comprise a solid solution oxide comprising tin atoms, titanium atoms, boron atoms, and optionally praseodymium atoms; when a solid solution oxide containing tin atoms, titanium atoms, boron atoms, and optionally praseodymium atoms is used as a catalyst support, it can be used for carbon monoxide oxidation.
In the present invention, the catalyst support is a solid solution oxide containing tin atoms, titanium atoms, boron atoms, and optionally praseodymium atoms, in which tin dioxide is not segregated. In addition, the catalyst carrier can generate lattice defects after being doped with atoms such as tin, titanium, boron and optional praseodymium, and is beneficial to activating oxygen molecules to generate active oxygen species which can oxidize carbon monoxide.
Preferably, the molar amount of tin atoms is 10% to 50%, based on 100% of the total molar amount of the catalyst, for example: 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.; the molar amount of the titanium atoms is 10% to 90%, for example: 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.; the molar amount of the boron atom is 1 to 10%, for example: 2%, 4%, 6%, 8%, etc.; the molar amount of praseodymium atoms is 0 to 5%, for example: 1%, 2%, 3%, 4%, etc. When the molar amounts of the tin atom, the titanium atom, the boron atom and the praseodymium atom, if any, are within the above-mentioned ranges, a denitration rate of 80 to 95% and an oxidation activity of carbon monoxide of 70 to 95% can be achieved.
In some specific embodiments, the molar amount of titanium atoms in the catalyst support is equal to or greater than the sum of the molar amounts of tin atoms, boron atoms, and optionally praseodymium atoms. In the catalyst carrier, the titanium atom content is high, so that the basic form of the formed solid solution oxide is rutile phase titanium dioxide, and the titanium dioxide is shown in fig. 4.
Active ingredient
In the catalyst carrier, active oxygen generated by activating oxygen by the catalyst carrier can oxidize carbon monoxide, but has weak affinity with ammonia and nitrogen oxides, and has poor reduction performance on the nitrogen oxides. The present invention is therefore useful for the removal of nitrogen oxides by using active components. The active component of the present invention has poor affinity with carbon monoxide and thus has poor oxidation activity on carbon monoxide, but it does not affect the oxidation of carbon monoxide by the catalyst support.
In some specific embodiments, the active component comprises cerium oxide, iron oxide, and optionally nickel oxide; preferably, the content of the cerium oxide is 1 to 10% based on 100% of the total mass of the catalyst, for example: 2%, 4%, 6%, 8%, etc.; the content of the iron oxide is 1 to 3%, for example: 1.5%, 2%, 2.5%, etc.; the nickel oxide content is 0 to 3%, for example: 1%, 1.5%, 2%, 2.5%, etc. The active component of the invention has excellent removal effect on nitrogen oxides.
Specifically, in the present invention, the cerium oxide may be cerium oxide, the iron oxide is ferric oxide, and the nickel oxide is nickel oxide.
In some specific embodiments, the content of cerium oxide is greater than the content of iron oxide on a mass basis. When the content of cerium oxide is larger than that of iron oxide, the method is beneficial to improving the removal effect of nitrogen oxides in the cooperative control process.
The invention is based on the reaction mechanism of carbon monoxide catalytic oxidation and selective catalytic reduction, separates the carbon monoxide catalytic oxidation and selective catalytic reduction reaction in the catalyst carrier and the active component, reduces the mutual influence between the two catalytic reactions, regulates and controls the interaction between the carrier and the active component, and constructs the denitration synergistic carbon monoxide oxidation high-efficiency catalyst.
< second aspect >
A second aspect of the present invention provides a method for producing a catalyst according to the first aspect of the present invention, comprising the step of supporting an active component on the surface and/or inside of the catalyst support. The preparation method is simple and feasible, raw materials are easy to obtain, and the preparation method is suitable for mass production.
In some specific embodiments, the preparation method comprises the steps of:
step 1) preparing the catalyst carrier by using an ice bath coprecipitation method;
and 2) loading the active components on the surface and/or the inside of the catalyst carrier by using an impregnation method to obtain the catalyst.
Preparation of catalyst support
In the present invention, the preparation step of the catalyst carrier may include:
mixing precursors of the catalyst carrier under the condition of ice-water bath to obtain a precursor mixture;
dissolving a precipitant in a first solvent under the condition of ice-water bath to obtain a first solution;
mixing the precursor mixture with the first solution to obtain a precipitate;
and drying and roasting the precipitate to obtain the catalyst carrier.
In the invention, under the condition of ice-water bath, the precursor of the catalyst carrier is mixed to obtain a precursor mixture; specifically, the precursors of the catalyst carrier can be uniformly mixed by stirring or ultrasonic means. The time of stirring or ultrasonic treatment is not particularly limited, and may be selected according to the degree of mixing. Specifically, the time period may be 30 minutes or more.
As for the precursor of the catalyst support, in the present invention, the precursor of the catalyst support includes one or a combination of two or more of soluble salts of metal elements. Specifically, the soluble salts may be one or a mixture of two or more of their respective inorganic acid salts such as nitrate, sulfate, hydrochloride, etc., or their hydrates, or may be one or a mixture of two or more of organic acid salts such as acetate, oxalate, etc., or their hydrates.
In some specific embodiments, the precursor of the catalyst support comprises a soluble salt of elemental tin, a soluble salt of elemental titanium, a soluble salt of elemental boron, and optionally a soluble salt of elemental praseodymium.
Further, in the present invention, the precursor of the catalyst support preferably includes titanium tetrachloride, tin tetrachloride, ammonium borate, and optionally praseodymium nitrate. When the four precursors are used for preparation, lattice defects can be generated, which is beneficial to activating oxygen molecules to generate active oxygen species, and the active oxygen species can oxidize carbon monoxide.
In some specific embodiments, the molar amount of titanium tetrachloride is 10% to 90%, based on 100% of the total molar amount of precursor of the catalyst support, for example: 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.; the molar amount of tin tetrachloride is 10% to 50%, for example: 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.; the molar amount of ammonium borate is 1 to 10%, for example: 2%, 4%, 6%, 8%, etc.; the molar amount of praseodymium nitrate is 0 to 5%, for example: 1%, 2%, 3%, 4%, etc. When the content of each component of the precursor of the catalyst support is within the above-described range, a desired catalyst support can be obtained.
Further, in the present invention, the molar content of titanium tetrachloride is equal to or greater than the sum of the molar contents of the three components of tin tetrachloride, ammonium borate and praseodymium nitrate. When the molar content of titanium tetrachloride is high, the basic morphology of the solid solution oxide formed is rutile phase titanium dioxide.
Further, the precipitant was dissolved in the first solvent, also under ice-water bath conditions, to obtain a first solution. The first solution is used to precipitate a precursor of the catalyst support.
The present invention is not particularly limited, and may be a conventional one in the art. Preferably, the precipitant may be aqueous ammonia and/or ammonium carbonate.
Specifically, in the present invention, the ratio of the molar amount of the precipitant to the sum of the molar amounts of the precursors of the catalyst carrier is 3 to 6:1, for example: 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, etc.
After mixing the precursor mixture and the first solution under the action of the precipitant, a precipitate is generated, specifically, by rapid stirring or ultrasonic means, so as to generate the precipitate. And then obtaining a precipitate by a solid-liquid separation mode. The mode of solid-liquid separation is not particularly limited, and may be a mode commonly used in the art, for example: filtration, centrifugation, and the like.
In the present invention, the first solvent is not particularly limited, and may be a polar solvent commonly used in the art, and preferably, the first solvent may be water.
And drying and roasting the precipitate to obtain the catalyst carrier. The temperature and time of drying are not particularly limited, and may be generally 60 to 120 ℃, for example: 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and the like; the drying time is 6 to 24 hours, for example: 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, etc.
In some specific embodiments, to obtain a catalyst support with excellent performance, the calcination is at 1 to 5 ℃/min, for example: heating rates of 2 ℃/min, 3 ℃/min, 4 ℃/min and the like, and heating to a baking temperature of 200-600 ℃, for example: 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, etc.; the calcination time is 2 to 6 hours, for example: 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, etc. Further, in the present invention, the firing may be performed under an air atmosphere.
Further, in the present application, in order to obtain a catalyst support having a proper crystal lattice, the calcination may be performed in stages, specifically, the calcination may be performed by heating to 200 to 349 ℃ at a heating rate of 1 to 5 ℃/min, then continuously heating to 350 to 600 ℃ and then calcining for 2 to 5 hours. Preferably, in the present invention, the firing may be performed under an air atmosphere.
Loading of active ingredient
In the present invention, the loading of the active ingredient may include the steps of:
dissolving a precursor of the active component in a second solvent to obtain a second solution;
placing the catalyst carrier in the second solution and condensing and refluxing under the condition of oil bath to obtain an impregnation product;
and drying and roasting the impregnated product to obtain the catalyst carrier.
Specifically, dissolving a precursor of an active component in a second solvent to obtain a second solution; specifically, the precursor of the catalyst support may be dissolved by stirring or ultrasonic means. The time of stirring or ultrasonic treatment is not particularly limited, and may be selected according to the degree of mixing. Specifically, the time period may be 30 minutes or more.
As for the precursor of the active component, in the present invention, the precursor of the active component includes one or a combination of two or more of soluble salts of metal elements. Specifically, the soluble salts may be one or a mixture of two or more of their respective inorganic acid salts such as nitrate, sulfate, hydrochloride, etc., or their hydrates, or may be one or a mixture of two or more of organic acid salts such as acetate, oxalate, etc., or their hydrates.
In some specific embodiments, the precursor of the active component includes a soluble salt of elemental cerium, a soluble salt of elemental iron, and optionally a soluble salt of elemental nickel.
Further, in the present invention, the precursor of the active component preferably includes nitrate and/or chloride salts of cerium element, nitrate and/or chloride salts of iron element, and optionally nitrate and/or chloride salts of nickel element. By using nitrate and/or chloride salts, the active sites on the surface of the catalyst support for the oxidation of carbon monoxide are not occupied.
Which is the same as or different from the first solvent for the second solvent. Specifically, the present invention is not particularly limited, and may be a polar solvent commonly used in the art, and preferably, the first solvent may be water.
Further, the second solution may be heated prior to impregnation, which is advantageous for improving the dispersibility of the active ingredient. The heating temperature is not particularly limited, and may be generally 50 to 100 ℃, for example: 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the like.
Further, the catalyst carrier is placed in the second solution and condensed and refluxed under the oil bath condition to obtain an impregnated product, and the dispersibility of the active component is also advantageously improved by condensing and refluxing under the oil bath condition.
For the temperature of the oil bath, it may be 80-120 ℃, for example: 90 ℃, 100 ℃, 110 ℃, etc.; for the oil bath time, it may be 1 to 5 hours, for example: 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, etc. In the oil bath, stirring may be suitably performed to make the impregnation more complete.
Finally, drying and roasting the impregnated product to obtain the catalyst. The temperature and time of drying are not particularly limited, and may be generally 60 to 120 ℃, for example: 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and the like; the drying time is 6 to 24 hours, for example: 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, etc.
In some specific embodiments, to obtain a catalyst with excellent performance, the calcination is at 1 to 5 ℃/min, for example: heating rates of 2 ℃/min, 3 ℃/min, 4 ℃/min, etc.; raising the baking temperature to 200-600 ℃, for example: 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, etc.; the calcination time is 1 to 5 hours, for example: 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, etc. Further, in the present invention, the firing may be performed under an air atmosphere.
< third aspect >
In a third aspect the present invention provides the use of a catalyst according to the first aspect of the invention for the synergistic removal of nitrogen oxides and carbon monoxide in industrial flue gas.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Carrier Sn 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 Is prepared from
Mixing titanium tetrachloride, tin tetrachloride, ammonium borate and praseodymium nitrate according to a molar ratio of 0.48:0.5:0.01:0.01 under the condition of ice water bath, and stirring for half an hour to obtain a precursor mixture; then, under the ice water bath condition, dissolving precipitator ammonia water in deionized water to form a second solution; gradually adding the precursor mixture into a second solution under the ice water bath condition, rapidly stirring to obtain a precipitate, fully washing with deionized water, drying, and roasting in an air atmosphere, wherein the roasting procedure is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, roasting for 2 hours, and then continuously heating to 500 ℃ for roasting for 3 hours to obtain a catalyst carrier, wherein the catalyst carrier is marked as: sn (Sn) 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 。
Example 2
(1) Carrier Sn 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 Is prepared from
Mixing titanium tetrachloride, tin tetrachloride, ammonium borate and praseodymium nitrate according to a molar ratio of 0.48:0.5:0.01:0.01 under the condition of ice water bath, and stirring for half an hour to obtain a precursor mixture; then, under the ice water bath condition, dissolving precipitator ammonia water in deionized water to form a second solution; gradually adding the precursor mixture into a second solution under the ice water bath condition, rapidly stirring to obtain a precipitate, fully washing with deionized water, drying, and roasting in an air atmosphere, wherein the roasting procedure is as follows: and (3) heating to 250 ℃ at a heating rate of 2 ℃/min, roasting for 2 hours, and then continuously heating to 450 ℃ and roasting for 3 hours to obtain the catalyst carrier.
(2) Active component Ce 0.05 Fe 0.01 ：
Cerium nitrate and ferric nitrate are respectively dissolved in deionized water according to the loading amounts of 5% and 1% of the mass content, so as to obtain a second solution; heating the second solution to 80 ℃; adding the carrier manufactured in the step (1) into a second solution, transferring the obtained mixed product into a distillation flask, condensing and refluxing by adopting an oil bath at 100 ℃, stirring for 3 hours, and filtering to obtain an impregnated product; drying the impregnated product, and roasting in an air atmosphere, wherein the roasting procedure is as follows: the mixture is heated to 400 ℃ at a heating rate of 2 ℃/min and baked for 3 hours to obtain a catalyst, which is marked as: ce (Ce) 0.05 Fe 0.01 /Sn 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 。
The ammonia oxidation rate was measured using an infrared spectrum gas analyzer DX-4000 manufactured by GASMET corporation, finland. The resulting catalyst had an ammoxidation rate of about 36% at 400℃and a test atmosphere of 500ppm NH 3 +3％ O 2 Airspeed of 20000h -1 . The ratio of Lewis acid/(Lewis acid+Bronsted acid) is about 30%, the test method is pyridine adsorption infrared experiment, specifically, the catalyst is crushed into powder and then pressed into tablets for test, and the test temperature is 150 ℃; detecting the specific surface area of the catalyst by adopting a substance adsorption instrument, calculating the specific surface area of the catalyst according to a BET equation and a nitrogen adsorption and desorption curve, wherein the specific surface area of the catalyst is about 60m 2 /g。
Example 3
Carrier Sn 0.3 Ti 0.6 B 0.1 O 2 Is prepared from the following steps:
mixing titanium tetrachloride, tin tetrachloride and ammonium borate according to a molar ratio of 0.3:0.6:0.1 under the ice water bath condition, and stirring for half an hour to obtain a precursor mixture; then, under the ice water bath condition, dissolving precipitator ammonia water in deionized water to form a second solution; gradually adding the precursor mixture into a second solution under the ice water bath condition, rapidly stirring to obtain a precipitate, fully washing with deionized water, drying, and roasting in an air atmosphere, wherein the roasting procedure is as follows: and (3) heating to 250 ℃ at a heating rate of 2 ℃/min, roasting for 2 hours, and then continuously heating to 500 ℃ and roasting for 3 hours to obtain the catalyst carrier.
(2) Active component Ce 0.07 Fe 0.02 Ni 0.01
Cerium nitrate, ferric nitrate and nickel nitrate are respectively dissolved in deionized water according to the loading amounts of 7%, 2% and 1% of the mass content, so as to obtain a second solution; heating the second solution to 80 ℃; adding the carrier manufactured in the step (1) into the second solution to obtain a mixed product, transferring the mixed product into a distillation flask, condensing and refluxing the mixed product by adopting an oil bath at 100 ℃, stirring the mixed product for 3 hours, filtering the mixed product, drying the filtered product, and roasting the dried product in an air atmosphere, wherein the roasting procedure is as follows: heating to 450 ℃ at a heating rate of 2 ℃/min, and roasting for 3 hours to obtain a catalyst, which is recorded as: ce (Ce) 0.07 Fe 0.02 Ni 0.01 /Sn 0.3 Ti 0.6 B 0.1 O 2 。
The ammonia oxidation rate was measured using an infrared spectrum gas analyzer DX-4000 manufactured by GASMET corporation, finland. The resulting catalyst had an ammoxidation rate of about 50% at 400℃and a test atmosphere of 500ppm NH 3 +3％ O 2 Airspeed of 20000h -1 . The ratio of Lewis acid/(Lewis acid+Bronsted acid) is about 40%, the test method is pyridine adsorption infrared experiment, specifically, the catalyst is crushed into powder and then pressed into tablets for test, and the test temperature is 150 ℃; detecting the specific surface area of the catalyst by adopting a substance adsorption instrument, calculating the specific surface area of the catalyst according to a BET equation and a nitrogen adsorption and desorption curve, wherein the specific surface area of the catalyst is about 70m 2 /g。
Example 4
Carrier Sn 0.49 Ti 0.5 B 0.01 O 2 Is prepared from
Under the ice water bath condition, titanium tetrachloride, stannic chloride and ammonium borate are mixed according to mole ratioMixing at a molar ratio of 0.49:0.5:0.01, and stirring for half an hour to obtain a precursor mixture; then, under the ice water bath condition, dissolving precipitator ammonia water in deionized water to form a second solution; gradually adding the precursor mixture into a second solution under the ice water bath condition, rapidly stirring to obtain a precipitate, fully washing with deionized water, drying, and roasting in an air atmosphere, wherein the roasting procedure is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, roasting for 2 hours, and then continuously heating to 500 ℃ for roasting for 3 hours to obtain a catalyst carrier, wherein the catalyst carrier is marked as: sn (Sn) 0.49 Ti 0.5 B 0.01 O 2 。
Example 5
Carrier Sn 0.2 Ti 0.75 B 0.05 O 2 Is prepared from
Mixing titanium tetrachloride, tin tetrachloride and ammonium borate according to a molar ratio of 0.2:0.75:0.05 under the ice water bath condition, and stirring for half an hour to obtain a precursor mixture; then, under the ice water bath condition, dissolving precipitator ammonia water in deionized water to form a second solution; gradually adding the precursor mixture into a second solution under the ice water bath condition, rapidly stirring to obtain a precipitate, fully washing with deionized water, drying, and roasting in an air atmosphere, wherein the roasting procedure is as follows: heating to 250 ℃ at a heating rate of 2 ℃/min, roasting for 2 hours, and then continuously heating to 500 ℃ for roasting for 3 hours to obtain a catalyst carrier, wherein the catalyst carrier is marked as: sn (Sn) 0.2 Ti 0.75 B 0.05 O 2 。
Example 6
Carrier Sn 0.1 Ti 0.89 B 0.01 O 2 Is prepared from
Under the ice water bath condition, mixing titanium tetrachloride, tin tetrachloride and ammonium borate according to the molar ratio of 0.1:0.89:0.01, and stirring for half an hour to obtain a precursor mixture; then, under the ice water bath condition, dissolving precipitator ammonia water in deionized water to form a second solution; gradually adding the precursor mixture into a second solution under the ice water bath condition, rapidly stirring to obtain a precipitate, fully washing with deionized water, drying, and roasting in an air atmosphere, wherein the roasting procedure is as follows: at 2 ℃/minThe temperature rate is raised to 250 ℃ for roasting for 2 hours, and then the temperature is raised to 500 ℃ for roasting for 3 hours, so as to obtain a catalyst carrier, which is marked as: sn (Sn) 0.1 Ti 0.89 B 0.01 O 2 。
CuK was used with the catalyst supports of examples 4-6 using powder X-ray diffraction α The 2 theta (°) of the diffraction peak and the intensity of the diffraction peak are shown in fig. 4 when the irradiation experimental conditions were analyzed. As can be seen from fig. 4, in the catalyst carrier of the present application, the basic morphology of the solid solution oxide formed is rutile phase titanium dioxide due to the higher content of titanium atoms.
Performance testing
The catalyst support of example 1, and the catalysts of examples 2-3 were subjected to the out-of-stock and carbon monoxide oxidation activity tests, wherein the test conditions were: carbon monoxide concentration 1000ppm, nitrogen oxide concentration 500ppm, ammonia concentration 500ppm, oxygen concentration 5%. During test, the running temperature is 270-420 ℃ and the airspeed is 60000h -1 The results are shown in FIGS. 1-3.
As can be seen from FIG. 1, the catalyst support Sn of example 1 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 The carbon monoxide oxidation activity of (2) is more than 90%, but the denitration activity is only 10-35%. As can be seen from FIG. 2, catalyst Ce of example 2 0.05 Fe 0.01 /Sn 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 The carbon monoxide oxidation activity of (2) is more than 90%, and the denitration activity is also more than 95%.
Catalyst Ce of example 1 0.05 Fe 0.01 /Sn 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 With catalyst support Sn of example 2 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 In contrast, the carbon monoxide oxidation activity is not much different, but the denitration activity is greatly increased, because of the active ingredient used for denitration.
As can be seen from FIG. 3, catalyst Ce of example 3 0.07 Fe 0.02 Ni 0.01 /Sn 0.3 Ti 0.6 B 0.1 O 2 The carbon monoxide oxidation activity is more than 90%, and the denitration activity is also more than 95%.
Pilot test experiment
Pilot test performed in coal-fired power plant, smoke amount is 6000m 3 And/h, the inlet flue gas temperature is about 320 ℃. Pilot scale Ce of example 2 using integral extrusion molding 0.05 Fe 0.01 /Sn 0.48 Ti 0.5 B 0.01 Pr 0.01 O 2 Catalyst, space velocity of 5000h -1 The pilot run time was 30 days. In the pilot plant test process, an infrared spectrum gas analyzer DX-4000 produced by GASMET company of Finland is adopted to continuously detect NO in inlet and outlet flue gas on line 2 、CO、CO 2 、SO 2 And H 2 The effect after pilot stabilization is shown in Table 1.
TABLE 1 example 2 Pilot plant stabilization Effect of catalyst
| Sequence number | Name of the name | Unit (B) | An inlet | Outlet 1h mean value | Efficiency of |
| 1 | NO x | mg/Nm 3 | ～300 | 12.5 | 95％ |
| 2 | CO | mg/Nm 3 | ～1100 | 55 | 90.1％ |
| 3 | SO 2 | mg/Nm 3 | ～200 | 165 | 17.5％ |
| 4 | H 2 O | ％ | 8.3 | 8.1 | - |
As can be seen from table 1, the denitration synergistic carbon monoxide oxidation catalyst has excellent denitration and carbon monoxide oxidation performances, and can provide an effective strategy for the synergistic removal of nitrogen oxides and carbon monoxide in industrial flue gas.
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Claims (10)
1. A catalyst, characterized in that the catalyst comprises:
a catalyst support, and, in addition,
an active component supported on the surface and/or inside of the catalyst carrier; wherein the content of the active component is 1-10% and the content of the catalyst carrier is 90-99% based on the total mass of the catalyst.
2. The catalyst according to claim 1, wherein the catalyst support comprises a solid solution oxide containing tin atoms, titanium atoms, boron atoms, and optionally praseodymium atoms; preferably, the molar amount of the tin atoms is 10% to 50%, the molar amount of the titanium atoms is 10% to 90%, the molar amount of the boron atoms is 1% to 10%, and the molar amount of the praseodymium atoms is 0% to 5% based on 100% of the total molar amount of the catalyst.
3. The catalyst according to claim 2, wherein the molar amount of titanium atoms in the catalyst carrier is equal to or greater than the sum of the molar amounts of tin atoms, boron atoms, and optionally praseodymium atoms.
4. A catalyst according to any one of claims 1 to 3, wherein the active component comprises cerium oxide, iron oxide and optionally nickel oxide; preferably, the content of the cerium oxide is 1 to 10%, the content of the iron oxide is 1 to 3%, and the content of the nickel oxide is 0 to 3% based on 100% of the total mass of the catalyst.
5. The catalyst according to claim 4, wherein the content of cerium oxide is greater than the content of iron oxide by mass.
6. A process for the preparation of a catalyst according to any one of claims 1 to 5, characterized in that: comprising the step of supporting an active component on the surface and/or inside of the catalyst support.
7. The preparation method according to claim 6, characterized in that the preparation method comprises the steps of:
step 1) preparing the catalyst carrier by using an ice bath coprecipitation method;
and 2) loading the active components on the surface and/or the inside of the catalyst carrier by using an impregnation method to obtain the catalyst.
8. The method of preparing a catalyst carrier according to claim 7, wherein the step of preparing the catalyst carrier comprises:
mixing precursors of the catalyst carrier under the condition of ice-water bath to obtain a precursor mixture;
dissolving a precipitant in a first solvent under the condition of ice-water bath to obtain a first solution;
mixing the precursor mixture with the first solution to obtain a precipitate;
and drying and roasting the precipitate to obtain the catalyst carrier.
9. The method according to claim 7 or 8, wherein,
dissolving a precursor of the active component in a second solvent to obtain a second solution;
placing the catalyst carrier in the second solution and condensing and refluxing under the condition of oil bath to obtain an impregnation product;
and drying and roasting the impregnated product to obtain the catalyst carrier.
10. Use of a catalyst according to any one of claims 1-5 for the synergistic removal of nitrogen oxides and carbon monoxide in industrial flue gas.
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