CN115301281A - Sulfur-resistant and water-resistant catalyst, and preparation method and application thereof - Google Patents
Sulfur-resistant and water-resistant catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 38
- 239000011593 sulfur Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 15
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 39
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000011282 treatment Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 30
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910005438 FeTi Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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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- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to the technical field of catalysts, in particular to a sulfur-resistant and water-resistant catalyst and a preparation method and application thereof. The sulfur-resistant and water-resistant catalyst is mainly prepared from the following components in parts by weight: 5 to 7 parts of molecular sieve carrier, 8 to 12 parts of ferromanganese ore and 0.5 to 5 parts of ilmenite. The preparation method comprises the following steps: and drying the mixture of the molecular sieve carrier, the ferromanganese ore and the ilmenite, roasting in an air atmosphere, and treating in a CO atmosphere to obtain the catalyst. The catalyst disclosed by the invention has good low-temperature denitration activity, excellent sulfur-resistant and water-resistant performances and stable denitration performance in low-temperature SCR denitration.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a sulfur-resistant and water-resistant catalyst and a preparation method and application thereof.
Background
Among the numerous precursors that form haze, nitrogen Oxides (NO) x ) Is an important one. NO x Not only can cause the problems of acid rain, ozone layer damage and the like, but also is easy to react with SO in the atmosphere 2 、NH 3 And compounds of hydrocarbonsThe substances form secondary particles through complex chemical reaction, which brings great harm to human health and ecological environment. Selective Catalytic Reduction (SCR) is currently the removal of NO x The most efficient method. SCR technology with NH 3 As a reducing agent, adding NO x Selective catalytic reduction to N 2 The core of this technology is the catalyst.
The SCR technology and the catalyst system thereof with good application effect in the middle-high temperature range (200 ℃ -400 ℃) are formed at present, but the low temperature range (<200 ℃ C. Still remains to be broken through. The manganese-based catalyst has better low-temperature SCR activity due to good oxidation-reduction property. The denitration process corresponding to the tail end of the low-temperature SCR still has a certain amount of SO in the flue gas after the dedusting and desulfurization processes 2 And H 2 O, which is easily poisoned and deactivated by covering active sites of the Mn-based catalyst. Therefore, the development of a low-temperature denitration catalyst with high sulfur resistance and water resistance on NO x Has important significance in high-efficiency treatment.
The existing preparation method of the catalyst has various steps and limits on raw material components. Therefore, the development of the low-temperature denitration catalyst which is low in cost, simple in process, strong in sulfur resistance and water resistance and high in activity is of great significance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a sulfur-resistant and water-resistant catalyst, which solves the technical problems of insufficient sulfur-resistant and water-resistant properties of the catalyst in the prior art and the like.
Another object of the present invention is to provide a method for preparing a sulfur-resistant and water-resistant catalyst.
The invention also aims to provide the application of the sulfur-resistant and water-resistant catalyst in low-temperature denitration.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the sulfur-resistant and water-resistant catalyst is mainly prepared from the following components in parts by weight:
5 to 7 parts of molecular sieve carrier, 8 to 12 parts of ferromanganese ore and 0.5 to 5 parts of ilmenite.
The sulfur-resistant and water-resistant catalyst has the advantages of simple raw materials, wide sources and low cost; in addition, the catalyst has excellent sulfur-resistant and water-resistant effects and has stable and efficient denitration activity.
In a particular embodiment of the invention, the molecular sieve support comprises any one or more of a NaY-type zeolite molecular sieve support, ZSM-5 and MCM-41.
In a specific embodiment of the present invention, the ferromanganese ore has a Mn content of 23wt% to 25wt% and a Fe content of 25.5wt% to 29.5wt%. The ferromanganese ore comprises FeO and Fe 2 O 3 And MnO 2 And the like.
In a specific embodiment of the invention, the ilmenite contains 25.5wt% to 29.5wt% Ti and 31.5wt% to 35.5wt% Fe. The ilmenite includes Fe 2 TiO 5 、FeTiO 3 、Fe 2 TiO 4 And FeTi 5 O 10 And the like.
The invention also provides a preparation method of the sulfur-resistant and water-resistant catalyst, which comprises the following steps:
and drying the mixture of the molecular sieve carrier, the ferromanganese ore and the ilmenite, roasting in an air atmosphere, and treating in a CO atmosphere to obtain the catalyst.
The preparation method of the catalyst of the invention does not need the steps of dipping or hydrothermal treatment, mixing or aging, drying by distillation and the like, has simple and convenient operation steps and is suitable for large-scale production.
In a specific embodiment of the present invention, the drying process comprises: the drying temperature is 100-110 ℃, and the drying time is 1-24 h.
In the specific embodiment of the invention, the temperature of the roasting treatment is 430-470 ℃, and the time of the roasting treatment is 2-5 h.
In a specific embodiment of the invention, the temperature of the CO atmosphere treatment is 430-470 ℃, and the time of the CO atmosphere treatment is 10-60 min.
The invention also provides an application of any one of the sulfur-resistant and water-resistant catalysts in low-temperature denitration.
In bookIn a specific embodiment of the invention, the low-temperature denitration is low-temperature NH 3 -SCR denitration.
In a specific embodiment of the present invention, the low-temperature denitration temperature is in a range of 125 to 200 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The catalyst disclosed by the invention has good low-temperature denitration activity, excellent sulfur-resistant and water-resistant performances and stable denitration performance in low-temperature SCR denitration;
(2) The preparation method of the catalyst has the advantages of wide raw material source, low cost, no need of complex process steps, simple and convenient operation and suitability for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an XRD pattern of ferromanganese ore used in an example of the present invention;
FIG. 2 is an XRD pattern of ilmenite used in an embodiment of the invention;
FIG. 3 is an XRD pattern of the catalyst prepared in example 1 of the present invention;
FIG. 4 shows denitration activity with SO of catalysts of example 1 and comparative example 3 of the present invention 2 A graph of concentration change;
FIG. 5 shows denitration activity against H of catalysts of example 1 and comparative example 3 of the present invention 2 And (4) a change graph of the O content.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The sulfur-resistant and water-resistant catalyst is mainly prepared from the following components in parts by weight:
5 to 7 parts of molecular sieve carrier, 8 to 12 parts of ferromanganese ore and 0.5 to 5 parts of ilmenite.
The sulfur-resistant and water-resistant catalyst has the advantages of simple raw materials, wide sources and low cost; in addition, the catalyst has excellent sulfur-resistant and water-resistant effects and stable and efficient denitration activity.
In the sulfur-resistant and water-resistant catalyst, the amount information of each component can be as follows (in parts by weight):
the molecular sieve support may be used in amounts of 5 parts, 5.2 parts, 5.4 parts, 5.5 parts, 5.6 parts, 5.8 parts, 6 parts, 6.2 parts, 6.4 parts, 6.5 parts, 6.6 parts, 6.8 parts, 7 parts, and the like;
the amount of ferromanganese ore may be 8 parts, 8.2 parts, 8.4 parts, 8.5 parts, 8.6 parts, 8.8 parts, 9 parts, 9.2 parts, 9.4 parts, 9.5 parts, 9.6 parts, 9.8 parts, 10 parts, etc.;
ilmenite may be used in amounts of 0.5 parts, 0.8 parts, 1 part, 1.2 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, 5 parts, etc.
In a specific embodiment of the invention, the sulfur-resistant and water-resistant catalyst is mainly prepared from the following components in parts by weight: 5.5 to 6.5 parts of molecular sieve carrier, 9 to 11 parts of ferromanganese ore and 1 to 3.6 parts of ilmenite.
In a preferred embodiment of the invention, the sulfur-resistant and water-resistant catalyst is mainly prepared from the following components in parts by weight: 5.8 to 6.2 parts of molecular sieve carrier, 9.6 to 10 parts of ferromanganese ore and 1.8 to 2.2 parts of ilmenite.
In a particular embodiment of the invention, the molecular sieve support comprises any one or more of a NaY-type zeolite molecular sieve support, ZSM-5 and MCM-41.
In a specific embodiment of the present invention, the ferromanganese ore has a Mn content of 23wt% to 25wt% and a Fe content of 26wt% to 29wt%. The ferromanganese ore comprises FeO and Fe 2 O 3 And MnO 2 And so on.
As in the different embodiments, the content of Mn in the ferromanganese ore may be 23wt%, 23.2wt%, 23.4wt%, 23.5wt%, 23.6wt%, 23.8wt%, 24wt%, 24.2wt%, 24.4wt%, 24.5wt%, 24.6wt%, 24.8wt%, 25wt%, and the like; the content of Fe may be 26wt%, 26.2wt%, 26.4wt%, 26.5wt%, 26.6wt%, 26.8wt%, 27wt%, 27.2wt%, 27.4wt%, 27.5wt%, 27.6wt%, 27.8wt%, 28wt%, 28.2wt%, 28.4wt%, 28.5wt%, 28.6wt%, 28.8wt%, 29wt%, etc.
In a specific embodiment of the invention, the ferromanganese ore comprises, by mass, 40% -42.5% of O, 1.5% -3% of Si, 2% -5% of Al, 23% -25% of Mn and 26% -29% of Fe; the balance also includes other ingredients.
In a particular embodiment of the invention, the ilmenite has a Ti content of 26-29 wt% and a Fe content of 32-35 wt%. The ilmenite comprises Fe 2 TiO 5 、FeTiO 3 、Fe 2 TiO 4 And FeTi 5 O 10 And so on.
As in the different embodiments, the content of Ti in the ilmenite may be 26wt%, 26.2wt%, 26.4wt%, 26.5wt%, 26.6wt%, 26.8wt%, 27wt%, 27.2wt%, 27.4wt%, 27.5wt%, 27.6wt%, 27.8wt%, 28wt%, 28.2wt%, 28.4wt%, 28.5wt%, 28.6wt%, 28.8wt%, 29wt%, and the like; the content of Fe may be 32.2wt%, 32.4wt%, 32.5wt%, 32.6wt%, 32.8wt%, 33wt%, 33.2wt%, 33.4wt%, 33.5wt%, 33.6wt%, 33.8wt%, 34wt%, 34.2wt%, 34.4wt%, 34.5wt%, 34.6wt%, 34.8wt%, 35wt%, etc.
In a specific embodiment of the invention, the ilmenite comprises, by mass, 27% -30% of O, 1.5% -3% of Si, 0.5% -3% of Al, 0.5% -1.5% of Mn, 32% -35% of Fe and 26% -29% of Ti; the balance also includes other ingredients.
In actual operation, the chemical composition of the ferromanganese ore is as follows by mass percent: 41.2% of O, 2.2% of Si, 3.4% of Al, 24.2% of Mn, 27.4% of Fe and 1.6% of the rest; the chemical composition of the ilmenite comprises the following components in percentage by mass: 28.4% of O, 2.3% of Si, 1.8% of Al, 0.9% of Mn, 33.5% of Fe, 27.5% of Ti and the other 5.6%.
In one embodiment of the present invention, the sulfur-resistant and water-resistant catalyst at least contains FeTi 5 O 10 、Fe 2 TiO 4 And Fe 4 (TiO 4 ) 3 。
The invention also provides a preparation method of the sulfur-resistant and water-resistant catalyst, which comprises the following steps:
and (3) drying the mixture of the molecular sieve carrier, the ferromanganese ore and the ilmenite, then roasting in air atmosphere, and then treating in CO atmosphere to obtain the catalyst.
The preparation method of the catalyst of the invention does not need the steps of dipping or hydrothermal, mixing or aging, drying by distillation and the like, has simple and convenient operation steps, and is suitable for large-scale production.
In a particular embodiment of the invention, the preparation of the mixture comprises: the molecular sieve carrier, the ferromanganese ore and the ilmenite are crushed and sieved in advance, and then mixed to obtain a mixture. Further, the screened size is 200 mesh or more, for example, 200 mesh, 250 mesh, 300 mesh, etc. can be used.
In a specific embodiment of the present invention, the drying process comprises: the drying temperature is 100-110 ℃, and the drying time is 1-24 h.
As in various embodiments, the temperature of the drying can be 100 ℃, 102 ℃, 104 ℃, 105 ℃, 106 ℃, 108 ℃, 110 ℃ and the like; the drying time may be 1h, 2h, 5h, 8h, 10h, 12h, 15h, 18h, 20h, 24h, and the like.
In actual operation, the drying time can be adjusted according to actual requirements until the materials are dried.
In the specific embodiment of the invention, the temperature of the roasting treatment is 430-470 ℃, and the time of the roasting treatment is 2-5 h.
As in the different embodiments, the temperature of the baking treatment may be 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, and the like; the time of the roasting treatment can be 2h, 3h, 4h, 5h and the like.
In a specific embodiment of the invention, the temperature of the roasting treatment is 450 +/-5 ℃, and the time of the roasting treatment is 3-4 h.
In a specific embodiment of the invention, the temperature of the CO atmosphere treatment is 430-470 ℃, and the time of the CO atmosphere treatment is 10-60 min.
As in the different embodiments, the temperature of the CO atmosphere treatment may be 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃ and the like; the time of the CO atmosphere treatment may be 10min, 20min, 30min, 40min, 50min, 60min, and the like.
In a specific embodiment of the invention, the temperature of the CO atmosphere treatment is 450 +/-5 ℃, and the time of the CO atmosphere treatment is 20-40 min.
In actual operation, after the roasting treatment in the air atmosphere, other treatments are not needed, and only the atmosphere is switched to the CO atmosphere, and then the CO atmosphere treatment is carried out by keeping the corresponding temperature.
The invention also provides an application of any one of the sulfur-resistant and water-resistant catalysts in low-temperature denitration.
In a specific embodiment of the present invention, the low temperature denitration is low temperature NH 3 -SCR denitration.
In the embodiment of the present invention, the low-temperature denitration temperature is in the range of 100 to 200 ℃, such as 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃ and the like.
In the following specific embodiments of the present invention, some material information may be used as follows, but is not limited thereto:
NaY type zeolite molecular sieve carrier (prepared by conventional hydrothermal synthesis method);
and the ferromanganese ore is derived from some ferromanganese ore in Hunan province.
Ilmenite, derived from ilmenite in Shandong.
Examples 1 to 5
The embodiment provides a preparation method of a sulfur-resistant and water-resistant catalyst, which comprises the following steps:
(1) Respectively taking zeolite (NaY) which is sieved by a 200-mesh sieve, ferromanganese ore and ilmenite, uniformly mixing the zeolite (NaY), the ferromanganese ore and the ilmenite according to a proportion, and then drying the mixture for 12 hours at 105 ℃.
(2) Roasting the material dried in the step (1) in an air atmosphere at 450 ℃ for 3.5h, then switching the CO atmosphere and continuously treating at 450 ℃ for 30min to obtain the sulfur-resistant and water-resistant catalyst.
In each example, the masses of the three substances are shown in Table 1.
TABLE 1 amounts (g) of the three substances of the different examples
| Numbering | Zeolite | Manganese iron ore | Ilmenite |
| Example 1 | 6 | 9.77 | 1.95 |
| Example 2 | 6 | 9.77 | 3.51 |
| Example 3 | 6 | 9.77 | 1.05 |
| Example 4 | 6.5 | 11 | 1.95 |
| Example 5 | 5.5 | 9 | 1.95 |
Wherein, the chemical compositions of the ferromanganese ore and the ilmenite are shown in the table 2, and the XRD patterns of the ferromanganese ore and the ilmenite are respectively shown in figure 1 and figure 2. The XRD pattern of the catalyst obtained in example 1 is shown in FIG. 3, and it can be seen from the graph that the catalyst obtained contains at least FeTi 5 O 10 、Fe 2 TiO 4 And Fe 4 (TiO 4 ) 3 。
TABLE 2 chemical composition of ferromanganese and ilmenite
| Elemental content (wt%) | O | Si | Al | Mn | Fe | Ti | Others (C) |
| Manganese iron ore | 41.2 | 2.2 | 3.4 | 24.2 | 27.4 | 0.0 | 1.6 |
| Ilmenite | 28.4 | 2.3 | 1.8 | 0.9 | 33.5 | 27.5 | 5.6 |
Comparative example 1
Comparative example 1 provides a method for preparing a catalyst, comprising the steps of:
(1) 9.77g of ferromanganese ore is taken, sieved by a 200-mesh sieve and then dried at 105 ℃ for 12 hours.
(2) And (2) roasting the material dried in the step (1) in an air atmosphere at 450 ℃ for 3.5h, and then switching the CO atmosphere to continue to treat at 450 ℃ for 30min to obtain the catalyst.
Comparative example 2
Comparative example 2 provides a method for preparing a catalyst, comprising the steps of:
(1) The zeolite (NaY) and the ferromanganese ore which are respectively sieved by a 200-mesh sieve are uniformly mixed according to the proportion (6 g of zeolite and 3.26g of ferromanganese ore), and then the mixture is dried for 12 hours at 105 ℃.
(2) And (2) roasting the material dried in the step (1) in an air atmosphere at 450 ℃ for 3.5h, and then switching the CO atmosphere to continue to treat at 450 ℃ for 30min to obtain the catalyst.
Comparative example 3
Comparative example 3 provides a method for preparing a catalyst, comprising the steps of:
(1) The zeolite (NaY) and the ferromanganese ore which are respectively sieved by a 200-mesh sieve are uniformly mixed according to the proportion (6 g of zeolite and 9.77g of ferromanganese ore), and then the mixture is dried for 12 hours at 105 ℃.
(2) And (2) roasting the material dried in the step (1) in an air atmosphere at 450 ℃ for 3.5h, and then switching the CO atmosphere to continue to treat at 450 ℃ for 30min to obtain the catalyst.
Comparative example 4
Comparative example 4 provides a preparation method of a catalyst, referring to the preparation method of example 2, except that the step (2) is different; step (2) of comparative example 4 is as follows:
(2) And (2) roasting the material dried in the step (1) for 3.5 hours in an air atmosphere at 450 ℃ to obtain the catalyst.
Comparative example 5
Comparative example 5 provides a method for preparing a catalyst comprising the steps of:
(1) Sieving with 200 mesh sieve to obtain zeolite (NaY), ferromanganese ore, and TiO 2 And Fe 2 O 3 Mixing uniformly according to the proportion (6 g of zeolite, 9.77g of ferromanganese ore and TiO) 2 0.83g、Fe 2 O 3 1.85 g) and then dried at 105 ℃ for 12h.
(2) And (2) roasting the material dried in the step (1) in an air atmosphere at 450 ℃ for 3.5h, and then switching the CO atmosphere to continue to treat at 450 ℃ for 30min to obtain the catalyst.
Experimental example 1
In order to comparatively illustrate the properties of the catalysts of the different examples and comparative examples, the denitration activities of the catalysts of examples 1 to 5 and comparative examples 1 to 5 were tested, and the test results are shown in table 3.
The denitration activity test method of the denitration catalyst comprises the following steps: simulating experimental smoke through a mixed gas steel cylinder, wherein the smoke components comprise NO and O 2 、N 2 (balance gas) and SO 2 And (when the water bath humidifier is used, a proper amount of deionized water is added into the gas washing bottle when the water bath humidifier is used). The gas is carried out in a tubular reactor with the inner diameter of about 1.5cm, the catalyst is positioned in the middle of the reactor, and the prepared simulated flue gas and NH directly entering the tubular reactor 3 The oxidation-reduction reaction is carried out on the catalyst, and the gas after the reaction passes through a phosphoric acid absorption bottle to remove unreacted NH 3 And then through a suck back prevention bottle (condensation bottle). The detection system consists of a display and an on-line infrared flue gas analyzer and is used for detecting NO and O at the inlet and the outlet of the reaction system 2 And SO 2 (when used as needed). NO and SO detected by the tail gas treatment system through the alkali liquor absorption on-line infrared flue gas analyzer 2 (when in use), the pollution to the external atmospheric environment is avoided.
The simulated smoke composition of the denitration activity test is as follows: 535.7mg/m 3 NO、333.9mg/m 3 NH 3 (i.e., ammonia nitrogen volume ratio is NH) 3 ﹕NO＝1.1﹕1)、5％O 2 、0～285.7mg/m 3 SO 2 (i.e., 0 to 100 ppm) 0 to 15% 2 O, in N 2 As the balance gas, the total flow rate of the gas is 200mL/min, and the gas space velocity (GHSV) is 2000h -1 NO and O at inlet and outlet of reaction system 2 And SO 2 The concentration of the active substance is detected by a GAS-board 3000 type online infrared smoke analyzer of Wuhan tetragonal photoelectric technology Limited, and the temperature range of the activity test is 100-300 ℃. The test result of the denitration activity of the catalyst takes the conversion rate of NO as an evaluation standard, and the calculation formula is shown as formula (1):
in the above formula, NO conversion (%) is NO x Conversion of (3), NO in And NO out Inlet and outlet concentrations of NO (mg/m) 3 )。
TABLE 3 denitration activity and sulfur and water resistance results for different catalysts
Remarking: a- (no SO) 2 Denitration efficiency of-50 ppm SO 2 Time denitration efficiency)/no SO 2 The denitration efficiency is improved; b- (without H) 2 O-time denitration efficiency-10% 2 Denitration efficiency at O)/H-free 2 Denitration efficiency at O
Taking the catalyst of example 1 as an example, the denitration efficiency at different temperatures is tested, and the denitration efficiency at 125-200 ℃ is respectively as follows: 125-96.4%, 150-96.3%, 175-97.5% and 200-97.2%.
Experimental example 2
To further explore SO 2 Concentration and H 2 The influence of the O content on the denitration activity of the different catalysts is illustrated by comparing the catalysts of example 1 and comparative example 3.
FIG. 4 is SO 2 The concentration has an influence on the denitration activity of the catalysts of example 1 and comparative example 3, and the reaction conditions are as follows: NO 535.7mg/m 3 ，NH 3 333.9mg/m 3 ，O 2 5％，SO 2 0～100ppm，GHSV＝2000h -1 Total flow 200mL/min, reaction temperature 175 ℃, (a) and (b) are denitration activity data of the catalysts of comparative example 3 and example 1, respectively. As is clear from the figure, the catalyst of example 1 of the present invention can be used at a high SO 2 At a concentration, the excellent low-temperature denitration activity is maintained, and the concentration of the catalyst is controlled in a way that 2 After removal, the original denitration activity can still be recovered.
FIG. 5 is H 2 The effect of the O content on the denitration activity of the catalysts of example 1 and comparative example 3 was that: NO 535.7mg/m 3 ，NH 3 333.9mg/m 3 ，O 2 5％，H 2 O 0～15％，GHSV＝2000h -1 Total flow 200mL/min, reaction temperature 175 ℃, (a) and (b) are denitration activity data of the catalysts of comparative example 3 and example 1, respectively. As is clear from the figure, the catalyst of example 1 of the present invention can be used at a high H 2 Maintaining excellent low-temperature denitration activity under the condition of O content, and maintaining excellent low-temperature denitration activity under the condition of H 2 When the O content is 15%, the denitration activity is not lowered.
From the above results, the catalyst of the present invention has excellent sulfur-resistant and water-resistant effects, stable and efficient denitration activity, and is suitable for the field of low temperature denitration.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The sulfur-resistant and water-resistant catalyst is characterized by being mainly prepared from the following components in parts by weight:
5 to 7 parts of molecular sieve carrier, 8 to 12 parts of ferromanganese ore and 0.5 to 5 parts of ilmenite.
2. The sulfur-resistant water-resistant catalyst according to claim 1, which is prepared from the following components in parts by weight: 5.5-6.5 parts of molecular sieve carrier, 9-11 parts of ferromanganese ore and 1-3.6 parts of ilmenite;
preferably, the composition is mainly prepared from the following components in parts by weight: 5.8 to 6.2 parts of molecular sieve carrier, 9.6 to 10 parts of ferromanganese ore and 1.8 to 2.2 parts of ilmenite.
3. The sulfur-tolerant water-resistant catalyst of claim 1, wherein the molecular sieve support comprises any one or more of NaY-type zeolite molecular sieve support, ZSM-5, and MCM-41.
4. The sulfur-resistant and water-resistant catalyst according to claim 1, wherein in the ferromanganese ore, the content of Mn is 23 to 25wt%, and the content of Fe is 26 to 29wt%;
preferably, the ferromanganese ore comprises, by mass, 40% -42.5% of O, 1.5% -3% of Si, 2% -5% of Al, 23% -25% of Mn and 26% -29% of Fe.
5. The sulfur-resistant and water-resistant catalyst according to claim 1, wherein in the ilmenite, the Ti content is 26 to 29wt%, and the Fe content is 32 to 35wt%;
preferably, the ilmenite comprises, by mass, 27% -30% of O, 1.5% -3% of Si, 0.5% -3% of Al, 0.5% -1.5% of Mn, 32% -35% of Fe and 26% -29% of Ti.
6. The method for preparing the sulfur-resistant and water-resistant catalyst according to any one of claims 1 to 5, comprising the steps of:
and drying the mixture of the molecular sieve carrier, the ferromanganese ore and the ilmenite, roasting in an air atmosphere, and treating in a CO atmosphere to obtain the catalyst.
7. The method for preparing the sulfur-resistant and water-resistant catalyst according to claim 6, wherein the drying treatment comprises: the drying temperature is 100-110 ℃, and the drying time is 1-24 h.
8. The method for preparing the sulfur-resistant and water-resistant catalyst according to claim 6, wherein the temperature of the roasting treatment is 430-470 ℃, and the time of the roasting treatment is 2-5 h;
the temperature of the CO atmosphere treatment is 430-470 ℃, and the time of the CO atmosphere treatment is 10-60 min.
9. The method of claim 6, wherein the preparing the mixture comprises: and crushing and sieving the molecular sieve carrier, the ferromanganese ore and the ilmenite in advance, and mixing to obtain the mixture.
10. Use of the sulfur-tolerant water-tolerant catalyst of any one of claims 1 to 5 for low temperature denitration;
preferably, the low-temperature denitration is low-temperature NH 3 -SCR denitration;
preferably, the temperature range of the low-temperature denitration is 125-200 ℃.
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