CN113578396A - High-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak regulation and preparation method thereof - Google Patents
High-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak regulation and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 164
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000013543 active substance Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 25
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 20
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 83
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 63
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 50
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 45
- 229910052720 vanadium Inorganic materials 0.000 claims description 40
- -1 vanadium anhydride ester Chemical class 0.000 claims description 40
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 39
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- CUQNSZSCQRIWQR-UHFFFAOYSA-N copper holmium Chemical compound [Cu].[Ho] CUQNSZSCQRIWQR-UHFFFAOYSA-N 0.000 claims description 38
- GQUNDNXVBXIIRU-UHFFFAOYSA-K azanium antimony(3+) oxalate Chemical compound [NH4+].[Sb+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GQUNDNXVBXIIRU-UHFFFAOYSA-K 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 29
- 229910052715 tantalum Inorganic materials 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 23
- 238000005299 abrasion Methods 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 20
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 20
- 239000004408 titanium dioxide Substances 0.000 claims description 19
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004090 dissolution Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 208000005374 Poisoning Diseases 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 208000008316 Arsenic Poisoning Diseases 0.000 abstract description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 27
- 238000001125 extrusion Methods 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 10
- 238000007792 addition Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229910052689 Holmium Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 2
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- HWEYZGSCHQNNEH-UHFFFAOYSA-N silicon tantalum Chemical compound [Si].[Ta] HWEYZGSCHQNNEH-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification 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
- 239000010959 steel Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004876 x-ray fluorescence 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention relates to a high-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak shaving and a preparation method thereof, belonging to the field of catalyst materials. The method uses LYX-07 main active substance to carry out antimony doping, can promote NO adsorption, and enables ammonium sulfate salt to be decomposed more easily, thereby enhancing the sulfur poisoning resistance of the catalyst. Meanwhile, antimony doping facilitates oxygen vacancy generation and can increase surface acidity, thereby increasing the catalytic reaction rate. The catalyst is loaded with active substances of ammonium ceric nitrate and molybdic anhydride, so that the low-temperature activity of the catalyst can be improved, the reaction temperature range of the catalyst is widened to 130-420 ℃, the catalyst has good denitration efficiency, selectivity and stability in the temperature range, and meanwhile, the finally generated molybdenum oxide can also improve the arsenic poisoning resistance of the catalyst.
Description
Technical Field
The invention belongs to the field of catalyst materials, and particularly relates to a high-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak shaving and a preparation method thereof.
Background
The Selective Catalytic Reduction (SCR) denitration is one of the most widely applied and technically mature flue gas denitration technologies internationally, and the technical core of the SCR denitration lies in the use of a denitration catalyst, so that the SCR denitration catalyst has the advantages of high purification rate, reliable operation and the like. The denitration catalyst used in the coal-fired power plant has been commercially applied for many years, the technology is mature, and the operation temperature of the medium-high temperature catalyst is usually 320-420 ℃. However, in the face of increasingly severe pollution control situation, the emission of nitrogen oxides of other industrial furnaces is also strictly controlled, and national standards for emission of pollutants are published in industries such as coking, cement, glass, steel and the like.
The conventional traditional denitration catalyst cannot normally operate when the temperature of the denitration inlet flue gas is 130-430 ℃, so that the emission of nitrogen oxides exceeds standard, ammonia escape is increased, the air expectation blockage is caused, the catalyst is invalid, and even the failure of environmental protection equipment is caused, so that the power generation benefit is reduced. The traditional coping strategy is to adopt the coal economizer bypass modification, which has high cost and can cause the reduction of the thermal efficiency of the boiler.
In addition, the conventional commercial denitration SCR catalyst in the current market can only meet one or two of the five characteristics of high denitration performance, a larger reaction temperature range, good sulfur resistance, good water resistance and good wear resistance. Because the flue gas working conditions of various industrial furnaces are very complicated at present, the denitration catalyst which can only meet the requirements of two characteristic capacities cannot ensure that the emission of the industrial furnace reaches the standard in the complicated flue gas. Can cause the poisoning and the inactivation of the catalyst, and is easy to collapse or peel off under the high-dust washing, thereby greatly reducing the service life of the denitration catalyst.
Disclosure of Invention
The invention aims to provide a high-sulfur-resistant and wear-resistant denitration catalyst which can simultaneously meet the requirements of high denitration performance, a larger reaction temperature range, good sulfur resistance, good water resistance and good wear resistance and is suitable for deep peak regulation, and a preparation method thereof, so as to solve the technical problems.
To this end, the invention provides a high-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak regulation, which comprises a precursor, LYX-07 main active substances and a holmium copper alloy, wherein the precursor comprises tantalum, silicon dioxide and titanium dioxide, the LYX-07 main active substances comprise antimony, vanadium anhydride ester, ammonium cerium nitrate and molybdic anhydride, and the molar ratio of the tantalum, the LYX-07 main active substances to the holmium copper alloy is 1: (1-3): (2-10).
Preferably, the molar ratio of tantalum, silicon and titanium is 1: (2-6): (40-75).
Preferably, the molar ratio of antimony, vanadium, cerium and molybdenum in the LYX-07 main active substance is (1-2): 3: (0.2-1.0): (1-2).
Preferably, the median particle size of the titanium dioxide is 1.00-1.50 um, the median particle size of the antimony is 3.50-4.50 um, the median particle size of the vanadium anhydride ester is 1.00-2.00 um, and the median particle size of the molybdic anhydride is 1.50-2.00 um.
Preferably, the specific surface area of the catalyst is 41m2/g～81 m2The denitration efficiency is over 97 percent under the conditions that the sulfur content is 2000ppm and the water vapor content is 25 percent for a long time.
In addition, the invention also provides a preparation method of the high-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak shaving, which comprises the following steps:
step one, adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of a LYX-07 main active substance for later use;
step two, keeping the temperature of the hydrothermal solution of the LYX-07 main active substance at 50-70 ℃ for 2-18 hours;
step three, uniformly mixing tantalum, silicon dioxide and titanium dioxide, adding deionized water and dodecanoic acid, and uniformly stirring to obtain pug;
step four, heating and stirring the pug mixed in the step three to 90-130 ℃, and continuously stirring for 3-5 hours at the temperature;
step five, adding the hydrothermal solution of the LYX-07 main active substance obtained in the step two into the pug obtained in the step four, continuously stirring for 3-5 hours, adding the carboxymethyl cellulose, and continuously stirring;
sixthly, adding holmium copper alloy powder, wherein the mass ratio of the holmium copper alloy powder to the mass of the whole pug is (0.02-0.1): 1, heating to 80-100 ℃ and stirring for 2-3 hours;
and seventhly, after the pug is stirred to be yellow and slightly gray, adding part of deionized water until the pug is gravel, extruding, drying, calcining and molding.
Preferably, the preparation method of the antimony ammonium oxalate solution comprises the following steps: mixing and stirring 0.5-5 mol/L oxalic acid and 2mol/L ammonium oxalate solution according to the volume ratio of 1:4, heating to 50 ℃, keeping, adding antimony oxide with the solid-liquid ratio of 1:2, and stirring for reaction to obtain the ammonium antimony oxalate solution.
Preferably, the preparation method of the LYX-07 main active substance comprises the following steps:
step one, heating an ammonium antimony oxalate solution to 75 ℃, adding vanadium anhydride ester, wherein the molar ratio of ammonium antimony oxalate to vanadium anhydride ester is (1-2): 3;
adding 2-hydroxyethylamine, stirring and accelerating dissolution;
and step three, adding ammonium ceric nitrate and molybdic anhydride and continuing stirring, wherein the molar ratio of ammonium antimony oxalate to vanadium anhydride to ammonium ceric nitrate to molybdic anhydride is (1-2): 3: (0.2-1.0): (1-2);
step four, adding ammonia water to adjust the pH value to 8.5-9.5;
step five, adding dodecanoic acid, and uniformly stirring to form a suspension;
and sixthly, cooling to 50-70 ℃ to obtain a hydrothermal solution of the LYX-07 main active substance.
Preferably, the method for mixing tantalum, silicon dioxide and titanium dioxide is as follows: tantalum and silicon dioxide are first mixed homogeneously, and then silicon dioxide is added thereto and mixed homogeneously.
Preferably, the calcination in the seventh step is divided into two stages, the calcination temperature in the first stage is 250-370 ℃, and the calcination time is 1.5-3 hours; the calcination temperature of the second stage is 580-700 ℃, and the calcination time is 2-3 hours.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
(1) according to the invention, the tantalum and the silicon dioxide are uniformly mixed, then the titanium dioxide is mixed and uniformly mixed to obtain the precursor, so that the double anti-wear elements tantalum and silicon are introduced into the catalyst precursor, and the mechanical life of the catalyst can be greatly prolonged. Compared with the traditional method of adding silicon dioxide into titanium dioxide for mixing, the precursor is more uniform in a microscopic level, and the precursor is beneficial to ensuring more uniform loading of active substances and avoiding agglomeration of the precursor. And a layer of uniform tantalum-silicon binary oxide film can be formed after the catalyst is calcined, so that the catalyst has higher wear resistance and longer service life. In addition, compared with the direct addition of tantalum, the tantalum-doped silicon dioxide can enable the catalyst to achieve the wear-resistant effect more quickly.
(2) The method uses LYX-07 main active substance to carry out antimony doping, can promote NO adsorption, and enables ammonium sulfate salt to be decomposed more easily, thereby enhancing the sulfur poisoning resistance of the catalyst. Meanwhile, antimony doping facilitates oxygen vacancy generation and can increase surface acidity, thereby increasing the catalytic reaction rate.
(3) The invention can ensure more convenient mixing in the production mixing process section by adding the antimony solution. The pug caking or the uneven mixing of the antimony are not easy to cause, and the mixing time is greatly shortened.
(4) According to the invention, the catalyst is loaded with active substances of ammonium ceric nitrate and molybdic anhydride, so that the low-temperature activity of the catalyst can be improved, the reaction temperature range of the catalyst is widened to 130-420 ℃, the catalyst has good denitration efficiency, selectivity and stability in the temperature range, and meanwhile, the finally generated molybdenum oxide can also improve the arsenic poisoning resistance of the catalyst.
(5) Compared with the conventional method that vanadium oxide as the main active substance is directly added in mixing, the main active substance LYX-07 of the invention is added in the form of solution in the mixing of ordered complex substances consisting of antimony, vanadium anhydride ester, ammonium ceric nitrate and molybdic anhydride, can more quickly and uniformly enter a precursor, can optimize the activity on the basis of the conventional activity and has various characteristics.
(6) According to the invention, holmium copper alloy is used as an auxiliary agent, and the holmium copper alloy can form a pm-3m space point group structure in a catalyst. The structure has excellent ductility, and has the characteristics of fine crystal grains, numerous slip systems, low unstable stacking fault energy and the like which are beneficial to deformation, so that a water blocking net layer can be formed on the surface of the catalyst. Can effectively prevent partial water molecules from permeating into the catalyst body, and ensures that the catalyst has certain water resistance. In addition, due to the addition of the holmium copper alloy, part of holmium oxide can be generated after calcination. The holmium oxide surface has a large number of Bronsted acid sites, which is a necessary condition for the SCR denitration reaction to smoothly proceed at low temperature.
(7) According to the invention, holmium copper alloy is used as an auxiliary agent, and after holmium is doped, Ce can be caused by observation of an XRD peak spectrogram4+The peak became higher and larger, indicating that Ce was present4+The ratio of (a) to (b) increases. Ce4+And Ce3+The redox cycling between results in oxygen storage and release, which creates oxygen vacancies and forms unsaturated chemical bonds. The generation of oxygen vacancy improves the oxygen mobility and the oxidation reduction capability and is beneficial to the conversion of NO to NO2Thereby promoting the SCR reaction.
Drawings
FIG. 1 is an XRD spectrum of a sample doped with holmium at various contents, in which a curve represents 1Ce/0Ho, b curve represents 1Ce/0.01 Ho, c curve represents 1Ce/0.02 Ho, d curve represents 2.5 Ce/0.01 Ho, e curve represents 2.5 Ce/0.02 Ho, and f curve represents 2.5 Ce/0.03 Ho.
Fig. 2 is an enlarged schematic view of a portion a of curves a, b, and c in fig. 1.
Fig. 3 is an enlarged schematic view of a portion B of curves a, B and c in fig. 1.
Fig. 4 is a crystal structure of a holmium copper alloy.
Detailed Description
In order to make the technical means, innovative features, objectives and functions realized by the present invention easy to understand, the present invention is further described below.
The examples described herein are specific embodiments of the present invention, are intended to be illustrative and exemplary in nature, and are not to be construed as limiting the scope of the invention. In addition to the embodiments described herein, those skilled in the art will be able to employ other technical solutions which are obvious based on the disclosure of the claims and the specification of the present application, and these technical solutions include technical solutions which make any obvious replacement or modification for the embodiments described herein.
The invention provides a high-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak regulation, which comprises a precursor, LYX-07 main active substances and a holmium copper alloy, wherein the precursor comprises tantalum, silicon dioxide and titanium dioxide, the LYX-07 main active substances comprise antimony, vanadium anhydride ester, ammonium cerium nitrate and molybdic anhydride, and the molar ratio of the tantalum to the LYX-07 main active substances to the holmium copper alloy is 1: (1-3): (2-10). Wherein the molar ratio of tantalum to silicon to titanium is 1: (2-6): (40-75). The molar ratio of antimony, vanadium, cerium and molybdenum in the LYX-07 main active substance is (1-2): 3: (0.2-1.0): (1-2). The specific surface area of the resulting catalyst was 41m2/g～81 m2G, abrasion resistance of 0.06-0.1%/kg.
The invention optimizes the performance of the catalyst by modifying the particle size and distribution of titanium dioxide, antimony, vanadium anhydride ester and molybdic anhydride. The median particle size of titanium dioxide is 1.00-1.50 um, the median particle size of antimony is 3.50-4.50 um, the median particle size of the vanadium anhydride ester is 1.00-2.00 um, and the median particle size of the molybdic anhydride is 1.50-2.00 um. The manufacturers of titanium dioxide, antimony, vanadium anhydride ester and molybdic anhydride are Shanghai Qizhi chemical industry Co., Ltd, the type of the vanadium anhydride ester is LYTZV-115, the type of the molybdic anhydride is LYTZM-117, and the type of the titanium dioxide is LYTZT-165.
The preparation method of the high-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak shaving comprises the following steps:
step one, mixing and heating oxalic acid and an ammonium oxalate solution, adding antimony oxide, stirring and reacting to obtain an ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into the ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of the LYX-07 main active substance for later use.
And secondly, preserving the heat of the hydrothermal solution of the LYX-07 main active substance for 2-18 hours at 50-70 ℃.
And step three, uniformly mixing the tantalum, the silicon dioxide and the titanium dioxide, adding deionized water and dodecanoic acid, and uniformly stirring to obtain a pug shape. Specifically, the method for mixing tantalum, silicon dioxide and titanium dioxide comprises the following steps: tantalum and silicon dioxide are first mixed homogeneously, and then silicon dioxide is added thereto and mixed homogeneously. The obtained mixture of tantalum, silicon dioxide and titanium dioxide is more uniform, which is beneficial to more uniformly loading active substances and is not easy to generate agglomeration phenomenon. And a layer of uniform tantalum-silicon binary oxide film can be formed after the subsequent catalyst is calcined, so that the catalyst has higher wear resistance and longer service life. In addition, compared with the direct addition of tantalum, the tantalum-doped silicon dioxide can enable the catalyst to achieve the wear-resistant effect more quickly.
Step four, heating and stirring the pug mixed in the step three to 90-130 ℃, and continuously stirring for 3-5 hours at the temperature.
And step five, adding the hydrothermal solution of the LYX-07 main active substance obtained in the step two into the pug obtained in the step four, continuously stirring for 3-5 hours, adding the carboxymethyl cellulose, and continuously stirring.
Sixthly, adding holmium copper alloy powder, wherein the mass ratio of the holmium copper alloy powder to the mass of the whole pug is (0.02-0.1): 1, heating to 80-100 ℃ and stirring for 2-3 hours.
And seventhly, after the pug is stirred to be yellow and slightly gray, adding part of deionized water until the pug is gravel, extruding, drying, calcining and molding. Drying until the water content is not more than 15%, wherein the drying time is 3-9 hours. The calcination is divided into two stages, the calcination temperature of the first stage is 250-370 ℃, and the calcination time is 1.5-3 hours; the calcination temperature of the second stage is 550-700 ℃, and the calcination time is 2-3 hours.
Specifically, the preparation method of the LYX-07 main active substance comprises the following steps:
step one, heating an ammonium antimony oxalate solution to 75 ℃, adding vanadium anhydride ester, wherein the molar ratio of ammonium antimony oxalate to vanadium anhydride ester is (1-2): 3;
adding 2-hydroxyethylamine, stirring and accelerating dissolution;
and step three, adding ammonium ceric nitrate and molybdic anhydride and continuing stirring, wherein the molar ratio of ammonium antimony oxalate to vanadium anhydride to ammonium ceric nitrate to molybdic anhydride is (1-2): 3: (0.2-1.0): (1-2);
step four, adding ammonia water to adjust the pH value to 8.5-9.5;
step five, adding dodecanoic acid, and uniformly stirring to form a suspension;
and sixthly, cooling to 50-70 ℃ to obtain a hydrothermal solution of the LYX-07 main active substance.
The specific surface area was measured by using a fully automatic specific surface area analyzer (micromeritics-TriStar II-3020), the abrasion resistance was measured by using the national standard method (GB T31587-2015), the denitration performance was measured by using the national standard method (GB/T31587-2015), the catalyst composition was analyzed by using an X-ray fluorescence spectrometer (ZSX-Primus-II), and the crystal form and peak spectrum of the catalyst element were measured by using an X-ray diffractometer (ultima IV).
Example 1
Mixing and heating 0.1mol/L oxalic acid and 0.15mol/L ammonium oxalate solution, adding antimony oxide powder, stirring and reacting for 10-15 minutes to form an ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of LYX-07 main active substances, wherein the molar ratio of antimony, vanadium, cerium and molybdenum elements is 1: 3: 0.2: 1, the mass fraction of the solution is 30 percent. Specifically, oxalic acid with the concentration of 0.5-5 mol/L and ammonium oxalate with the concentration of 2mol/L are mixed and stirred according to the volume ratio of 1:4, at the moment, the temperature is increased to 50 ℃ and kept, modified antimony oxide powder with the solid-to-liquid ratio of 1:2 is added, and stirring is carried out until the modified antimony oxide powder is dissolved to form an antimony ammonium oxalate solution. The solution was warmed to 75 ℃ and ceric ammonium nitrate and anhydride vanadate were added, since the anhydride vanadate dissolved in this solution slowly, the dissolution was accelerated by adding 2-hydroxyethylamine and stirring (the ratio of the two additions was 3: 1). The temperature is kept constant at 75 ℃ in a water bath, and at the moment, the molybdic anhydride is added for dissolution. As the catalytic formulation system is an alkaline system, ammonia water (35% by mass) is added to adjust the pH value, and the ammonia water is added until the pH value reaches 8.5-9.5. Finally, adding dodecanoic acid organic substance which is difficult to dissolve in the solution and needs to be stirred uniformly to form a suspension. The material mainly aims at improving the plasticity of the pug in the mixing process of the catalyst, and can increase the diffusion activity of the pug in an alkaline environment, so that metal ions are dispersed in the pug more uniformly. Cooling to 50-70 ℃ and preserving, and completing the preparation of the LYX-07 hydrothermal solution. The hydrothermal solution of LYX-07 was stirred at 50 ℃ and incubated for 4 hours. Adding tantalum and silicon dioxide into a mixing pot, mixing uniformly, then adding silicon dioxide powder, mixing uniformly, wherein the molar ratio of tantalum, silicon and titanium elements is 1: 5: 75. adding deionized water and dodecanoic acid, and stirring to obtain uniform paste. Heating the pug to 120 ℃, stirring, adding a hydrothermal solution of LYX-07 main active substances after 3 hours, mixing the pug for 3.5 hours, adding 0.002 percent of carboxymethyl cellulose, continuously stirring for 0.5 hour, adding 0.02 percent of holmium copper alloy, and continuously stirring for 2 hours (the temperature is about 90 ℃). After the slurry was stirred to a yellowish gray color, deionized water was added in an amount of 0.005% and extrusion was carried out (20-hole extrusion). And (3) drying the extruded catalyst in a drying oven at 90 ℃ for 3-9 hours until the water content is not more than 25%. Taking out and calcining at 300 ℃ for 2 hours, and then calcining at 550 ℃ for 3 hours to obtain the catalyst.
The test shows that the specific surface area of the catalyst is 67m2/g, and the abrasion resistance is 0.09%/kg (the wind speed in the catalyst pore channel is 14.5m/s, and the concentration of the abrasion agent is 50g/m 3).
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, and the components of the flue gas are NO (500ppm) and NH3(500ppm), 02(5%) and N as carrier gas2The space velocity is 10000h-1, the denitration efficiency of the catalyst is stabilized above 86 percent in the reaction temperature range, and N is2The selectivity is greater than 94%.
And (3) testing the sulfur resistance of the catalyst: continuously introducing 1000ppm SO based on the denitration performance test condition225 percent of water vapor for 24 hours, other testing conditions are unchanged, the denitration efficiency of the catalyst is stabilized to be more than 80 percent in the reaction temperature range, and N is2The selectivity is greater than 90%.
Example 2
0.05mol/L oxalic acid and 0.1mol/L ammonium oxalate solution are mixed and heated, and then antimony oxide powder is added to be stirred and reacted for 20 minutes to form the ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of LYX-07 main active substances, wherein the molar ratio of antimony, vanadium, cerium and molybdenum elements is 1: 3: 0.3: 1.5, the mass fraction of the solution is 30 percent. Specifically, oxalic acid with the concentration of 0.5-5 mol/L and ammonium oxalate with the concentration of 2mol/L are mixed and stirred according to the volume ratio of 1:4, at the moment, the temperature is increased to 50 ℃ and kept, modified antimony oxide powder with the solid-to-liquid ratio of 1:2 is added, and stirring is carried out until the modified antimony oxide powder is dissolved to form an antimony ammonium oxalate solution. The solution was warmed to 75 ℃ and ceric ammonium nitrate and anhydride vanadate were added, since the anhydride vanadate dissolved in this solution slowly, the dissolution was accelerated by adding 2-hydroxyethylamine and stirring (the ratio of the two additions was 3: 1). The temperature is kept constant at 75 ℃ in a water bath, and at the moment, the molybdic anhydride is added for dissolution. As the catalytic formulation system is an alkaline system, ammonia water (35% by mass) is added to adjust the pH value, and the ammonia water is added until the pH value reaches 8.5-9.5. Finally, adding dodecanoic acid organic substance which is difficult to dissolve in the solution and needs to be stirred uniformly to form a suspension. The material mainly aims at improving the plasticity of the pug in the mixing process of the catalyst, and can increase the diffusion activity of the pug in an alkaline environment, so that metal ions are dispersed in the pug more uniformly. Cooling to 50-70 ℃ and preserving, and completing the preparation of the LYX-07 hydrothermal solution. The hydrothermal solution of LYX-07 was stirred at 50 ℃ and incubated for 4 hours. Adding tantalum and silicon dioxide into a mixing pot, mixing uniformly, then adding silicon dioxide powder, mixing uniformly, wherein the molar ratio of tantalum, silicon and titanium elements is 1: 6: 74. adding deionized water and dodecanoic acid, and stirring to obtain uniform paste. Heating the pug to 120 ℃, stirring, adding a hydrothermal solution of LYX-07 main active substances after 3 hours, mixing the pug for 4 hours, adding 0.002 percent of carboxymethyl cellulose, continuously stirring for 0.5 hour, adding 0.03 percent of holmium copper alloy, and continuously stirring for 2 hours (the temperature is about 90 ℃). After the slurry was stirred to a yellowish gray color, deionized water was added in an amount of 0.005% and extrusion was carried out (20-hole extrusion). And (3) drying the extruded catalyst in a drying oven at 90 ℃ for 3-9 hours until the water content is not more than 25%. Taking out and calcining at 300 ℃ for 2 hours, and then calcining at 580 ℃ for 3 hours to obtain the catalyst.
The specific surface area of the catalyst is 71m after testing2/g, the abrasion resistance is 0.08%/kg (the air speed in the pore channels of the catalyst is 14.5m/s, and the concentration of the abrasion agent is 50g/m 3).
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, and the components of the flue gas are NO (500ppm) and NH3(500ppm)、02(5%) carrier gas N2Airspeed of 10000h-1In the reaction temperature range, the denitration efficiency of the catalyst is stabilized to be more than 90 percent, and N is2The selectivity is greater than 95%.
And (3) testing the sulfur resistance of the catalyst: continuously introducing 1500ppm SO based on the denitration performance test condition225 percent of water vapor for 24 hours, other test conditions are unchanged, the denitration efficiency of the catalyst is stabilized to be more than 87 percent in the reaction temperature range, and N is2The selectivity is greater than 95%.
Example 3
0.03mol/L oxalic acid and 0.05mol/L ammonium oxalate solution are mixed and heated, and then antimony oxide powder is added to be stirred and reacted for 20 minutes to form the ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of LYX-07 main active substances, wherein the molar ratio of antimony, vanadium, cerium and molybdenum elements is 1: 3: 0.5: 2, the mass fraction of the solution is 30 percent. Specifically, oxalic acid with the concentration of 0.5-5 mol/L and ammonium oxalate with the concentration of 2mol/L are mixed and stirred according to the volume ratio of 1:4, at the moment, the temperature is increased to 50 ℃ and kept, modified antimony oxide powder with the solid-to-liquid ratio of 1:2 is added, and stirring is carried out until the modified antimony oxide powder is dissolved to form an antimony ammonium oxalate solution. The solution was warmed to 75 ℃ and ceric ammonium nitrate and anhydride vanadate were added, since the anhydride vanadate dissolved in this solution slowly, the dissolution was accelerated by adding 2-hydroxyethylamine and stirring (the ratio of the two additions was 3: 1). The temperature is kept constant at 75 ℃ in a water bath, and at the moment, the molybdic anhydride is added for dissolution. As the catalytic formulation system is an alkaline system, ammonia water (35% by mass) is added to adjust the pH value, and the ammonia water is added until the pH value reaches 8.5-9.5. Finally, adding dodecanoic acid organic substance which is difficult to dissolve in the solution and needs to be stirred uniformly to form a suspension. The material mainly aims at improving the plasticity of the pug in the mixing process of the catalyst, and can increase the diffusion activity of the pug in an alkaline environment, so that metal ions are dispersed in the pug more uniformly. Cooling to 50-70 ℃ and preserving, and completing the preparation of the LYX-07 hydrothermal solution. The hydrothermal solution of LYX-07 was stirred at 50 ℃ and incubated for 4 hours. Adding tantalum and silicon dioxide into a mixing pot, mixing uniformly, then adding silicon dioxide powder, mixing uniformly, wherein the molar ratio of tantalum, silicon and titanium elements is 1: 2: 40. adding deionized water and dodecanoic acid, and stirring to obtain uniform paste. Heating the pug to 120 ℃, stirring, adding a hydrothermal solution of LYX-07 main active substances after 3.6 hours, mixing the pug for 5 hours, adding 0.002 percent of carboxymethyl cellulose, continuously stirring for 0.5 hour, adding 0.05 percent of holmium copper alloy, and continuously stirring for 2 hours (the temperature is about 90 ℃). After the slurry was stirred to a yellowish gray color, deionized water was added in an amount of 0.005% and extrusion was carried out (20-hole extrusion). And (3) drying the extruded catalyst in a drying oven at 90 ℃ for 3-9 hours until the water content is not more than 25%. Taking out and calcining at 300 ℃ for 2 hours, and then calcining at 600 ℃ for 3 hours to obtain the catalyst.
The specific surface area of the catalyst is tested to be 77m2G, abrasion resistance 0.06%/kg (air speed in catalyst pore channel is 14.5m/s, concentration of abrasion agent is 50 g/m)3）。
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, and the components of the flue gas are NO (500ppm) and NH3(500ppm), 02(5%) and N as carrier gas2Airspeed of 10000h-1In the reaction temperature range, the denitration efficiency of the catalyst is stabilized to be more than 95 percent, and N is2The selectivity is greater than 96%.
And (3) testing the sulfur resistance of the catalyst: continuously introducing 2000ppm SO based on the denitration performance test condition225 percent of water vapor for 24 hours, other test conditions are unchanged, the denitration efficiency of the catalyst is stabilized to be more than 90 percent in the reaction temperature range, and N is2The selectivity is greater than 95%.
Example 4
0.01mol/L oxalic acid and 0.03mol/L ammonium oxalate solution are mixed and heated, and then antimony oxide powder is added to be stirred and reacted for 20 minutes to form the ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of LYX-07 main active substances, wherein the molar ratio of antimony, vanadium, cerium and molybdenum elements is 1.5: 3: 0.8: 2, the mass fraction of the solution is 30 percent. Specifically, oxalic acid with the concentration of 0.5-5 mol/L and ammonium oxalate with the concentration of 2mol/L are mixed and stirred according to the volume ratio of 1:4, at the moment, the temperature is increased to 50 ℃ and kept, modified antimony oxide powder with the solid-to-liquid ratio of 1:2 is added, and stirring is carried out until the modified antimony oxide powder is dissolved to form an antimony ammonium oxalate solution. The solution was warmed to 75 ℃ and ceric ammonium nitrate and anhydride vanadate were added, since the anhydride vanadate dissolved in this solution slowly, the dissolution was accelerated by adding 2-hydroxyethylamine and stirring (the ratio of the two additions was 3: 1). The temperature is kept constant at 75 ℃ in a water bath, and at the moment, the molybdic anhydride is added for dissolution. As the catalytic formulation system is an alkaline system, ammonia water (35% by mass) is added to adjust the pH value, and the ammonia water is added until the pH value reaches 8.5-9.5. Finally, adding dodecanoic acid organic substance which is difficult to dissolve in the solution and needs to be stirred uniformly to form a suspension. The material mainly aims at improving the plasticity of the pug in the mixing process of the catalyst, and can increase the diffusion activity of the pug in an alkaline environment, so that metal ions are dispersed in the pug more uniformly. Cooling to 50-70 ℃ and preserving, and completing the preparation of the LYX-07 hydrothermal solution. The hydrothermal solution of LYX-07 was stirred at 50 ℃ and incubated for 4 hours. Adding tantalum and silicon dioxide into a mixing pot, mixing uniformly, then adding silicon dioxide powder, mixing uniformly, wherein the molar ratio of tantalum, silicon and titanium elements is 1: 3: 75. adding deionized water and dodecanoic acid, and stirring to obtain uniform paste. Heating the pug to 120 ℃, stirring, adding a hydrothermal solution of LYX-07 main active substances after 3 hours, mixing the pug for 4.5 hours, adding 0.002 percent of carboxymethyl cellulose, continuously stirring for 1 hour, adding 0.05 percent of holmium copper alloy, and continuously stirring for 2 hours (the temperature is about 90 ℃). After the slurry was stirred to a yellowish gray color, deionized water was added in an amount of 0.005% and extrusion was carried out (20-hole extrusion). And (3) drying the extruded catalyst in a drying oven at 90 ℃ for 3-9 hours until the water content is not more than 25%. After taking out, the catalyst was calcined at 300 ℃ for 2 hours, and then at 650 ℃ for 3 hours to obtain a catalyst.
The specific surface area of the catalyst is 81m after being tested2G, abrasion resistance 0.06%/kg (air speed in catalyst pore channel is 14.5m/s, concentration of abrasion agent is 50 g/m)3）。
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, and the components of the flue gas are NO (500ppm) and NH3(500ppm), 02(5%) and N as carrier gas2Airspeed of 10000h-1In the reaction temperature range, the denitration efficiency of the catalyst is stabilized to be more than 97 percent, and N is2The selectivity is greater than 96%.
And (3) testing the sulfur resistance of the catalyst: continuously introducing 2000ppm SO based on the denitration performance test condition225 percent of water vapor for 24 hours, other test conditions are unchanged, the denitration efficiency of the catalyst is stabilized to be more than 95 percent in the reaction temperature range, and N is2The selectivity is greater than 96%.
Example 5
0.05mol/L oxalic acid and 0.05mol/L ammonium oxalate solution are mixed and heated, and then antimony oxide powder is added to be stirred and reacted for 35 minutes to form the ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of LYX-07 main active substances, wherein the molar ratio of antimony, vanadium, cerium and molybdenum elements is 2: 3: 1:2, the mass fraction of the solution is 30 percent. Specifically, oxalic acid with the concentration of 0.5-5 mol/L and ammonium oxalate with the concentration of 2mol/L are mixed and stirred according to the volume ratio of 1:4, at the moment, the temperature is increased to 50 ℃ and kept, modified antimony oxide powder with the solid-to-liquid ratio of 1:2 is added, and stirring is carried out until the modified antimony oxide powder is dissolved to form an antimony ammonium oxalate solution. The solution was warmed to 75 ℃ and ceric ammonium nitrate and anhydride vanadate were added, since the anhydride vanadate dissolved in this solution slowly, the dissolution was accelerated by adding 2-hydroxyethylamine and stirring (the ratio of the two additions was 3: 1). The temperature is kept constant at 75 ℃ in a water bath, and at the moment, the molybdic anhydride is added for dissolution. As the catalytic formulation system is an alkaline system, ammonia water (35% by mass) is added to adjust the pH value, and the ammonia water is added until the pH value reaches 8.5-9.5. Finally, adding dodecanoic acid organic substance which is difficult to dissolve in the solution and needs to be stirred uniformly to form a suspension. The material mainly aims at improving the plasticity of the pug in the mixing process of the catalyst, and can increase the diffusion activity of the pug in an alkaline environment, so that metal ions are dispersed in the pug more uniformly. Cooling to 50-70 ℃ and preserving, and completing the preparation of the LYX-07 hydrothermal solution. The hydrothermal solution of LYX-07 was stirred at 50 ℃ and incubated for 4 hours. Adding tantalum and silicon dioxide into a mixing pot, mixing uniformly, then adding silicon dioxide powder, mixing uniformly, wherein the molar ratio of tantalum, silicon and titanium elements is 1: 4: 75. adding deionized water and dodecanoic acid, and stirring to obtain uniform paste. Heating the pug to 120 ℃, stirring, adding a hydrothermal solution of LYX-07 main active substances after 3 hours, mixing the pug for 4.5 hours, adding 0.002 percent of carboxymethyl cellulose, continuously stirring for 1 hour, adding 0.05 percent of holmium copper alloy, and continuously stirring for 2.5 hours (the temperature is about 90 ℃). After the slurry was stirred to a yellowish gray color, deionized water was added in an amount of 0.005% and extrusion was carried out (20-hole extrusion). And (3) drying the extruded catalyst in a drying oven at 90 ℃ for 3-9 hours until the water content is not more than 25%. After taking out, the catalyst was calcined at 300 ℃ for 2 hours, and then calcined at 700 ℃ for 3 hours to obtain a catalyst.
The specific surface area of the catalyst is 41m2G, abrasion resistance0.1%/kg (air speed in catalyst pore channel is 14.5m/s, and concentration of abradant is 50 g/m)3）。
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, and the components of the flue gas are NO (500ppm) and NH3(500ppm)、02(5%) carrier gas N2Airspeed of 10000h-1In the reaction temperature range, the denitration efficiency of the catalyst is stabilized to be more than 91 percent, and N is2The selectivity is greater than 93%.
And (3) testing the sulfur resistance of the catalyst: continuously introducing 2000ppm SO based on the denitration performance test condition225 percent of water vapor for 24 hours, other test conditions are unchanged, the denitration efficiency of the catalyst is stabilized to be over 84 percent in the reaction temperature range, and N is2The selectivity is greater than 88%.
In addition, in order to research the influence of the content of the holmium copper alloy on trivalent cerium and tetravalent cerium in the catalyst, two groups of experiments are set.
In the first set of experiments, 0.1mol/L oxalic acid and 0.1mol/L ammonium oxalate solution are mixed and heated, and antimony oxide is added to stir for reaction for 20 minutes to form an ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of LYX-07 main active substances, wherein the molar ratio of antimony, vanadium, cerium and molybdenum elements is 1: 3: 1: 1.5, the mass fraction of the solution is 30 percent. The mixture was stirred and incubated at 50 ℃ for 3.5 hours. Adding tantalum and silicon dioxide into a mixing pot, mixing uniformly, then adding silicon dioxide powder, mixing uniformly, wherein the molar ratio of tantalum, silicon and titanium elements is 1: 6: 74. adding deionized water and dodecanoic acid, and stirring to obtain uniform paste. Heating the pug to 120 ℃, stirring, adding a hydrothermal solution of LYX-07 main active substance after 3 hours, mixing the pug for 4 hours, adding 0.002 percent of carboxymethyl cellulose, continuously stirring for 0.5 hour, adding 0.01 percent of copper oxide powder, and continuously stirring for 2 hours (the temperature is about 90 ℃). After the slurry was stirred to a yellowish gray color, deionized water was added in an amount of 0.005% and extrusion was carried out (20-hole extrusion). And (3) putting the extruded catalyst into a 90 ℃ oven for drying until the water content is not more than 15%, taking out the extruded catalyst, calcining the extruded catalyst at 300 ℃ for 2 hours, and calcining the extruded catalyst at 580 ℃ for 3 hours to obtain the catalyst.
The catalyst was sampled, ground and tableted, and XRD detection was carried out, and the result is shown in a curve in fig. 1.
The above experiment was repeated by replacing the copper oxide powder with 0.01% holmium copper alloy to obtain a catalyst, and the rest was unchanged, and a sample of the catalyst was ground and pressed to obtain a tablet, and XRD detection was performed, and the result is shown in the b curve in fig. 1.
The above experiment was repeated by replacing the copper oxide powder with 0.02% holmium copper alloy to obtain a catalyst, and the rest was unchanged, and the catalyst was subjected to sampling, grinding, tabletting and XRD detection, and the result is shown in the c curve in fig. 1.
As can be seen from FIGS. 1 to 3, when the amount of cerium added is constant, the amount of holmium copper alloy added is gradually increased, Ce4+The occupation ratio of (A) is gradually increased, and Ce4+/Ce3+The ratio of (a) gradually increases.
In the second set of experiments, 0.1mol/L oxalic acid and 0.1mol/L ammonium oxalate solution are mixed and heated, and antimony oxide is added to stir for reaction for 20 minutes to form an ammonium antimony oxalate solution. Adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of LYX-07 main active substances, wherein the molar ratio of antimony, vanadium, cerium and molybdenum elements is 1: 3: 2.5: 1.5, the mass fraction of the solution is 30 percent. The mixture was stirred and incubated at 50 ℃ for 3.5 hours. Adding tantalum and silicon dioxide into a mixing pot, mixing uniformly, then adding silicon dioxide powder, mixing uniformly, wherein the molar ratio of tantalum, silicon and titanium elements is 1: 6: 74. adding deionized water and dodecanoic acid, and stirring to obtain uniform paste. Heating the pug to 120 ℃, stirring, adding a hydrothermal solution of LYX-07 main active substances after 3 hours, mixing the pug for 4 hours, adding 0.002 percent of carboxymethyl cellulose, continuously stirring for 0.5 hour, adding 0.01 percent of holmium copper alloy, and continuously stirring for 2 hours (the temperature is about 90 ℃). After the slurry was stirred to a yellowish gray color, deionized water was added in an amount of 0.005% and extrusion was carried out (20-hole extrusion). And (3) putting the extruded catalyst into a 90 ℃ oven for drying until the water content is not more than 15%, taking out the extruded catalyst, calcining the extruded catalyst at 300 ℃ for 2 hours, and calcining the extruded catalyst at 580 ℃ for 3 hours to obtain the catalyst.
The catalyst was sampled, ground and tabletted, and subjected to XRD detection. The results are shown in the d-curve of FIG. 1.
The above experiment was repeated by replacing the copper oxide powder with 0.02% holmium copper alloy to obtain a catalyst, and the rest was unchanged, and the catalyst was subjected to sampling, grinding, tabletting and XRD detection, and the result is shown in e-curve in fig. 1.
The above experiment was repeated by replacing the copper oxide powder with 0.02% holmium copper alloy to obtain a catalyst, and the rest was unchanged, and the catalyst was subjected to sampling, grinding, tabletting and XRD detection, and the result is shown as the f-curve in FIG. 1.
As can be seen from FIGS. 1 to 3, similarly, the amount of the holmium copper alloy added was gradually increased with the amount of cerium added being constant, and Ce was added4+The occupation ratio of (A) is gradually increased, and Ce4+/Ce3+The ratio of (a) gradually increases.
The holmium copper alloy is added, so that the proportion of Ce4+ in the catalyst can be effectively improved. Particularly, when the content of Ce is increased, the proportion of holmium-copper alloy is larger, and Ce4+The larger the proportion in the catalyst. And Ce4+The larger the proportion in the catalyst, the more Ce4+And Ce3+The more intense the redox cycling between, the resulting oxygen storage and release, which creates oxygen vacancies and forms unsaturated chemical bonds. The generation of oxygen vacancy improves the oxygen mobility and the oxidation reduction capability and is beneficial to the conversion of NO to NO2Thereby promoting the SCR reaction.
Comparative example 1
Different from example 1, in the third step of this comparative example, tantalum was not added, only silicon dioxide and titanium dioxide were uniformly mixed, and then deionized water and dodecanoic acid were added and uniformly stirred until a paste was formed, and the rest was the same as example 1.
The specific surface area of the catalyst is tested to be 60m2G, abrasion resistance is 0.12%/kg (air speed in catalyst pore channel is 14.5m/s, concentration of abrasion agent is 50 g/m)3）。
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, and the smoke components areNO(500ppm)、NH3(500ppm)、02(5%) carrier gas N2Airspeed of 10000h-1In the reaction temperature range, the denitration efficiency of the catalyst is stabilized to be more than 85 percent, and N is2The selectivity is greater than 94%.
And (3) testing the sulfur resistance of the catalyst: continuously introducing 2000ppm SO based on the denitration performance test condition225 percent of water vapor for 24 hours, other testing conditions are unchanged, the denitration efficiency of the catalyst is stabilized to be more than 80 percent in the reaction temperature range, and N is2The selectivity is greater than 90%.
As can be seen from comparison of example 1 and comparative example 1, the dual abrasion resistance factor formed after the addition of tantalum is increased mainly by the abrasion resistance of the catalyst, and the abrasion resistance is increased by 25% in comparison. Although the specific surface area is also improved, the amplitude is smaller and is only improved by 11 percent. Because the promotion of specific surface area can adhere to more acid sites to the catalyst surface, improve denitration efficiency.
Comparative example 2
Unlike example 1, the main active material was replaced with vanadium pentoxide powder in step 1 of this comparative example, and the rest was the same as example 1.
The catalyst was tested to have a specific surface area of 62m2G, abrasion resistance is 0.09%/kg (air speed in catalyst pore channels is 14.5m/s, concentration of abrasion agent is 50 g/m)3）。
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, the components of the flue gas are NO (500ppm), NH3(500ppm), 02(5%), the carrier gas is N2, the space velocity is 10000h < -1 >, the denitration efficiency of the catalyst is stabilized above 67% in the reaction temperature range, and the selectivity of N2 is greater than 73%.
And (3) testing the sulfur resistance of the catalyst: on the basis of denitration performance test conditions, 2000ppm SO2 and 25% steam are continuously introduced for 24 hours, other test conditions are unchanged, in the reaction temperature range, the denitration efficiency of the catalyst is 19%, and the selectivity of N2 is 26%.
It can be known from comparative example 1 and comparative example 2 that the denitration efficiency of the catalyst under the working conditions of high sulfur and high water content can be greatly improved after the main active substance is replaced by LYX-07. Because the LYX-07 introduces the molybdic anhydride and the ammonium antimony oxalate, the temperature window of the catalyst can be greatly improved, and the catalyst also has excellent denitration efficiency in an ultra-wide temperature range; the vanadium anhydride ester and the ammonium ceric nitrate are added into the catalyst, so that the catalyst has excellent sulfur resistance and the denitration efficiency of the catalyst is not influenced. According to data comparison, the denitration efficiency is improved by 28% relatively after LYX-07 is used under the condition that SO2 and water are not introduced; in the case of introducing SO2 and water, the denitration efficiency is improved by 321% after LYX-07 is used.
Comparative example 3
Unlike example 1, the present comparative example was the same as example 1 except that no holmium copper alloy was added.
The catalyst has the specific surface area of 64 percent and the abrasion resistance strength of 0.09 percent/kg (the air speed in the pore channels of the catalyst is 14.5m/s, and the concentration of the abrasion agent is 50g/m 3) through tests.
Testing the denitration performance of the catalyst: the reaction temperature is 130-420 ℃, the components of the flue gas are NO (500ppm), NH3(500ppm), 02(5%), the carrier gas is N2, the space velocity is 10000h < -1 >, the denitration efficiency of the catalyst is 74% and the selectivity of N2 is 80% in the reaction temperature range.
And (3) testing the sulfur resistance of the catalyst: on the basis of denitration performance test conditions, 2000ppm SO2 and 25% steam are continuously introduced for 24 hours, other test conditions are unchanged, in the reaction temperature range, the denitration efficiency of the catalyst is 17%, and the selectivity of N2 is 23%.
As can be seen from comparative example 1 and comparative example 3, after adding holmium copper alloy to the catalyst, holmium copper alloy can form pm-3m space dot cluster structure in the catalyst, as shown in fig. 4. The structure has excellent ductility, and has the characteristics of fine crystal grains, numerous slip systems, low unstable stacking fault energy and the like which are beneficial to deformation, so that a water blocking net layer can be formed on the surface of the catalyst. Can effectively block partial hydrone and permeate in the catalyst organism, guarantee that the catalyst possesses certain water resistance, and can furthest guarantee that NOx is "caught" by the acid site pore volume on catalyst surface and not filled by other impurity, so compare in certain degree conventional catalyst and also can improve its denitration efficiency. According to the comparative data, the denitration efficiency is improved by 16% in comparison with that of the holmium copper alloy under the condition that SO2 and water are not introduced; and under the condition of introducing SO2 and water, the denitration efficiency is improved by 370% after the holmium copper alloy is used.
The above embodiments are merely illustrative, and not restrictive, of the scope of the claims, and other alternatives that may occur to those skilled in the art from consideration of the specification should be construed as being within the scope of the claims.
Claims (10)
1. The utility model provides a high resistant sulphur wear-resisting denitration catalyst suitable for degree of depth peak regulation which characterized in that: the holmium copper alloy precursor comprises tantalum, silicon dioxide and titanium dioxide, the LYX-07 main active substance comprises antimony, vanadium anhydride ester, ammonium cerium nitrate and molybdic anhydride, and the holmium copper alloy, wherein the molar ratio of the tantalum to the LYX-07 main active substance to the holmium copper alloy is 1: (1-3): (2-10).
2. The high sulfur-resistant wear-resistant denitration catalyst suitable for deep peak shaving according to claim 1, characterized in that: wherein the molar ratio of tantalum to silicon to titanium is 1: (2-6): (40-75).
3. The high sulfur-resistant wear-resistant denitration catalyst suitable for deep peak shaving according to claim 1, characterized in that: the molar ratio of antimony, vanadium, cerium and molybdenum in the LYX-07 main active substance is (1-2): 3: (0.2-1.0): (1-2).
4. The high sulfur-resistant wear-resistant denitration catalyst suitable for deep peak shaving according to claim 1, characterized in that: the median particle size of titanium dioxide is 1.00-1.50 um, the median particle size of antimony is 3.50-4.50 um, the median particle size of the vanadium anhydride ester is 1.00-2.00 um, and the median particle size of the molybdic anhydride is 1.50-2.00 um.
5. The high sulfur-resistant wear-resistant denitration catalyst suitable for deep peak shaving according to claim 1, characterized in that: the specific surface area of the catalyst is 41m 2/g-81 m2/g, the abrasion resistance is 0.06-0.1%/kg, the reaction temperature range is 130-420 ℃, and the denitration efficiency of more than 97% is realized for a long time under the conditions that the sulfur content is 2000ppm and the water vapor content is 25%.
6. A method for preparing the high sulfur-resistant abrasion-resistant denitration catalyst suitable for deep peak shaving according to any one of claims 1 to 5, which is characterized by comprising the following steps:
step one, adding vanadium anhydride ester, ammonium ceric nitrate, 2-hydroxyethylamine, dodecanoic acid, ammonia water and molybdic anhydride into an ammonium antimony oxalate solution, and uniformly stirring to obtain a hydrothermal solution of a LYX-07 main active substance for later use;
step two, keeping the temperature of the hydrothermal solution of the LYX-07 main active substance at 50-70 ℃ for 2-18 hours;
step three, uniformly mixing tantalum, silicon dioxide and titanium dioxide, adding deionized water and dodecanoic acid, and uniformly stirring to obtain pug;
step four, heating and stirring the pug mixed in the step three to 90-130 ℃, and continuously stirring for 3-5 hours at the temperature;
step five, adding the hydrothermal solution of the LYX-07 main active substance obtained in the step two into the pug obtained in the step four, continuously stirring for 3-5 hours, adding the carboxymethyl cellulose, and continuously stirring;
sixthly, adding holmium copper alloy powder, wherein the mass ratio of the holmium copper alloy powder to the mass of the whole pug is (0.02-0.1): 1, heating to 80-100 ℃ and stirring for 2-3 hours;
and seventhly, after the pug is stirred to be yellow and slightly gray, adding part of deionized water until the pug is gravel, extruding, drying, calcining and molding.
7. The preparation method of the high sulfur-resistant wear-resistant denitration catalyst suitable for deep peak shaving according to claim 6, wherein the preparation method of the antimony ammonium oxalate solution comprises the following steps: mixing and stirring 0.5-5 mol/L oxalic acid and 2mol/L ammonium oxalate solution according to the volume ratio of 1:4, heating to 50 ℃, keeping, adding antimony oxide with the solid-liquid ratio of 1:2, and stirring for reaction to obtain the ammonium antimony oxalate solution.
8. The method for preparing the high-sulfur-resistance wear-resistant denitration catalyst suitable for deep peak shaving according to claim 7, wherein the method for preparing the LYX-07 main active substance comprises the following steps:
step one, heating an ammonium antimony oxalate solution to 75 ℃, adding vanadium anhydride ester, wherein the molar ratio of ammonium antimony oxalate to vanadium anhydride ester is (1-2): 3;
adding 2-hydroxyethylamine, stirring and accelerating dissolution;
and step three, adding ammonium ceric nitrate and molybdic anhydride and continuing stirring, wherein the molar ratio of ammonium antimony oxalate to vanadium anhydride to ammonium ceric nitrate to molybdic anhydride is (1-2): 3: (0.2-1.0): (1-2);
step four, adding ammonia water to adjust the pH value to 8.5-9.5;
step five, adding dodecanoic acid, and uniformly stirring to form a suspension;
and sixthly, cooling to 50-70 ℃ to obtain a hydrothermal solution of the LYX-07 main active substance.
9. The method for preparing the high sulfur-resistant and wear-resistant denitration catalyst suitable for deep peak shaving according to claim 6, wherein the method for mixing tantalum, silicon dioxide and titanium dioxide comprises the following steps: tantalum and silicon dioxide are first mixed homogeneously, and then silicon dioxide is added thereto and mixed homogeneously.
10. The preparation method of the high sulfur-resistant wear-resistant denitration catalyst suitable for deep peak shaving according to claim 6, characterized in that: the calcination in the seventh step is divided into two stages, wherein the calcination temperature in the first stage is 250-370 ℃, and the calcination time is 1.5-3 hours; the calcination temperature of the second stage is 580-700 ℃, and the calcination time is 2-3 hours.
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