CN103240077A - Denitration catalyst with low sulfur dioxide oxidation rate and preparation method thereof - Google Patents
Denitration catalyst with low sulfur dioxide oxidation rate and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003647 oxidation Effects 0.000 title abstract 3
- 238000007254 oxidation reaction Methods 0.000 title abstract 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 17
- 239000000084 colloidal system Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 11
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 8
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims description 36
- 230000001590 oxidative effect Effects 0.000 claims description 28
- 238000000465 moulding Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 11
- 239000011593 sulfur Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007493 shaping process Methods 0.000 abstract 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract 2
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- 239000003245 coal Substances 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000006213 oxygenation reaction Methods 0.000 description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a denitration catalyst with a low sulfur dioxide oxidation rate and a preparation method thereof. The denitration catalyst mainly comprises the following components in parts by mass: 70-92 parts of titanium dioxide, 0.3-1.5 parts of vanadium pentoxide, 2-10 parts of tungsten trioxide, 1-5 parts of niobium oxide, 2-5 parts of rare earth oxide and 2-14 parts of silica-alumina mixed oxide. The preparation method comprises the following steps: 1) preparing the silica-alumina mixed oxide; 2) fully mixing and stirring a formula amount of silica-alumina mixed oxide, titanium dioxide, ammonium metavanadate, ammonium paratungstate, niobium nitrate, rare earth oxide, auxiliary shaping materials, deionized water and oxalic acid; and 3) performing extrusion molding on the shaping colloid obtained in the step 2) through a thin-walled die, drying and roasting. The activity of the denitration catalyst is equivalent to that of a common SCR (selective catalytic reduction) denitration catalyst under the high-temperature high-sulfur conditions, and the sulfur dioxide oxidation rate is only 60-80 percent of that of the SCR denitration catalyst.
Description
Technical field
The present invention relates to SCR denitrating catalyst technical field, be specifically related to denitrating catalyst of a kind of low oxidizing sulfur dioxide rate and preparation method thereof.
Background technology
Along with being on the rise that discharged nitrous oxides pollutes, country has strengthened the control dynamics to discharged nitrous oxides during " 12 ".More for the anti-sulphur Journal of Sex Research of catalyst under the mechanism of poisoning of SCR catalyst and the low temperature both at home and abroad, but for reducing SO
2The research of the catalyst formulation of oxygenation efficiency also rarely has and relates to, and this mainly is because existing SCR catalyst (SO under low sulfur-bearing situation
2Concentration is less than 6000mg/Nm
3) anti-sulphur better, SO
2Oxygenation efficiency can reach engine request substantially less than 1%.But China's ature of coal complicated condition, and most of sulfur content is far above abroad, divides according to " sulphur content grading standard in the CHINESE COAL ", and sulfur content is sulphur coal more than 3% in the coal.The big great variety of goods of China's sulphur coal reserves, total resources account for national coal resources total amount greatly about about 10%, be distributed in the less southern area of coal resources more, according to statistics, 67,200,000,000 tons of provinces and regions such as Zhejiang, Hubei, Guangxi, Hainan, Sichuan, Tibet proved reserves in 2005, average sulphur content 3.9%, the total thermoelectricity installed capacity of sulphur coal is greatly about 7,000 ten thousand kilowatts, and sulphur coal denitrating catalyst market capacity will reach more than 1,500,000,000 yuan.
The use of worst hot case medium-high sulfur coal not only makes the desulphurization system heavy-duty service of power plant, and (3% sulphur content produces 6000mg/Nm at least in the coal
3SO
2), increased cost, and at high temperature its oxygenation efficiency causes a large amount of SO far above middle temperature area
3Generation, the ammonium hydrogen sulfate of generation then influences the operation of denitrating system greatly.Therefore, press for a kind of denitrating catalyst that is applicable to the low oxidizing sulfur dioxide rate of Combustion in High Temperature High Sulfur coal-fired plant, and under the Combustion in High Temperature High Sulfur condition (380～427 ℃, 3000～5000ppm SO
2) reduction oxidizing sulfur dioxide rate when guaranteeing the denitration rate.
Summary of the invention
In view of this, the invention provides denitrating catalyst of a kind of low oxidizing sulfur dioxide rate and preparation method thereof, this denitrating catalyst guarantees to reduce the oxidizing sulfur dioxide rate in the denitration rate under the Combustion in High Temperature High Sulfur condition.
The denitrating catalyst of low oxidizing sulfur dioxide rate of the present invention, the key component of described denitrating catalyst and mass fraction thereof are: 70～92 parts of titanium dioxide, 0.3～1.5 part of vanadic anhydride, 2～10 parts of tungstic acids, 1～5 part of niobium oxide, 2～5 parts of rare earth oxides, 2～14 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 1～10:1.
Further, the key component of described denitrating catalyst and mass fraction thereof are: 77 parts of titanium dioxide, 1 part of vanadic anhydride, 5 parts of tungstic acids, 3 parts of niobium oxide, 3 parts of rare earth oxides, 8 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 4:1.
The preparation method of the denitrating catalyst of low oxidizing sulfur dioxide rate of the present invention may further comprise the steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 1～3mol/L, add ethyl orthosilicate, in 50～80 ℃ of water-bath heating 1～4 hour, form clear solution; The aluminium isopropoxide that adds formula ratio afterwards in this clear solution continues to stir 12～24 hours, and control pH value is between 4～6; Afterwards the gained material is carried out suction filtration, descended dry 12～14 hours at 100～120 ℃ then, then in 400～500 ℃ of following roastings 4～5 hours, make the sial composite oxides;
2) sial composite oxides, titanium dioxide, ammonium metavanadate, ammonium paratungstate, nitric acid niobium and the rare earth oxide of getting formula ratio fully mixes stirring with moulding auxiliary material, deionized water and oxalic acid, gets moulding colloid;
3) with step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, then 100～140 ℃ dry 12～24 hours down, 400～600 ℃ of following roastings obtain described denitrating catalyst after 4～10 hours.
Beneficial effect of the present invention is: the present invention has added the auxiliary agent of multiple different efficacies on the prescription basis of existing SCR denitrating catalyst, having formed with the vanadic anhydride is that activated centre, tungstic acid are that main auxiliary agent, titanium dioxide are that carrier, niobium oxide and rare earth oxide are that main additive, sial composite oxides are the denitrating catalyst of main support modification agent, and wherein niobium oxide can effectively completely cut off SO
2In the deposition of catalyst surface, effectively reduce the output of total oxide with the interaction energy of vanadium, and rare earth element has good storage oxygen performance, the abundant acid potential energy in sial composite oxides surface is effectively to TiO
2Carrier carries out acid position modification, and three's synergy makes that denitrating catalyst of the present invention guarantees to have reduced the oxidizing sulfur dioxide rate in the denitration rate under the Combustion in High Temperature High Sulfur condition.In the experiment of simulation Combustion in High Temperature High Sulfur, work as SO
2Concentration is 3000～5000ppm, and reaction temperature is in 380～427 ℃ of intervals, and the activity of denitrating catalyst of the present invention is suitable with common SCR denitrating catalyst, but the oxidizing sulfur dioxide rate only is 60%～80% of common SCR denitrating catalyst.
The specific embodiment
Below will be described in detail the preferred embodiments of the present invention.
Embodiment 1
The preparation method of the denitrating catalyst of the low oxidizing sulfur dioxide rate of present embodiment may further comprise the steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 1mol/L, add the 24.3kg ethyl orthosilicate, in 50 ℃ of water-bath heating 1 hour, form clear solution; The aluminium isopropoxide that adds 9.1kg afterwards in this clear solution continues to stir 12 hours, and control pH value is about 4; Afterwards the gained material is carried out suction filtration, descended dry 12 hours at 100 ℃ then, then in 400 ℃ of following roastings 4 hours, make the sial composite oxides;
2) get 8kg sial composite oxides, 77kg titanium dioxide, 1kg ammonium metavanadate, 9kg ammonium paratungstate, 3kg nitric acid niobium and 3kg rare earth oxide and fully mix stirring with the oxalic acid of 3kg moulding auxiliary material, appropriate amount of deionized water and 0.5mol/L, get moulding colloid;
3) with step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, then 110 ℃ dry 16 hours down, 500 ℃ of following roastings obtain described denitrating catalyst after 9 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidizing sulfur dioxide rate that present embodiment prepares are: 77 parts of titanium dioxide, 1 part of vanadic anhydride, 5 parts of tungstic acids, 3 parts of niobium oxide, 3 parts of rare earth oxides, 8 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 4:1.
Embodiment 2
The preparation method of the denitrating catalyst of the low oxidizing sulfur dioxide rate of present embodiment may further comprise the steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 2mol/L, add the 56.7kg ethyl orthosilicate, in 60 ℃ of water-bath heating 2 hours, form clear solution; The aluminium isopropoxide that adds 28.4kg afterwards in this clear solution continues to stir 13 hours, and control pH value is about 5; Afterwards the gained material is carried out suction filtration, descended dry 13 hours at 110 ℃ then, then in 450 ℃ of following roastings 5 hours, make the sial composite oxides;
2) get 15kg sial composite oxides, 80kg titanium dioxide, 1.5kg ammonium metavanadate, 10kg ammonium paratungstate, 1.5kg nitric acid niobium and 2.5kg rare earth oxide and fully mix stirring with the oxalic acid of 4kg moulding auxiliary material, appropriate amount of deionized water and 0.3mol/L, get moulding colloid;
3) with step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, then 120 ℃ dry 14 hours down, 450 ℃ of following roastings obtain described denitrating catalyst after 10 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidizing sulfur dioxide rate that present embodiment prepares are: 72 parts of titanium dioxide, 1 part of vanadic anhydride, 9 parts of tungstic acids, 1 part of niobium oxide, 2 parts of rare earth oxides, 13 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 3:1.
Embodiment 3
The preparation method of the denitrating catalyst of the low oxidizing sulfur dioxide rate of present embodiment may further comprise the steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 3mol/L, add the 74.7kg ethyl orthosilicate, in 70 ℃ of water-bath heating 3 hours, form clear solution; The aluminium isopropoxide that adds 56.1kg afterwards in this clear solution continues to stir 14 hours, and control pH value is about 6; Afterwards the gained material is carried out suction filtration, descended dry 14 hours at 120 ℃ then, then in 500 ℃ of following roastings 4.5 hours, make the sial composite oxides;
2) get 3kg sial composite oxides, 81kg titanium dioxide, 1kg ammonium metavanadate, 8kg ammonium paratungstate, 4kg nitric acid niobium and 4kg rare earth oxide and fully mix stirring with the oxalic acid of 3kg moulding auxiliary material, appropriate amount of deionized water and 0.2mol/L, get moulding colloid;
3) with step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, then 130 ℃ dry 13 hours down, 550 ℃ of following roastings obtain described denitrating catalyst after 7 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidizing sulfur dioxide rate that present embodiment prepares are: 81 parts of titanium dioxide, 1 part of vanadic anhydride, 6 parts of tungstic acids, 3 parts of niobium oxide, 3 parts of rare earth oxides, 3 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 2:1.
Embodiment 4
The preparation method of the denitrating catalyst of the low oxidizing sulfur dioxide rate of present embodiment may further comprise the steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 2.5mol/L, add the 43.5kg ethyl orthosilicate, in 80 ℃ of water-bath heating 4 hours, form clear solution; The aluminium isopropoxide that adds 65.3kg afterwards in this clear solution continues to stir 12 hours, and control pH value is about 4; Afterwards the gained material is carried out suction filtration, descended dry 12 hours at 120 ℃ then, then in 500 ℃ of following roastings 4 hours, make the sial composite oxides;
2) get 6kg sial composite oxides, 80kg titanium dioxide, 0.5kg ammonium metavanadate, 6kg ammonium paratungstate, 5kg nitric acid niobium and 5kg rare earth oxide and fully mix stirring with the oxalic acid of 1.5kg moulding auxiliary material, appropriate amount of deionized water and 0.1mol/L, get moulding colloid;
3) with step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, then 140 ℃ dry 12 hours down, 600 ℃ of following roastings obtain described denitrating catalyst after 4 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidizing sulfur dioxide rate that present embodiment prepares are: 80 parts of titanium dioxide, 0.5 part of vanadic anhydride, 5 parts of tungstic acids, 3.5 parts of niobium oxide, 3.5 parts of rare earth oxides, 6 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 1:1.
Comparative example 1
Comparative example 1 is common SCR denitrating catalyst, and its preparation method may further comprise the steps:
1) gets 86kg titanium dioxide, 1.5kg ammonium metavanadate and 10kg ammonium paratungstate and fully mix stirring with the oxalic acid of 5kg moulding auxiliary material, appropriate amount of deionized water and 0.5mol/L, get moulding colloid;
2) the moulding colloid with the step 1) gained passes through the extrusion molding of thin-walled mould, descends dry 16 hours at 110 ℃ then, and 500 ℃ of following roastings obtain described denitrating catalyst after 9 hours.
Key component and the mass fraction thereof of the common SCR denitrating catalyst that comparative example 1 prepares are: 86 parts of titanium dioxide, 1 part of vanadic anhydride, 8 parts of tungstic acids.
The denitrating catalyst of the low oxidizing sulfur dioxide rate that embodiment 1～4 is prepared and the common SCR denitrating catalyst that comparative example 1 prepares carry out catalyst activity and SO
2The oxygenation efficiency test:
A) experiment condition
Catalyst hole count: 5*5; Length: 200mm; The catalyst number of plies: 1 layer;
B) Gas Parameters
Reaction temperature: 420 ℃; Face velocity (AV): 18.64Nm
3/ m
2h
Flue gas composition: NO=500ppm; NH
3=500ppm; SO
2=5000ppm; O
2=3%; H
2O=4.52%;
C) experimental result
Denitration rate and SO with the common SCR denitrating catalyst of the denitrating catalyst of the low oxidizing sulfur dioxide rate of embodiment 1～4 and comparative example 1
2Oxygenation efficiency is done contrast, and the result is as shown in the table:
| Case study on implementation | The denitration rate | SO 2Oxygenation efficiency |
| The denitrating catalyst of the low oxidizing sulfur dioxide rate of embodiment 1 | 71.2 | 0.66 |
| The denitrating catalyst of the low oxidizing sulfur dioxide rate of embodiment 2 | 71.5 | 0.67 |
| The denitrating catalyst of the low oxidizing sulfur dioxide rate of embodiment 3 | 70.6 | 0.77 |
| The denitrating catalyst of the low oxidizing sulfur dioxide rate of embodiment 4 | 69.2 | 0.71 |
| The common SCR denitrating catalyst of comparative example 1 | 70.2 | 0.95 |
This shows that under the Combustion in High Temperature High Sulfur condition, the activity of denitrating catalyst of the present invention is suitable with common SCR denitrating catalyst, but the oxidizing sulfur dioxide rate only is 60%～80% of common SCR denitrating catalyst.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (3)
1. the denitrating catalyst of a low oxidizing sulfur dioxide rate, it is characterized in that: the key component of described denitrating catalyst and mass fraction thereof are: 70～92 parts of titanium dioxide, 0.3～1.5 part of vanadic anhydride, 2～10 parts of tungstic acids, 1～5 part of niobium oxide, 2～5 parts of rare earth oxides, 2～14 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 1～10:1.
2. the denitrating catalyst of low oxidizing sulfur dioxide rate according to claim 1, it is characterized in that: the key component of described denitrating catalyst and mass fraction thereof are: 77 parts of titanium dioxide, 1 part of vanadic anhydride, 5 parts of tungstic acids, 3 parts of niobium oxide, 3 parts of rare earth oxides, 8 parts of sial composite oxides; In the described sial composite oxides, the mass ratio of silica and alundum (Al is 4:1.
3. the preparation method of the denitrating catalyst of claim 1 or 2 described low oxidizing sulfur dioxide rates is characterized in that: may further comprise the steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 1～3mol/L, add ethyl orthosilicate, in 50～80 ℃ of water-bath heating 1～4 hour, form clear solution; The aluminium isopropoxide that adds formula ratio afterwards in this clear solution continues to stir 12～24 hours, and control pH value is between 4～6; Afterwards the gained material is carried out suction filtration, descended dry 12～14 hours at 100～120 ℃ then, then in 400～500 ℃ of following roastings 4～5 hours, make the sial composite oxides;
2) sial composite oxides, titanium dioxide, ammonium metavanadate, ammonium paratungstate, nitric acid niobium and the rare earth oxide of getting formula ratio fully mixes stirring with moulding auxiliary material, deionized water and oxalic acid, gets moulding colloid;
3) with step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, then 100～140 ℃ dry 12～24 hours down, 400～600 ℃ of following roastings obtain described denitrating catalyst after 4～10 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732546A (en) * | 2016-12-28 | 2017-05-31 | 南京德普瑞克催化器有限公司 | A kind of spherical SCR denitration and preparation method thereof |
| CN107149941A (en) * | 2016-03-03 | 2017-09-12 | 许承柱 | Utilize the low-temperature denitration catalyst and its manufacture method of the Chemoselective reduction for being catalyzed discarded object |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107149941A (en) * | 2016-03-03 | 2017-09-12 | 许承柱 | Utilize the low-temperature denitration catalyst and its manufacture method of the Chemoselective reduction for being catalyzed discarded object |
| CN107149941B (en) * | 2016-03-03 | 2020-03-10 | 许承柱 | Low-temperature denitration catalyst using selective reduction reaction of catalytic waste and method for manufacturing same |
| CN106732546A (en) * | 2016-12-28 | 2017-05-31 | 南京德普瑞克催化器有限公司 | A kind of spherical SCR denitration and preparation method thereof |
| CN106732546B (en) * | 2016-12-28 | 2019-03-01 | 南京德普瑞克催化器有限公司 | A kind of spherical shape SCR denitration and preparation method thereof |
| JP2021502893A (en) * | 2017-11-14 | 2021-02-04 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフトＵｍｉｃｏｒｅ ＡＧ ＆ Ｃｏ．ＫＧ | SCR catalyst |
| US11492945B2 (en) * | 2017-11-14 | 2022-11-08 | Umicore Ag & Co. Kg | SCR catalyst |
| US20230038263A1 (en) * | 2017-11-14 | 2023-02-09 | Umicore Ag & Co. Kg | SCR Catalyst |
| JP7323520B2 (en) | 2017-11-14 | 2023-08-08 | ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト | SCR catalyst |
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| CN103240077B (en) | 2014-12-24 |
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Address after: 401336 Chongqing City, South Bank of the Yangtze River Road, No. 11 Patentee after: State Power Investment Group Yuanda environmental protection catalyst Co., Ltd. Address before: 401336 Chongqing City, South Bank of the Yangtze River Road, No. 11 Patentee before: Chongqing Yuanda Catalyst Manufacturing Co., Ltd. |