CN103240077B - 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
- Publication number
- CN103240077B CN103240077B CN201310192488.8A CN201310192488A CN103240077B CN 103240077 B CN103240077 B CN 103240077B CN 201310192488 A CN201310192488 A CN 201310192488A CN 103240077 B CN103240077 B CN 103240077B
- Authority
- CN
- China
- Prior art keywords
- parts
- hours
- composite oxides
- denitrating catalyst
- sial composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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 20
- 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 19
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 18
- 239000000084 colloidal system Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 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
- 238000007493 shaping process Methods 0.000 claims abstract description 10
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 9
- 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 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 16
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 10
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 239000008236 heating water Substances 0.000 claims description 7
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 239000011593 sulfur Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 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 6
- 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
- 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
- 239000002253 acid Substances 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
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 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
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 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
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000005619 thermoelectricity Effects 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
Landscapes
- Catalysts (AREA)
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 denitration technical field, be specifically related to denitrating catalyst of a kind of low oxidation rate of sulfur dioxide and preparation method thereof.
Background technology
That pollutes along with discharged nitrous oxides is on the rise, and country increases the control dynamics to discharged nitrous oxides in " 12 " period.Study more for the mechanism of poisoning of SCR catalyst and the resistance to SO_2 of low temperature catalyst both at home and abroad, but for reduction SO
2the catalyst formulation research of oxygenation efficiency also rarely has and relates to, and this is mainly because existing SCR catalyst (SO in low sulfur-bearing situation
2concentration is less than 6000mg/Nm
3) resistance to SO_2 better, SO
2oxygenation efficiency is less than 1%, substantially can reach engine request.But China's ature of coal complicated condition, and most of sulfur content is far above abroad, divide according to " the Sulfur In Chinese Coal graduation criteria for classifying ", in coal, sulfur content more than 3% is sulphur coal.The large great variety of goods of China's sulphur coal reserves, total resources accounts for the large about about 10% of national coal resources total amount, be distributed in the southern area that coal resources are less more, according to statistics, the provinces and regions such as Zhejiang, Hubei, Guangxi, Hainan, Sichuan, Tibet proved reserves in 2005 67200000000 tons, 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 (in coal, the sulphur content of 3% at least produces 6000mg/Nm
3sO
2), add cost, and at high temperature its oxygenation efficiency, far above middle temperature area, causes a large amount of SO
3generation, the ammonium hydrogen sulfate of generation then affects the operation of denitrating system greatly.Therefore, in the urgent need to a kind of denitrating catalyst being applicable to the low oxidation rate of sulfur dioxide of Combustion in High Temperature High Sulfur coal-fired plant, and under Combustion in High Temperature High Sulfur condition (380 ~ 427 DEG C, 3000 ~ 5000ppm SO
2) ensure denitration rate while reduce oxidation rate of sulfur dioxide.
Summary of the invention
In view of this, the invention provides denitrating catalyst of a kind of low oxidation rate of sulfur dioxide and preparation method thereof, while this denitrating catalyst ensures denitration rate under Combustion in High Temperature High Sulfur condition, reduce oxidation rate of sulfur dioxide.
The denitrating catalyst of low oxidation rate of sulfur dioxide of the present invention, the key component of described denitrating catalyst and mass fraction thereof are: titanium dioxide 70 ~ 92 parts, vanadic anhydride 0.3 ~ 1.5 part, tungstic acid 2 ~ 10 parts, niobium oxide 1 ~ 5 part, rare earth oxide 2 ~ 5 parts, sial composite oxides 2 ~ 14 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 1 ~ 10:1.
Further, the key component of described denitrating catalyst and mass fraction thereof are: titanium dioxide 77 parts, vanadic anhydride 1 part, tungstic acid 5 parts, niobium oxide 3 parts, rare earth oxide 3 parts, sial composite oxides 8 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 4:1.
The preparation method of the denitrating catalyst of low oxidation rate of sulfur dioxide of the present invention, comprises the following steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 1 ~ 3mol/L, adds ethyl orthosilicate, in 50 ~ 80 DEG C of heating water baths 1 ~ 4 hour, forms clear solution; In this clear solution, add the aluminium isopropoxide of formula ratio afterwards, continue stirring 12 ~ 24 hours, control ph is between 4 ~ 6; Afterwards gained material is carried out suction filtration, then at 100 ~ 120 DEG C dry 12 ~ 14 hours, then roasting 4 ~ 5 hours at 400 ~ 500 DEG C, obtained sial composite oxides;
2) get the sial composite oxides of formula ratio, titanium dioxide, ammonium metavanadate, ammonium paratungstate, nitric acid niobium and rare earth oxide and shaping auxiliary material, deionized water and oxalic acid carry out abundant mix and blend, obtain moulding colloid;
3) by step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, and then at 100 ~ 140 DEG C dry 12 ~ 24 hours, at 400 ~ 600 DEG C, roasting obtained described denitrating catalyst after 4 ~ 10 hours.
Beneficial effect of the present invention is: the present invention with the addition of the auxiliary agent of multiple different efficacies on the formula basis of existing SCR denitration, the denitrating catalyst that to define with vanadic anhydride be activated centre, tungstic acid is main auxiliary agent, titanium dioxide is carrier, niobium oxide and rare earth oxide are main additive, sial composite oxides are main carriers modifier, wherein niobium oxide effectively can completely cut off SO
2in the deposition of catalyst surface, effectively reduce the output of total oxide, and rare earth element has good Oxygen storage capacity with the interaction energy of vanadium, the acid potential energy that sial complex oxide surface enriches is effectively to TiO
2carrier carries out the modification of sour position, the synergy of three, reduces oxidation rate of sulfur dioxide while making denitrating catalyst of the present invention ensure denitration rate under 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 DEG C of intervals, and the activity of denitrating catalyst of the present invention is suitable with common SCR denitration, but oxidation rate of sulfur dioxide is only 60% ~ 80% of common SCR denitration.
Detailed description of the invention
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 oxidation rate of sulfur dioxide of the present embodiment, comprises the following steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 1mol/L, adds 24.3kg ethyl orthosilicate, in 50 DEG C of heating water baths 1 hour, forms clear solution; In this clear solution, add the aluminium isopropoxide of 9.1kg afterwards, continue stirring 12 hours, control ph is about 4; Afterwards gained material is carried out suction filtration, then at 100 DEG C dry 12 hours, then roasting 4 hours at 400 DEG C, obtained sial composite oxides;
2) oxalic acid getting 8kg sial composite oxides, 77kg titanium dioxide, 1kg ammonium metavanadate, 9kg ammonium paratungstate, 3kg nitric acid niobium and 3kg rare earth oxide and the shaping auxiliary material of 3kg, appropriate amount of deionized water and 0.5mol/L carries out abundant mix and blend, obtains moulding colloid;
3) by step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, and then at 110 DEG C dry 16 hours, at 500 DEG C, roasting obtained described denitrating catalyst after 9 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidation rate of sulfur dioxide that the present embodiment prepares are: titanium dioxide 77 parts, vanadic anhydride 1 part, tungstic acid 5 parts, niobium oxide 3 parts, rare earth oxide 3 parts, sial composite oxides 8 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 4:1.
Embodiment 2
The preparation method of the denitrating catalyst of the low oxidation rate of sulfur dioxide of the present embodiment, comprises the following steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 2mol/L, adds 56.7kg ethyl orthosilicate, in 60 DEG C of heating water baths 2 hours, forms clear solution; In this clear solution, add the aluminium isopropoxide of 28.4kg afterwards, continue stirring 13 hours, control ph is about 5; Afterwards gained material is carried out suction filtration, then at 110 DEG C dry 13 hours, then roasting 5 hours at 450 DEG C, obtained sial composite oxides;
2) oxalic acid getting 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 the shaping auxiliary material of 4kg, appropriate amount of deionized water and 0.3mol/L carries out abundant mix and blend, obtains moulding colloid;
3) by step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, and then at 120 DEG C dry 14 hours, at 450 DEG C, roasting obtained described denitrating catalyst after 10 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidation rate of sulfur dioxide that the present embodiment prepares are: titanium dioxide 72 parts, vanadic anhydride 1 part, tungstic acid 9 parts, niobium oxide 1 part, rare earth oxide 2 parts, sial composite oxides 13 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 3:1.
Embodiment 3
The preparation method of the denitrating catalyst of the low oxidation rate of sulfur dioxide of the present embodiment, comprises the following steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 3mol/L, adds 74.7kg ethyl orthosilicate, in 70 DEG C of heating water baths 3 hours, forms clear solution; In this clear solution, add the aluminium isopropoxide of 56.1kg afterwards, continue stirring 14 hours, control ph is about 6; Afterwards gained material is carried out suction filtration, then at 120 DEG C dry 14 hours, then roasting 4.5 hours at 500 DEG C, obtained sial composite oxides;
2) oxalic acid getting 3kg sial composite oxides, 81kg titanium dioxide, 1kg ammonium metavanadate, 8kg ammonium paratungstate, 4kg nitric acid niobium and 4kg rare earth oxide and the shaping auxiliary material of 3kg, appropriate amount of deionized water and 0.2mol/L carries out abundant mix and blend, obtains moulding colloid;
3) by step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, and then at 130 DEG C dry 13 hours, at 550 DEG C, roasting obtained described denitrating catalyst after 7 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidation rate of sulfur dioxide that the present embodiment prepares are: titanium dioxide 81 parts, vanadic anhydride 1 part, tungstic acid 6 parts, niobium oxide 3 parts, rare earth oxide 3 parts, sial composite oxides 3 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 2:1.
Embodiment 4
The preparation method of the denitrating catalyst of the low oxidation rate of sulfur dioxide of the present embodiment, comprises the following steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 2.5mol/L, adds 43.5kg ethyl orthosilicate, in 80 DEG C of heating water baths 4 hours, forms clear solution; In this clear solution, add the aluminium isopropoxide of 65.3kg afterwards, continue stirring 12 hours, control ph is about 4; Afterwards gained material is carried out suction filtration, then at 120 DEG C dry 12 hours, then roasting 4 hours at 500 DEG C, obtained sial composite oxides;
2) oxalic acid getting 6kg sial composite oxides, 80kg titanium dioxide, 0.5kg ammonium metavanadate, 6kg ammonium paratungstate, 5kg nitric acid niobium and 5kg rare earth oxide and the shaping auxiliary material of 1.5kg, appropriate amount of deionized water and 0.1mol/L carries out abundant mix and blend, obtains moulding colloid;
3) by step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, and then at 140 DEG C dry 12 hours, at 600 DEG C, roasting obtained described denitrating catalyst after 4 hours.
Key component and the mass fraction thereof of the denitrating catalyst of the low oxidation rate of sulfur dioxide that the present embodiment prepares are: titanium dioxide 80 parts, vanadic anhydride 0.5 part, tungstic acid 5 parts, niobium oxide 3.5 parts, rare earth oxide 3.5 parts, sial composite oxides 6 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 1:1.
Comparative example 1
Comparative example 1 is common SCR denitration, and its preparation method comprises the following steps:
1) oxalic acid getting 86kg titanium dioxide, 1.5kg ammonium metavanadate and 10kg ammonium paratungstate and the shaping auxiliary material of 5kg, appropriate amount of deionized water and 0.5mol/L carries out abundant mix and blend, obtains moulding colloid;
2) by the moulding colloid of step 1) gained by the extrusion molding of thin-walled mould, then at 110 DEG C dry 16 hours, at 500 DEG C, roasting obtained described denitrating catalyst after 9 hours.
The key component of the common SCR denitration that comparative example 1 prepares and mass fraction thereof are: titanium dioxide 86 parts, vanadic anhydride 1 part, tungstic acid 8 parts.
The common SCR denitration that the denitrating catalyst of low oxidation rate of sulfur dioxide embodiment 1 ~ 4 prepared and comparative example 1 prepare carries out catalyst activity and SO
2oxygenation efficiency is tested:
A) experiment condition
Catalyst hole count: 5*5; Length: 200mm; The catalyst number of plies: 1 layer;
B) Gas Parameters
Reaction temperature: 420 DEG C; 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
By the denitration rate of the denitrating catalyst of the low oxidation rate of sulfur dioxide of embodiment 1 ~ 4 and the common SCR denitration of comparative example 1 and SO
2oxygenation efficiency contrasts, and result is as shown in the table:
| Case study on implementation | Denitration rate | SO 2Oxygenation efficiency |
| The denitrating catalyst of the low oxidation rate of sulfur dioxide of embodiment 1 | 71.2 | 0.66 |
| The denitrating catalyst of the low oxidation rate of sulfur dioxide of embodiment 2 | 71.5 | 0.67 |
| The denitrating catalyst of the low oxidation rate of sulfur dioxide of embodiment 3 | 70.6 | 0.77 |
| The denitrating catalyst of the low oxidation rate of sulfur dioxide of embodiment 4 | 69.2 | 0.71 |
| The common SCR denitration of comparative example 1 | 70.2 | 0.95 |
As can be seen here, under Combustion in High Temperature High Sulfur condition, the activity of denitrating catalyst of the present invention is suitable with common SCR denitration, but oxidation rate of sulfur dioxide is only 60% ~ 80% of common SCR denitration.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by referring to the preferred embodiments of the present invention, invention has been described, but those of ordinary skill in the art is to be understood that, various change can be made 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 oxidation rate of sulfur dioxide, it is characterized in that: the key component of described denitrating catalyst and mass fraction thereof are: titanium dioxide 70 ~ 92 parts, vanadic anhydride 0.3 ~ 1.5 part, tungstic acid 2 ~ 10 parts, niobium oxide 1 ~ 5 part, rare earth oxide 2 ~ 5 parts, sial composite oxides 2 ~ 14 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 1 ~ 10:1; Described denitrating catalyst is prepared according to the following steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 1 ~ 3mol/L, adds ethyl orthosilicate, in 50 ~ 80 DEG C of heating water baths 1 ~ 4 hour, forms clear solution; In this clear solution, add the aluminium isopropoxide of formula ratio afterwards, continue stirring 12 ~ 24 hours, control ph is between 4 ~ 6; Afterwards gained material is carried out suction filtration, then at 100 ~ 120 DEG C dry 12 ~ 14 hours, then roasting 4 ~ 5 hours at 400 ~ 500 DEG C, obtained sial composite oxides;
2) get the sial composite oxides of formula ratio, titanium dioxide, ammonium metavanadate, ammonium paratungstate, nitric acid niobium and rare earth oxide and shaping auxiliary material, deionized water and oxalic acid carry out abundant mix and blend, obtain moulding colloid;
3) by step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, and then at 100 ~ 140 DEG C dry 12 ~ 24 hours, at 400 ~ 600 DEG C, roasting obtained described denitrating catalyst after 4 ~ 10 hours.
2. the denitrating catalyst of low oxidation rate of sulfur dioxide according to claim 1, it is characterized in that: the key component of described denitrating catalyst and mass fraction thereof are: titanium dioxide 77 parts, vanadic anhydride 1 part, tungstic acid 5 parts, niobium oxide 3 parts, rare earth oxide 3 parts, sial composite oxides 8 parts; In described sial composite oxides, the mass ratio of silica and alundum (Al2O3) is 4:1.
3. the preparation method of the denitrating catalyst of the low oxidation rate of sulfur dioxide described in claim 1 or 2, is characterized in that: comprise the following steps:
1) preparation of sial composite oxides: the dilute nitric acid solution of configuration concentration 1 ~ 3mol/L, adds ethyl orthosilicate, in 50 ~ 80 DEG C of heating water baths 1 ~ 4 hour, forms clear solution; In this clear solution, add the aluminium isopropoxide of formula ratio afterwards, continue stirring 12 ~ 24 hours, control ph is between 4 ~ 6; Afterwards gained material is carried out suction filtration, then at 100 ~ 120 DEG C dry 12 ~ 14 hours, then roasting 4 ~ 5 hours at 400 ~ 500 DEG C, obtained sial composite oxides;
2) get the sial composite oxides of formula ratio, titanium dioxide, ammonium metavanadate, ammonium paratungstate, nitric acid niobium and rare earth oxide and shaping auxiliary material, deionized water and oxalic acid carry out abundant mix and blend, obtain moulding colloid;
3) by step 2) the moulding colloid of gained is by the extrusion molding of thin-walled mould, and then at 100 ~ 140 DEG C dry 12 ~ 24 hours, at 400 ~ 600 DEG C, roasting obtained described denitrating catalyst after 4 ~ 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310192488.8A CN103240077B (en) | 2013-05-22 | 2013-05-22 | Denitration catalyst with low sulfur dioxide oxidation rate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310192488.8A CN103240077B (en) | 2013-05-22 | 2013-05-22 | Denitration catalyst with low sulfur dioxide oxidation rate and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103240077A CN103240077A (en) | 2013-08-14 |
| CN103240077B true CN103240077B (en) | 2014-12-24 |
Family
ID=48920160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310192488.8A Active CN103240077B (en) | 2013-05-22 | 2013-05-22 | Denitration catalyst with low sulfur dioxide oxidation rate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103240077B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| EP3482824A1 (en) * | 2017-11-14 | 2019-05-15 | Umicore Ag & Co. Kg | Scr catalytic converter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133184A (en) * | 1997-10-03 | 2000-10-17 | Nippon Shokubai Co., Ltd. | Catalyst for catalytic oxidation use |
| CN101185886A (en) * | 2007-11-21 | 2008-05-28 | 北京博奇电力科技有限公司 | A kind of SCR denitration catalyst and preparation method thereof |
| CN101380543A (en) * | 2008-09-11 | 2009-03-11 | 南京工业大学 | A kind of flue gas denitrification composite catalyst and preparation method thereof |
-
2013
- 2013-05-22 CN CN201310192488.8A patent/CN103240077B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133184A (en) * | 1997-10-03 | 2000-10-17 | Nippon Shokubai Co., Ltd. | Catalyst for catalytic oxidation use |
| CN101185886A (en) * | 2007-11-21 | 2008-05-28 | 北京博奇电力科技有限公司 | A kind of SCR denitration catalyst and preparation method thereof |
| CN101380543A (en) * | 2008-09-11 | 2009-03-11 | 南京工业大学 | A kind of flue gas denitrification composite catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Relationship between sulfur dioxide oxidation and selective catalytic no reduction by ammonia on V2O5-TiO2 catalysts doped with WO3 and Nb2O5;N.N.Sazonova et al.;《React.Kinet.Catal.Lett.》;19941231;第52卷(第1期);摘要，"实验部分" * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103240077A (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105817220B (en) | A kind of rare earth modified sulfur resistive low-temperature SCR catalyst and preparation method thereof | |
| CN101502796B (en) | Integral honeycomb selective catalytic reduction catalyst for flue gas denitration and method for preparing the same | |
| CN102631921B (en) | Nitric acid exhaust gas denitration catalyst and preparation method thereof | |
| CN101829573B (en) | Composite oxidant SCR (Selective Catalytic Reduction) denitrating catalyst, preparation method and applications thereof | |
| CN102773090B (en) | Integral honeycomb denitrification catalyst for WO3 addition process and preparation method thereof | |
| CN103301863B (en) | Steel-slag-based selective catalytic reduction (SCR) denitration catalyst and preparation method thereof | |
| CN103816799B (en) | Improve denitrfying agent of SNCR denitration efficiency and preparation method thereof | |
| CN102886266B (en) | Integrally-extruded honeycomb catalyst for selective catalytic reduction (SCR) smoke denitration and preparation process of catalyst | |
| CN103007923A (en) | SCR (Selective Catalytic Reduction) denitration catalyst and preparation method thereof | |
| CN102773091B (en) | Composite-carrier honeycomb monolithic denitration catalyst and preparing method thereof | |
| CN103962124A (en) | Flue gas denitration catalyst | |
| CN103801325A (en) | Co-precipitation preparation method of composite oxide denitration catalyst | |
| CN107597177A (en) | A kind of iron Cu oxide and molecular sieve composite honeycomb formula denitrating catalyst and preparation method thereof | |
| CN103240077B (en) | Denitration catalyst with low sulfur dioxide oxidation rate and preparation method thereof | |
| CN101791549A (en) | Method for preparing formed selective catalytic reduction denitration catalyst by using ultrasonic mixing sedimentation method | |
| CN102416321B (en) | Preparation method of SCR (Selective Catalytic Reduction) vanadium-series catalyst used in denitration of tail gas of diesel vehicle | |
| CN112403485A (en) | V/Cu/B/W-TiO2-ZrO2Production method of composite low-temperature denitration catalyst | |
| CN106268786A (en) | A kind of low-temperature denitration catalyst and preparation method thereof | |
| CN102962055A (en) | A kind of molybdenum-based low-temperature denitrification catalyst and preparation method thereof | |
| CN102101049A (en) | Intermediate temperature sulfur-resistant type composite oxide catalyst as well as preparation thereof and application thereof | |
| CN110694670A (en) | Preparation method of molecular sieve for purifying diesel vehicle tail gas | |
| CN108579731A (en) | A kind of preparation method of low-temperature denitration carbon-supported catalysts | |
| CN113499783A (en) | Preparation method of ultralow-temperature SCR denitration catalyst | |
| CN103007925A (en) | Manganese-tungsten composite oxide catalyst, and preparation method and purposes thereof | |
| CN105727965A (en) | Copper, zirconium, cerium and titanium composite oxide catalyst for flue gas denitrification and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
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. |