CN103752349A - Titanium dioxide for denitration catalyst and preparation method of titanium dioxide - Google Patents
Titanium dioxide for denitration catalyst and preparation method of titanium dioxide Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 212
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 42
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000000694 effects Effects 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910018540 Si C Inorganic materials 0.000 claims abstract description 6
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 6
- 239000003607 modifier Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 14
- 239000011800 void material Substances 0.000 claims description 14
- 239000011859 microparticle Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- -1 poly-methyl trifluoro propyl carbon silane Chemical compound 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910003089 Ti–OH Inorganic materials 0.000 claims description 5
- 239000005955 Ferric phosphate Substances 0.000 claims description 4
- 230000008901 benefit Effects 0.000 claims description 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- 229920003257 polycarbosilane Polymers 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- LGUJZAHTSAGVMX-UHFFFAOYSA-N [Bi].P(O)(O)(O)=O Chemical compound [Bi].P(O)(O)(O)=O LGUJZAHTSAGVMX-UHFFFAOYSA-N 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 24
- 239000003546 flue gas Substances 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003044 adaptive effect Effects 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses titanium dioxide for a denitration catalyst and a preparation method of the titanium dioxide. The titanium dioxide for the denitration catalyst is characterized by consisting of industrial-grade anatase titanium dioxide and a carbon silicon polymer, and specifically comprising the following components in parts by weight: 85-90 parts of anatase titanium dioxide, 5-10 parts of carbon silicon polymer and 1-3 parts of crystal lattice modifying agents. The preparation method disclosed by the invention comprises the following steps: refining the industrial-grade anatase titanium dioxide to be micron level by mechanical force fine dispersion, extending a crystal lattice modifying agent into crystal lattices on the surfaces of anatase titanium dioxide micron particles so as to increase surface crystal lattice clearances, further mixing and dispersing a carbon silicon polymer in a conical screw extruder so as to enable the silicon carbon reactive bond Si-C and the surface hydroxyl group of titanium dioxide to form Ti-C-Si, thereby forming stable crystal lattice clearances. Crystal particles are effectively prevented from growing at high temperature, and when the titanium dioxide for the denitration catalyst is used for a denitration catalyst carrier, the titanium dioxide for the denitration catalyst not only has small crystal particles and high surface activity, but also is wide in thermal adaptability; when at the temperature above 1100 DEG C, crystal lattice clearances are difficult to grow into rutile types; when an active material V2O5 is loaded, the crystal lattice clearances can prevent the active material and titanium dioxide from undergoing a crystal phase reaction; the activity of the catalyst is ensured and improved, and the service life of the catalyst is ensured and prolonged.
Description
Technical field
The present invention relates to environment-friendly materials field, be specifically related to a kind of carrier material for catalyst for denitrating flue gas, this carrier material is a kind of titanium dioxide, and further relates to the preparation method of titanium dioxide for this kind of denitrating catalyst.
Background technology
There is haze weather on a large scale in China in recent years, affected by this, and a lot of local air qualities are all six grades of above severe contaminations.Trace it to its cause, along with national economy and industry high speed development, industrial waste gas, industrial coal, thermal power generation fire coal, vehicle exhaust discharge capacity rise year by year.Particularly the nitrogen oxide (NOX) in coal-fired flue-gas discharge forms nitric acid in air, causes the generation of PM2.5 particle, finally forms haze.Therefore what nitrogen oxide (NOx) became current atmosphere pollution mainly contains one of harmful substances, except the nitrogen oxide (NOx) in flue gas removing very urgent.SCR (selective catalytical reduction, abbreviation SCR) denitration refers under uniform temperature and catalyst action, utilize reducing agent (NH3, methane, thiocarbamide, CO, H2 etc.) optionally nitrogen oxide (Nox) to be reduced to free of contamination nitrogen, thereby reach the object purifying air.The advantages such as to have reaction temperature lower due to SCR technology, and purifying rate is high, reliable, and secondary pollution is little are most widely used gas denitrifying technologies at present.In SCR system, the performance of catalyst directly affects the removal effect of NOx, and the anatase titanium dioxide (TiO2) of take is carrier, and load barium oxide, as active material, is the denitrating catalyst being most widely used at present.Wherein denitration catalyst carrier belongs to core material, accounts for the 80%-90% of denitrating catalyst weight, and its performance is directly connected to denitration rate.
Titanium dioxide, owing to having good quantum size effect, skin effect, has obvious advantage when for catalyst carrier.Present stage can be produced the TiO2 carrier that is applicable to SCR catalyst abroad, and the preparation technology of the type TiO2 carrier is secrecy technology.Domestic to the preparation of denitration catalyst carrier TiO2 mainly adopt configuration titanium predecessor (as titanium sulfate, titanium tetrachloride, metatitanic acid etc., titanate esters etc.) thus slurries by mixing tungsten, activation dispersion, high-temperature roasting obtain Nano titanium dioxide, during denitration carrier, owing to being subject to high temperature impact, when surpassing 600 ℃, the fine-grain of anatase titanium dioxide is very easily grown and is changed to rutile-type, cause the rigid reunion of large crystal grain, specific area declines, and catalytic activity declines.Its shortcoming is mainly reflected in that denitration efficiency is low, service life is short.The SCR catalyst denitration rate that the domestic TiO2 of take is carrier at present only has 80%～85%, and be 25000h left and right service life, if be subject to the impact of high-temperature flue gas, the life-span is shorter, not only increased denitration and do not reached requirement, and it is huge frequently to change engineering.
Chinese invention patent publication number CN101757907A discloses a kind of tungstenic titanium dioxide powder of preparing for honeycomb-shaped SCR denitrating catalyst and preparation method thereof, the method is made slurries A by metatitanic acid, tungsten is dissolved in simultaneously and in deionized water, is prepared into solution B, then solution B is added in slurries A,, 300-550 ℃ calcining 3-7 hour dry through spraying, obtain titanium tungsten denitration powder, tungsten oxide can effectively stop titanium dioxide to be changed to rutile-type by anatase titanium dioxide.But the method is owing to tungsten being scattered in completely in titanium liquid and high-temperature calcination obtains, most of tungsten is covered by titanium dioxide, utilization rate significantly reduces, cause cost to raise, in particular for denitrating flue gas temperature, in lattice, oxygen defect increases during higher than 600 ℃, very easily cause catalyst carrier to rutile-type crystal transfer, catalysqt deactivation.
Chinese invention patent publication number CN102773098A discloses a kind of preparation technology of nano titanium oxide denitrating catalyst, the method is by substep doped metallic elements lanthanum and gold in titanium tetrachloride solution, by high-temperature calcination, obtain, utilize Precious Metals-Gold to improve catalytic performance, utilize lanthanum to improve heat endurance.But the nano titanic oxide catalyst of the method gained only has good activity at 550-600 ℃, and catalytic activity too high or too low for temperature is fast reducing all, so thermal adaptability is narrower, and adopt noble metal cost high, be difficult to use on a large scale.
Chinese invention patent publication number CN1891335A discloses a kind of method and product of preparing nano titanium oxide, this invention be take titanium tetrachloride as raw material, by hydrolysis, realize in lattice and adulterating, the element dopings such as N, S, AL, Si, Sn, Fe, Cu, in nano titanium oxide lattice, are formed to lattice defect and have higher photocatalytic activity.But this titanium dioxide is a kind of mixed crystal, contain higher rutile-type, be not therefore suitable for denitration catalyst carrier.
According to above-mentioned, because the crystal grain of anatase titanium dioxide is less, specific area is suitable for more greatly doing denitration catalyst carrier.But the crystal formation of anatase titanium dioxide titanium dioxide is easily subject to temperatures involved and occurs to change mutually in actual applications, be applied to the rutile titanium dioxide that the continuous growth of denitration catalyst carrier anatase titanium dioxide crystal grain when flue gas reaches more than 600 ℃ is converted into large crystal grain, finally cause specific surface area of catalyst to reduce, catalyst loses activity, denitration efficiency is low, and shorten service life.
Summary of the invention
The present invention is directed to the defect that above-mentioned denitration titanium dioxide exists, propose a kind of denitrating catalyst titanium dioxide, it is characterized in that denitrating catalyst is comprised of technical grade anatase titanium dioxide and carbon silicon polymer with titanium dioxide.
Further aim of the present invention is to provide the preparation method of titanium dioxide for a kind of denitrating catalyst, this preparation method makes technical grade anatase titanium dioxide be refined to micron order by the fine dispersion of mechanical force, and utilize lattice modifier to extend in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap, further utilize the mixing dispersion in conical screw extruder of carbon silicon polymer, make the surface hydroxyl Ti-OH of silicon-carbon active bond Si-C and titanium dioxide form Ti-C-Si, thereby form stable interstitial void, when high temperature, effectively stop the growth of crystal grain, during for denitration catalyst carrier, not only there is less crystal grain and high surface, and thermal adaptability is wide, when more than 1100 ℃ high temperature, interstitial void is difficult to grow into rutile-type, as supported active material V
2o
5time interstitial void can stop active material to react with titanium dioxide generation crystalline phase, fully guarantee and improved activity and the life-span of catalyst.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of denitrating catalyst titanium dioxide of the present invention, is characterized in that: technical grade anatase titanium dioxide and carbon silicon polymer, consist of, each component of composition is counted by weight:
Anatase titanium dioxide 85-90 part,
Carbon silicon polymer 5-10 part,
Lattice modifier 1-3 part,
Wherein said anatase titanium dioxide is selected other conventional anatase titanium dioxide of technical grade; Described carbon silicon polymer is selected Polycarbosilane; Described lattice modifier is selected at least one in bismuth phosphate, α-silicic acid molybdenum, aluminum phosphate, ferric phosphate.
Above-mentioned a kind of denitrating catalyst is with in the composition of titanium dioxide, described Polycarbosilane is poly-methyl carbon silane preferably, poly-methyl ethoxy carbon silane, poly-methyl trifluoro propyl carbon silane, poly-methyl ethylene carbon silane, poly-methyl hydroxyl carbon silane, at least one in poly-ethyl carbon silane, by forming stable interstitial void with anatase titanium dioxide, its outstanding advantage is that carbon silicon polymer changes to carborundum when more than 1100 ℃ high temperature, can stablize and suppress the crystal transfer of anatase titanium dioxide, improved activity and the service life of catalyst when high temperature.
Above-mentioned a kind of denitrating catalyst is used in the composition of titanium dioxide, described lattice modifier preferably phosphoric acid bismuth.
A kind of denitrating catalyst titanium dioxide of the present invention, is characterized in that preparation method carries out in the following manner:
1) by the lattice modifier of the anatase titanium dioxide of 85-90 weight portion, 1-3 weight portion grinding 10-20min in vibromill, vibromill grinding rotating speed 400-500r/min, anatase titanium dioxide crystal grain in vibromill miniaturization process reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap;
2) by step 1) titanium dioxide fine particles obtaining mixes and sends into double screw extruder extruding pelletization with the carbon silicon polymer of 5-10 weight portion;
3) by step 2) pellet that obtains obtains fluffy denitrating catalyst titanium dioxide at 300-400 ℃ of condition carbonization 10-20min.
Above-mentioned a kind of denitrating catalyst is with in the preparation method of titanium dioxide, wherein the vibromill described in step 1) is vibration type mill for producing extra micro powder, vibration type mill for producing extra micro powder is by upper mill tube, lower mill tube forms, between upper mill tube and lower mill tube, be equipped with oscillator, in vibration processes, mechanical force intense impact and mill stripping effect make titanium dioxide granule miniaturization to≤5 microns, anatase titanium dioxide crystal grain in vibromill miniaturization reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap.
Above-mentioned a kind of denitrating catalyst is with in the preparation method of titanium dioxide, step 2 wherein) described double screw extruder is co-rotating conical twin-screw extruder, screw slenderness ratio >=52:1, screw speed 100-300rpm, each district's temperature is controlled at: a district 200-220 ℃; Two district 230-240 ℃; Three district 250-270 ℃; Four district 280-300 ℃; Five district 280-260 ℃, by the mixing dispersion of screw extruder, the surface hydroxyl Ti-OH of silicon-carbon active bond Si-C and titanium dioxide forms Ti-C-Si, thereby forms stable interstitial void.
For checking denitrating catalyst of the present invention is used for the adaptability of denitration catalyst carrier under different high temperature with titanium dioxide, embodiment 1 sample is calcined to 5 hours respectively under 200 ℃, 500 ℃, 800 ℃, 1100 ℃, 1300 ℃ hot conditions, and utilize X-ray diffractometer to analyze crystal phase structure and the specific area under 5 kinds of temperature conditions.Test result is as following table:
| Test condition |
200 |
500℃ | 800℃ | 1100℃ | 1300℃ |
| Anatase crystal type (%) | 100 | 100 | 100 | 98.2 | 95.3 |
| Rutile crystal type (%) | 0 | 0 | 0 | 0.8 | 4.7 |
| BET specific area m2/g | 312 | 345 | 352 | 348 | 341 |
According to test result, denitration of the present invention keeps stable anatase titanium dioxide crystalline phase when the high temperature with titanium dioxide, especially under 800 ℃ of conditions, specific area is the highest, can guarantee the denitration of flue gas under 400-800 ℃ of condition completely, even if run into superhigh temperature (more than 1100 ℃) flue gas, specific area is without obvious reduction, so denitrating catalyst of the present invention is wide with titanium dioxide adaptive temperature, has improved high temperature life.
The denitration that the embodiment of the present invention 1 is obtained titanium dichloride load V
2o
5carry out the test of denitration rate, test adopts simulated flue gas (NO accounts for 95%), records: in the time of 400 ℃, denitration rate is greater than 98.2%; In the time of 600 ℃, denitration rate is greater than 99%.
By commercially available denitrating catalyst and the supported V of the present invention of h in service lifes 25000
2o
5carry out denitration test in service life, test condition is: power-plant flue gas denitration is used 30 days.Record: commercially available to urge the amplitude declining than agent specific area be 1.35%; Specific area fall of the present invention is 0.11%, and the crystal particles of catalyst is without the phenomenon of uniting, and apparently higher than commercial catalyst, extrapolate and surpass 50000h service life service life.
While the present invention is directed to current domestic denitration titanium dioxide for denitration catalyst carrier, there is the easy sintering growth of high temperature crystal grain, specific surface area of catalyst reduces, catalytic efficiency reduces, the defect that shorten service life, a kind of denitrating catalyst titanium dioxide is proposed, it is characterized in that directly utilizing technical grade anatase titanium dioxide cheaply, by the fine dispersion of mechanical force, make technical grade anatase titanium dioxide be refined to micron order, and utilize lattice modifier to extend in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap, further utilize the mixing dispersion in conical screw extruder of carbon silicon polymer, make the surface hydroxyl Ti-OH of silicon-carbon active bond Si-C and titanium dioxide form Ti-C-Si, thereby form stable interstitial void, the interstitial void that carbon silicon forms on anatase titanium dioxide surface, when high temperature, effectively stop the growth of crystal grain, during for denitration catalyst carrier, not only there is less crystal grain and surface-active, and thermal adaptability is wide, even if interstitial void is difficult to grow into rutile-type when temperature surpasses 1100 ℃ of high temperature, and as supported active material V
2o
5time interstitial void can stop active material to react with titanium dioxide generation crystalline phase, fully guarantee and improved activity and the life-span of catalyst.
A kind of denitrating catalyst of the present invention is used titanium dioxide and preparation method compared with prior art, and its outstanding feature is:
1, the present invention proposes a kind of denitrating catalyst titanium dioxide, directly by technical grade anatase titanium dioxide and carbon silicon polymer, formed, thereby form stable interstitial void, not only crystal grain is little, active high, and interstitial void has hindered the growth of crystal grain when high temperature, its denitration adaptive temperature wide ranges, has lasting activity at 200-800 ℃, surpasses 50000h service life;
2, the present invention proposes a kind of denitrating catalyst titanium dioxide, during for denitration catalyst carrier not with the active material V of load
2o
5generation crystalline phase reaction, when in the time of 400 ℃, denitration rate is greater than 98.2%, 600 ℃, denitration rate is greater than 99%, fully guarantees and has improved denitration efficiency;
3, the present invention proposes a kind of denitrating catalyst titanium dioxide, its preparation method adopts mechanical force and chemical to increase titanium dioxide fine particles surface Gibbs free energy, thereby completing lattice surface gap improves, by the mixing surface hydroxyl Ti-OH formation Ti-C-Si with disperseing to make silicon-carbon active bond Si-C and titanium dioxide of strong shearing of conical screw extruder, thereby form stable interstitial void, produce continuously, technique is easily controlled, non-pollutant discharge, investment of production is little, be suitable for large-scale industrial production, the titanium dioxide cost of gained is low, denitration catalyst carrier applicable to various high and low temperature flue gases.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 is calcined the X-ray diffractogram of 5 hours under 1100 ℃ of conditions.
The specific embodiment
Below by the specific embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following example.In the situation that not departing from said method thought of the present invention, various replacements or the change according to ordinary skill knowledge and customary means, made, all should be within the scope of the present invention.
embodiment 1
1) by α-silicic acid molybdenum grinding 20min in vibromill of the anatase titanium dioxide of 85 weight portions, 1 weight portion, vibromill grinding rotating speed 500r/min, anatase titanium dioxide crystal grain in vibromill miniaturization process reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap;
2) by step 1) titanium dioxide fine particles obtaining and the poly-methyl carbon silane mixture of 10 weight portions evenly send into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy denitrating catalyst titanium dioxide at 400 ℃ of condition carbonization 20min.
The sample obtaining is calcined to 5 hours under 200 ℃, 500 ℃, 800 ℃, 1100 ℃, 1300 ℃ hot conditions, and utilize X-ray diffractometer to analyze crystal phase structure variation and and specific area.According to test result, the present embodiment titanium dioxide still keeps stable anatase titanium dioxide crystalline phase when high temperature, especially under 800 ℃ of conditions, specific area is the highest, can guarantee the denitration of flue gas under 400-800 ℃ of condition completely, even if run into superhigh temperature (more than 1100 ℃) flue gas, also only have a small amount of crystal transition, and specific area is without obvious reduction, fully guarantees catalytic activity and the denitration rate of denitration.Further, continue calcining 10 hours under 1300 ℃ of hot conditions, rutile crystal type is less than 5%, so this denitration has high temperature resistant persistence with titanium dioxide.
embodiment 2
1) by the aluminum phosphate of the anatase titanium dioxide of 90 weight portions, 2 weight portions grinding 15min in vibromill, vibromill grinding rotating speed 400r/min, anatase titanium dioxide crystal grain in vibromill miniaturization process reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap;
2) by step 1) titanium dioxide fine particles obtaining and the poly-methyl ethoxy carbon silane mixture of 8 weight portions evenly send into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy denitrating catalyst titanium dioxide at 300 ℃ of condition carbonization 20min.
embodiment 3
1) by the bismuth phosphate of the anatase titanium dioxide of 85 weight portions, 1 weight portion grinding 10min in vibromill, vibromill grinding rotating speed 450r/min, anatase titanium dioxide crystal grain in vibromill miniaturization process reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap;
2) by step 1) titanium dioxide fine particles obtaining and the poly-methyl trifluoro propyl carbon silane mixture of 5 weight portions evenly send into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy denitrating catalyst titanium dioxide at 350 ℃ of condition carbonization 20min.
The sample obtaining is calcined 5 hours under 800 ℃ of hot conditions, and BET specific area is 322m2/g; Sample load 5% V2O5 is calcined 5 hours under 800 ℃ of hot conditions, and BET specific area is 325m2/g; Therefore the present invention does not make TiO2 anatase titanium dioxide occur to the phase transformation of rutile-type under hot conditions, and after supported V 2O5, there is not vanadium titanium polymerisation in V2O5 and titanium dioxide under hot conditions, guaranteed the utilization rate of active material V2O5, extended catalyst life.
embodiment 4
1) by the ferric phosphate of the anatase titanium dioxide of 90 weight portions, 3 weight portions grinding 20min in vibromill, vibromill grinding rotating speed 500r/min, anatase titanium dioxide crystal grain in vibromill miniaturization process reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap;
2) by step 1) titanium dioxide fine particles obtaining and the poly-methyl ethylene carbon silane mixture of 10 weight portions evenly send into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy denitrating catalyst titanium dioxide at 400 ℃ of condition carbonization 10min.
embodiment 5
1) by the ferric phosphate of the anatase titanium dioxide of 85 weight portions, 1 weight portion grinding 10min in vibromill, vibromill grinding rotating speed 400r/min, anatase titanium dioxide crystal grain in vibromill miniaturization process reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap;
2) by step 1) titanium dioxide fine particles obtaining and the poly-ethyl carbon silane mixture of 5 weight portions evenly send into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy denitrating catalyst titanium dioxide at 400 ℃ of condition carbonization 15min.
Claims (6)
1. a denitrating catalyst titanium dioxide, is characterized in that: technical grade anatase titanium dioxide and carbon silicon polymer, consist of, each component of composition is counted by weight:
Anatase titanium dioxide 85-90 part,
Carbon silicon polymer 5-10 part,
Lattice modifier 1-3 part,
Wherein said anatase titanium dioxide is selected other conventional anatase titanium dioxide of technical grade; Described carbon silicon polymer is Polycarbosilane; Described lattice modifier is selected at least one in bismuth phosphate, α-silicic acid molybdenum, aluminum phosphate, ferric phosphate.
2. a kind of denitrating catalyst titanium dioxide according to claim 1, it is characterized in that: described Polycarbosilane preferably gathers methyl carbon silane, poly-methyl ethoxy carbon silane, poly-methyl trifluoro propyl carbon silane, poly-methyl ethylene carbon silane, poly-methyl hydroxyl carbon silane, gathers at least one in ethyl carbon silane, can form stable interstitial void with anatase titanium dioxide, its outstanding advantage is that carbon silicon polymer changes to carborundum when more than 1100 ℃ high temperature, can stablize and suppress the crystal transfer of anatase titanium dioxide.
3. a kind of denitration catalyst carrier according to claim 1, is characterized in that: described lattice modifier preferably phosphoric acid bismuth.
4. the preparation method of titanium dioxide for a kind of denitrating catalyst as claimed in claim 1, is characterized in that: comprise the steps:
1) by the lattice modifier of the anatase titanium dioxide of 85-90 weight portion, 1-3 weight portion grinding 10-20min in vibromill, vibromill grinding rotating speed 400-500r/min, anatase titanium dioxide crystal grain in vibromill miniaturization process reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap;
2) by step 1) titanium dioxide fine particles obtaining mixes and sends into double screw extruder extruding pelletization with the carbon silicon polymer of 5-10 weight portion;
3) by step 2) pellet that obtains obtains fluffy denitrating catalyst titanium dioxide at 300-400 ℃ of condition carbonization 10-20min.
5. the preparation method of titanium dioxide for a kind of denitrating catalyst according to claim 4, it is characterized in that in preparation method, the vibromill described in step 1) is vibration type mill for producing extra micro powder, vibration type mill for producing extra micro powder is by upper mill tube, lower mill tube forms, between upper mill tube and lower mill tube, be equipped with oscillator, in vibration processes, mechanical force intense impact and mill stripping effect make titanium dioxide granule miniaturization to≤5 microns, anatase titanium dioxide crystal grain in vibromill miniaturization reduces, specific area improves, Gibbs free energy increases, thereby promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap.
6. the preparation method of titanium dioxide for a kind of denitrating catalyst according to claim 4, it is characterized in that step 2 in preparation method) described double screw extruder is co-rotating conical twin-screw extruder, screw slenderness ratio >=52:1, screw speed 100-300rpm, each district's temperature is controlled at: a district 200-220 ℃; Two district 230-240 ℃; Three district 250-270 ℃; Four district 280-300 ℃; Five district 280-260 ℃, by the mixing dispersion of screw extruder, the surface hydroxyl Ti-OH of siloxicon active bond Si-C and titanium dioxide forms Ti-C-Si, thereby forms stable interstitial void.
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| US20030005772A1 (en) * | 2001-05-09 | 2003-01-09 | Frank Hegner | Device with moisture filter |
| CN1502039A (en) * | 2001-05-09 | 2004-06-02 | ������˹�ͺ�ɪ�����Ϲ�˾ | Device with moisture filter |
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