CN103752349B - A kind of titanium dioxide for denitration catalyst and preparation method thereof - Google Patents
A kind of titanium dioxide for denitration catalyst and preparation method thereof Download PDFInfo
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- CN103752349B CN103752349B CN201310726062.6A CN201310726062A CN103752349B CN 103752349 B CN103752349 B CN 103752349B CN 201310726062 A CN201310726062 A CN 201310726062A CN 103752349 B CN103752349 B CN 103752349B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 201
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 32
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 230000000694 effects Effects 0.000 claims abstract description 18
- 239000011800 void material Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000011859 microparticle Substances 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910018540 Si C Inorganic materials 0.000 claims abstract description 6
- 229910003089 Ti–OH Inorganic materials 0.000 claims abstract description 6
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 14
- -1 poly-methyl carbon silane Chemical compound 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- 230000001737 promoting effect Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-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
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000002994 raw material Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 9
- 229960005196 titanium dioxide Drugs 0.000 description 53
- 235000010215 titanium dioxide Nutrition 0.000 description 50
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 239000003546 flue gas Substances 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 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
- 230000008859 change Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002002 slurry Substances 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
- 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
- 239000002245 particle Substances 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IKXDEFIEGAVNOZ-UHFFFAOYSA-N [SiH4].[C] Chemical compound [SiH4].[C] IKXDEFIEGAVNOZ-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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application 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
- 230000007423 decrease 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
- 230000006872 improvement Effects 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
- 229910052710 silicon Inorganic materials 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
- 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 present invention proposes a kind of titanium dioxide for denitration catalyst and preparation method thereof.It is characterized in that: be made up of technical grade anatase titanium dioxide and carbon silicon polymer, 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.Preparation method of the present invention makes technical grade anatase titanium dioxide be refined to micron order by mechanical force fine dispersion, and utilize lattice modifier to extend in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap, utilize the mixing dispersion in conical screw extruder of carbon silicon polymer further, the surface hydroxyl Ti-OH of silicon-carbon active bond Si-C and titanium dioxide is made to form Ti-C-Si, thus form stable interstitial void, the growth of crystal grain is effectively stoped when high temperature, for not only there is less crystal grain and high surface during denitration catalyst carrier, and thermal adaptability is wide, being difficult to grow into rutile-type more than interstitial void during 1100 DEG C of high temperature, as supported active material V
2o
5time interstitial void active material and titanium dioxide generation crystalline phase can be stoped to react, ensure and improve activity and the service life of catalyst.
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 relates to the preparation method of this kind of titanium dioxide for denitration catalyst further.
Background technology
There is wide range of haze weather in China in recent years, affects by this, and a lot of local air quality is all the severe contamination of more than six grades.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.Nitrogen oxide (NOX) particularly in coal-fired flue-gas discharge forms nitric acid in atmosphere, causes the generation of PM2.5 particle, finally forms haze.What therefore nitrogen oxide (NOx) became current atmosphere pollution mainly contains one of harmful substances, except the nitrogen oxide (NOx) in flue gas removing is very urgent.SCR (selective catalytical reduction, being called for short 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, thus reach the object purified air.Due to SCR technology, to have reaction temperature lower, and the advantages such as purifying rate is high, reliable, and secondary pollution is little are gas denitrifying technologies most widely used at present.In SCR system, the performance of catalyst directly affects the removal effect of NOx, and with anatase titanium dioxide (TiO2) for carrier, load barium oxide, as active material, is the denitrating catalyst be most widely used at present.Wherein denitration catalyst carrier belongs to core material, and account for the 80%-90% of denitrating catalyst weight, its performance is directly connected to denitration rate.
Titanium dioxide owing to having good quantum size effect, skin effect, for having obvious advantage during catalyst carrier.Present stage can produce the TiO2 carrier being applicable to SCR catalyst abroad, and the preparation technology of the type TiO2 carrier is secrecy technology.The domestic preparation to denitration catalyst carrier TiO2 mainly adopts predecessor (as titanium sulfate, titanium tetrachloride, metatitanic acid etc., the titanate esters etc.) slurries of configuration titanium by mixing tungsten, activation dispersion, high-temperature roasting thus obtain Nano titanium dioxide, during denitration carrier, owing to being subject to high temperature impact, when more than 600 DEG C, the fine-grain of anatase titanium dioxide very easily grows and changes to rutile-type, cause the rigid reunion of large grain size, specific area declines, and catalytic activity declines.Its shortcoming is mainly reflected in that denitration efficiency is low, service life is short.Domestic is at present that the SCR catalyst denitration rate of carrier only has 80% ~ 85% with TiO2, and service life is about 25000h, if be subject to the impact of high-temperature flue gas, the life-span is shorter, not only adds denitration and does not reach requirement, and frequent to change engineering huge.
Chinese invention patent publication number CN101757907A discloses a kind of tungstenic titanium dioxide powder prepared for honeycomb-shaped SCR denitrating catalyst and preparation method thereof, metatitanic acid is made slurries A by the method, tungsten is dissolved in deionized water simultaneously and is prepared into solution B, then solution B is added in slurries A, through spraying dry, 300-550 DEG C calcining 3-7 hour, 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 be scattered in tungsten completely in titanium liquid and high-temperature calcination and obtaining, major part tungsten is covered by titanium dioxide, utilization rate significantly reduces, cost is caused to raise, increase higher than oxygen defect in lattice when 600 DEG C in particular for denitrating flue gas temperature, 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 nanometer titanium-dioxide denitration catalyst, the method is by substep doped metallic elements lanthanum and gold in titanium tetrachloride solution, obtained by high-temperature calcination, 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 DEG C, and catalytic activity too high or too low for temperature reduces all fast, and therefore 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 the product of preparing nano titanium oxide, this invention take titanium tetrachloride as raw material, realize adulterating in lattice by hydrolysis, by element dopings such as N, S, AL, Si, Sn, Fe, Cu in nano titanium oxide lattice, form lattice defect and there is higher photocatalytic activity.But this titanium dioxide is a kind of mixed crystal, containing 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 easily there is phase in version by temperatures involved in the crystal formation of anatase titanium dioxide titanium dioxide in actual applications, be applied to denitration catalyst carrier anatase titanium dioxide crystal grain when flue gas reaches more than 600 DEG C and constantly grow the rutile titanium dioxide being converted into large grain size, specific surface area of catalyst is finally caused to reduce, catalyst loses activity, denitration efficiency is low, and service life shortens.
Summary of the invention
The present invention is directed to the defect that above-mentioned denitration titanium dioxide exists, propose a kind of titanium dioxide for denitration catalyst, it is characterized in that titanium dioxide for denitration catalyst is made up of technical grade anatase titanium dioxide and carbon silicon polymer.
Further aim of the present invention is to provide a kind of preparation method of titanium dioxide for denitration catalyst, this preparation method makes technical grade anatase titanium dioxide be refined to micron order by mechanical force fine dispersion, and utilize lattice modifier to extend in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap, utilize the mixing dispersion in conical screw extruder of carbon silicon polymer further, the surface hydroxyl Ti-OH of silicon-carbon active bond Si-C and titanium dioxide is made to form Ti-C-Si, thus form stable interstitial void, the growth of crystal grain is effectively stoped when high temperature, for not only there is less crystal grain and high surface during denitration catalyst carrier, and thermal adaptability is wide, during high temperature more than 1100 DEG C, interstitial void is difficult to grow into rutile-type, as supported active material V
2o
5time interstitial void active material and titanium dioxide generation crystalline phase can be stoped to react, fully ensure and improve activity and the life-span of catalyst.
For achieving the above object, the technical scheme that the present invention takes is:
A kind of titanium dioxide for denitration catalyst of the present invention, it is characterized in that: be made up of technical grade anatase titanium dioxide and carbon silicon polymer, 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 selects other conventional anatase titanium dioxide of technical grade; Described carbon silicon polymer selects Polycarbosilane; At least one in bismuth phosphate, α-silicic acid molybdenum, aluminum phosphate, ferric phosphate selected by described lattice modifier.
In the composition of above-mentioned a kind of titanium dioxide for denitration catalyst, 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-methylhydroxy carbon silane, at least one in poly-ethyl carbon silane, by forming stable interstitial void with anatase titanium dioxide, when its outstanding advantage is the high temperature more than 1100 DEG C, carbon silicon polymer is to carbide conversion, can stablize and suppress the crystal transfer of anatase titanium dioxide, improve the activity of catalyst when high temperature and service life.
In the composition of above-mentioned a kind of titanium dioxide for denitration catalyst, described lattice modifier preferably phosphoric acid bismuth.
A kind of titanium dioxide for denitration catalyst 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, thus promoting the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increases lattice surface gap;
2) by step 1) titanium dioxide fine particles that obtains mixes with the carbon silicon polymer of 5-10 weight portion and sends into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy titanium dioxide for denitration catalyst at 300-400 DEG C of condition carbonization 10-20min.
In the preparation method of above-mentioned a kind of titanium dioxide for denitration catalyst, vibromill wherein 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 is formed, oscillator is equipped with between upper mill tube and lower mill tube, 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, thus promote the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap.
In the preparation method of above-mentioned a kind of titanium dioxide for denitration catalyst, wherein step 2) described in double screw extruder be co-rotating conical twin-screw extruder, screw slenderness ratio >=52:1, screw speed 100-300rpm, each district temperature controls: a district 200-220 DEG C; Two district 230-240 DEG C; Three district 250-270 DEG C; Four district 280-300 DEG C; Five district 280-260 DEG C, 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, thus forms stable interstitial void.
For checking titanium dioxide for denitration catalyst of the present invention is used for the adaptability of denitration catalyst carrier under different high temperature, embodiment 1 sample is calcined 5 hours respectively under 200 DEG C, 500 DEG C, 800 DEG C, 1100 DEG C, 1300 DEG C hot conditions, and utilizes X-ray diffractometer to analyze crystal phase structure under 5 kinds of temperature conditions and specific area.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 surface area m2/g | 312 | 345 | 352 | 348 | 341 |
According to test result, dioxide for denitration through use of titanium of the present invention keeps stable anatase titanium dioxide crystalline phase when high temperature, especially under 800 DEG C of conditions, specific area is the highest, the denitration of flue gas under 400-800 DEG C of condition can be ensured completely, even if run into superhigh temperature (more than 1100 DEG C) flue gas, specific area is without obvious reduction, and therefore titanium dioxide for denitration catalyst adaptive temperature of the present invention is wide, improves high temperature life.
The dioxide for denitration through use of titanium supported V that the embodiment of the present invention 1 is obtained
2o
5carry out the test of denitration rate, test adopts simulated flue gas (NO accounts for 95%), records: when 400 DEG C, denitration rate is greater than 98.2%; When 600 DEG C, denitration rate is greater than 99%.
By service life 25000 h commercially available denitrating catalyst and supported V of the present invention
2o
5carry out denitration test in service life, test condition is: power-plant flue gas denitration uses 30 days.Record: commercially available urge than agent specific area decline amplitude be 1.35%; Specific area fall of the present invention is 0.11%, and the crystal particles of catalyst is without phenomenon of uniting, and service life, apparently higher than commercial catalyst, extrapolates service life more than 50000h.
The present invention is directed to current domestic denitration titanium dioxide and easily sinter growth for there is high temperature crystal grain during denitration catalyst carrier, specific surface area of catalyst reduces, catalytic efficiency reduces, the defect that service life shortens, a kind of titanium dioxide for denitration catalyst is proposed, it is characterized in that the technical grade anatase titanium dioxide directly utilizing low cost, technical grade anatase titanium dioxide is made to be refined to micron order by mechanical force fine dispersion, and utilize lattice modifier to extend in lattice at anatase titanium dioxide microparticle surfaces, increase lattice surface gap, utilize the mixing dispersion in conical screw extruder of carbon silicon polymer further, the surface hydroxyl Ti-OH of silicon-carbon active bond Si-C and titanium dioxide is made to form Ti-C-Si, thus form stable interstitial void, the interstitial void that carbon silicon is formed on anatase titanium dioxide surface, the growth of crystal grain is effectively stoped when high temperature, for not only there is less crystal grain and surface-active during denitration catalyst carrier, and thermal adaptability is wide, even if be difficult to grow into rutile-type more than interstitial void during 1100 DEG C of high temperature in temperature, and as supported active material V
2o
5time interstitial void active material and titanium dioxide generation crystalline phase can be stoped to react, fully ensure and improve activity and the life-span of catalyst.
Compared with prior art, its outstanding feature is for a kind of titanium dioxide for denitration catalyst of the present invention and preparation method:
1, the present invention proposes a kind of titanium dioxide for denitration catalyst, directly be made up of technical grade anatase titanium dioxide and carbon silicon polymer, thus form stable interstitial void, not only crystal grain is little, active high, and interstitial void hinders the growth of crystal grain when high temperature, its denitration adaptive temperature wide ranges, have lasting activity at 200-800 DEG C, service life is more than 50000h;
2, the present invention proposes a kind of titanium dioxide for denitration catalyst, for during denitration catalyst carrier not with the active material V of load
2o
5generation crystalline phase is reacted, and when 400 DEG C, denitration rate is greater than 98.2%, and when 600 DEG C, denitration rate is greater than 99%, fully ensures and improves denitration efficiency;
3, the present invention proposes a kind of titanium dioxide for denitration catalyst, its preparation method adopts mechanical force and chemical to increase titanium dioxide fine particles surface Gibbs free energy, thus complete the improvement of lattice surface gap, the surface hydroxyl Ti-OH of silicon-carbon active bond Si-C and titanium dioxide is made to form Ti-C-Si by the Strong shear of conical screw extruder is mixing with dispersion, thus 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, be applicable to the denitration catalyst carrier of various high and low temperature flue gas.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram that the embodiment of the present invention 1 is calcined 5 hours under 1100 DEG C of conditions.
Detailed description of the invention
Below by way of detailed description of the invention, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from said method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
embodiment 1
1) by the α of the anatase titanium dioxide of 85 weight portions, 1 weight portion-silicic acid molybdenum 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, thus promoting the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increases lattice surface gap;
2) by step 1) the poly-methyl carbon silane mixture of the titanium dioxide fine particles that obtains and 10 weight portions evenly sends into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy titanium dioxide for denitration catalyst at 400 DEG C of condition carbonization 20min.
The sample obtained is calcined 5 hours under 200 DEG C, 500 DEG C, 800 DEG C, 1100 DEG C, 1300 DEG C hot conditions, and utilizes X-ray diffractometer to analyze crystal phase structure change 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 DEG C of conditions, specific area is the highest, the denitration of flue gas under 400-800 DEG C of condition can be ensured completely, even if run into superhigh temperature (more than 1100 DEG C) flue gas, also only have a small amount of crystal transition, and specific area is without obvious reduction, fully ensures catalytic activity and the denitration rate of denitration.Further, under 1300 DEG C of hot conditions, continue calcining 10 hours, rutile crystal type is less than 5%, and therefore this dioxide for denitration through use of titanium has high temperature resistant persistence.
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, thus promoting the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increases lattice surface gap;
2) by step 1) the poly-methyl ethoxy carbon silane mixture of the titanium dioxide fine particles that obtains and 8 weight portions evenly sends into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy titanium dioxide for denitration catalyst at 300 DEG C 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, thus promoting the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increases lattice surface gap;
2) by step 1) the poly-methyl trifluoro propyl carbon silane mixture of the titanium dioxide fine particles that obtains and 5 weight portions evenly sends into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy titanium dioxide for denitration catalyst at 350 DEG C of condition carbonization 20min.
Calcined 5 hours under 800 DEG C of hot conditions by the sample obtained, BET specific surface area is 322m2/g; Calcined 5 hours under 800 DEG C of hot conditions by sample load 5% V2O5, BET specific surface area is 325m2/g; Therefore the present invention does not make TiO2 that the phase transformation of anatase titanium dioxide to rutile-type occurs under the high temperature conditions, and after supported V 2O5, there is not vanadium titanium polymerisation in V2O5 and titanium dioxide under the high temperature conditions, ensure that the utilization rate of active material V2O5, extend 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, thus promoting the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increases lattice surface gap;
2) by step 1) the poly-methyl ethylene carbon silane mixture of the titanium dioxide fine particles that obtains and 10 weight portions evenly sends into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy titanium dioxide for denitration catalyst at 400 DEG C 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, thus promoting the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increases lattice surface gap;
2) by step 1) the poly-ethyl carbon silane mixture of the titanium dioxide fine particles that obtains and 5 weight portions evenly sends into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy titanium dioxide for denitration catalyst at 400 DEG C of condition carbonization 15min.
Claims (6)
1. a titanium dioxide for denitration catalyst, is characterized in that: be prepared from by the raw material of following weight ratio:
Anatase titanium dioxide 85-90 part,
Carbon silicon polymer 5-10 part,
Lattice modifier 1-3 part,
Wherein said anatase titanium dioxide selects other conventional anatase titanium dioxide of technical grade; Described carbon silicon polymer is Polycarbosilane; At least one in bismuth phosphate, α-silicic acid molybdenum, aluminum phosphate, ferric phosphate selected by described lattice modifier.
2. a kind of titanium dioxide for denitration catalyst according to claim 1, it is characterized in that: described Polycarbosilane is poly-methyl carbon silane, poly-methyl ethoxy carbon silane, poly-methyl trifluoro propyl carbon silane, poly-methyl ethylene carbon silane, at least one of gathering in methylhydroxy carbon silane, poly-ethyl carbon silane preferably, stable interstitial void can be formed with anatase titanium dioxide, when its outstanding advantage is the high temperature more than 1100 DEG C, carbon silicon polymer is to carbide conversion, can stablize and suppress the crystal transfer of anatase titanium dioxide.
3. a kind of titanium dioxide for denitration catalyst according to claim 1, is characterized in that: described lattice modifier preferably phosphoric acid bismuth.
4. a preparation method for titanium dioxide for denitration catalyst according to 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, thus promoting the generation of Mechanochemical Effect, lattice modifier extends in lattice at anatase titanium dioxide microparticle surfaces, increases lattice surface gap;
2) by step 1) titanium dioxide fine particles that obtains mixes with the carbon silicon polymer of 5-10 weight portion and sends into double screw extruder extruding pelletization;
3) by step 2) pellet that obtains obtains fluffy titanium dioxide for denitration catalyst at 300-400 DEG C of condition carbonization 10-20min.
5. the preparation method of titanium dioxide for denitration catalyst according to claim 4, it is characterized in that the vibromill in preparation method 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 is formed, oscillator is equipped with between upper mill tube and lower mill tube, 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, thus 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 denitration catalyst according to claim 4, it is characterized in that step 2 in preparation method) described in double screw extruder be co-rotating conical twin-screw extruder, screw slenderness ratio >=52:1, screw speed 100-300rpm, each district temperature controls: a district 200-220 DEG C; Two district 230-240 DEG C; Three district 250-270 DEG C; Four district 280-300 DEG C; Five district 280-260 DEG C, 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, thus forms stable interstitial void.
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