CN109603922A - A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst - Google Patents
A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst Download PDFInfo
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- CN109603922A CN109603922A CN201811445470.3A CN201811445470A CN109603922A CN 109603922 A CN109603922 A CN 109603922A CN 201811445470 A CN201811445470 A CN 201811445470A CN 109603922 A CN109603922 A CN 109603922A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000004113 Sepiolite Substances 0.000 claims abstract description 14
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 14
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 14
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 4
- GYXHHICIFZSKKZ-UHFFFAOYSA-N 2-sulfanylacetamide Chemical compound NC(=O)CS GYXHHICIFZSKKZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052726 zirconium Inorganic materials 0.000 claims 2
- 238000001125 extrusion Methods 0.000 abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 210000001161 mammalian embryo Anatomy 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000004519 manufacturing process 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
A kind of composite titanium dioxide and preparation method thereof for high-ratio surface denitrating catalyst, is made of following substance percentage by weight: 100 parts of titanium dioxides, 9-21 parts of activated diatomaceous earths, 4-11 parts of sepiolite powders, 2.8-5.6 parts of zirconium oxides, 0.8-7.9 parts of ammonium paratungstates, 0.5-5.8 parts of cerium oxide, 0.6-2.8 parts of bridging silsesquioxanes, 0.1-0.28 parts of hyper-dispersants.The catalyst pug that the composite titanium dioxide that the present invention is prepared is prepared has the characteristics that plasticity is high, water retention property is good, extrusion is smooth, and the specific surface area of catalyst being prepared is higher than conventional catalyst.
Description
Technical field
The present invention relates to denitrating catalyst preparation technical fields more particularly to a kind of for high-ratio surface denitrating catalyst
Composite titanium dioxide and preparation method thereof.
Background technique
Nitrogen oxide NOx (NO, NO2And N2O) be global atmosphere pollution one of major pollutants, cause photochemical fog,
The environmental problems such as acid rain, depletion of the ozone layer seriously affect the living environment and quality of life of people, attract wide attention, control
The discharge amount of NOx processed has great significance for improving air quality, construction Eco-friendly society.In numerous denitration sides
In method, selective catalytic reduction (SCR) is efficient with it, mature, stable denitration performance gradually occupies industrial denitration field and leads
Head status, currently, most common SCR denitration is medium temperature (300-420 DEG C), 18 hole homogeneous catalysis, still, some
Gas fired-boiler, or after dust-removal and desulfurizing, dustiness and the relatively low boiler of sulfur content, are urged using conventional 18 holes in flue gas
Agent can have the problems such as catalyst usage amount is big, and catalytic inner flow velocity is high, and denitration efficiency is low, therefore, 30 holes, 40 holes, 50
The high-ratio surface denitrating catalyst of the even higher hole count in hole comes into being.
Chinese patent CN201610891414.7 discloses a kind of for NH in denitrating flue gas4HSO4The vanadium base of decomposition is compound
The preparation method of titanium dioxide catalyst, the load and vanadium base of preparation, vanadium including composite titanium dioxide on composite titanium dioxide are compound
The roasting of titanium dioxide；It is compound that vanadium base has been prepared by loading a certain amount of vanadic anhydride on composite titanium dioxide in the present invention
Titanium dioxide catalyst reduces the decomposition temperature of ammonium hydrogen sulfate；The preparation method simple process, strong operability, are applicable to
Heavy industrialization.
Chinese patent CN201010513687.0 discloses a kind of for removing the catalyst of NOx comprising major catalyst,
Carrier and glass fibre, the major catalyst are the vanadic anhydride (V2O5) for accounting for weight percentage and being 0.05~3%, institute
Stating carrier is the composite titanium dioxide for accounting for weight percentage and being 85%~97%, and the glass fibre accounts for weight percentage and is
3%~7%；Its manufacturing method is that raw material is mediated, filters aging, extrusion forming, drying, roasting reinforcing, cutting finished product, end
Face hardening, detection packaging and exhaust-gas treatment manufacture high value added product and waste water recycling and the grinding reuse of dust waste etc.
Auxiliary process.Catalyst of the invention realizes green zero-emission in preparation, can be used for removing NOx and takes off suitable for SCR
Nitre technique, while the activity of catalyst has obtained stabilization with the service life, is an important breakthrough of catalyst industry.
But directly prepare that high there is pug viscosity than table catalyst using conventional titanium white powder and common process at present
Not enough, the problems such as water retention property is bad, and plasticity is bad results in the catalyst mud embryo appearance that catalyst extruded velocity is slow and squeezes out
The problems such as easy to crack, yield rate is extremely low, and therefore, developing a kind of dedicated composite titanium dioxide of high-ratio surface denitrating catalyst is extremely
It is necessary.
Summary of the invention
Height is directly prepared the purpose of the present invention is to solve conventional titanium white powder and common process to exist than table catalyst
Pug viscosity not enough, the problems such as water retention property is bad, and plasticity is bad, result in that catalyst extruded velocity is slow and what is squeezed out urges
Agent mud embryo is easy the problems such as cracking, provides a kind of composite titanium dioxide dedicated for preparing high-specific surface area denitrating catalyst
Preparation process, the catalyst pug that the composite titanium dioxide being prepared is prepared has that plasticity is high, water retention property is good, squeezes out
Smooth feature, the specific surface area of catalyst being prepared are higher than conventional catalyst.
The invention adopts the following technical scheme:
Composite titanium dioxide for high-ratio surface denitrating catalyst of the invention is made of by weight following substance:
100 parts of titanium dioxides, 9-21 parts of activated diatomaceous earths, 4-11 parts of sepiolite powders, 2.8-5.6 parts of zirconium oxides, 0.8-7.9 parts of para-tungstic acids
Ammonium, 0.5-5.8 part cerium oxide, 0.6-2.8 parts of bridging silsesquioxanes, 0.1-0.28 parts of hyper-dispersants.
One of as a preferred technical scheme: composite titanium dioxide of the invention is made of by weight following substance: 100
Part titanium dioxide, 12 parts of activated diatomaceous earths, 8 parts of sepiolite powders, 4 parts of zirconium oxides, 0.8 part of ammonium paratungstate, 0.8 part of cerium oxide, 1 part of bridge
Join silsesquioxane, 0.1 part of hyper-dispersant.
The bridging silsesquioxane is KH560-660 and/or KH560-540.
The hyper-dispersant is end mercaptoacetylamide polymethyl acrylate.
The preparation method of composite titanium dioxide for high-ratio surface denitrating catalyst of the invention, it is characterised in that: described
Specific step is as follows for method:
(1) titanium dioxide, activated diatomaceous earth, zirconium oxide, ammonium paratungstate, cerium oxide, bridging silsesquioxane, demineralized water are mixed
It closes, suspension is made, suspension mass concentration is 25%-35%, stirs 0.5-2h at 30-80 DEG C；
(2) suspension in step (1) is placed in ball mill, carries out wet ball grinding after hyper-dispersant is added, ball milling is complete
At rear washing and drying；
(3) it can be obtained after being sufficiently mixed composite powder obtained in step (2) and sepiolite powder in blender
To the composite titanium dioxide for being used to prepare high-ratio surface denitrating catalyst.
In step (1), 1h preferably is stirred at 50 DEG C.
In step (1), preferably suspension mass concentration is 30%.
In step (2), ball milling granularity is 2000-5000 mesh.
In step (3), sepiolite powder granularity is 800-1500 mesh.
In step (3), mixing time 1-2h.
The beneficial effects of the present invention are:
(1) present invention improves the modeling of pug by increasing Component Vectors ingredient activated diatomaceous earth and Activated Sepiolite powder
Property, improve the mobility and water-retaining property of pug by adjusting the grain composition of different carriers component powders.
(2) present invention improves powder property by addition part of the metal oxide active constituent zirconium oxide and cerium oxide,
The denitration activity of product is improved simultaneously.
(3) present invention uses bridging silsesquioxane to improve powder characteristics as surfactant, and powder is prepared
Pug have preferably viscosity, while the organic long-chain being embedded after calcining can catalytic inner formed large number of orifices
Road improves the specific surface area of catalyst.
(4) the catalyst pug that the composite titanium dioxide that the present invention is prepared is prepared has plasticity height, water retention property
Well, smooth feature is squeezed out, the specific surface area of catalyst being prepared is higher than conventional catalyst.
Specific embodiment
The embodiment recorded herein is specific specific embodiment of the invention, for illustrating design of the invention,
Be it is explanatory and illustrative, should not be construed as the limitation to embodiment of the present invention and the scope of the invention.Except what is recorded herein
Outside embodiment, those skilled in the art can also based on the claim of this application book and specification disclosure of that using aobvious and
The other technical solutions being clear to, these technical solutions include using any obvious to making for the embodiment recorded herein
The technical solution of substitutions and modifications.
Embodiment 1
By 500kg titanium dioxide, 60kg activated diatomaceous earth, 20kg zirconium oxide, 4kg cerium oxide, secondary tungsten acid ammonium solution (WO3It accounts for
Total mass ratio 5%), the mixing of 5kg bridging silsesquioxane KH560-660 and 1300L demineralized water, then 50 DEG C of stirring 1h turn
It moves in ball mill, the end 0.5kg mercaptoacetylamide polymethyl acrylate is added and carries out wet ball-milling, grind size is 5000 mesh.
It is washed after grinding and dry.The powder and 40kg Activated Sepiolite powder (1000 mesh) obtained after the completion of will be dry is in blender
The high-specific surface area denitrating catalyst specific complex titanium dioxide is obtained after middle stirring 1.5h.
Embodiment 2
By 500kg titanium dioxide, 80kg activated diatomaceous earth, 10kg zirconium oxide, 2.5kg cerium oxide, secondary tungsten acid ammonium solution (WO3
Account for total mass ratio 5%), 6kg bridging silsesquioxane KH560-660 and 1400L demineralized water mixing, 50 DEG C of stirring 1h, then
It is transferred in ball mill, 0.5kg hyper-dispersant is added and carries out wet ball-milling, grind size is 4000 mesh.It is washed after grinding
And it is dry.The powder obtained after the completion of will be dry obtains after stirring 2h in blender with 40kg Activated Sepiolite powder (800 mesh)
The high-specific surface area denitrating catalyst specific complex titanium dioxide.
Embodiment 3
By 500kg titanium dioxide, 90kg activated diatomaceous earth, 12kg zirconium oxide, 10kg cerium oxide, secondary tungsten acid ammonium solution (WO3It accounts for
Total mass ratio 5%), the mixing of 8kg bridging silsesquioxane KH560-660 and 1400L demineralized water, then 50 DEG C of stirring 1h turn
It moves in ball mill, 0.5kg hyper-dispersant is added and carries out wet ball-milling, grind size is 5000 mesh.It is washed simultaneously after grinding
It is dry.The powder and 40kg Activated Sepiolite powder (800 mesh) obtained after the completion of will be dry obtains institute after stirring 2h in blender
State high-specific surface area denitrating catalyst specific complex titanium dioxide.
Embodiment 4
By 500kg titanium dioxide, 80kg activated diatomaceous earth, 12kg zirconium oxide, 10kg cerium oxide, secondary tungsten acid ammonium solution (WO3It accounts for
Total mass ratio 5%), the mixing of 8kg bridging silsesquioxane KH560-660 and 1400L demineralized water, then 50 DEG C of stirring 1h turn
It moves in ball mill, 0.5kg hyper-dispersant is added and carries out wet ball-milling, grind size is 3000 mesh.It is washed simultaneously after grinding
It is dry.The powder obtained after the completion of will be dry obtains after stirring 1.5h in blender with 40kg Activated Sepiolite powder (1000 mesh)
The high-specific surface area denitrating catalyst specific complex titanium dioxide.
The pug that moisture is 28% is prepared using above-described embodiment respectively, at room temperature by the same quality of same shape
The naked leakage of pug sample surveys its weight-loss ratio every 4h, the results are shown in Table 1 in outdoor:
Table 1
| Sample | 4 hours | 8 hours | 12 hours | 16 hours | 20 hours |
| Embodiment 1 | 0.3% | 0.5% | 0.9% | 1.2% | 1.5% |
| Embodiment 2 | 0.6% | 0.9% | 1.3% | 1.6% | 2.0% |
| Embodiment 3 | 0.6% | 0.8% | 1.2% | 1.6% | 1.9% |
| Embodiment 4 | 0.5% | 0.7% | 1.0% | 1.3% | 1.7% |
| Conventional titanium dioxide | 1.2% | 2.1% | 3.3% | 4.5% | 6.1% |
It can significantly see that the pug water retention property of embodiment powder preparation is better than conventional pug.
The extrusion for carrying out catalyst mud embryo using above-mentioned pug respectively, records the ratio of extruded velocity and last finished catalyst
Surface area and denitration efficiency (standard laboratory conditions: temperature: 380 DEG C；NOx:500ppm；SO2:≤100ppm；O2: 5%；H2O:
10%；NH3/ NOx:1/1；Lv:6m/s.):
Table 2
This it appears that using this method prepare composite titanium dioxide made from plasticity of slurry it is more preferable, in extrusioning catalyst
When extruded velocity faster, the specific surface area of catalyst being prepared is higher, and denitration efficiency is also higher.
Claims (10)
1. a kind of composite titanium dioxide for high-ratio surface denitrating catalyst, it is characterised in that: the composite titanium dioxide be by
Following substance forms by weight: 100 parts of titanium dioxides, 9-21 parts of activated diatomaceous earths, 4-11 parts of sepiolite powders, 2.8-5.6 parts of oxygen
Change zirconium, 0.8-7.9 parts of ammonium paratungstates, 0.5-5.8 parts of cerium oxide, 0.6-2.8 parts of bridging silsesquioxanes, 0.1-0.28 parts of oversubscription
Powder.
2. being used for the composite titanium dioxide of high-ratio surface denitrating catalyst as described in claim 1, it is characterised in that: described answers
It closes titanium dioxide to be made of by weight following substance: 100 parts of titanium dioxides, 12 parts of activated diatomaceous earths, 8 parts of sepiolite powders, 4 parts of oxygen
Change zirconium, 0.8 part of ammonium paratungstate, 0.8 part of cerium oxide, 1 part of bridging silsesquioxane, 0.1 part of hyper-dispersant.
3. being used for the composite titanium dioxide of high-ratio surface denitrating catalyst as described in claim 1, it is characterised in that: the bridge
Connection silsesquioxane is KH560-660 and/or KH560-540.
4. being used for the composite titanium dioxide of high-ratio surface denitrating catalyst as described in claim 1, it is characterised in that: described is super
Dispersing agent is end mercaptoacetylamide polymethyl acrylate.
5. a kind of side for preparing the composite titanium dioxide according to any one of claims 1-4 for high-ratio surface denitrating catalyst
Method, it is characterised in that: specific step is as follows for the method:
(1) titanium dioxide, activated diatomaceous earth, zirconium oxide, ammonium paratungstate, cerium oxide, bridging silsesquioxane, demineralized water are mixed,
Suspension is made, suspension mass concentration is 25%-35%, stirs 0.5-2h at 30-80 DEG C；
(2) suspension in step (1) is placed in ball mill, carries out wet ball grinding after hyper-dispersant is added, after the completion of ball milling
It washs and dries；
(3) use can be obtained after being sufficiently mixed composite powder obtained in step (2) and sepiolite powder in blender
In the composite titanium dioxide for preparing high-ratio surface denitrating catalyst.
6. preparation method as claimed in claim 5, it is characterised in that: in step (1), stir 1h at 50 DEG C.
7. preparation method as claimed in claim 5, it is characterised in that: in step (1), suspension mass concentration is 30%.
8. preparation method as claimed in claim 5, it is characterised in that: in step (2), ball milling granularity is 2000-5000 mesh.
9. preparation method as claimed in claim 5, it is characterised in that: in step (3), sepiolite powder granularity is 800-1500
Mesh.
10. preparation method as claimed in claim 5, it is characterised in that: in step (3), mixing time 1-2h.
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