CN103127926A - Photocatalytic material used for nitric oxide catalytic purification and preparation method thereof - Google Patents
Photocatalytic material used for nitric oxide catalytic purification and preparation method thereof Download PDFInfo
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- CN103127926A CN103127926A CN 201110392237 CN201110392237A CN103127926A CN 103127926 A CN103127926 A CN 103127926A CN 201110392237 CN201110392237 CN 201110392237 CN 201110392237 A CN201110392237 A CN 201110392237A CN 103127926 A CN103127926 A CN 103127926A
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Abstract
The invention discloses a photocatalytic material used for nitric oxide catalytic purification and a preparation method thereof. The photocatalytic material is prepared by utilizing cordierite honeycomb ceramic as a carrier, coating the surface of the carrier evenly with a layer of nanometer titanium/aluminum oxide (TiO2/Al2O3) active coating, and loading rare earth oxide. The photocatalytic material comprises 1-10% of Al2O3, 5-20% of TiO2, and 70-94% of the cordierite honeycomb ceramic. The mass percent of the rare earth oxide is 0.1-5% of the mass of the TiO2/Al2O3 active coating. According to the photocatalytic material as a novel integrated type photocatalytic material, the highest conversion rate for nitric oxide after four hours can reach 81.2%. Sources of utilized raw materials are rich, preparation technology is simple, the prepared catalyst has good photocatalytic performance on the nitric oxide purification and is non-toxic, stability is good, cost is low, and catalytic activity is controllable.
Description
Technical field
The present invention relates to the Catalysts and its preparation method in a kind of depollution of environment field and heterogeneous catalysis technology field, specifically relate to a kind of for catalytic purification of nitroxide catalysis material and preparation method.
Background technology
Be the main energy because China's industrial combustion adopts coal mostly, major part belongs to direct burning, low-altitude discharged and flue-gas cleaning devices and falls behind, the nitrogen oxide (NO that discharges in flue gas
x) become main dusty gas.NO
xHealth hazard to human body and plant is very large, forms acid rain, acid mist, photochemical fog, damages the ozone layer etc., influence ecological environment.
The removal methods of nitrogen oxide mainly contains: catalytic reduction method, absorption method, liquid absorption method, bioanalysis, plasma method etc.Catalytic reduction method is to utilize different reducing agents, under the effect of uniform temperature and catalyst, is harmless N with reduction of nitrogen oxide
2And H
2O, catalyst commonly used have two kinds of non-selective reducing catalyst and selective reduction catalysts.What generally use now is selective reduction catalyst.Semiconductor light-catalyst gets more and more people's extensive concerning in sewage disposal and waste gas pollution control and treatment gradually in recent years.Due to nano-TiO
2Photocatalytic activity is high, and oxidability is strong, stable chemical nature, nontoxic, cost is low, more easily is carried on various carriers, so most light-catalyzed reaction is all with nano-TiO
2Be catalyst.But nano-TiO
2There are easy inactivation, the easy shortcoming such as cohesion and difficult recovery.With cordierite honeycomb ceramic as nano-TiO
2Carrier can improve decentralization and the catalytic activity of catalyst, solve catalyst and easily condense the problems such as difficult recovery.Be used at present load TiO
2Carrier zeolite is arranged, mesopore molecular sieve, active carbon, silica gel, glass fibre etc.
Prior art discloses a kind of nitrogen oxides in effluent selective reduction catalyst and its preparation method and application, and this catalyst adopts the sol-gel process substep with Al
2O
3And TiO
2Load on ceramic monolith respectively, then carrier be impregnated in repeatedly in the mixed aqueous solution of ammonium metavanadate, ammonium molybdate, ammonium tungstate, the drying roasting makes finished catalyst.Catalyst 250～550 ℃, ammonia nitrogen can be up to 98% to the removal efficiency of NOx than 0.6～1.6 o'clock.But because reaction temperature is higher, be not suitable for removing of NOx under normal temperature, and in catalyst preparation process in order to make Al
2O
3, TiO
2Reach setting value with the load capacity of active component, adopt repeatedly the method for dipping to increase preparation technology's loaded down with trivial details property.
Prior art also discloses a kind of preparation method of carbon nanometer tube loaded type modified Nano catalysis material of the nitrogen oxide of degrading, the nano titanium oxide mixed crystal to be placed in put into liquor argenti nitratis ophthalmicus after the ultrasonic dispersion of water and obtain silver ion modified nano-titanium dioxide mixed crystal, be mixed to get carbon nanometer tube loaded type modified Nano catalysis material with CNT again, this catalysis material possess under better nitrogen oxide photocatalysis effect, especially visible light effect be improved significantly.This catalysis material under visible light to continuously by concentration be the photocatalysis efficiency of nitrogen dioxide of 30 ppm only up to 76.5%, and along with the reaction time extends, photocatalysis efficiency descends very fast, successive reaction is after 7.5 hours, photocatalysis efficiency is down to 48.3%.
Summary of the invention
The object of the present invention is to provide a kind of catalysis material for the NOx catalytic purification and preparation method thereof.The present invention is achieved by the following technical solutions:
The invention provides and a kind ofly it is characterized in that for the catalytic purification of nitroxide catalysis material, this catalysis material is take cordierite honeycomb ceramic as carrier, nano titanium oxide/alundum (Al2O3) (TiO
2/ Al
2O
3) be active coating, the supported rare earth oxide modifying is prepared from; Described catalysis material component and mass percent are: alundum (Al2O3) is 1～10%, nano titanium oxide is 5～20%, and cordierite honeycomb ceramic is 70～94%; The mass percent of rare earth oxide is 0.1～5% of nano titanium oxide/alundum (Al2O3) active coating quality.
Described rare earth oxide is a kind of or its combination in cerium oxide, neodymia, lanthana, thorium oxide, gadolinium oxide, yittrium oxide, terbium oxide, dysprosia.
The invention provides a kind of preparation method for the catalytic purification of nitroxide catalysis material, it is characterized in that comprising the following steps:
The first step, with boehmite, ethylene glycol, butyl titanate, deionized water is mixed making beating and is made slurry, is 2.5～4 with rare nitric acid adjusting slurry pH value;
Second step, cordierite honeycomb ceramic carrier be impregnated in slurry 5～10 minutes, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 80～150 ℃ of oven dry, 500～700 ℃ of roastings 2～6 hours make and contain the ceramic monolith that nano titanium oxide/alundum (Al2O3) is active coating;
The rare-earth metal nitrate solution of the 3rd step, preparation desired concn, the ceramic monolith that will contain active coating was placed in one incipient impregnation after 1～5 hour, in 60～150 ℃ of dryings 2～10 hours, then 500～600 ℃ of lower roastings 2～6 hours, make finished catalyst.
Described rare-earth metal nitrate is a kind of or its combination in cerous nitrate, neodymium nitrate, lanthanum nitrate, thorium nitrate, gadolinium nitrate, yttrium nitrate, terbium nitrate, dysprosium nitrate.
The Model-46i HL type NOx analyzer that in the present invention, nitrous oxides concentration adopts U.S. power ﹠ light company to produce records that in unstripped gas, nitrous oxides concentration is 10 ppm, NO and NO
2Ratio is about 9:1, and light source adopts visible light or ultraviolet light all can.
Compared with prior art, it is carrier that the present invention adopts cordierite honeycomb ceramic, evenly applies one deck nano-TiO at carrier surface
2/ Al
2O
3Active coating, the supported rare earth Preparation forms.The present invention has the following advantages: as a kind of novel monoblock type catalysis material, NOx had good purifying property, after 4 hours, transformation efficiency of the oxides of nitrogen is up to 81.2%, the raw material that adopt are originated abundant, preparation technology is simple, purification has good photocatalysis performance, stablizes prepared catalyst to NOx, and with low cost, catalytic activity is controlled and nontoxic.
The specific embodiment
The below elaborates to embodiments of the invention: the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Blank sample:
With 2 g boehmites, 0.5 g ethylene glycol, 2.26 g butyl titanates, 15 g deionized waters are mixed making beating and are made slurry, and regulating slurry pH value with rare nitric acid is 3; 5 cm*5 cm*1 cm cordierite honeycomb ceramic carriers be impregnated in 5 min in slurry, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 150 ℃ of oven dry, 500 ℃ of roasting 4 h make and contain nano-TiO
2/ Al
2O
3Ceramic monolith for active coating.
Embodiment 1:
With 2 g boehmites, 0.5 g ethylene glycol, 2.26 g butyl titanates, 15 g deionized waters are mixed making beating and are made slurry, and regulating slurry pH value with rare nitric acid is 3; 5 cm*5 cm*1 cm cordierite honeycomb ceramic carriers be impregnated in 5min in slurry, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 150 ℃ of oven dry, 500 ℃ of roasting 4 h make and contain nano-TiO
2/ Al
2O
3Ceramic monolith for active coating.
The cerous nitrate that takes 0.025 g is dissolved in and is mixed with maceration extract in deionized water, and the ceramic monolith that will contain active coating is placed in one after incipient impregnation 2 h, in 120 ℃ of drying 4 h, then in 600 ℃ of lower roasting 3 h, makes finished catalyst.
Embodiment 2:
With 2 g boehmites, 0.5 g ethylene glycol, 2.82 g butyl titanates, 20 g deionized waters are mixed making beating and are made slurry, and regulating slurry pH value with rare nitric acid is 3; 5 cm*5 cm*1 cm cordierite honeycomb ceramic carriers be impregnated in 5 min in slurry, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 150 ℃ of oven dry, 500 ℃ of roasting 4 h make and contain nano-TiO
2/ Al
2O
3Ceramic monolith for active coating.
The yttrium nitrate that takes 0.0339 g is dissolved in and is mixed with maceration extract in deionized water, and the ceramic monolith that will contain active coating is placed in one after incipient impregnation 2 h, in 120 ℃ of drying 4 h, then in 600 ℃ of lower roasting 3 h, makes finished catalyst.
Embodiment 3:
With 2 g boehmites, 0.5 g ethylene glycol, 2.82 g butyl titanates, 20 g deionized waters are mixed making beating and are made slurry, and regulating slurry pH value with rare nitric acid is 3; 5 cm*5 cm*1 cm cordierite honeycomb ceramic carriers be impregnated in 5 min in slurry, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 150 ℃ of oven dry, 500 ℃ of roasting 4 h make and contain nano-TiO
2/ Al
2O
3Ceramic monolith for active coating.
The lanthanum nitrate that takes 0.0266 g is dissolved in and is mixed with maceration extract in deionized water, and the ceramic monolith that will contain active coating is placed in one after incipient impregnation 2 h, in 120 ℃ of drying 4 h, then in 600 ℃ of lower roasting 3 h, makes finished catalyst.
Embodiment 4:
With 2 g boehmites, 0.5 g ethylene glycol, 2.82 g butyl titanates, 20 g deionized waters are mixed making beating and are made slurry, and regulating slurry pH value with rare nitric acid is 3; 5 cm*5 cm*1 cm cordierite honeycomb ceramic carriers be impregnated in 5 min in slurry, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 150 ℃ of oven dry, 500 ℃ of roasting 4 h make and contain nano-TiO
2/ Al
2O
3Ceramic monolith for active coating.
The neodymium nitrate that takes 0.026 g is dissolved in and is mixed with maceration extract in deionized water, and the ceramic monolith that will contain active coating is placed in one after incipient impregnation 2 h, in 120 ℃ of drying 4 h, then in 600 ℃ of lower roasting 3 h, makes finished catalyst.
Embodiment 5:
With 2 g boehmites, 0.5 g ethylene glycol, 2.82 g butyl titanates, 20 g deionized waters are mixed making beating and are made slurry, and regulating slurry pH value with rare nitric acid is 3; 5 cm*5 cm*1 cm cordierite honeycomb ceramic carriers be impregnated in 5 min in slurry, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 150 ℃ of oven dry, 500 ℃ of roasting 4 h make and contain nano-TiO
2/ Al
2O
3Ceramic monolith for active coating.
The dysprosium nitrate that takes 0.0186 g is dissolved in and is mixed with maceration extract in deionized water, and the ceramic monolith that will contain active coating is placed in one after incipient impregnation 2 h, in 120 ℃ of drying 4 h, then in 600 ℃ of lower roasting 3 h, makes finished catalyst.
The photocatalytic activity of table 1 catalyst to NOx
| NOx purification efficiency/% | Blank sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| 1h | 57.3 | 76.9 | 82.6 | 93.4 | 91.5 | 81.0 |
| 2h | 41.8 | 57.1 | 76.4 | 74.1 | 86.7 | 63.8 |
| 4h | 21.6 | 43.9 | 70.9 | 59.7 | 81.2 | 41.5 |
Claims (4)
1. one kind is used for the catalytic purification of nitroxide catalysis material, it is characterized in that, this catalysis material is take cordierite honeycomb ceramic as carrier, nano titanium oxide/alundum (Al2O3) (TiO
2/ Al
2O
3) be active coating, the supported rare earth oxide modifying is prepared from; Described catalysis material component and mass percent are: alundum (Al2O3) is 1～10%, nano titanium oxide is 5～20%, and cordierite honeycomb ceramic is 70～94%; The mass percent of rare earth oxide is 0.1～5% of nano titanium oxide/alundum (Al2O3) active coating quality.
2. a kind of for the catalytic purification of nitroxide catalysis material according to claim 1, it is characterized in that, described rare earth oxide is a kind of or its combination in cerium oxide, neodymia, lanthana, thorium oxide, gadolinium oxide, yittrium oxide, terbium oxide, dysprosia.
3. according to claim 1, or 2 described a kind of preparation methods for the catalytic purification of nitroxide catalysis material, it is characterized in that comprising the following steps:
The first step, with boehmite, ethylene glycol, butyl titanate, deionized water is mixed making beating and is made slurry, is 2.5～4 with rare nitric acid adjusting slurry pH value;
Second step, cordierite honeycomb ceramic carrier be impregnated in slurry 5～10 minutes, then purge the unnecessary slurry in ceramic monolith surface by pressure-air, at last with ceramic monolith in 80～150 ℃ of oven dry, 500～700 ℃ of roastings 2～6 hours make and contain the ceramic monolith that nano titanium oxide/alundum (Al2O3) is active coating;
The rare-earth metal nitrate solution of the 3rd step, preparation desired concn, the ceramic monolith that will contain active coating was placed in one incipient impregnation after 1～5 hour, in 60～150 ℃ of dryings 2～10 hours, then 500～600 ℃ of lower roastings 2～6 hours, make finished catalyst.
4. a kind of preparation method for the catalytic purification of nitroxide catalysis material according to claim 3, it is characterized in that, described rare-earth metal nitrate is a kind of or its combination in cerous nitrate, neodymium nitrate, lanthanum nitrate, thorium nitrate, gadolinium nitrate, yttrium nitrate, terbium nitrate, dysprosium nitrate.
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|---|---|---|---|
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|---|---|---|---|
| CN 201110392237 CN103127926A (en) | 2011-12-01 | 2011-12-01 | Photocatalytic material used for nitric oxide catalytic purification and preparation method thereof |
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| CN107159304A (en) * | 2017-05-09 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of honeycomb catalyst of nano rare earth doping and preparation method thereof |
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| CN107159304A (en) * | 2017-05-09 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of honeycomb catalyst of nano rare earth doping and preparation method thereof |
| CN109225181A (en) * | 2018-08-10 | 2019-01-18 | 江苏大学 | A kind of hollow boron glass microballoon@TiO2The preparation method and its usage of catalyst |
| CN113318719A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalytic unit and application thereof |
| CN113318722A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst and preparation method and application thereof |
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| CN113318726A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst with negative oxygen ion releasing function and preparation method and application thereof |
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| CN113318721B (en) * | 2020-02-28 | 2023-08-01 | 中科粤能净(山东)新材料有限公司 | Photocatalysis unit with negative oxygen ion release function and application thereof |
| CN112573734A (en) * | 2020-12-01 | 2021-03-30 | 苏州美源达环保科技股份有限公司 | Environment-friendly discharge method of ammonia nitrogen wastewater in regeneration and recycling process of etching solution |
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Application publication date: 20130605 |