CN102266761A - SCR (selective catalyctic reduction) flue gas denitration catalyst based on TiO2-ZrO2 composite carrier and preparation method thereof - Google Patents

SCR (selective catalyctic reduction) flue gas denitration catalyst based on TiO2-ZrO2 composite carrier and preparation method thereof Download PDF

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CN102266761A
CN102266761A CN 201110158422 CN201110158422A CN102266761A CN 102266761 A CN102266761 A CN 102266761A CN 201110158422 CN201110158422 CN 201110158422 CN 201110158422 A CN201110158422 A CN 201110158422A CN 102266761 A CN102266761 A CN 102266761A
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flue gas
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CN102266761B (en
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张俊姣
陆强
苏淑华
杨勇平
董长青
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Beijing Huadian Everbright environmental Limited by Share Ltd
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North China Electric Power University
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Abstract

The invention mainly relates to a SCR (selective catalyctic reduction) flue gas denitration catalyst based on a TiO2-ZrO2 composite metal oxide carrier, belonging to the field of environment protection and environment catalysis. According to the invention, with the nanometer TiO2-ZrO2 as a carrier, WO3 and CeO2 as assistants and V2O5 as an active component, a low-and-medium temperature flue gas denitration catalyst based on the TiO2-ZrO2 composite carrier is obtained. The nanometer TiO2-ZrO2 substitutes the traditional nanometer TiO2 and is used as a carrier, thus the specific area, the heat stability and the acidity of the catalyst are improved; and denitration activity of the catalyst is improved through mutual action among V2O5, WO3 and CeO2; when the ammonia is used as a reducing agent, the catalyst can show very good catalyzing activity at150-450 DEG C.

Description

Based on TiO<sub〉2</sub 〉-ZrO<sub〉2</sub〉the SCR catalyst for denitrating flue gas and the preparation method of complex carrier
Technical field
The invention belongs to environmental protection and environmental catalysis field, be specifically related to a kind of novel based on TiO 2-ZrO 2The SCR catalyst for denitrating flue gas of composite metal oxide carrier.
Background technology
Nitrogen oxide (NOx) is main atmosphere pollution, and the destruction that can cause acid rain, photochemical fog, greenhouse effects and ozone layer also has serious harm to health.The NOx63% of occurring in nature industrial pollution and traffic pollution are 2 times of naturally-occurring source, and wherein the discharging of power industry accounts for 40%, and discharging therefore how effectively to control coal fired power plant NOx enjoys people to pay close attention to.It is a global environment problem that NOx pollutes, and various countries are also strict day by day to the requirement of NOx discharging in recent years.In all kinds of denitration technologies, ammine selectivity catalytic reduction (SCR) method since its denitration efficiency, selectivity are good efficiently, and technology maturation is a main coal fired power plant denitration technology at present.
The key of SCR denitration technology is a catalyst.The catalyst of the active height of exploitation, Heat stability is good, good endurance is the emphasis of research.The present NH of stationary source power plant 3-SCR generally uses V 2O 5/ WO 3/ TiO 2Commercial catalysts, wherein V 2O 5Be active component, bringing into play main catalytic effect; WO 3Be auxiliary agent, can further improve heat endurance, denitration activity and the anti-middle toxicity of catalyst; Detitanium-ore-type TiO 2Be carrier, have sulfur poisoning-resistant ability preferably, sulfate is at TiO 2The stability on surface is also than a little less than other oxide surfaces.Yet the denitrating catalyst catalytic activity temperature range of this commerce is narrower, normally 300-400 ℃, and also catalytic activity also awaits further raising.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, SCR catalyst for denitrating flue gas of a kind of active height, Heat stability is good, active temperature windows broad and preparation method thereof is provided, this catalyst utilizes composite metal oxide TiO 2-ZrO 2Be carrier, substantially improve the performance of carrier, pass through simultaneously and V 2O 5, WO 3And CeO 2Between interaction, improved the denitration activity of catalyst and widened the catalytic activity temperature window.
Consisting of of this denitrating catalyst: at nano-TiO 2-ZrO 2On the complex carrier, load auxiliary agent WO 3And CeO 2, active component V 2O 5Common formation composite catalyst; Wherein, at described nano-TiO 2-ZrO 2In the complex carrier, TiO 2Shared mass percent is 50-95%; In the composite catalyst that makes, TiO 2-ZrO 2Mass percent be 83.5-94.5%, V 2O 5, WO 3, CeO 2Shared separately mass percent is respectively 0.5-1.5%, 4-10% and 1-5%.
A kind of based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier may further comprise the steps:
(1) preparation of complex carrier:
Measure a certain amount of titanium source, slowly splash into to the ethanol solution of 4-10 times of volume, measure a certain amount of zirconium source in addition and slowly splash into to the above-mentioned ethanol solution that contains the titanium source, make the TiO that finally obtains 2-ZrO 2TiO in the composite metal oxide 2Shared mass percent is 50-95%; Under intense stirring condition, slowly drip precipitating reagent and reach about 9 until the pH value, obtain precipitation of hydroxide and leave standstill certain hour; Then said mixture is filtered, washs, uses AgNO 3Detection, dry, roasting promptly obtain nano-TiO 2-ZrO 2Composite metal oxide;
(2) load of complex carrier auxiliary agent and active component:
According to equi-volume impregnating, measure a certain amount of cerous nitrate and be dissolved in the deionized water, TiO 2-ZrO 2Complex carrier adds in the above-mentioned cerous nitrate solution, and ultrasonic processing is also left standstill certain hour; Then above-mentioned material is carried out drying, roasting, promptly obtain CeO 2/ TiO 2-ZrO 2
Configuration 5% oxalic acid solution according to equi-volume impregnating, is measured a certain amount of ammonium metavanadate, and ammonium tungstate or ammonium metatungstate be dissolved in the oxalic acid solution, with CeO 2/ TiO 2-ZrO 2Add in the above-mentioned solution, ultrasonic processing is also left standstill certain hour; Then above-mentioned material is carried out drying, roasting, promptly obtain V 2O 5/ WO 3-CeO 2/ TiO 2-ZrO 2Composite catalyst; And V 2O 5, WO 3, CeO 2The quality separately and the mass percent of composite catalyst are respectively 0.5-1.5%, 4-10% and 1-5%.
Time of repose in described step (1) or (2) is 2-24h.
The ultrasonic processing time in the described step (2) is 1-3h.
Drying in described step (1) or (2) is that nature dries in the shade, and be 24-72h drying time.
Drying in described step (1) or (2) is the drying box drying, and baking temperature is 60-120 ℃, and be 2-24h drying time.
Sintering temperature in described step (1) or (2) is 350-600 ℃, and temperature programming speed is 0.5-10 ℃/min, and temperature retention time is 1-4h.
Described titanium source is titanium tetrachloride or tetra-n-butyl titanate, and described zirconium source is zirconium chloride, zirconium oxychloride or propyl alcohol zirconium, and described precipitating reagent is an ammoniacal liquor.
Beneficial effect of the present invention is:
The present invention adopts nano-TiO 2-ZrO 2Composite metal oxide is a carrier, has the advantages that specific area is big, heat endurance is high and acidic site is many; Wherein bigger specific area and more acidic site help catalyst to gaseous state NH 3Absorption, thereby promote the carrying out of denitration reaction, higher heat endurance then has and is used in the service life of improving catalyst.
The present invention introduces CeO 2As auxiliary agent, CeO 2Being a kind of comparatively cheap oxide, also is the highest active a kind of oxide catalyst in the rare earth oxide series, has higher storage oxygen-oxygen release ability and stronger OR performance, with CeO 2Introduce in the denitrating catalyst temperature window that helps to improve the denitration activity of catalyst and widen catalytic activity.
In addition, TiO 2-ZrO 2And V 2O 5, WO 3And CeO 2Between exist interaction, can further improve the denitration activity of catalyst, and make catalyst in 150-450 ℃ temperature range, all show superior catalytic activity.
The specific embodiment
The invention provides a kind of based on TiO 2-ZrO 2The SCR catalyst for denitrating flue gas and the preparation method of complex carrier, the present invention will be further described below in conjunction with the specific embodiment.
Percentage composition among the following embodiment is the quality percentage composition if no special instructions.
Embodiment 1
(1) complex carrier preparation: measure mass ratio and be 5: 4 titanium tetrachloride and butter of tin, be specially the titanium tetrachloride of measuring 9.96g, slowly splash into to the ethanol solution of 60mL; Measure the zirconium chloride of 7.94g in addition, slowly splash into to the above-mentioned ethanol solution that contains titanium tetrachloride; Under intense stirring condition, slowly dropping ammonia reaches about 9 until the pH value, obtains precipitation of hydroxide and leaves standstill 24h; Said mixture is filtered, washs and (use AgNO 3Detect no Cl -), and be placed on 500 ℃ of following roastings (temperature programming speed is 2 ℃/min, and temperature retention time is 3h) in dry 3h, the Muffle furnace under 110 ℃ in the common air dry oven, promptly obtain nano-TiO 2-ZrO 2Composite metal oxide, wherein, TiO 2/ TiO 2-ZrO 2=50%.
(2) measuring mass ratio is 9.69: 1: 8.46 cerous nitrate, ammonium metavanadate and ammonium tungstate, and concrete operations are: according to equi-volume impregnating, the cerous nitrate of measuring 1.26g is dissolved in the 8.08g deionized water, with TiO 2-ZrO 2Complex carrier adds in the above-mentioned cerous nitrate solution, and ultrasonic processing 1h also leaves standstill 2h; Then above-mentioned material is placed common air dry oven 110 ℃ of following dry 3h, 450 ℃ of roasting 3h of Muffle furnace (temperature programming speed is 2 ℃/min, and temperature retention time is 3h), promptly obtain CeO 2/ TiO 2-ZrO 2According to equi-volume impregnating, the oxalic acid solution 8g of configuration 5%, the ammonium metavanadate and the 1.1g ammonium tungstate of measuring 0.13g are dissolved in the oxalic acid solution, with CeO 2/ TiO 2-ZrO 2Add in the above-mentioned solution, ultrasonic processing 1h also leaves standstill 2h; Then above-mentioned material is placed common air dry oven 110 ℃ of following dry 3h, 450 ℃ of following roasting 3h of Muffle furnace, temperature programming speed is 2 ℃/min, and temperature retention time is 3h, promptly obtains 1%V 2O 5/ 10%WO 3-5%CeO 2/ TiO 2-ZrO 2(TiO 2/ TiO 2-ZrO 2=50%) composite catalyst.
Adopt the simulated flue gas condition that the performance of this denitrating catalyst is estimated, with NH 3Be reducing agent, under the typical flue gas operating mode: NO is 1000ppm, O 2Be 5% (v/v), the ammonia nitrogen ratio is 1: 1, N 2Be balance gas, air speed is 15000h -1, the denitration efficiency when reaction temperature is 150 ℃, 300 ℃, 450 ℃ is respectively 73.3%, 97.6%, 95.7%.
Embodiment 2
(1) complex carrier preparation: measure mass ratio and be 5: 4 titanium tetrachloride and butter of tin, concrete operations are: measure the titanium tetrachloride of 10.67g, slowly splash into to the ethanol solution of 65mL; Measure the zirconium chloride of 8.51g in addition, slowly splash into to the above-mentioned ethanol solution that contains titanium tetrachloride; Under intense stirring condition, slowly dropping ammonia reaches about 9 until the pH value, obtains precipitation of hydroxide and leaves standstill 24h; Said mixture is filtered, washs and (use AgNO 3Detect no Cl -), and be placed on 500 ℃ of following roastings (temperature programming speed is 2 ℃/min, and temperature retention time is 3h) in dry 3h, the Muffle furnace under 110 ℃ in the common air dry oven, promptly obtain nano-TiO 2-ZrO 2Composite metal oxide, and TiO 2/ TiO 2-ZrO 2=50%.
(2) measuring mass ratio is 5.85: 1: 5.08 cerous nitrate, ammonium metavanadate and ammonium tungstate, and concrete operations are: according to equi-volume impregnating, the cerous nitrate of measuring 0.76g is dissolved in the 8.64g deionized water, with TiO 2-ZrO 2Complex carrier adds in the above-mentioned cerous nitrate solution, and ultrasonic processing 1h also leaves standstill 3h; Then above-mentioned material is placed common air dry oven 110 ℃ of following dry 3h, 450 ℃ of roasting 3h of Muffle furnace (temperature programming speed is 2 ℃/min, and temperature retention time is 3h), promptly obtain CeO 2/ TiO 2-ZrO 2According to equi-volume impregnating, the oxalic acid solution 8.35g of configuration 5%, the ammonium metavanadate and the 0.66g ammonium tungstate of measuring 0.13g are dissolved in the oxalic acid solution, with CeO 2/ TiO 2-ZrO 2Add in the above-mentioned solution, ultrasonic processing 1h also leaves standstill 3h; Then above-mentioned material is placed common air dry oven 110 ℃ of following dry 3h, 500 ℃ of following roasting 3h of Muffle furnace (temperature programming speed is 2 ℃/min, and temperature retention time is 3h), promptly obtain 1%V 2O 5/ 6%WO 3-3%CeO 2/ TiO 2-ZrO 2(TiO 2/ TiO 2-ZrO 2=50%) composite catalyst.
Adopt the simulated flue gas condition that the performance of this denitrating catalyst is estimated, with NH 3Be reducing agent, under the typical flue gas operating mode: NO is 1000ppm, O 2Be 5% (v/v), the ammonia nitrogen ratio is 1: 1, N 2Be balance gas, air speed is 15000h -1, the denitration efficiency when reaction temperature is 150 ℃, 300 ℃, 450 ℃ is respectively 71%, 96%, 96.5%.
Embodiment 3
(1) complex carrier preparation: measure mass ratio and be 3.76: 1 titanium tetrachloride and butter of tin, concrete operations are: measure the titanium tetrachloride of 15.97g, slowly splash into to the ethanol solution of 98.9mL; Measure the zirconium chloride of 4.25g in addition, slowly splash into to the above-mentioned ethanol solution that contains titanium tetrachloride; Under intense stirring condition, slowly dropping ammonia reaches about 9 until the pH value, obtains precipitation of hydroxide and leaves standstill 24h; Said mixture is filtered, washs and (use AgNO 3Detect no Cl -), and be placed on 550 ℃ of following roastings (temperature programming speed is 2 ℃/min, and temperature retention time is 3h) in dry 3h, the Muffle furnace under 110 ℃ in the common air dry oven, promptly obtain nano-TiO 2-ZrO 2Composite metal oxide, and TiO 2/ TiO 2-ZrO 2=75%.
(2) measuring mass ratio is 8.08: 1: 2.82 cerous nitrate, ammonium metavanadate and ammonium tungstate, and concrete operations are: according to equi-volume impregnating, the cerous nitrate of measuring 1.26g is dissolved in the 8.06g deionized water, with TiO 2-ZrO 2Complex carrier adds in the above-mentioned cerous nitrate solution, and ultrasonic processing 1h also leaves standstill 3h; Then above-mentioned material is placed common air dry oven 110 ℃ of following dry 3h, 450 ℃ of roasting 3h of Muffle furnace (temperature programming speed is 2 ℃/min, and temperature retention time is 2h), promptly obtain CeO 2/ TiO 2-ZrO 2According to equi-volume impregnating, the oxalic acid solution 8.51g of configuration 5%, the ammonium metavanadate and the 0.44g ammonium tungstate of measuring 0.156g are dissolved in the oxalic acid solution, with CeO 2/ TiO 2-ZrO 2Add in the above-mentioned solution, ultrasonic processing 1h also leaves standstill 3h; Then above-mentioned material is placed common air dry oven 110 ℃ of following dry 3h, 550 ℃ of following roasting 3h of Muffle furnace (temperature programming speed is 2 ℃/min, and temperature retention time is 3h), promptly obtain 1.2%V 2O 5/ 4%WO 3-5%CeO 2/ TiO 2-ZrO 2(TiO 2/ TiO 2-ZrO 2=75%) composite catalyst.
Adopt the simulated flue gas condition that the performance of this denitrating catalyst is estimated, with NH 3Be reducing agent, under the typical flue gas operating mode: NO is 1000ppm, O 2Be 5% (v/v), the ammonia nitrogen ratio is 1: 1, N 2Be balance gas, air speed is 15000h -1, the denitration efficiency when reaction temperature is 150 ℃, 300 ℃, 450 ℃ is respectively 74%, 96.7%, 95.2%.
Embodiment 4
(1) complex carrier preparation: measure mass ratio and be 11.3: 1 titanium tetrachloride and butter of tin, concrete operations are: measure the titanium tetrachloride of 19g, slowly splash into to the ethanol solution of 120mL; Measure the zirconium chloride of 1.68g in addition, slowly splash into to the above-mentioned ethanol solution that contains titanium tetrachloride; Under intense stirring condition, slowly dropping ammonia reaches about 9 until the pH value, obtains precipitation of hydroxide and leaves standstill 24h; Said mixture is filtered, washs and (use AgNO 3Detect no Cl -), and be placed on 550 ℃ of following roastings (temperature programming speed is 2 ℃/min, and temperature retention time is 3h) in dry 3h, the Muffle furnace under 110 ℃ in the common air dry oven, promptly obtain nano-TiO 2-ZrO 2Composite metal oxide, and TiO 2/ TiO 2-ZrO 2=90%.
(2) measuring mass ratio is 2.40: 1: 10.60 cerous nitrates, ammonium metavanadate and ammonium tungstates, and concrete operations are: according to equi-volume impregnating, the cerous nitrate of measuring 0.25g is dissolved in the 8.37g deionized water, with TiO 2-ZrO 2Complex carrier adds in the above-mentioned cerous nitrate solution, and ultrasonic processing 1h also leaves standstill 3h; Then above-mentioned material is placed common air dry oven 110 ℃ of following dry 3h, 450 ℃ of roasting 3h of Muffle furnace (temperature programming speed is 2 ℃/min, and temperature retention time is 2h), promptly obtain CeO 2/ TiO 2-ZrO 2According to equi-volume impregnating, the oxalic acid solution 8.08g of configuration 5%, the ammonium metavanadate and the 1.102g ammonium tungstate of measuring 0.104g are dissolved in the oxalic acid solution, with CeO 2/ TiO 2-ZrO 2Add in the above-mentioned solution, ultrasonic processing 1h also leaves standstill 3h; Then above-mentioned material being placed common air dry oven 110 ℃ of following dry 3h, 550 ℃ of following roasting 3h temperature programming speed of Muffle furnace is 2 ℃/min, and temperature retention time is 3h, promptly obtains 0.8%V 2O 5/ 9.2%WO 3-1%CeO 2/ TiO 2-ZrO 2(TiO 2/ TiO 2-ZrO 2=90%) composite catalyst.
Adopt the simulated flue gas condition that the performance of this denitrating catalyst is estimated, with NH 3Be reducing agent, under the typical flue gas operating mode: NO is 1000ppm, O 2Be 5% (v/v), the ammonia nitrogen ratio is 1: 1, N 2Be balance gas, air speed is 15000h -1, the denitration efficiency when reaction temperature is 150 ℃, 300 ℃, 450 ℃ is respectively 68.8%, 97.2%, 94.1%.

Claims (8)

1. one kind based on TiO 2-ZrO 2The SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that: at nano-TiO 2-ZrO 2On the complex carrier, load auxiliary agent WO 3And CeO 2, active component V 2O 5Common formation composite catalyst; Wherein, at described nano-TiO 2-ZrO 2In the complex carrier, TiO 2Shared mass percent is 50-95%; In the composite catalyst that makes, TiO 2-ZrO 2Mass percent be 83.5-94.5%, V 2O 5, WO 3, CeO 2Shared separately mass percent is respectively 0.5-1.5%, 4-10% and 1-5%.
2. one kind based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that, may further comprise the steps:
(1) preparation of complex carrier:
Measure a certain amount of titanium source, slowly splash into to the ethanol solution of 4-10 times of volume, measure a certain amount of zirconium source in addition and slowly splash into to the above-mentioned ethanol solution that contains the titanium source, make the TiO that finally obtains 2-ZrO 2TiO in the composite metal oxide 2Shared mass percent is 50-95%; Under intense stirring condition, slowly drip precipitating reagent and reach 9 until the pH value, obtain precipitation of hydroxide and leave standstill certain hour; Then said mixture is filtered, washs, uses AgNO 3Detection, dry, roasting promptly obtain nano-TiO 2-ZrO 2Composite metal oxide;
(2) load of complex carrier auxiliary agent and active component:
According to equi-volume impregnating, measure a certain amount of cerous nitrate and be dissolved in the deionized water, TiO 2-ZrO 2Complex carrier adds in the above-mentioned cerous nitrate solution, and ultrasonic processing is also left standstill certain hour; Then above-mentioned material is carried out drying, roasting, promptly obtain CeO 2/ TiO 2-ZrO 2
Configuration 5% oxalic acid solution according to equi-volume impregnating, is measured a certain amount of ammonium metavanadate, and ammonium tungstate or ammonium metatungstate be dissolved in the oxalic acid solution, with CeO 2/ TiO 2-ZrO 2Add in the above-mentioned solution, ultrasonic processing is also left standstill certain hour; Then above-mentioned material is carried out drying, roasting, promptly obtain V 2O 5/ WO 3-CeO 2/ TiO 2-ZrO 2Composite catalyst; And V 2O 5, WO 3, CeO 2The quality separately and the mass percent of composite catalyst are respectively 0.5-1.5%, 4-10% and 1-5%.
3. according to claim 2 a kind of based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that, the time of repose in described step (1) or (2) is 2-24h.
4. according to claim 2 a kind of based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that, the ultrasonic processing time in the described step (2) is 1-3h.
5. according to claim 2 a kind of based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that, the drying in described step (1) or (2) is that nature dries in the shade, and be 24-72h drying time.
6. according to claim 2 a kind of based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that, the drying in described step (1) or (2) is the drying box drying, and baking temperature is 60-120 ℃, and be 2-24h drying time.
7. according to claim 2 a kind of based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that, the sintering temperature in described step (1) or (2) is 350-600 ℃, and temperature programming speed is 0.5-10 ℃/min, and temperature retention time is 1-4h.
8. according to claim 2 a kind of based on TiO 2-ZrO 2The preparation method of the SCR catalyst for denitrating flue gas of composite metal oxide carrier is characterized in that, described titanium source is titanium tetrachloride or tetra-n-butyl titanate, and described zirconium source is zirconium chloride, zirconium oxychloride or propyl alcohol zirconium, and described precipitating reagent is an ammoniacal liquor.
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