[go: up one dir, main page]

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

Info

Publication number
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
Authority
CN
China
Prior art keywords
tio
zro
flue gas
composite
metal oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 201110158422
Other languages
Chinese (zh)
Other versions
CN102266761B (en
Inventor
张俊姣
陆强
苏淑华
杨勇平
董长青
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Huadian Guangda Environment Co ltd
Original Assignee
North China Electric Power University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North China Electric Power University filed Critical North China Electric Power University
Priority to CN 201110158422 priority Critical patent/CN102266761B/en
Publication of CN102266761A publication Critical patent/CN102266761A/en
Application granted granted Critical
Publication of CN102266761B publication Critical patent/CN102266761B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

本发明属于环境保护与环境催化领域，具体涉及一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂。本发明是以纳米TiO2-ZrO2为载体、WO3和CeO2为助剂、V2O5为活性组分，获得基于TiO2-ZrO2复合载体的中低温烟气脱硝催化剂。采用纳米TiO2-ZrO2替代传统的纳米TiO2作为载体，不仅增加了催化剂的比表面积、热稳定性和酸性，而且通过和V2O5、WO3和CeO2之间的相互作用，提高了催化剂的脱硝活性；在以氨为还原剂，温度为150-450℃的范围内都表现出很好的催化活性。The invention belongs to the field of environmental protection and environmental catalysis, and in particular relates to an SCR flue gas denitrification catalyst based on a TiO 2 -ZrO 2 composite metal oxide carrier. The invention uses nano TiO 2 -ZrO 2 as carrier, WO 3 and CeO 2 as auxiliary agents, and V 2 O 5 as active component to obtain a medium and low temperature flue gas denitrification catalyst based on TiO 2 -ZrO 2 composite carrier. Using nano-TiO 2 -ZrO 2 instead of traditional nano-TiO 2 as a carrier not only increases the specific surface area, thermal stability and acidity of the catalyst, but also improves the The denitrification activity of the catalyst is improved; it shows good catalytic activity in the range of 150-450 ° C with ammonia as the reducing agent.

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)

1.一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂，其特征在于：在纳米TiO2-ZrO2复合载体上，负载助剂WO3和CeO2、活性组分V2O5共同构成复合型催化剂；其中，在所述纳米TiO2-ZrO2复合载体中，TiO2所占的质量百分比为50-95％；在制得的复合型催化剂中，TiO2-ZrO2的质量百分比为83.5-94.5％，V2O5、WO3、CeO2各自所占的质量百分比分别为0.5-1.5％、4-10％和1-5％。1. A SCR flue gas denitrification catalyst based on a TiO 2 -ZrO 2 composite metal oxide carrier, characterized in that: on the nanometer TiO 2 -ZrO 2 composite carrier, loading aids WO 3 and CeO 2 , active component V 2 O 5 together constitute a composite catalyst; wherein, in the nano-TiO 2 -ZrO 2 composite carrier, the mass percentage of TiO 2 is 50-95%; in the prepared composite catalyst, the TiO 2 -ZrO The mass percentage of 2 is 83.5-94.5%, and the respective mass percentages of V 2 O 5 , WO 3 and CeO 2 are 0.5-1.5%, 4-10% and 1-5%. 2.一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂的制备方法，其特征在于，包括以下步骤：2. A preparation method based on TiO 2 -ZrO 2 composite metal oxide carrier SCR flue gas denitration catalyst, characterized in that, comprising the following steps: (1)复合载体的制备：(1) Preparation of composite carrier: 量取一定量的钛源，缓慢滴入至4-10倍体积的无水乙醇溶液中，另外量取一定量的锆源缓慢滴入至上述含有钛源的无水乙醇溶液中，使最终得到的TiO2-ZrO2复合金属氧化物中TiO2所占的质量百分比为50-95％；在剧烈搅拌的条件下，缓慢滴加沉淀剂直至pH值达到9，得到氢氧化物沉淀并静置一定时间；而后对上述混合物过滤、洗涤、用AgNO3检测、干燥、焙烧，即得到纳米TiO2-ZrO2复合金属氧化物；Take a certain amount of titanium source, slowly drop it into 4-10 times the volume of absolute ethanol solution, and take a certain amount of zirconium source and slowly drop it into the above-mentioned absolute ethanol solution containing titanium source, so that the final The mass percentage of TiO 2 in the TiO 2 -ZrO 2 composite metal oxide is 50-95%; under the condition of vigorous stirring, the precipitating agent is slowly added dropwise until the pH value reaches 9, and the hydroxide precipitate is obtained and allowed to stand A certain period of time; then filter the above mixture, wash it, detect it with AgNO3 , dry it, and roast it to obtain nano- TiO2 - ZrO2 composite metal oxide; (2)复合载体助剂和活性组分的负载：(2) Loading of composite carrier additives and active components: 按照等体积浸渍法，量取一定量的硝酸铈溶于去离子水中，将TiO2-ZrO2复合载体加入上述硝酸铈溶液中，超声处理并静置一定时间；而后对上述物料进行干燥、焙烧，即得到CeO2/TiO2-ZrO2；According to the equal-volume impregnation method, measure a certain amount of cerium nitrate and dissolve it in deionized water, add the TiO 2 -ZrO 2 composite carrier into the above cerium nitrate solution, ultrasonically treat it and let it stand for a certain period of time; then dry and roast the above material , namely to obtain CeO 2 /TiO 2 -ZrO 2 ; 配置5％的草酸溶液，按照等体积浸渍法，量取一定量的偏钒酸铵，以及钨酸铵或偏钨酸铵溶于草酸溶液中，将CeO2/TiO2-ZrO2加入上述溶液中，超声处理并静置一定时间；而后对上述物料进行干燥、焙烧，即得到V2O5/WO3-CeO2/TiO2-ZrO2复合型催化剂；且V2O5、WO3、CeO2各自的质量与复合型催化剂的质量百分比分别为0.5-1.5％、4-10％和1-5％。Configure 5% oxalic acid solution, according to the equal volume dipping method, measure a certain amount of ammonium metavanadate, and ammonium tungstate or ammonium metatungstate dissolved in oxalic acid solution, add CeO 2 /TiO 2 -ZrO 2 to the above solution , ultrasonic treatment and standing for a certain period of time; then dry and roast the above materials to obtain V 2 O 5 /WO 3 -CeO 2 /TiO 2 -ZrO 2 composite catalyst; and V 2 O 5 , WO 3 , The respective mass percentages of CeO 2 and the composite catalyst are respectively 0.5-1.5%, 4-10% and 1-5%. 3.根据权利要求2所述的一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂的制备方法，其特征在于，所述步骤(1)或(2)中的静置时间为2-24h。3. a kind of preparation method based on TiO 2 -ZrO 2 composite metal oxide carrier SCR flue gas denitrification catalyst according to claim 2, it is characterized in that, the standing in described step (1) or (2) The time is 2-24h. 4.根据权利要求2所述的一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂的制备方法，其特征在于，所述步骤(2)中的超声处理时间为1-3h。4. a kind of preparation method based on TiO 2 -ZrO 2 composite metal oxide carrier SCR flue gas denitration catalyst according to claim 2, it is characterized in that, the ultrasonic treatment time in described step (2) is 1- 3h. 5.根据权利要求2所述的一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂的制备方法，其特征在于，所述步骤(1)或(2)中的干燥为自然阴干，干燥时间为24-72h。5. a kind of preparation method based on TiO 2 -ZrO 2 composite metal oxide carrier SCR flue gas denitration catalyst according to claim 2, it is characterized in that, the drying in described step (1) or (2) is Dry in the shade naturally, the drying time is 24-72h. 6.根据权利要求2所述的一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂的制备方法，其特征在于，所述步骤(1)或(2)中的干燥为干燥箱干燥，干燥温度为60-120℃，干燥时间为2-24h。6. a kind of preparation method based on TiO 2 -ZrO 2 composite metal oxide carrier's SCR flue gas denitration catalyst according to claim 2, is characterized in that, the drying in described step (1) or (2) is Drying in a drying oven, the drying temperature is 60-120°C, and the drying time is 2-24h. 7.根据权利要求2所述的一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂的制备方法，其特征在于，所述步骤(1)或(2)中的焙烧温度为350-600℃，程序升温速度为0.5-10℃/min，保温时间为1-4h。7. a kind of preparation method based on the SCR flue gas denitration catalyst of TiO 2 -ZrO 2 composite metal oxide carrier according to claim 2, it is characterized in that, the roasting temperature in described step (1) or (2) The temperature is 350-600°C, the heating rate is 0.5-10°C/min, and the holding time is 1-4h. 8.根据权利要求2所述的一种基于TiO2-ZrO2复合金属氧化物载体的SCR烟气脱硝催化剂的制备方法，其特征在于，所述钛源为四氯化钛或者钛酸四正丁酯，所述锆源为四氯化锆、氧氯化锆或者丙醇锆，所述沉淀剂为氨水。8. A method for preparing a SCR flue gas denitration catalyst based on a TiO 2 -ZrO 2 composite metal oxide carrier according to claim 2, wherein the titanium source is titanium tetrachloride or tetranormal titanate Butyl ester, the zirconium source is zirconium tetrachloride, zirconium oxychloride or zirconium propoxide, and the precipitation agent is ammonia water.
CN 201110158422 2011-06-13 2011-06-13 SCR flue gas denitrification catalyst based on TiO2-ZrO2 composite carrier and preparation method Active CN102266761B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201110158422 CN102266761B (en) 2011-06-13 2011-06-13 SCR flue gas denitrification catalyst based on TiO2-ZrO2 composite carrier and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201110158422 CN102266761B (en) 2011-06-13 2011-06-13 SCR flue gas denitrification catalyst based on TiO2-ZrO2 composite carrier and preparation method

Publications (2)

Publication Number Publication Date
CN102266761A true CN102266761A (en) 2011-12-07
CN102266761B CN102266761B (en) 2013-05-01

Family

ID=45049330

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201110158422 Active CN102266761B (en) 2011-06-13 2011-06-13 SCR flue gas denitrification catalyst based on TiO2-ZrO2 composite carrier and preparation method

Country Status (1)

Country Link
CN (1) CN102266761B (en)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102600856A (en) * 2012-02-27 2012-07-25 环境保护部华南环境科学研究所 High-sulfur-resistance medium and low-temperature catalyst and preparation method and application thereof
CN102728343A (en) * 2012-07-02 2012-10-17 长春市新瑞科贸有限责任公司 Preparation method of denitration catalyst cellular module
CN103406126A (en) * 2013-08-29 2013-11-27 天津大学 Ternary metal modified titanium dioxide catalyst and preparation method thereof as well as application thereof in removing oxynitrides in diesel engine exhaust
CN103537310A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Catalyst and method for preparing maleic anhydride by normal butane oxidization
CN103908970A (en) * 2014-03-27 2014-07-09 台州欧信环保净化器有限公司 Monolithic SCR (Selective Catalytic Reduction) honeycomb catalyst for processing diesel exhaust and preparation method of catalyst
CN104001497A (en) * 2014-06-20 2014-08-27 上海电力学院 Wide-temperature-window denitration catalyst and preparation method and application thereof
CN104209116A (en) * 2014-09-01 2014-12-17 东南大学 Vanadium-series middle-temperature and high-temperature SCR catalyst and preparation method thereof
CN104226296A (en) * 2014-09-01 2014-12-24 东南大学 Vanadium-loaded middle-temperature SCR catalyst and preparation method thereof
CN104258840A (en) * 2014-09-01 2015-01-07 东南大学 Cerium supported medium temperature SCR (selective catalytic reduction) catalyst and preparation method thereof
CN105148904A (en) * 2015-08-28 2015-12-16 武汉京运通环保工程有限公司 Flue gas denitration catalyst applied at a low temperature and preparation method thereof
CN105498755A (en) * 2016-01-14 2016-04-20 东南大学 SCR denitration catalyst and preparation method thereof
CN105642272A (en) * 2016-01-29 2016-06-08 大唐南京环保科技有限责任公司 SCR denitrification catalyst and preparing method thereof
CN106861392A (en) * 2017-02-21 2017-06-20 华北电力大学 A kind of nitrogen oxide removal process based on catalytic oxidation of hydrogen peroxide
CN106925259A (en) * 2015-12-31 2017-07-07 中国石油天然气股份有限公司 Catalyst for preparing isopropanol by propylene hydration through gas-liquid phase method and preparation method and application thereof
CN108212143A (en) * 2017-12-29 2018-06-29 浙江德创环保科技股份有限公司 It is a kind of for denitrating catalyst of porous wide temperature window and preparation method thereof
CN108273494A (en) * 2017-12-29 2018-07-13 浙江德创环保科技股份有限公司 A kind of denitrating catalyst and preparation method thereof for wide temperature window
CN108786783A (en) * 2018-06-11 2018-11-13 上海电力学院 The SCR catalyst and preparation method thereof that a kind of resistant to potassium for denitrating flue gas poisons
CN110252333A (en) * 2019-07-04 2019-09-20 湖北工程学院 A kind of preparation method and application of SCR mercury removal catalyst
CN111632585A (en) * 2019-03-01 2020-09-08 龙蟒佰利联集团股份有限公司 Denitration TiO2-ZrO2Composite carrier and preparation method thereof
CN112403486A (en) * 2020-11-19 2021-02-26 高化学（江苏）化工新材料有限责任公司 V/Cu/B/W-TiO2-ZrO2Composite low-temperature denitration catalyst and preparation method thereof
CN114477951A (en) * 2022-01-21 2022-05-13 福建省德化新艺美陶瓷有限公司 High-strength high-whiteness ceramic product and processing technology thereof
CN116478488A (en) * 2023-06-25 2023-07-25 广州澳通电线电缆有限公司 Anti-aging photovoltaic cable and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100998939A (en) * 2007-01-10 2007-07-18 浙江大学 MnOx/ZrO2-TiO2 low temperature selective catalytic reduction NOx catalyst possessing anti SO2 performance and its preparation technology
CN101433837A (en) * 2008-12-17 2009-05-20 天津大学 SCR catalyst with wide active temperature windows as well as preparation method and use thereof
CN101590404A (en) * 2009-06-26 2009-12-02 清华大学 A kind of low vanadium denitration catalyst and its preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100998939A (en) * 2007-01-10 2007-07-18 浙江大学 MnOx/ZrO2-TiO2 low temperature selective catalytic reduction NOx catalyst possessing anti SO2 performance and its preparation technology
CN101433837A (en) * 2008-12-17 2009-05-20 天津大学 SCR catalyst with wide active temperature windows as well as preparation method and use thereof
CN101590404A (en) * 2009-06-26 2009-12-02 清华大学 A kind of low vanadium denitration catalyst and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《物理化学学报》 20071231 林涛 等 ZrO2-TiO2-CeO2 的制备及其在NH3 选择性催化还原NO中的应用 第1851-1856页 1-8 第23卷, 第12期 *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102600856A (en) * 2012-02-27 2012-07-25 环境保护部华南环境科学研究所 High-sulfur-resistance medium and low-temperature catalyst and preparation method and application thereof
CN102728343A (en) * 2012-07-02 2012-10-17 长春市新瑞科贸有限责任公司 Preparation method of denitration catalyst cellular module
CN103537310A (en) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 Catalyst and method for preparing maleic anhydride by normal butane oxidization
CN103406126A (en) * 2013-08-29 2013-11-27 天津大学 Ternary metal modified titanium dioxide catalyst and preparation method thereof as well as application thereof in removing oxynitrides in diesel engine exhaust
CN103908970B (en) * 2014-03-27 2016-04-13 台州欧信环保净化器有限公司 For the monoblock type SCR honeycomb catalyst and preparation method thereof of exhaust gas from diesel vehicle process
CN103908970A (en) * 2014-03-27 2014-07-09 台州欧信环保净化器有限公司 Monolithic SCR (Selective Catalytic Reduction) honeycomb catalyst for processing diesel exhaust and preparation method of catalyst
CN104001497A (en) * 2014-06-20 2014-08-27 上海电力学院 Wide-temperature-window denitration catalyst and preparation method and application thereof
CN104001497B (en) * 2014-06-20 2017-01-04 上海电力学院 A kind of wide temperature window denitrating catalyst and its preparation method and application
CN104209116A (en) * 2014-09-01 2014-12-17 东南大学 Vanadium-series middle-temperature and high-temperature SCR catalyst and preparation method thereof
CN104258840A (en) * 2014-09-01 2015-01-07 东南大学 Cerium supported medium temperature SCR (selective catalytic reduction) catalyst and preparation method thereof
CN104226296A (en) * 2014-09-01 2014-12-24 东南大学 Vanadium-loaded middle-temperature SCR catalyst and preparation method thereof
CN105148904A (en) * 2015-08-28 2015-12-16 武汉京运通环保工程有限公司 Flue gas denitration catalyst applied at a low temperature and preparation method thereof
CN106925259A (en) * 2015-12-31 2017-07-07 中国石油天然气股份有限公司 Catalyst for preparing isopropanol by propylene hydration through gas-liquid phase method and preparation method and application thereof
CN105498755A (en) * 2016-01-14 2016-04-20 东南大学 SCR denitration catalyst and preparation method thereof
CN105642272A (en) * 2016-01-29 2016-06-08 大唐南京环保科技有限责任公司 SCR denitrification catalyst and preparing method thereof
CN106861392A (en) * 2017-02-21 2017-06-20 华北电力大学 A kind of nitrogen oxide removal process based on catalytic oxidation of hydrogen peroxide
CN108212143A (en) * 2017-12-29 2018-06-29 浙江德创环保科技股份有限公司 It is a kind of for denitrating catalyst of porous wide temperature window and preparation method thereof
CN108273494A (en) * 2017-12-29 2018-07-13 浙江德创环保科技股份有限公司 A kind of denitrating catalyst and preparation method thereof for wide temperature window
CN108786783A (en) * 2018-06-11 2018-11-13 上海电力学院 The SCR catalyst and preparation method thereof that a kind of resistant to potassium for denitrating flue gas poisons
CN111632585A (en) * 2019-03-01 2020-09-08 龙蟒佰利联集团股份有限公司 Denitration TiO2-ZrO2Composite carrier and preparation method thereof
CN110252333A (en) * 2019-07-04 2019-09-20 湖北工程学院 A kind of preparation method and application of SCR mercury removal catalyst
CN112403486A (en) * 2020-11-19 2021-02-26 高化学（江苏）化工新材料有限责任公司 V/Cu/B/W-TiO2-ZrO2Composite low-temperature denitration catalyst and preparation method thereof
CN114477951A (en) * 2022-01-21 2022-05-13 福建省德化新艺美陶瓷有限公司 High-strength high-whiteness ceramic product and processing technology thereof
CN116478488A (en) * 2023-06-25 2023-07-25 广州澳通电线电缆有限公司 Anti-aging photovoltaic cable and preparation method thereof
CN116478488B (en) * 2023-06-25 2023-08-25 广州澳通电线电缆有限公司 Anti-aging photovoltaic cable and preparation method thereof

Also Published As

Publication number Publication date
CN102266761B (en) 2013-05-01

Similar Documents

Publication Publication Date Title
CN102266761B (en) SCR flue gas denitrification catalyst based on TiO2-ZrO2 composite carrier and preparation method
CN105688974B (en) One kind is with SBA-15/TiO2For the denitrating catalyst and preparation method thereof of carrier
CN102205240B (en) Based on TiO 2-SnO 2the SCR catalyst for denitrating flue gas of complex carrier and preparation method
CN104741114B (en) A kind of flat high temperature SCR denitration and preparation method thereof
CN104324729B (en) A kind of preparation method of flue gas low-temperature denitration cobalt and manganese oxide catalyst
CN104998680B (en) A kind of anti-SO2And H2The low-temperature denitration catalyst and preparation method thereof of O poisonings
CN107824177A (en) A kind of CeO using Ce MOF as cerium precursor2/TiO2The preparation method of low-temperature SCR catalyst
CN105056923B (en) A kind of water resistant sulfur resistive type denitrating catalyst, preparation method and its usage
US9802180B2 (en) Catalyst for synergistic control of oxynitride and mercury and method for preparing the same
CN102259009B (en) SCR flue gas denitrification catalyst and preparation method based on sulfate-promoted TiO2 carrier
CN102658155B (en) Preparation method of supported type denitration catalyst
CN101954290A (en) Novel composite carrier SCR flue gas denitration catalyst
CN106179301B (en) A kind of preparation method of cerium-titanium composite oxide low-temperature SCR catalyst
CN103736479B (en) A kind of cerium titanium stannum composite oxide catalysts for denitrating flue gas and preparation method thereof
CN111992203A (en) NH (hydrogen sulfide)3-SCR low-temperature denitration catalyst and preparation method and application thereof
CN107649116A (en) Cerium tin composite oxides denitrating catalyst and its preparation method and application
CN102274723A (en) Mesoporous TiO2 carrier based SCR flue gas denitration catalyst and preparation method thereof
CN107126949B (en) A kind of SCR denitration and preparation method thereof of anti-arsenic poisoning
CN105854577A (en) Smoke desulfurizer and preparation method thereof
CN109092323A (en) Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application
CN105749937B (en) A copper chloride modified SCR catalyst and its preparation method and application
CN102489294A (en) Low-temperature SCR catalyst prepared by extrusion molding, and preparation method thereof
CN107376896A (en) A kind of cerium tungsten titanium composite oxide SCR denitration and preparation method thereof
CN108554398A (en) A kind of preparation method and applications of wide temperature window denitrating catalyst
CN103084182A (en) Vanadium-free denitration catalyst for flue gas denitration and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20111207

Assignee: BEIJING NATION POWER GROUP CO.,LTD.

Assignor: North China Electric Power University

Contract record no.: 2014990000161

Denomination of invention: SCR flue gas denitration catalyst based on TiO2-ZrO2 composite carrier and preparation method thereof

Granted publication date: 20130501

License type: Exclusive License

Record date: 20140331

LICC Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model
ASS Succession or assignment of patent right

Owner name: BEIJING HUATIAN TIANDE ASSET MANAGEMENT CO., LTD.

Free format text: FORMER OWNER: HUABEI POWER UNIV.

Effective date: 20150723

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20150723

Address after: No. 56 mailbox, North China Electric Power University

Patentee after: Beijing Huadian Tiande Asset Management Ltd.

Address before: 102206, Beijing, Changping District Desheng outside the door, Zhu Xin, North China Electric Power University

Patentee before: North China Electric Power University

EC01 Cancellation of recordation of patent licensing contract

Assignee: BEIJING NATION POWER GROUP CO.,LTD.

Assignor: North China Electric Power University

Contract record no.: 2014990000161

Date of cancellation: 20150710

LICC Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20170110

Address after: 102200 Changping District science and Technology Park, Beijing Road No. 37, building No. 16, floor 2, C1001

Patentee after: BEIJING NATION POWER GRORP Co.,Ltd.

Address before: No. 56 mailbox, North China Electric Power University

Patentee before: Beijing Huadian Tiande Asset Management Ltd.

TR01 Transfer of patent right

Effective date of registration: 20190104

Address after: 102200 C1034, 2nd floor, No. 16 Building, 37 Qianqian Road, Changping District Science Park, Beijing

Patentee after: BEIJING HUADIAN GUANGDA ENVIRONMENT CO.,LTD.

Address before: 102200 C1001, 2nd Floor, Building 16, 37 Qianqian Road, Changping District Science Park, Beijing

Patentee before: BEIJING NATION POWER GRORP Co.,Ltd.

TR01 Transfer of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: SCR flue gas denitrification catalyst and preparation method based on TiO2- ZrO22composite carrier

Granted publication date: 20130501

Pledgee: Beijing Rural Commercial Bank Co.,Ltd. Tiantongyuan Branch

Pledgor: BEIJING HUADIAN GUANGDA ENVIRONMENT CO.,LTD.

Registration number: Y2025980013393

PE01 Entry into force of the registration of the contract for pledge of patent right