CN103736479A - Cerium titanium tin composite oxide catalyst for fume denitration and preparation method thereof - Google Patents

Cerium titanium tin composite oxide catalyst for fume denitration and preparation method thereof Download PDF

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CN103736479A
CN103736479A CN201410000977.3A CN201410000977A CN103736479A CN 103736479 A CN103736479 A CN 103736479A CN 201410000977 A CN201410000977 A CN 201410000977A CN 103736479 A CN103736479 A CN 103736479A
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catalyst
solution
carrier
solid solution
tixsn
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CN103736479B (en
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董林
张雷
汤常金
高飞
邓昱
熊燕
李露露
曹原
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Nanjing University
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Abstract

The invention discloses a CeO2/TixSn(1-x)O2 composite oxide denitration catalyst which takes a TixSn (1-x)O2(O<x<1) solid solution as a carrier and is used for ammonia selectivity catalytic denitration. The preparation method provided by the invention comprises the following steps of uniformly mixing a TiCl4 ethanol solution and SnCl4 water solution according to a certain titanium-tin molar ratio, dropwise adding the ammonia in a mixed solution while acutely stirring until the PH of the solution is 9.0; completely depositing and aging overnight; washing away Cl<->, drying at 110 DEG C, and roasting at 550 DEG C for 4h in a muffle furnace under an air atmosphere to obtain a TixSn (1-x)O2; and with the TixSn (1-x)O2 solid solution as a carrier, loading an active constituent CeO2 by adopting an immersion method, stirring for 3h, carrying out oil bath, steaming out the moisture at 100 DEG C, drying for 12h at 110 DEG C, and roasting for 4h at 500 DEG C or 750 DEG C in an air atmosphere to obtain a CeO2/TixSn(1-x)O2 composite oxide catalyst. The catalyst provided by the invention has the advantages that the specific surface area is large, the heating stability is good, the catalyst has higher NH3-SCR activity compared with single-component carrier, the water-resistant and sulfur resisting properties are excellent, the catalyst is an environment-friendly catalyst, meanwhile, the preparation method of the catalyst is simple, the equipment is simple, and the raw materials are cheap and are easily available.

Description

A kind of cerium titanium tin composite oxide catalysts and method for making thereof for denitrating flue gas
Technical field:
The present invention relates to a kind of cerium titanium tin composite oxide catalysts that denitrating flue gas is object that is applied to.
Background technology:
Nitrogen oxide (NOx) is main air pollutants, and it is the arch-criminal who causes photochemical fog and acid rain, is directly threatening ecological environment.Therefore, emission control and the governing problem of countries in the world to NOx more and more paid attention to.Ammine selectivity catalytic reduction technology (NH 3-SCR) high owing to thering is denitration efficiency, operating cost is relatively low, is widely used in the denitration processing in Industrial Boiler and power station unit.At present, the business NH that success is runed 3-SCR catalyst is the V of Japan in nineteen seventies exploitation 2o 5-WO 3(or MO 3)/TiO 2catalyst.The feature of this catalyst is that the NOx removal efficiency in coal-burning boiler power station reaches more than 80%, and has good sulfur resistance, and operating temperature is 280-420 ℃.But, V 2o 5-WO 3(or MO 3)/TiO 2the active component V of catalyst 2o 5poisonous, anatase titanium dioxide TiO in catalyst 2it is rutile TiO that carrier at high temperature easily turns brilliant 2, cause specific surface area of catalyst to reduce, thereby catalyst activity reduced.
Summary of the invention
China is rare earth resources big country, and rare-earth oxide ceria (CeO 2) owing to thering is excellent storage oxygen release performance and redox property, in NOx catalysis, eliminate particularly and obtained actual utilization in three-effect catalysis.Meanwhile, Ti xsn 1-xo 2solid solution effectively combines TiO 2and SnO 2the feature of the two, in photocatalysis, the fields such as lithium battery and air-sensitive original paper have been subject to extensive concern.Research is found, the Ti preparing by coprecipitation xsn 1-xo 2solid solution has rutile-type crystal structure, and has specific area than single TiO 2and SnO 2greatly, the feature that after high-temperature roasting, structure remains unchanged.In addition, we study and find Ti xsn 1-xo 2solid solution is as carrier, CeO 2the CeO preparing for active component 2/ Ti xsn 1-xo 2catalyst is at NH 3in-SCR reaction than simple CeO 2/ TiO 2and CeO 2/ SnO 2catalyst has more significant advantage.And CeO 2/ Ti xsn 1-xo 2catalyst is also for solving V 2o 5-WO 3(or MO 3)/TiO 2the active component V of catalyst 2o 5shortcoming poisonous and high temperature deactivation provides new thinking.
We are by a kind of easy preparation method, in conjunction with CeO 2with Ti xsn 1-xo 2the advantage of solid solution has successfully been prepared a series of cerium titanium tin composite oxide catalysts, and it is at NH 3in-SCR catalysis, show excellent catalytic performance.Meanwhile, this catalyst is raw materials used cheap and easy to get, and preparation method is simple and efficient, less energy consumption, and environmental pollution is little, at NH 3there is potential application prospect in-SCR catalytic denitration field.
Object of the present invention: metal composite oxide catalyst and the method for making thereof of a kind of high activity, high thermo qualitative are provided, and it can be at NH 3in-SCR denitration catalyst, be applied.
Principle of the present invention is as follows: SnO 2there is rutile-type crystal structure, Sn 4+and Ti 4+ion NH 3h 2snO during O co-precipitation 2preferential formation rutile-type nucleus, then induce Ti 4+ion and the compound crystal seed of its formation rutile type titanium tin, grow up through crystal is aging, obtains rutile type titanium tin solid solution after roasting.Utilize the interaction of active component and carrier, by infusion process, make active component CeO 2on titanium tin solid solution surface, disperse, prepare metal composite oxide catalyst.
The object of the invention is to realize with following technical scheme:
A kind of with Ti xsn 1-xo 2the CeO that [0.25≤x≤0.75] solid solution is carrier 2/ Ti xsn 1-xo 2the preparation method of metal oxide catalyst, it comprises the steps:
The TiCl that step 1. is 1:3-3:1 by titanium tin mol ratio 4ethanolic solution and SnCl 4aqueous solution is even, then, under vigorous stirring, concentrated ammonia liquor is dropwise added in mixed solution, until the pH=9.0 of solution makes its precipitation completely, age overnight, eccysis Cl -, 110 ℃ of oven dry, then 550 ℃ of roasting 4h under air atmosphere in Muffle furnace, obtain Ti xsn 1-xo 2solid solution;
The Ti that step 2. obtains with step 1 xsn 1-xo 2solid solution is carrier, uses 0.1molL -1ce (NO 3) 36H 2o solution is maceration extract, is impregnated into Ti xsn 1-xo 2on carrier, active component CeO 2the mass fraction that accounts for catalyst is 4.5%-22.5%, stirs 3h, 100 ℃ of evaporating water of oil bath, and dry 12h at 110 ℃, lower 500 ℃ of-750 ℃ of roasting 4h of air atmosphere, obtain with Ti xsn 1-xo 2solid solution is the cerium oxide base catalyst of carrier.
A kind of by said method, made with Ti xsn 1-xo 2(0<x<1) CeO that solid solution is carrier 2/ Ti xsn 1-xo 2metal oxide catalyst.
Tool of the present invention has the following advantages:
1. raw materials used cheap and easy to get, preparation method is easy, and equipment is simple, environmental friendliness;
2. catalyst of the present invention has bigger serface Rutile structure, and catalyst Heat stability is good;
3. compared with single carrier, catalyst of the present invention has higher NH 3-SCR activity;
4. catalyst of the present invention has good water resistant and sulfur resistance.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of different proportion titanium tin solid solution catalyst.Figure 1A is the XRD figure of pure carrier, is anatase titanium dioxide TiO from the bottom up successively 2, rutile TiO 2, Ti 0.75sn 0.25o 2, Ti 0.5sn 0.5o 2, Ti 0.25sn 0.75o 2and SnO 2; Figure 1B has been load CeO 2the XRD figure of catalyst is 7.5Ce/TiO from the bottom up successively 2(anatase titanium dioxide), 7.5Ce/Ti 0.75sn 0.25o 2, 7.5Ce/Ti 0.5sn 0.5o 2, 7.5Ce/Ti 0.25sn 0.75o 2and 7.5Ce/SnO 2.
Fig. 2 is 7.5Ce/TiO 2, 7.5Ce/SnO 2, 7.5Ce/Ti xsn 1-xo 2the NO+NH of catalyst and industrial catalyst 3+ O 2the performance comparison result of reaction.Fig. 2 A is the conversion ratio of NO, and Fig. 2 B is N 2selective.
Fig. 3 is different content CeO 2/ Ti 0.5sn 0.5o 2the NO+NH of catalyst 3+ O 2the performance comparison result of reaction.
Fig. 4 is 7.5Ce/Ti 0.5sn 0.5o 2catalyst is the water resistant sulfur resistance result of 300 ℃.
Specific implementation method
Embodiment 1.CeO 2/ Ti xsn 1-xo 2the preparation of catalyst
By TiCl 4(x molL -1) ethanolic solution and SnCl 4(1-x molL -1) [0.25≤x≤0.75] aqueous solution equal-volume mixes, under vigorous stirring, ammoniacal liquor is dropwise added in mixed solution, until the pH=9.0 of solution makes its precipitation completely, age overnight, eccysis Cl -, 110 ℃ of oven dry, then 550 ℃ of roasting 4h under air atmosphere in Muffle furnace, obtain Ti xsn 1-xo 2solid solution.Preparation 0.1molL -1ce (NO 3) 36H 2o solution, then by above-mentioned solution impregnation in Ti xsn 1-xo 2carrier, makes CeO 2mass fraction account for 7.5% of catalyst gross mass, stir 3h, 100 ℃ of evaporates to dryness of oil bath, at 110 ℃ of dry 12h, the lower 500 ℃ of roasting 4h of air atmosphere, identified as samples is designated as 7.5Ce/Ti xsn 1-x, with TiO 2or SnO 2for the catalyst of carrier is labeled as 7.5Ce/Ti and 7.5Ce/Sn.Other condition is constant, changes 7.5Ce/Ti 0.5sn 0.5the sintering temperature of catalyst is 750 ℃, is labeled as 7.5Ce/Ti 0.5sn 0.5-750.The XRD of different carriers and catalyst and specific area are to such as shown in Fig. 1 and table 1.
Table 1
Figure BDA0000452542670000031
The NH of embodiment 2. catalyst 3-SCR performance evaluation
The catalyst of preparation in embodiment 1 is applied to NH 3-SCR reaction, 7.5Ce/Ti xsn 1-xshow the good catalytic activity that is better than one-component carrier, without SO 2and H 2under O condition, the active form of the catalyst of preparing after titanium tin constituent optimization is wider than industrial catalyst, and it the results are shown in Figure 2.Meanwhile, 7.5Ce/Ti 0.5sn 0.5the Performance Ratio of catalyst after high temperature (750oC) is aging is better without the Ce/Ti catalyst performance of high temperature ageing, has confirmed that Ce/TiSn catalyst has good heat endurance.This reaction is carried out on micro-catalytic reaction device, and reacting gas consists of 500ppm NH 3, 500ppm NO, 5%O 2, residual air is N 2, air speed is 100,000h -1, catalyst amount is 0.1 g, the temperature of catalytic reaction is 150-450 ℃, NO conversion ratio and the N of reaction 2selective use infrared method detect.
Embodiment 3 different content CeO 2/ Ti 0.5sn 0.5o 2the NH of catalyst 3-SCR performance evaluation
According to the method in embodiment 1, prepare different content CeO 2/ Ti 0.5sn 0.5o 2catalyst, CeO 2load capacity be respectively the x(x=4.5%-22.5% of catalyst gross mass), identified as samples is designated as xCe/TiSn.Meanwhile, the NH to catalyst according to the method in embodiment 2 3-SCR performance is evaluated, and it the results are shown in Figure 3.Can find, at selected CeO 2load capacity within the scope of, Ce/TiSn catalyst all shows excellent NO conversion ratio and N 2selectively.
The anti-SO of embodiment 4 catalyst 2with anti-H 2o performance evaluation
With the 7.5Ce/Ti of preparation in embodiment 1 0.5sn 0.5catalyst carries out anti-SO 2with anti-H 2o performance test, its result is as Fig. 4.Reacting gas consists of 500ppm NH 3, 500ppm NO, 5%O 2, 100ppm SO 2(during anti-sulphur test, using), 3.5%H 2o (g)(during water resistant test, using), residual air is N 2, air speed is 100,000h -1, catalyst amount is 0.1g, reaction temperature is 300 ℃.

Claims (3)

1. one kind with Ti xsn 1-xo 2the CeO that [0.25≤x≤0.75] solid solution is carrier 2/ Ti xsn 1-xo 2the preparation method of metal oxide catalyst, is characterized in that it comprises the steps:
The TiCl that step 1. is 1:3-3:1 by titanium tin mol ratio 4ethanolic solution and SnCl 4aqueous solution is even, then, under vigorous stirring, concentrated ammonia liquor is dropwise added in mixed solution, until the pH=9.0 of solution makes its precipitation completely, age overnight, eccysis Cl -, 110 ℃ of oven dry, then 550 ℃ of roasting 4h under air atmosphere, obtain Ti xsn 1-xo 2solid solution;
The Ti that step 2. obtains with step 1 xsn 1-xo 2solid solution is carrier, uses 0.1molL -1ce (NO 3) 36H 2o solution is maceration extract, is impregnated into Ti xsn 1-xo 2on carrier, active component CeO 2the mass fraction that accounts for catalyst is 4.5%-22.5%, stirs 3h, 100 ℃ of evaporating water of oil bath, and dry 12h at 110 ℃, lower 500 ℃ of-750 ℃ of roasting 4h of air atmosphere, obtain with Ti xsn 1-xo 2solid solution is the cerium oxide catalyst of carrier.
One kind by method described in claim 1, made with Ti xsn 1-xo 2(0<x<1) CeO that solid solution is carrier 2/ Ti xsn 1-xo 2metal oxide catalyst.
3. the application of cerium titanium tin composite oxide catalysts claimed in claim 2 in smoke catalytic denitration.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104209115A (en) * 2014-09-01 2014-12-17 东南大学 Vanadium-series loading type high-temperature SCR catalyst and preparation method thereof
CN106268754A (en) * 2016-08-18 2017-01-04 王欧庭 A kind of Environmentally-friedenitration denitration catalyst and preparation technology thereof
CN109174094A (en) * 2018-09-18 2019-01-11 贵州大学 A kind of preparation method and application of Rutile Type solid-solution material
CN110270342A (en) * 2019-07-04 2019-09-24 南京大学 A kind of iron cerium aluminum oxide catalyst, preparation method and applications
CN113198452A (en) * 2021-05-18 2021-08-03 贵州大学 Rutile phase solid solution denitration catalyst, preparation method and application
CN113522316A (en) * 2021-08-27 2021-10-22 济南大学 Gas-phase cerium titanium sulfide loaded tin oxide catalyst and preparation method and application thereof
CN113522267A (en) * 2021-08-27 2021-10-22 济南大学 Tin-cerium-titanium composite oxide catalyst and preparation method and application thereof

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CN101204650A (en) * 2006-12-20 2008-06-25 中国科学院生态环境研究中心 Cerium and titanium compound oxide catalyst for flue gases denitration
CN102500355A (en) * 2011-11-07 2012-06-20 南京大学 Preparation method for supported metal oxide nanocatalyst using TixSn1-xO2 solid solution as carrier
CN102861565A (en) * 2012-09-14 2013-01-09 上海电力学院 Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101204650A (en) * 2006-12-20 2008-06-25 中国科学院生态环境研究中心 Cerium and titanium compound oxide catalyst for flue gases denitration
CN102500355A (en) * 2011-11-07 2012-06-20 南京大学 Preparation method for supported metal oxide nanocatalyst using TixSn1-xO2 solid solution as carrier
CN102861565A (en) * 2012-09-14 2013-01-09 上海电力学院 Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104209115A (en) * 2014-09-01 2014-12-17 东南大学 Vanadium-series loading type high-temperature SCR catalyst and preparation method thereof
CN106268754A (en) * 2016-08-18 2017-01-04 王欧庭 A kind of Environmentally-friedenitration denitration catalyst and preparation technology thereof
CN109174094A (en) * 2018-09-18 2019-01-11 贵州大学 A kind of preparation method and application of Rutile Type solid-solution material
CN110270342A (en) * 2019-07-04 2019-09-24 南京大学 A kind of iron cerium aluminum oxide catalyst, preparation method and applications
CN113198452A (en) * 2021-05-18 2021-08-03 贵州大学 Rutile phase solid solution denitration catalyst, preparation method and application
CN113522316A (en) * 2021-08-27 2021-10-22 济南大学 Gas-phase cerium titanium sulfide loaded tin oxide catalyst and preparation method and application thereof
CN113522267A (en) * 2021-08-27 2021-10-22 济南大学 Tin-cerium-titanium composite oxide catalyst and preparation method and application thereof
CN113522316B (en) * 2021-08-27 2023-09-29 济南大学 Gas phase cerium-titanium sulfide supported tin oxide catalyst and preparation method and application thereof

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