CN103182312A - Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof - Google Patents
Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof Download PDFInfo
- Publication number
- CN103182312A CN103182312A CN2011104586719A CN201110458671A CN103182312A CN 103182312 A CN103182312 A CN 103182312A CN 2011104586719 A CN2011104586719 A CN 2011104586719A CN 201110458671 A CN201110458671 A CN 201110458671A CN 103182312 A CN103182312 A CN 103182312A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- flue gas
- water vapor
- tio
- vapor content
- 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.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a low temperature NH3-SCR denitration catalyst for a flue gas with low water vapor content. The catalyst is an oxide prepared by an impregnation method with TiO2 as a carrier loaded with Mn, Ce and Nb. The invention also discloses a preparation process of the catalyst. A preparation process of the catalyst is simple and easy to operate. The addition of Nb increases denitration performance of the catalyst for the flue gas with water vapor content as high as 12% and SO2 content of 1,000 ppm. The denitration rate at a temperature of 160 DEG C and in presence of 12% of water vapor and 1,000 ppm of SO2 can reach over 80%.
Description
Technical field
The present invention relates to a kind of catalyst, more specifically, the present invention relates to a kind of low temperature NH for high water vapor content denitrating flue gas
3-SCR catalyst and preparation method.
Background technology
Oxynitrides (NO, NO
2, N
2O and N
2O
3Deng) be one of main air pollution sources, human respiratory there is spread effect, be the main cause that photochemical fog, acid rain, ozone cavity and greenhouse effects form.Selective catalytic reduction (SCR, Selective Catalytic Reduction) is the most effective method of denitration at present.Use NH
3Key reaction as reducing agent
[1]Have:
4NO+4NH
3+O
2→4N
2+6H
2O
2NO
2+4NH
3+O
2→3N
2+6H
2O
The more successful SCR denitrating catalyst of commercial mainly is with titanium vanadium base (V
2O
5/ TiO
2) be main high temperature SCR denitrating catalyst, by adding WO
3 [2], MO
3 [3], CeO
2 [4]Improve the stability of catalyst Deng auxiliary agent.Though vanadium titanium catalyst series has very high denitration activity and opposing SO
2Ability, but also have a lot of shortcomings.This catalyst only just has higher activity greater than 350 ℃ the time, and high temperature SCR denitrification apparatus is located at after the economizer, before air preheater and the desulfurizer, because flue gas does not carry out dust removal process, cause the catalyst duct to stop up easily, influence catalyst life.Be arranged in after the desulfurization if will contain the denitrification apparatus of high temperature SCR catalyst, want to reach SCR activity of such catalysts temperature in this case and must heat flue gas, increased energy consumption.Therefore a lot of researchers have the research of the SCR catalyst of greater activity when developing low temperature.The good low-temperature SCR catalyst of having reported at present of catalytic performance mainly contains metal oxide catalyst, molecular sieve catalyst, carbon base catalyst and noble metal catalyst etc., and is wherein of greatest concern with the various transition metal oxides of load on the carrier.As MgO-CeO
2 [5], MnOx/Al
2O
3 [6]And MnOx-CeO
2 [7]Represented different denitration activity at 80-250 ℃.M.Richter
[8]Prepared the Mn/NaY catalyst of eggshell type with coprecipitation, be lower than 200 ℃ in temperature, air speed is 30000-50000h
-1The time NO conversion ratio reach 80%-100%.Qi
[9]The composite catalyst Mn-CeO of the manganese of report
2Be the highest active catalyst in the low-temperature SCR catalyst of reporting at present, experimental study shows that the mol ratio at Mn (Mn+Ce) is at 0.3 o'clock, and this catalyst is under 120 ℃ low temperature, and air speed is 42000h
-1The time keep nearly 100% denitration efficiency, but generally all do not investigate high concentration water's steam and SO
2There is the influence to catalyst activity simultaneously.Water vapour content is very high in the flue gas that boiler combustion produces in some large-scale steel mills, and this just need consider the resistance to water of catalyst.
Niobium compound is the novel catalysis material of a class, has obtained a lot of application in acid catalyzed reaction, both can be used as the activity of such catalysts major constituent in this class Preparation of catalysts process, also can be used as auxiliary agent.The compound of niobium is modal to be niobium pentaoxide, stable in the air, water insoluble.Because MnOx-CeOx/TiO
2Active and the problem that exists of good low temperature SCR denitration, this present invention has adopted immersion process for preparing Mn-Ce/TiO
2And Nb-Mn-Ce/TiO
2Catalyst obtains good low temperature active, can keep good activity simultaneously in the presence of high concentration water's steam and sulfur dioxide.
List of references
[1]M.Rcihter，R.Eckelt，B.Parlitz，et?al.Low-temperature?conversion?of?NOx?to?N
2?by?zeolite-fixed?ammonium?ions[J].Applied?Catalysis?B：Enviromental，1998，15：129-146
[2]J.P.Chen，R.T.Yang.Role?of?WO
3?in?mixed?V
2O
5-WO
3/TiO
2?catalysts?for?selective?catalytic?reduction?of?nitric?oxide?with?ammonia[J].Applied?Catalysis?A：General，1992，80(1，2)：135-148
[3]Laura?Casagrande，Luca?Lietti，Isabella?Nova，et?al.SCR?of?NO?by?NH
3?over?TiO
2-support?V
2O
5-MoO
3?catalysts?reactivity?and?redox?behavior[J].Applied?Catalysis?B：Enviromental，1992，22：63-67
[4]HUANG?Yan，TONG?Zhi-quan，WU?Bing，et?al.Low?temperature?selective?catalytic?reduction?of?NO?by?ammonia?over?V
2O
5-CeO
2/TiO
2[J].J?Fuel?Chem?Technol，2008，36(5)：616-620
[5]Costas?N.Costa，Angelos?M.Efstathiou.Low-temperature?H
2-SCR?of?NO?on?a?novel?Pt/MgO-CeO
2?catalyst[J].Applied?Catalysis?B：Environmental，2007，72：240-252
[6]L.Singoredjo，F.Kapteijn.Alumina?Supported?Manganese?Catalysts?for?Low?Temperature?Selective?Catalytic?Reduction?of?NO?with?NH
3[J].Surface?Science?and?Catalysis，1993，75：2705-2708
[7]Maria?Casapu，Oliver?Krocher，Martin?Elsener.Screening?of?doped?MnOx-CeO
2for?low?temperature?NO-SCR[J].Applied?Catalysis?B：Enviromental，2009，88：413-419
[8]M.Rcihter，A.Trunschke，U.Bentrup，et?al.Selective?catalytic?reduction?of?nitric?oxide?by?ammonia?over?egg-shell?MnOx/NaY?composite?catalysts[J].Journal?of?Catalysis，2002，206：98-113
[9]Gongshin?Qi，Ralph?T.Yang.Performance?and?kinetics?study?for?low-temperature?SCR?of?NO?with?NH
3?over?MnOx-CeO
2?catalyst[J].Journal?of?Catalysis，2003，217：434-441
[10]Kozo?Tanabe.Catalytic?application?of?niobium?compounds[J].Catalysis?Today，2003，78：65-77
[11]K.Tanabe，S.Okazaki.Various?reactions?catalyzed?by?niobium?compounds?and?materials[J].Applied?Catalysis?A：General，1995，133：191-218
[12] Li Yingcheng, Yue Bin, Yang Weimin etc. the application [J] of niobic acid/niobium oxide in heterogeneous catalytic reaction. chemistry circular, 2005, (3): 172-178
[13] Zhang Junfeng, Zhang Hongmei, Li Yaqin. the niobium amount [J] in the gravimetric detemination niobium oxalate. Hunan non-ferrous metal, 2010,26 (3): 66-69
[14]Boxiong?Shen，Ting?Liu，Ning?Zhao，et?al.Iron-doped?Mn-Ce/TiO
2?catalyst?for?low?temperature?selective?catalytic?reduction?of?NO?with?ammonia[J].Journal?of?Environmental?Sciences，2010，22(9)：1447-1454
[15] Liu Wei, Tong Zhiquan, Luo Jie .Ce-Mn/TiO
2The low temperature active of catalyst selectivity Reduction of NO and antitoxin voltinism energy [J]. ACTA Scientiae Circumstantiae, 2006,26 (8): 1240-1245
[16] Liu Xiyao. the industrial catalyst analytical test characterizes [M]. Beijing: hydrocarbon processing publishing house, 1990:344-345.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of high water vapor content flue gas low-temperature NH3-SCR denitrating catalyst and preparation method thereof.
The present invention realizes by following technical scheme:
A kind of low temperature NH that is applicable to high water vapor content denitrating flue gas
3-SCR catalyst, described catalyst is for using infusion process with TiO
2Be carrier, the oxide of load Mn, Ce and Nb.
Described catalyst is Ni (x)-Mn-Ce-TiO
2, x≤0.1, wherein x is Ni, Ti mol ratio.
The Mn element that adds in the described catalyst is 0.2 with the ratio of the mole of Ti element.
The Ce element that adds in the described catalyst is 0.3 with the ratio of the mole of Ti element.
The Nb element that adds in the described catalyst is 0-0.1 with the ratio of the mole of Ti element.
A kind of high water vapor content flue gas low-temperature NH
3The preparation method of-SCR denitrating catalyst, it comprises the steps: to be dissolved in a certain amount of niobium oxalate 50 ℃-80 ℃ quantitative deionized water, after described niobium oxalate dissolves fully, add a certain amount of cerium salt and manganese salt and be configured to mixed solution, add through pretreated TiO
2Keep mixed solution to stir 1-5 hour down at 50 ℃-80 ℃, left standstill 1-5 hour; Descended dry 10-15 hour at 100 ℃-150 ℃, at 550 ℃ of-600 ℃ of following roasting 6-10 hours, sieving obtained being applicable to the low temperature NH of high water vapor content denitrating flue gas
3-SCR catalyst.
The manganese salt that uses among the described preparation method comprises manganese nitrate, manganese acetate and manganese sulfate.
The cerium salt that uses among the described preparation method comprises cerous sulfate, cerous nitrate, cerous acetate and ammonium ceric nitrate.
Among the described preparation method again reaction temperature in 80-200 ℃ of scope to the NH of high water vapor content flue gas
3-SCR denitration conversion ratio reaches more than 50%.
A kind of described catalyst is at the NH that is suitable for high water vapor content flue gas low-temperature
3Application in the-SCR denitration reaction.
Beneficial effect of the present invention is: catalyst preparation process of the present invention is simple, and is easy to operate, and the catalyst of this technology preparation is applicable to the NH of high water vapor content flue gas
3-SCR denitration has very high low temperature active.The Nb of preparation and the mol ratio of Ti are 0.025 Nb-Mn-Ce/TiO
2Catalyst is at 160 ℃ of temperature, air speed 20000h
-1, NO, NH
3And SO
2Concentration 1000ppm, O
2Content is that the denitration rate can reach more than 83.6% under 1%, 12% steam existed.
Description of drawings
Fig. 1 is catalyst activity evaluating apparatus flow chart of the present invention;
Fig. 2 is Nb of the present invention (x)-Mn-Ce/TiO
2The denitration activity of catalyst;
Fig. 3 is Mn-Ce/TiO under the differential responses condition of the present invention
2Activity of such catalysts;
Fig. 4 is Nb under the differential responses condition of the present invention
(0.1)-Mn-Ce/TiO
2Activity of such catalysts;
Fig. 5 is the NH of different catalysts of the present invention
3The contrast of-TPD collection of illustrative plates;
Fig. 6 is that the present invention adds Nb front and back catalyst to the resistance contrast of high concentration water's steam and SO2.
The specific embodiment
The invention provides a kind of low temperature NH that is applicable to high water vapor content denitrating flue gas
3-SCR catalyst and preparation method below will the present invention will be further described by specific embodiment.
Embodiment 1
Take by weighing the 7.44g niobium oxalate and be dissolved in 50 ℃ 20ml deionized water, treat that niobium oxalate dissolves fully after, in niobium oxalate solution, add the 21.05g cerous nitrate and the 7.92g manganese acetate is configured to mixed solution, in mixed solution, add 12.91g TiO
2Make mixture, keep mixture to stir 1 hour down at 50 ℃, make mixture full and uniform, left standstill 1 hour.Drying is 12 hours under 120 ℃, at 550 ℃ of following roasting 6h.Product of roasting cooling back is pulverized, sieve, get less than 80 order powder standby.It is even less than the boehmite powder of 80 purpose powder and 3.00g to take by weighing 7.00g, the 10wt% salpeter solution that adds 2.0ml in mixed-powder is mixed into the dough shape and puts into syringe and be extruded into strip, drying is 12 hours under 120 ℃, at 550 ℃ of following roasting 6h.Cool off after the roasting, crushing screening is got 20-40 order part as catalyst.
The denitration rate detection method of the catalyst for preparing is: at first measure by the NO concentration in the simulated flue gas before the reactor with the NOx nitrogen-oxide analyzer,, then catalyst is placed in the tubular fixed-bed reactor, by electric furnace reactor is heated to needed temperature, feeds simulated flue gas and reducing agent NH
3, with the NO concentration in the NOx nitrogen-oxide analyzer, measurement reactor outlet flue gas, the denitration rate calculating formula of catalyst is:
In the following formula: Co is for entering the preceding NO concentration of reactor; C is the NO concentration of reactor outlet.
Detect catalyst to SO
2During with the resistance of steam, in simulated flue gas, feed 1000ppmSO
2With 12% steam.
The result obtains by active testing, and this catalyst is at 160 ℃ of temperature, air speed 20000h
-1, NO, NH
3And SO
2Concentration 1000ppm, O
2Content is that the denitration rate can reach 82.8% under 1%, 12% steam existed.
Take by weighing the 1.86g niobium oxalate and be dissolved in 50 ℃ 20ml deionized water, treat that niobium oxalate dissolves fully after, in niobium oxalate solution, add the 21.05g cerous nitrate and the 7.92g manganese acetate is configured to mixed solution, in mixed solution, add 12.91g TiO
2Make mixture, keep mixture to stir 1 hour down at 50 ℃, make mixture full and uniform, left standstill 1 hour.Drying is 12 hours under 120 ℃, at 550 ℃ of following roasting 6h.Product of roasting cooling back is pulverized, sieve, get less than 80 order powder standby.It is even less than the boehmite powder of 80 purpose powder and 3.00g to take by weighing 7.00g, the 10wt% salpeter solution that adds 2.0ml in mixed-powder is mixed into the dough shape and puts into syringe and be extruded into strip, drying is 12 hours under 120 ℃, at 550 ℃ of following roasting 6h.Cool off after the roasting, crushing screening is got 20-40 order part as catalyst.
The denitration rate detection method of the catalyst for preparing is with embodiment 1.
The result obtains by active testing, and this catalyst is at 160 ℃ of temperature, air speed 20000h
-1, NO, NH
3And SO
2Concentration 1000ppm, O
2Content is that the denitration rate can reach 83.6% under 1%, 12% steam existed.
Embodiment 3
Take by weighing 21.05g cerous nitrate and 7.92g manganese acetate and be dissolved in 50 ℃ 20ml deionized water, be configured to mixed solution, in mixed solution, add 12.91g TiO
2Make mixture, keep mixture to stir 1 hour down at 50 ℃, make mixture full and uniform, left standstill 1 hour.Drying is 12 hours under 120 ℃, at 550 ℃ of following roasting 6h.Product of roasting cooling back is pulverized, sieve, get less than 80 order powder standby.It is even less than the boehmite powder of 80 purpose powder and 3.00g to take by weighing 7.00g, the 10wt% salpeter solution that adds 2.0ml in mixed-powder is mixed into the dough shape and puts into syringe and be extruded into strip, drying is 12 hours under 120 ℃, at 550 ℃ of following roasting 6h.Cool off after the roasting, crushing screening is got 20-40 order part as catalyst.
The denitration rate detection method of the catalyst for preparing is with embodiment 1.
The result obtains by active testing, and this catalyst is at 160 ℃ of temperature, air speed 20000h
-1, NO, NH
3And SO
2Concentration 1000ppm, O
2Content is that the denitration rate can reach 68.7% under 1%, 12% steam existed.
Accompanying drawing 6 can find out obviously that adding Nb rear catalyst is to high concentration water's steam and SO
2Resistance be significantly improved.
Embodiment
1 experimental section
1.1 Preparation of catalysts
Preparation of catalysts adopts infusion process, is dissolved in 50 ℃ quantitative deionized water with a certain amount of niobium oxalate, after niobium oxalate dissolves fully, adds a certain amount of cerous nitrate and manganese acetate and is configured to mixed solution, adds through pretreated titanium dioxide.Keep temperature to stir 1 hour down for 50 ℃, left standstill 1 hour.Drying is 12 hours under 120 ℃, at 550 ℃ of following roasting 6h.The ratio of Mn and Ti mole be 0.2, Ce with the ratio of Ti mole is 0.3 in all catalyst of preparation.Catalyst Nb (x)-Mn-Ce/TiO
2Expression, the wherein mole of the Nb that represents of x and Ti such as Nb (0.1)-Mn-Ce/TiO
2Testing used niobium oxalate is Ningxia tantalum industry company product, and manganese acetate is that Xing Ta chemical plant, Kingsoft, Shanghai produces, and cerous nitrate and titanium dioxide are from Chemical Reagent Co., Ltd., Sinopharm Group.Quartz sand is that Shanghai Ling Feng chemical reagent Co., Ltd produces.
1.2 the mensuration of content of niobium in the niobium oxalate
Niobium oxalate comprises (NH
4)
3[NbO (C
2O
4)
3], NH
4[NbO (C
2O
4)
2] and NH
4[NbO
2C
2O
4] serial complex compound, different with working condition according to raw material, the content difference of niobium in the niobium oxalate.Resolve into niobium pentaoxide at 250 ℃.Content of niobium is one of important control index of producing niobium oxalate.The content of concrete niobium is indeterminate in the niobium oxalate that this paper adopts, and adopts the content of niobium in the gravimetric detemination niobium oxalate, has optimized condition determination, and the niobium oxalate calcination is become niobium pentaoxide, comes the content of niobium in the calculating oxalate niobium by weight difference before and after the calcination.Take by weighing a certain amount of niobium oxalate and put into the good porcelain crucible of constant weight, put into Muffle furnace, every group arranges different calcining heats, the calcining regular hour, and take out and to be cooled to room temperature, weigh, by the content that comes niobium in the calculating oxalate niobium of poor quality.Respectively calcining heat is set at 650 ℃, 750 ℃ and 850 ℃ in the test, calcination time is set at 2 hours, 4 hours and 6 hours.Discovery in calcining heat that this test is set and time range different calcining heats and time to recording not obviously influence of content of niobium in the niobium oxalate at last.The mass fraction that records niobium in the niobium oxalate at last is 20.0578%.
1.3 catalyst activity property testing
SCR denitration activity to catalyst in fixed bed reactors is tested, and reactor is vertical tube shape, and fill with quartz sand at two ends up and down, the middle catalyst of placing.Active testing device schematic diagram as shown in Figure 1.All cyclinder gas are all opened Gas Technologies LLC from last sea God.Gas flow is controlled with the CS200A type mass flowmenter of Beijing Qixing Huachuang Electronics Co., Ltd.Steam is to enter blender by nitrogen through the steam generator.What be used for controlling the water vapor generation device temperature is that Beijing letter reaches the SDC-6 type low temperature thermostat bath that new occasion bio tech ltd is produced.Reactor and mixer temperature are controlled by the program temperature controller.Water vapor generation device has insulation belt control temperature to pipeline and the blender of blender to pipe reactor.Import and export NO
xThe 42iHL-DNSBDAB type high concentration chemoluminescence method NO-NO that concentration is produced by U.S. Thermo Scientific company
2-NO
xAnalyzer carries out online detection.Enter NO at blender
xUse the NH in the phosphoric acid absorption liquid absorption gaseous mixture before the analyzer
3, in order to avoid influence the NOx testing result.NO
xAnalyze outlet tail gas and absorb the sour gas that exports with alkali lye, prevent from polluting the laboratory air.At water vapor generation device, NH
3Before absorption bottle and the tail gas absorption bottle safety flack is housed all, prevents liquid suck-back infringement laboratory apparatus.
NO and NH in the reacting gas
3Concentration is 1000ppm, and oxygen is 1% of total gas volume.Detect and add SO when sulfur dioxide and steam influence catalyst activity
2Concentration be 1000ppm, steam accounts for 12% of total sample introduction gas volume, remains to be nitrogen.Reaction temperature is got a probe temperature from 80 ℃ to 240 ℃ every 20 degrees centigrade.Air speed is 20000h
-1Each change experiment condition after, wait the NOx assay readings stable and keep reading behind the 30min.
1.4 the sign of catalyst
Characterize crystal structure and the form of analysis of catalyst with XRD (X-ray diffraction), used instrument is the D/max2550V type X-ray diffractometer of Japanese Co., Ltd. of science, and Cu K α is radiographic source, and tube voltage is 40kV, and tube current is 100mA.XPS (X-ray photoelectron spectroscopic analysis) is used for detecting the surface atom attitude of catalyst, the X ray electron spectrometer, and Al K α monochromatic radiation is radiographic source.Adopt XRF (X-ray fluorescence spectra analysis) to come the content of each element in the analysis of catalyst, use be the XRF-1800 type sequential scanning Xray fluorescence spectrometer that day island proper Feng company produces.
The AutoChem2920 type NH that uses Micromeritics company to produce
3-TPD analyzer carries out the temperature programmed desorption analysis, uses catalytic amount to be 0.3g.Analyze room temperature when analyzing beginning and rise to 250 ℃ from room temperature, per minute heats up 20 ℃, and temperature-rise period is swept with the He air-blowing, maintains the temperature under 250 ℃ of environment the He air-blowing and sweeps one hour.In He compression ring border, be cooled to room temperature then, feed gas NH
3Adsorb, keep 10 minutes saturated to adsorbing.Adsorb the sample after saturated, swept 30 minutes 100 ℃ of following He air-blowings.Treat to begin desorption after the baseline stability, set temperature controller with the speed of 10 ℃ of per minutes from 100 ℃ to 600 ℃.With the TCD detector to NH
3Desorption quantitatively detects.
2 results and discussion
2.1 the Nb of different niobium load capacity (x)-Mn-Ce/TiO
2Catalyst
2.1.1 the Nb of different niobium load capacity (x)-Mn-Ce/TiO
2Activity of such catalysts
In order to obtain the optimum addition of Nb in the niobium modified catalyst, using reagent, preparation method and calcining heat have all prepared Nb (the x)-Mn-Ce/TiO that adds different N b content under the identical situation
2Catalyst.
As shown in Figure 2, investigated Mn-Ce/TiO respectively
2, Nb (0.0125)-Mn-Ce/TiO
2, Nb (0.025)-Mn-Ce/TiO
2, Nb (0.05)-Mn-Ce/TiO
2And Nb (0.1)-Mn-Ce/TiO
2Five kinds of catalyst are from 80 ℃ to 240 ℃ denitration activity.Enter NH in the mist of reactor
3With NO be 1000ppm, O
2Account for total gas volume 1%, all the other are N
2, air speed is 20000h
-1As can be seen from Figure 2, all Nb (x)-Mn-Ce/TiO
2The denitration activity of catalyst raises along with the rising of temperature.When temperature was lower than 160 ℃, catalyst denitration activity ascensional range was bigger, and after temperature surpassed 160 ℃, ascensional range slowed down, and tended towards stability after 200 ℃.By relatively different N b addition catalyst activity discovery, at 80 ℃ to 180 ℃, when the Nb/Ti of catalyst mol ratio rises to 0.025 from 0, activity of such catalysts increases along with the increase of Nb addition under the same reaction temperature, illustrates that the interpolation of Nb can significantly improve Mn-Ce/TiO
2The low-temperature catalytic activity of catalyst.But the Nb/Ti mol ratio rises to 0.1 from 0.025, and the catalyst denitration activity does not almost change, and between 120 ℃ to 160 ℃ even reduce, may be owing to be Nb in 0.025 o'clock catalyst in the Nb/Ti mol ratio
2O
5Can well be dispersed in the catalyst, increase catalytic activity, and the addition that further increases Nb may make too much Nb
2O
5Cover the activity of such catalysts center surface and influence catalytic activity.When temperature range was 180 ℃ to 240 ℃, the interpolation of Nb almost can not change activity of such catalysts.Nb (0.025)-Mn-Ce/TiO in general
2The denitration activity of catalyst is the highest, and in the time of 80 ℃, denitration activity is 69.3%, and at 240 ℃, denitration activity reaches 95.7%.
2.1.2 the Nb of different niobium load capacity (x)-Mn-Ce/TiO
2The XRD characterization result of catalyst
Low load
[14]Nb (x)-Mn-Ce-TiO of Nb (mol ratio of Nb/Ti＜0.15)
2Catalyst X is 25.3 ° in the 2 θ angles of diffraction, and 37.8 °, 48.1 °, 53.9 °, 55.1 °, 62.7 ° of peak values are the strongest, this and Detitanium-ore-type TiO
2Highest peak is almost completely consistent in the spectrogram, is 27.48 ° in the 2 θ angles of diffraction, 36.1 ° and rutile TiO
2The spectrogram correspondence, the principal phase that titanium dioxide in the catalyst is described is anatase, also is attended by rutile TiO
2Do not have Mn and Nb oxide obvious diffraction peak, illustrate that the oxide of Mn and Nb is in amorphous state, and high degree of dispersion.Be 27.5 ° in the 2 θ angles of diffraction, 28.9 ° and 56.6 ° of peaks of locating and CeO
2The diffraction maximum correspondence, illustrate that the ceria of fixing crystalline phase exists.Compare b, c, d, e spectrogram, 27.5 °, 28.9 °, 56.6 the intensity of ° locating the peak broadens along with the growth of the mol ratio of Nb/Ti diminishes on the whole, illustrates that the crystal formation along with the increase ceria of Nb addition diminishes, and is tending towards disperse, reason may be that ceria is covered by Nb, suppresses the formation of ceria crystal formation.Compare a, b two spectrograms, along with the Nb/Ti mol ratio is increased to 0.1 from 0.05, it is 27.5 ° in the 2 θ angles of diffraction, 28.9 ° and each diffraction maximums of 56.6 ° of ceria crystal formations of locating grow to some extent, when its reason may arrive to a certain degree for Nb content, the formation of ceria crystal hindered diminish, so that crystal formation becomes is big.Compare a, b, c, d, the e spectrogram, finding increases along with the addition of Nb, is 37.0 ° in the 2 θ angles of diffraction, locates Detitanium-ore-type TiO for 48.0 ° and 62.7 °
2Diffraction maximum narrow down, come to a point, this shows along with the addition of Nb increases, can make that small change takes place the crystal state of titanium dioxide in the catalyst, may be because the addition increase of Nb provide better titanium ore type TiO
2The crystal grain formation condition makes the TiO of Detitanium-ore-type
2It is big that crystal grain becomes.
2.2Mn-Ce/TiO
2And Nb (0.1)-Mn-Ce/TiO
2Catalyst
2.2.1Mn-Ce/TiO
2Activity of such catalysts
Investigated adding SO
2And at SO
2There is Mn-Ce/TiO under the situation simultaneously with high concentration water's steam
2The variation of the denitration activity of catalyst.As shown in Figure 3, add 1000ppmSO
2After, under less than 140 ℃ low temperature condition, Mn-Ce/TiO
2The denitration activity fall of catalyst is very little, and this is that the ammonium sulfate of part generates owing to have only seldom under low temperature environment, so very little to the catalyst activity influence.Along with the rising of reaction temperature, the active amplitude that reduces can increase.Explanation is greater than 200 ℃ of following SO
2Can make Mn-Ce/TiO
2The denitration activity of catalyst obviously reduces, and along with this influence of the rising of reaction temperature is more obvious, this is owing to the rising along with temperature, the growing amount of hydrogen sulfate ammonium salt increases, be attached to the activity of such catalysts center, the blocking catalyst duct makes catalysqt deactivation.At 1000ppmSO
2Exist simultaneously down with 12% steam, it is very big that catalyst activity reduces amplitude, and the reduction that at this moment causes catalytic activity may be because steam in active sites absorption has taken place, and has reduced NH
3In the absorption of catalyst surface, further influenced the reduction of nitrogen oxide
[15]Adding 1000ppmSO
2Under 12% steam situation, Mn-Ce/TiO
2The denitration activity of catalyst still increases along with the rising of temperature generally.
2.2.2Nb (0.1)-Mn-Ce/TiO
2Activity of such catalysts
In order relatively to add the Nb rear catalyst to the variation of steam and sulfur dioxide resistivity, tested Mn-Ce/TiO
2Catalyst is at SO
2Investigated Nb (0.1)-Mn-Ce/TiO simultaneously after the denitration activity variation down with the existence of high concentration water's steam
2The variation of catalyst denitration activity.As shown in Figure 4, add 1000ppmSO
2After, under less than 100 ℃ low temperature condition, Nb (0.1)-Mn-Ce/TiO
2The denitration activity of catalyst does not almost change, and along with the rising of reaction temperature, the active amplitude that reduces can increase, this and Mn-Ce/TiO
2Adding SO
2Back denitration activity changes corresponding, catalyst is improved anti-SO after adding Nb be described
2Ability does not have help clearly.Adding 1000ppmSO
2Add 12% steam on the basis again, catalyst activity adds SO relatively
2The time to reduce amplitude very little, pass through NH
3-TPD finds, L (lewis) acid amount and the total acid content of the catalyst after the adding Nb modification all obviously increase, because it mainly is because in active sites absorption has taken place that the catalyst activity that steam causes reduces, the quantity of active sites increases after adding Nb, has explained the reason that the catalyst after the Nb modification increases the steam resistivity.
2.2.3Mn-Ce/TiO
2And Nb (0.1)-Mn-Ce/TiO
2NH
3-TPD
Use NH
3-TPD acid test detects acid strength and the acidity of catalyst.When the alkaline gas molecule contacts with solid catalyst surface, except gas-solid physical absorption takes place, also chemisorbed can take place, i.e. the strong absorption of alkaline gaseous molecular on the acidity of catalyst position.This kind suction-operated is earlier from the strong acid position, and progressively to the weak acid sites development, desorption process is opposite in this
[16]
Pass through NH
3-TPD acid test has obtained Nb (0.1)-Mn-Ce/TiO
2And Mn-Ce/TiO
2NH
3The desorption signal peak.As shown in Figure 5, at the NH of two catalyst
3All occurred 3 signal peaks in the-TPD collection of illustrative plates, be considered to the physics desorption less than 100 ℃ signal peaks, the physics desorption signal peak complete-superposing of two samples.Second desorption peaks appears between 100-300 ℃, the desorption signal peak that is considered to the sour adsorption potential of L (Lewis), the peak area at second peak of catalyst after the Nb modification obviously increases and skew to the right, and acid enhancing of L acid of Nb modification rear catalyst is described, and L acid acid amount also increases.The 3rd peak appears between 300-550 ℃, be one than the NH of highly acid position
3Desorption peaks, the Nb after the Nb modification (0.1)-Mn-Ce/TiO
2The peak area at second peak of catalyst is compared Mn-Ce/TiO
2Catalyst increases a lot, and acid enhancing of strong acid of Nb modification rear catalyst is described.Two desorption peaks are totally compared, and L acid and the total acid content of Nb modification rear catalyst all obviously increase.
2.2.4Mn-Ce/TiO
2And Nb (0.1)-Mn-Ce/TiO
2XPS
2.2.5Mn-Ce/TiO
2And Nb (0.1)-Mn-Ce/TiO
2XRF
The XRF of preparation catalyst the results are shown in Table 1.Find Mn-Ce/TiO with calculating by analysis
2The Mn/Ti mol ratio is that 0.3, Ce/Ti mol ratio is near 0.23 in the catalyst; Nb (0.1)-Mn-Ce/TiO
2The Mn/Ti mol ratio is that 0.27, Ce/Ti mol ratio is 0.09 near 0.2, Nb/Ti mol ratio in the catalyst.This is all corresponding with the element proportioning of adding in the Preparation of Catalyst, illustrates that the loss amount of preparation process element is very little.Catalyst after the Nb modification with respect to modification before, the mass fraction of oxygen element significantly increases, and the mol ratio between all metallic elements does not almost not change, and illustrate that the valence state that adds metal oxide in the Nb rear catalyst raises, the relative amount rising of oxygen element.
The rerum natura of table 1 different catalysts
3 conclusions
(1) Mn-Ce/TiO
2Catalyst has good low temperature SCR denitration activity, but to SO
2Poor with the resistance of steam, at steam and SO
2There is down Mn-Ce/TiO simultaneously
2Activity declines by a big margin, and the denitration rate drops to 68.7% by original 89.2% in the time of 160 ℃.
(2) Nb (the x)-Mn-Ce/TiO behind the interpolation niobium
2Catalyst denitration rate less than 160 ℃ the time increases along with the increase of Nb addition, and when the Nb/Ti ratio was 0.025, the denitration rate reached the highest, and the addition denitration rate that increases Nb does not more change.
(3) catalyst after the Nb modification has strengthened the resistance to high concentration water's steam, at 1000ppmSO
2There is Nb (0.1)-Mn-Ce/TiO down with 12% steam
2Denitration activity still can reach 82.8% at 160 ℃.。But experiment is not to Nb (x)-Mn-Ce/TiO
2The denitration activity of catalyst is tested for a long time, Nb (x)-Mn-Ce/TiO
2The stability of catalyst and activity cycle remain further to be detected.
(4) characterize discovery, Nb (x)-Mn-Ce/TiO by XRD
2The oxide of manganese and niobium does not have tangible crystal formation in the catalyst, is tending towards disperse, is in the state of high degree of dispersion.Valence state by metal in the metal oxide after the XRF characterization result discovery Nb modification uprises.NH
3-TPD acid test shows that L (Lewis) acid amount and total acid content obviously increase behind the adding Nb.
The above only is the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any variation or replacement of expecting without creative work all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (10)
1. low temperature NH who is used for high water vapor content denitrating flue gas
3-SCR catalyst is characterized in that: described catalyst is for using infusion process with TiO
2Be carrier, the oxide of load Mn, Ce and Nb.
2. the low temperature NH for high water vapor content denitrating flue gas as claimed in claim 1
3-SCR catalyst is characterized in that: described catalyst is Ni (x)-Mn-Ce-TiO
2, x≤0.1, wherein x is Ni, Ti mol ratio.
3. as claim 1 or 2 arbitrary described low temperature NH for high water vapor content denitrating flue gas
3-SCR catalyst is characterized in that: the Mn element that adds in the described catalyst is 0.2 with the ratio of the mole of Ti element.
4. as claim 1 or 2 arbitrary described low temperature NH for high water vapor content denitrating flue gas
3-SCR catalyst is characterized in that: the Ce element that adds in the described catalyst is 0.3 with the ratio of the mole of Ti element.
5. as claim 1 or 2 arbitrary described low temperature NH that are applicable to high water vapor content denitrating flue gas
3-SCR catalyst is characterized in that: the Nb element that adds in the described catalyst is 0-0.1 with the ratio of the mole of Ti element.
6. one kind as claim 1 or 2 arbitrary described low temperature NH for high water vapor content denitrating flue gas
3-SCR Preparation of catalysts method, it comprises the steps: to be dissolved in a certain amount of niobium oxalate 50 ℃-80 ℃ quantitative deionized water, after described niobium oxalate dissolves fully, add a certain amount of cerium salt and manganese salt and be configured to mixed solution, add through pretreated TiO2; Keep mixed solution to stir 1-5 hour down at 50 ℃-80 ℃, left standstill 1-5 hour; Descended dry 10-15 hour at 100 ℃-150 ℃, at 550 ℃ of-600 ℃ of following roasting 6-10 hours, sieving obtained being applicable to the low temperature NH3-SCR catalyst of high water vapor content denitrating flue gas.
7. preparation method as claimed in claim 6, it is characterized in that: the manganese salt that uses among the described preparation method comprises manganese nitrate, manganese acetate and manganese sulfate.
8. preparation method as claimed in claim 6, it is characterized in that: the cerium salt that uses among the described preparation method comprises cerous sulfate, cerous nitrate, cerous acetate and ammonium ceric nitrate.
9. preparation method as claimed in claim 6 is characterized in that: among the described preparation method again reaction temperature in 80-200 ℃ of scope to the NH of high water vapor content flue gas
3-SCR denitration conversion ratio reaches more than 50%.
One kind as claim 1 or 2 arbitrary described catalyst at the NH that is used for high water vapor content flue gas low-temperature
3Application in the-SCR denitration reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104586719A CN103182312A (en) | 2011-12-31 | 2011-12-31 | Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104586719A CN103182312A (en) | 2011-12-31 | 2011-12-31 | Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103182312A true CN103182312A (en) | 2013-07-03 |
Family
ID=48673907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104586719A Pending CN103182312A (en) | 2011-12-31 | 2011-12-31 | Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103182312A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084165A (en) * | 2013-01-23 | 2013-05-08 | 广东电网公司电力科学研究院 | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof |
| CN104062393A (en) * | 2014-07-04 | 2014-09-24 | 江苏龙源催化剂有限公司 | Mini-type test evaluation device for integral SCR denitration catalyst reaction performance test and application method thereof |
| CN104258872A (en) * | 2014-09-21 | 2015-01-07 | 北京工业大学 | Preparation method of denitration catalytic material of low-temperature wide-active-temperature-range window |
| CN105032417A (en) * | 2015-06-05 | 2015-11-11 | 华南理工大学 | High-sulphur-resistance SCR denitration catalyst as well as preparation method and application 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 |
| CN105363434A (en) * | 2015-11-17 | 2016-03-02 | 安徽省元琛环保科技有限公司 | Manganese based SCR catalyst for low temperature denitration and preparation method thereof |
| CN105510532A (en) * | 2015-12-16 | 2016-04-20 | 河北省电力建设调整试验所 | Denitration catalytic performance evaluation system and method |
| CN105879858A (en) * | 2016-04-15 | 2016-08-24 | 中国建筑材料科学研究总院 | Denitrification catalyst and preparation method thereof |
| CN108333290A (en) * | 2018-04-17 | 2018-07-27 | 河北工业大学 | A kind of test device and test method of cement kiln low-temperature denitration of flue gas catalyst sulfur resistive water resistance |
| CN108837820A (en) * | 2018-06-06 | 2018-11-20 | 中北大学 | A kind of Ce-NbOx/ mesoporous TiO 2 high-efficiency denitration catalyst and preparation method thereof |
| CN111111647A (en) * | 2020-01-19 | 2020-05-08 | 北京科技大学 | Niobite type manganese-niobium-based SCR denitration catalyst and preparation method thereof |
| CN111167437A (en) * | 2020-01-09 | 2020-05-19 | 华侨大学 | Honeycomb low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof |
| CN117019170A (en) * | 2023-08-07 | 2023-11-10 | 江苏宁天环境科技有限公司 | Ultralow-temperature flue gas denitration catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724149A (en) * | 2005-06-24 | 2006-01-25 | 湘潭大学 | Low temp. multiple component capalyst for flue gas denitration and its preparation process |
| CN101352680A (en) * | 2008-09-08 | 2009-01-28 | 浙江大学 | TiO2 supported manganese-cerium composite oxide catalyst and preparation method thereof |
| US20090081098A1 (en) * | 2007-01-09 | 2009-03-26 | Golden Stephen J | Ammonia SCR catalyst and method of using the catalyst |
-
2011
- 2011-12-31 CN CN2011104586719A patent/CN103182312A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1724149A (en) * | 2005-06-24 | 2006-01-25 | 湘潭大学 | Low temp. multiple component capalyst for flue gas denitration and its preparation process |
| US20090081098A1 (en) * | 2007-01-09 | 2009-03-26 | Golden Stephen J | Ammonia SCR catalyst and method of using the catalyst |
| CN101443116A (en) * | 2007-01-09 | 2009-05-27 | 田中贵金属工业株式会社 | Ammonia SCR catalyst and method of using the catalyst |
| CN101352680A (en) * | 2008-09-08 | 2009-01-28 | 浙江大学 | TiO2 supported manganese-cerium composite oxide catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MARIA CASAPU ET AL: ""Screening of doped MnOx-CeO2 catalysts for low-temperature NO-SCR"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 88, 5 November 2008 (2008-11-05) * |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103084165A (en) * | 2013-01-23 | 2013-05-08 | 广东电网公司电力科学研究院 | Demercuration catalyst for elemental mercury in oxidated coal-fired flue gas and preparation method thereof |
| CN104062393A (en) * | 2014-07-04 | 2014-09-24 | 江苏龙源催化剂有限公司 | Mini-type test evaluation device for integral SCR denitration catalyst reaction performance test and application method thereof |
| CN104062393B (en) * | 2014-07-04 | 2015-12-16 | 江苏龙源催化剂有限公司 | For miniature test evaluation device and the using method thereof of overall SCR denitration reactivity worth test |
| CN104258872A (en) * | 2014-09-21 | 2015-01-07 | 北京工业大学 | Preparation method of denitration catalytic material of low-temperature wide-active-temperature-range window |
| CN105032417B (en) * | 2015-06-05 | 2018-07-20 | 华南理工大学 | A kind of SCR denitration and the preparation method and application thereof of high sulfur resistive |
| CN105032417A (en) * | 2015-06-05 | 2015-11-11 | 华南理工大学 | High-sulphur-resistance SCR denitration catalyst as well as preparation method and application 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 |
| CN105363434A (en) * | 2015-11-17 | 2016-03-02 | 安徽省元琛环保科技有限公司 | Manganese based SCR catalyst for low temperature denitration and preparation method thereof |
| CN105510532A (en) * | 2015-12-16 | 2016-04-20 | 河北省电力建设调整试验所 | Denitration catalytic performance evaluation system and method |
| CN105879858A (en) * | 2016-04-15 | 2016-08-24 | 中国建筑材料科学研究总院 | Denitrification catalyst and preparation method thereof |
| CN105879858B (en) * | 2016-04-15 | 2019-02-19 | 中国建筑材料科学研究总院 | Denitrating catalyst and preparation method thereof |
| CN108333290A (en) * | 2018-04-17 | 2018-07-27 | 河北工业大学 | A kind of test device and test method of cement kiln low-temperature denitration of flue gas catalyst sulfur resistive water resistance |
| CN108837820A (en) * | 2018-06-06 | 2018-11-20 | 中北大学 | A kind of Ce-NbOx/ mesoporous TiO 2 high-efficiency denitration catalyst and preparation method thereof |
| CN108837820B (en) * | 2018-06-06 | 2021-09-28 | 中北大学 | Ce-NbOx/mesoporous titanium dioxide efficient denitration catalyst and preparation method thereof |
| CN111167437A (en) * | 2020-01-09 | 2020-05-19 | 华侨大学 | Honeycomb low-temperature vanadium titanium-based SCR denitration catalyst for promoting ABS decomposition and preparation method thereof |
| CN111111647A (en) * | 2020-01-19 | 2020-05-08 | 北京科技大学 | Niobite type manganese-niobium-based SCR denitration catalyst and preparation method thereof |
| CN111111647B (en) * | 2020-01-19 | 2021-11-16 | 北京科技大学 | Niobite type manganese-niobium-based SCR denitration catalyst and preparation method thereof |
| CN117019170A (en) * | 2023-08-07 | 2023-11-10 | 江苏宁天环境科技有限公司 | Ultralow-temperature flue gas denitration catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103182312A (en) | Low temperature NH3-SCR denitration catalyst for flue gas with low water vapor content, and preparation method thereof | |
| Li et al. | Ho-modified Mn-Ce/TiO2 for low-temperature SCR of NOx with NH3: Evaluation and characterization | |
| Yan et al. | Unraveling the unexpected offset effects of Cd and SO2 deactivation over CeO2-WO3/TiO2 catalysts for NO x reduction | |
| Chang et al. | Comparison of preparation methods for ceria catalyst and the effect of surface and bulk sulfates on its activity toward NH3-SCR | |
| Guo et al. | Effect of preparation methods on the performance of CeO2/Al2O3 catalysts for selective catalytic reduction of NO with NH3 | |
| Peng et al. | Investigation of the Poisoning Mechanism of Lead on the CeO2 WO3 Catalyst for the NH3–SCR Reaction via in Situ IR and Raman Spectroscopy Measurement | |
| Peng et al. | Identification of the active sites on CeO2–WO3 catalysts for SCR of NOx with NH3: An in situ IR and Raman spectroscopy study | |
| Kang et al. | Enhancing the K resistance of CeTiOx catalyst in NH3-SCR reaction by CuO modification | |
| Zeng et al. | Novel Fe-doped CePO4 catalyst for selective catalytic reduction of NO with NH3: The role of Fe3+ ions | |
| Shu et al. | Enhancement of catalytic activity over the iron-modified Ce/TiO2 catalyst for selective catalytic reduction of NO x with ammonia | |
| Pitkäaho et al. | Oxidation of dichloromethane over Pt, Pd, Rh, and V2O5 catalysts supported on Al2O3, Al2O3–TiO2 and Al2O3–CeO2 | |
| Guo et al. | The poisoning effect of heavy metals doping on Mn/TiO2 catalyst for selective catalytic reduction of NO with NH3 | |
| Xu et al. | Direct catalytic decomposition of N2O over bismuth modified NiO catalysts | |
| Gong et al. | Enhancement of the NH3-SCR property of Ce-Zr-Ti by surface and structure modification with P | |
| Xiong et al. | Selective catalytic reduction of NOx with NH3 over iron-cerium-tungsten mixed oxide catalyst prepared by different methods | |
| Xiong et al. | Influence of partial substitution of iron oxide by titanium oxide on the structure and activity of iron–cerium mixed oxide catalyst for selective catalytic reduction of NOx with NH3 | |
| Pacultová et al. | On the stability of alkali metal promoters in Co mixed oxides during direct NO catalytic decomposition | |
| Xu et al. | Development of MgCo 2 O 4–BaCO 3 composites as microwave catalysts for the highly effective direct decomposition of NO under excess O 2 at a low temperature | |
| Wang et al. | Improvement of SO2 resistance of low-temperature Mn-based denitration catalysts by Fe doping | |
| Wang et al. | Effect of iron loading on the performance and structure of Fe/ZSM-5 catalyst for the selective catalytic reduction of NO with NH 3 | |
| WEI et al. | Performance of Mn-Ce co-doped siderite catalysts in the selective catalytic reduction of NOx by NH3 | |
| Pan et al. | Efficient catalysis for low-temperature CO selective catalytic reduction over an Fe-Cu bimetal oxide catalyst supported on amorphous SiO2 | |
| Bai et al. | Carbon nanotubes loaded with vanadium oxide for reduction NO with NH3 at low temperature | |
| Wu et al. | Enhanced activity and alkali metal resistance in vanadium SCR catalyst via co-modification with Mo and Sb | |
| Zhang et al. | Satisfactory Anti-Interference and High Performance of the 1Co–1Ce/Mn@ ZSM-5 Catalyst for Simultaneous Removal of NO and Hg0 in Abominable Flue Gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130703 |