CN105749920B - Sulfur resistive denitrification metal composite oxide NH3SCR catalyst and preparation method thereof - Google Patents

Sulfur resistive denitrification metal composite oxide NH3SCR catalyst and preparation method thereof Download PDF

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CN105749920B
CN105749920B CN201610154018.6A CN201610154018A CN105749920B CN 105749920 B CN105749920 B CN 105749920B CN 201610154018 A CN201610154018 A CN 201610154018A CN 105749920 B CN105749920 B CN 105749920B
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citric acid
chromium
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CN105749920A (en
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李雪辉
罗洋
王乐夫
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South China University of Technology SCUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/864—Cobalt and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/868—Chromium copper and chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses sulfur resistive denitrification metal composite oxide NH3SCR catalyst and preparation method thereof；Belong to environmental protection and environmental catalysis field.The catalyst includes that molar ratio is 0.25~1：2~4：5~8 structural auxiliary element M, chromium and Ce elements.Preparation method includes：1) metal precursor is dissolved in respectively in citric acid, is stirred and evenly mixed, stood 0.5~2h, respectively obtain M metal citrates solution, chromium metal citrate solution and ce metal citric acid solution；2) each metal citrate solution is dropped evenly in container and is stirred continuously simultaneously, continue to stir after being added dropwise；3) dry, 350~500 DEG C of calcination in Muffle furnace are placed in baking oven；4) it will be ground up, sieved after burning forging product tabletting.The catalyst has preferable resistance to SO_2 and low temperature high activity simultaneously, can be applied to vehicle exhaust NOxProcessing or stationary source coal-burning power plant out of stock device.

Description

Sulfur resistive denitrification metal composite oxide NH3SCR catalyst and preparation method thereof
Technical field
The present invention relates to NH3SCR catalyst, more particularly to a kind of sulfur resistive denitrification metal composite oxide NH3- SCR catalyst and preparation method thereof, the catalyst are suitable for NH under low temperature3Selective catalytic reduction (NH3- SCR) nitrogen oxides (NOx) field of environment protection catalysis reaction；Belong to environmental protection and environmental catalysis field.
Background technology
Energy resource structure of the China based on coal, will not change within the long duration from now on.However it burns coal and generates A large amount of sulfur dioxide SO2, nitrogen oxides NOxWith the pollutants such as particle.Flue gas desulfurization technique is increasingly skillful at present, and NOxImprovement Difficulty is really larger.About denitration technology, it is also to apply most technologies that selective catalytic reduction (SCR), which is most effective,.
SCR reactors can be divided into three kinds of cloth such as high dirt SCR, low dirt SCR and tail portion SCR according to the position in technological process It sets.Current industrialized metal oxide catalyst V2O5-WO(MoO3)/TiO2It is used in high dirt SCR reactors, Gao Chen High sulfur environment easily causes the detrimental effects such as catalyst abrasion, blocking and poisoning, to influence the service life of catalyst.Low dirt SCR reactors are placed between electrostatic precipitator and desulfurizer, the high-temperature flue gas after dedusting, and ash flies to reduce, and reduces to SCR The abrasion of catalyst extends the service life of catalyst, but the poisoning effect of sulfur dioxide still remains；In addition electrostatic precipitation Device or bag filter also can not normally (300~400 DEG C) operations at high temperature.Tail portion SCR reactors are placed in desulfurization and dedusting After equipment, catalyst works in low dirt low-sulfur environment, largely avoids the winged abrasion of ash and SO2, heavy metal and Alkali metal poisons, and largely improves the service life of catalyst；But flue-gas temperature is only 60 DEG C at this time, is needed The burner or vapor heat exchanger of add fuel or natural gas are to heat the reaction temperature for reaching catalyst in flue, to increase energy Source consumes and operating cost.
Low-temperature SCR catalyst is broadly divided into metal oxide-type catalyst, precious metal based catalysts, molecular sieve and urges at present Four classes such as agent and charcoal base carrier class catalyst.Precious metal based catalysts there are poor selectivity and it is of high cost the problems such as, molecular sieve The problems such as class catalyst is not high poor with hydrothermal stability there are low temperature active, there are stability difference and machines for charcoal base carrier class catalyst The problems such as tool intensity is not high.And under equal conditions, metal oxide-type catalyst low-temperature selective catalytic reduction highest, tool There is good application prospect.
Cr/Ce binary oxides (200910080836.6), Cr/V/Ce ternary oxides (201110452611.6) conduct The technical solution of low-temperature SCR catalyst discloses, but Cr/Ce binary oxides have that Sulfur tolerance is poor；And Cr/ V/Ce ternary oxides introduce V, improve its Sulfur tolerance, but to reduce low temperature active as cost, so need further Research.Chinese invention patent application 2015100410566 adjusts Cr members and usually prepares chromium zirconium cerium ternary oxide by introducing zirconium The problems such as catalyst, the catalyst is not high there are Sulfur tolerance.
Described in summary, it is that this field is badly in need of to prepare one kind having preferable resistance to SO_2 and low temperature high activity SCR catalyst simultaneously The technical issues of solution.
Invention content
To overcome above-mentioned the deficiencies in the prior art and disadvantage, the primary purpose of the present invention is that providing one kind simultaneously With preferable resistance to SO_2 and low temperature high activity sulfur resistive denitrification metal composite oxide NH3SCR catalyst；The catalyst Be one kind in low temperature (100 DEG C~200 DEG C) high-speed (60000h-1) under the conditions of high activity removing nitrogen oxides and can preferably support again Anti- SO2The NH poisoned3SCR catalyst.
It is another object of the present invention to provide the preparation methods of above-mentioned catalyst.
The purpose of the present invention is realized by following technical proposals：A kind of sulfur resistive denitrification metal composite oxide NH3SCR catalyst, the catalyst include structural auxiliary element M, chromium and Ce elements.
The structural auxiliary element M is Co, Ni or Cu.
The molar ratio of the structural auxiliary element M, chromium and Ce elements are 0.25~1：5~8：2~4.
Above-mentioned sulfur resistive denitrification metal composite oxide NH3The preparation method of SCR catalyst, including following operation Step：
(1) structural auxiliary element M metal precursors, chromium metal precursor and ce metal presoma are dissolved in one respectively It in the citric acid for determining concentration, stirs and evenly mixs, after standing 0.5~2h, respectively obtains M metal citrates solution, chromium metal citrate Solution and ce metal citric acid solution；The structural auxiliary element M metal precursors are the nitrate of structural auxiliary element M Or acetate；The chromium metal precursor is the nitrate or acetate of chromium；The ce metal presoma is Ce elements Nitrate or acetate；
(2) M metal citrates solution, chromium metal citrate solution and ce metal citric acid solution are dropped evenly simultaneously It in container and keeps being stirred continuously, continues 1~3h of stirring after being added dropwise, obtain mixed solution；
(3) mixed solution is placed in baking oven and 8~15h is dried with 100~150 DEG C of condition, with temperature in Muffle furnace 350~500 DEG C of 180~360min of calcination of degree；
(4) it after burning forging product tabletting, will be ground up, sieved as particle, obtain sulfur resistive denitrification metal composite oxide NH3SCR catalyst.
The citric acid solution concentration of step (1) the different metal presoma dissolving can differ.
Step (1) the structural auxiliary element M metal precursors, chromium metal precursor or ce metal presoma and lemon The molar ratio of acid solution is 1：1~1：3.
A concentration of 1~3mol ﹒ L of step (1) described citric acid solution-1。
Step (2) dropwise addition is with 5~15mLmin of overall flow rate-1Speed be added dropwise.
Step (4) described tabletting is that tabletting is carried out under 5~10Kpa pressure；The particle is 40~60 mesh.
The principle of the present invention is：So that two or more metal salt is formed collosol and gel using citric acid, passes through roasting NEW TYPE OF COMPOSITE oxide is formed, is prepared into certain resistance to SO_2 NH3SCR catalyst.M is introduced, it is multiple to form M/ chromium/cerium ternary Oxide is closed, (reduce the absorption to sulfur dioxide reduces ammonium salt or metal sulphur to reach by the coordinative role between three The formation of compound), to improve the Sulfur tolerance of composite oxides.
In patent 2015101717957, Co or Cu play the dispersing characteristic and crystallization for improving active component on carrier The effect of characteristic；And Co of the present invention or Cu primarily serve the absorption work for reducing M/ chromium/cerium ternary compound oxides to sulfur dioxide With.
The present invention has the following advantages compared with the prior art and advantageous effect：
(1) sulfur resistive denitrification metal composite oxide NH of the present invention3SCR catalyst has under low temperature high-speed The ability of high activity and preferable sulfur poisoning-resistant；Due to intermetallic synergistic effect, the effect of nitrogen oxides is removed in low temperature Under high-speed (150 DEG C, air speed 60000h-1) with 94% NOxConversion ratio, particularly, in 100ppm SO2There are the case where Lower 48 hours life experiment (175 DEG C, air speed 10000h-1) after, catalyst is still with 82.5% denitrification effect.
(2) prepared by the present invention is simple and convenient to operate, is of low cost and be easy to the features such as mechanical-moulded.
Specific implementation mode
To more fully understand the present invention, with reference to embodiment, the invention will be further described, it should be noted that real It applies example and does not constitute restriction to the claimed scope of the invention.
Embodiment 1
(1) it is 7 by metal molar ratio：3 chromic nitrate and cerous nitrate respectively with citric acid molar ratio 1：1 ratio dissolving To 1mol ﹒ L-1Citric acid solution in, stand 0.5 hour after, respectively obtain chromic nitrate citric acid solution and cerous nitrate lemon Acid solution；
(2) by chromic nitrate citric acid solution and cerous nitrate citric acid solution with 5mLmin-1Overall flow rate simultaneously uniformly drop It is added in beaker and keeps being stirred continuously, continue to stir 1h after being added dropwise, obtain mixed solution；
(3) mixed solution is placed in baking oven under conditions of 100 DEG C dry 15h, with 400 DEG C of temperature in Muffle furnace It is calcined 240min；
(4) after burning forging product being carried out tabletting under 6KPa pressure, grinding 40~60 mesh particles of screening obtain sulfur resistive and denitrogenate Oxide metal composite oxide NH3SCR catalyst.
SCR activity evaluation is carried out in assigned temperature window to above-mentioned catalyst：
Catalyst sample is fitted into fixed bed reactors, reactor is put into temperature programmed control reacting furnace, controls temperature 100 DEG C~200 DEG C；At 100 DEG C, 125 DEG C, 150 DEG C, 175 DEG C, 200 DEG C of equal points use the SWG-300 types of MRU companies of Germany production Each gas concentration, is calculated by the following formula NO in flue gas analysis monitoring reaction coursexConversion ratio：
Wherein [NOx]=[NO]+[NO2], subscript in and out indicate inlet concentrations and gas outlet concentration respectively.Repeat with Upper step is passed through SO at 150 DEG C or 175 DEG C of constant temperature2, detect the sulfur resistance of catalyst.
Evaluating catalyst the result shows that, become in the flue gas group of simulation： N2For Balance Air.Air speed is 60000h-1, when temperature is 150 DEG C, the transformation efficiency of the oxides of nitrogen of catalyst reaches 85.1%, 175 DEG C~200 DEG C when transformation efficiency of the oxides of nitrogen reach 97.8% or more.Become in the flue gas group of simulation：N2Under conditions of Balance Air, temperature is 175 DEG C, gas Body overall flow rate 600mLmin-1, air speed 60000h-1Under the conditions of, the denitrification effect of 4h rear catalysts is 61.2%.
Embodiment 2
(1) it is 0.75 by metal molar ratio：7：3 cobalt nitrate, chromic nitrate and cerous nitrate respectively with citric acid molar ratio 1：1 ratio is dissolved into 1mol ﹒ L-1Citric acid solution in, stand 0.5 hour after, it is molten to respectively obtain cobalt nitrate citric acid Liquid, chromic nitrate citric acid solution and cerous nitrate citric acid solution；
(2) by cobalt nitrate citric acid solution, chromic nitrate citric acid solution and cerous nitrate citric acid solution with 5mLmin-1's Overall flow rate drops evenly in beaker and keeps being stirred continuously simultaneously, continues to stir 1h after being added dropwise, obtains mixed solution；
(3) mixed solution is placed in baking oven under conditions of 100 DEG C dry 15h, with 400 DEG C of temperature in Muffle furnace It is calcined 240min；
(4) after burning forging product being carried out tabletting under 6KPa pressure, grinding 40~60 mesh particles of screening obtain sulfur resistive and denitrogenate Oxide metal composite oxide NH3SCR catalyst.
SCR activity evaluation is carried out in assigned temperature window to above-mentioned catalyst：
Catalyst sample is fitted into fixed bed reactors, reactor is put into temperature programmed control reacting furnace, controls temperature 100 DEG C~200 DEG C；At 100 DEG C, 125 DEG C, 150 DEG C, 175 DEG C, 200 DEG C of equal points use the SWG-300 types of MRU companies of Germany production Each gas concentration in flue gas analysis monitoring reaction course calculates transformation efficiency of the oxides of nitrogen；Repeat above step, 150 DEG C of constant temperature or It is passed through SO at 175 DEG C2, detect the sulfur resistance of catalyst.
Evaluating catalyst the result shows that, become in the flue gas group of simulation： N2For Balance Air.Air speed is 60000h-1, when temperature is 150 DEG C, the transformation efficiency of the oxides of nitrogen of catalyst reaches 90.3%, 175 DEG C~200 DEG C when transformation efficiency of the oxides of nitrogen reach 98% or more.Become in the flue gas group of simulation： N2Under conditions of Balance Air, temperature is 175 DEG C, gas Overall flow rate 600mLmin-1, air speed 60000h-1Under the conditions of, the denitrification effect of 4h rear catalysts is 78%.
Become in the flue gas group of simulation：N2For Under conditions of Balance Air, temperature is 175 DEG C, gas overall flow rate 600mLmin-1, air speed 10000h-1Under the conditions of, it is urged after 48h The denitrification effect of agent still has 82.5%.
Embodiment 3
(1) it is 0.75 by metal molar ratio：6：4 cobalt nitrate, chromic nitrate and cerous nitrate respectively with citric acid molar ratio 1：1 ratio is dissolved into 2mol ﹒ L-1Citric acid solution in, stand 1h after, respectively obtain cobalt nitrate citric acid solution, nitric acid Chrome lemon acid solution and cerous nitrate citric acid solution；
(2) by cobalt nitrate citric acid solution, chromic nitrate citric acid solution and cerous nitrate citric acid solution with 10mLmin-1 Overall flow rate drop evenly in beaker simultaneously and keep being stirred continuously, continue to stir 2h after being added dropwise, obtain mixed solution；
(3) mixed solution is placed in baking oven under conditions of 120 DEG C dry 12h, with temperature in Muffle furnace, 400 DEG C calcination 180min；
(4) after burning forging product being carried out tabletting under 8KPa pressure, grinding 40~60 mesh particles of screening obtain sulfur resistive and denitrogenate Oxide metal composite oxide NH3SCR catalyst.
SCR activity evaluation is carried out in assigned temperature window to above-mentioned catalyst：
Catalyst sample is fitted into fixed bed reactors, reactor is put into control temperature 100 in temperature programmed control reacting furnace DEG C~250 DEG C；At 100 DEG C, 125 DEG C, 150 DEG C, 175 DEG C, 200 DEG C of equal points use the SWG-300 types of MRU companies of Germany production Each gas concentration in flue gas analysis monitoring reaction course calculates transformation efficiency of the oxides of nitrogen；Repeat above step, 150 DEG C of constant temperature or It is passed through SO at 175 DEG C2, detect the sulfur resistance of catalyst.
Evaluating catalyst the result shows that, become in the flue gas group of simulation： N2For Balance Air.Air speed is 60000h-1, when temperature is 150 DEG C, the transformation efficiency of the oxides of nitrogen of catalyst reaches 88%, 175 DEG C~ Transformation efficiency of the oxides of nitrogen reaches 95% or more at 200 DEG C.Become in the flue gas group of simulation： N2Under conditions of Balance Air, temperature is 150 DEG C, gas overall flow rate 600mLmin-1, Air speed is 60000h-1Under the conditions of, the denitrification effect of 4h rear catalysts still has 78%.
Embodiment 4
(1) it is 1 by metal molar ratio：7：3 nickel nitrate, chromic nitrate and cerous nitrate respectively with citric acid molar ratio 1： 1 Ratio be dissolved into 2mol ﹒ L-1Citric acid solution in, stand 1h after, respectively obtain nickel nitrate citric acid solution, chromic nitrate lemon Lemon acid solution and cerous nitrate citric acid solution；
(2) by nickel nitrate citric acid solution, chromic nitrate citric acid solution and cerous nitrate citric acid solution with 5mLmin-1's Overall flow rate drops evenly in beaker and keeps being stirred continuously simultaneously, continues to stir 2h after being added dropwise, obtains mixed solution；
(3) mixed solution is placed in baking oven under conditions of 120 DEG C dry 12h, with temperature in Muffle furnace, 400 DEG C calcination 240min；
(4) after burning forging product being carried out tabletting under 6KPa pressure, grinding 40~60 mesh particles of screening obtain sulfur resistive and denitrogenate Oxide metal composite oxide NH3SCR catalyst.
SCR activity evaluation is carried out in assigned temperature window to above-mentioned catalyst：
Catalyst sample is fitted into fixed bed reactors, reactor is put into control temperature 100 in temperature programmed control reacting furnace DEG C~200 DEG C；At 100 DEG C, 125 DEG C, 150 DEG C, 175 DEG C, 200 DEG C of equal points use the SWG-300 types of MRU companies of Germany production Each gas concentration in flue gas analysis monitoring reaction course calculates transformation efficiency of the oxides of nitrogen；Repeat above step, 150 DEG C of constant temperature or It is passed through SO at 175 DEG C2, detect the sulfur resistance of catalyst.
Evaluating catalyst the result shows that, become in the flue gas group of simulation： N2For Balance Air.Air speed is 60000h-1, when temperature is 150 DEG C, the transformation efficiency of the oxides of nitrogen of catalyst reaches 88.4%, 175 DEG C~200 DEG C when transformation efficiency of the oxides of nitrogen reach 97.6% or more.Become in the flue gas group of simulation：N2Under conditions of Balance Air, temperature is 175 DEG C, gas Body overall flow rate 600mLmin-1, air speed 60000h-1Under the conditions of, the denitrification effect of 4h rear catalysts still has 70.6%.
Embodiment 5
(1) it is 1 by metal molar ratio：7：3 copper nitrate, chromic nitrate and cerous nitrate respectively with citric acid molar ratio 1： 1 Ratio be dissolved into 2mol ﹒ L-1Citric acid solution in, stand 1h after, respectively obtain copper nitrate citric acid solution, chromic nitrate lemon Lemon acid solution and cerous nitrate citric acid solution；
(2) by copper nitrate citric acid solution, chromic nitrate citric acid solution and cerous nitrate citric acid solution with 5mLmin-1's Overall flow rate drops evenly in beaker and keeps being stirred continuously simultaneously, continues to stir 2h after being added dropwise, obtains mixed solution；
(3) mixed solution is placed in baking oven under conditions of 120 DEG C dry 12h, with temperature in Muffle furnace, 450 DEG C calcination 360min；
(4) after burning forging product being carried out tabletting under 8KPa pressure, grinding 40~60 mesh particles of screening obtain sulfur resistive and denitrogenate Oxide metal composite oxide NH3SCR catalyst.
SCR activity evaluation is carried out in assigned temperature window to above-mentioned catalyst：
Catalyst sample is fitted into fixed bed reactors, reactor is put into control temperature 100 in temperature programmed control reacting furnace DEG C~200 DEG C；At 100 DEG C, 125 DEG C, 150 DEG C, 175 DEG C, 200 DEG C of equal points use the SWG-300 types of MRU companies of Germany production Each gas concentration in flue gas analysis monitoring reaction course calculates transformation efficiency of the oxides of nitrogen；Repeat above step, 150 DEG C of constant temperature or It is passed through SO at 175 DEG C2, detect the sulfur resistance of catalyst.
Evaluating catalyst the result shows that, become in the flue gas group of simulation： N2For Balance Air.Air speed is 60000h-1, when temperature is 150 DEG C, the transformation efficiency of the oxides of nitrogen of catalyst reaches 72.6%, 175 DEG C~200 DEG C when transformation efficiency of the oxides of nitrogen reach 97.5% or more.Become in the flue gas group of simulation：N2Under conditions of Balance Air, temperature is 150 DEG C, gas Body overall flow rate 600mLmin-1, air speed 60000h-1Under the conditions of, the denitrification effect of 4h rear catalysts still has 68.8%.From It is found that after present invention addition metal M (Co, Ni and Cu), the Sulfur tolerance for forming M/ chromium/cerium ternary compound oxides obtains embodiment Preferable enhancing, while the low temperature active of catalysis is not influenced.M/ chromium of the present invention/cerium ternary compound oxides catalyst is that one kind exists Low temperature high activity NH with certain sulfur poisoning resistance under high-speed3SCR catalyst, there is preparation to be simple and convenient to operate, It is of low cost and be easy to the features such as mechanical-moulded.Particularly Co/Cr/Ce ternary compound oxides catalyst removes nitrogen oxidation The effect of object under low temperature high-speed (150 DEG C, air speed 60000h-1) with 94% NOxConversion ratio；In 100ppm SO2It deposits In case 48h life experiment (175 DEG C, air speed 10000h-1) after, catalyst is still with 82.5% denitration effect. Cr/Ce binary oxides (200910080836.6) compared with the existing technology and Cr/V/Ce ternary oxides (201110452611.6), sulfur resistive denitrification metal composite oxide NH of the present invention3SCR catalyst has preferably simultaneously The characteristics of resistance to SO_2 and low temperature high activity, preferably solves the problems, such as the prior art.

Claims (10)

1. sulfur resistive denitrification metal composite oxide NH3The preparation method of SCR catalyst, it is characterised in that including following behaviour Make step：
(1) structural auxiliary element M metal precursors, chromium metal precursor and ce metal presoma are dissolved in citric acid respectively It in solution, stirs and evenly mixs, after standing 0.5~2h, respectively obtains M metal citrates solution, chromium metal citrate solution and cerium gold Belong to citric acid solution；The structural auxiliary element M metal precursors are the nitrate or acetate of structural auxiliary element M； The chromium metal precursor is the nitrate or acetate of chromium；The ce metal presoma is the nitrate or vinegar of Ce elements Hydrochlorate；The structural auxiliary element M is Co, Ni or Cu；
(2) M metal citrates solution, chromium metal citrate solution and ce metal citric acid solution are dropped evenly into container simultaneously In and keep be stirred continuously, continue to stir after being added dropwise, obtain mixed solution；
(3) mixed solution is placed in baking oven and 8~15h is dried with 100~150 DEG C of condition, be calcined then at 350~500 DEG C；
(4) it by after burning forging product tabletting, is ground up, sieved, obtains sulfur resistive denitrification composite type metallic oxide SCR catalyst Particle.
2. preparation method according to claim 1, it is characterised in that：A concentration of 1~3mol ﹒ L of the citric acid solution-1。
3. preparation method according to claim 1, it is characterised in that：The structural auxiliary element M metal precursors, chromium Metal precursor or the molar ratio of ce metal presoma and citric acid solution are 1：1~1：3.
4. preparation method according to claim 1, it is characterised in that：The dropwise addition is with 5~15mLmin of overall flow rate-1's Speed is added dropwise.
5. preparation method according to claim 1, it is characterised in that：The tabletting is pressed under 5~10Kpa pressure Piece；The grain size of the particle is 40~60 mesh.
6. preparation method according to claim 1, it is characterised in that：The time of the calcination is 180~360min.
7. preparation method according to claim 1, it is characterised in that：The time for continuing stirring is 1~3 hour.
8. preparation method according to claim 1, it is characterised in that：The calcining is carried out in Muffle furnace.
9. preparation method according to claim 1, it is characterised in that：The structural auxiliary element M metal precursors, chromium Metal precursor and ce metal presoma are dissolved in the citric acid solution of same concentrations respectively.
10. a kind of sulfur resistive denitrification metal composite oxide NH3SCR catalyst, it is characterised in that：It is by claim 1- Any one of 9 preparation methods are made；The catalyst includes structural auxiliary element M, chromium and Ce elements；The structure Property auxiliary element M, chromium and Ce elements molar ratio be 0.25~1：6~8：2~4.
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