CN103566948A - A low-temperature denitrification MnOx-CuO-TiO2-Al2O3 catalyst and its preparation method and application - Google Patents
A low-temperature denitrification MnOx-CuO-TiO2-Al2O3 catalyst and its preparation method and application Download PDFInfo
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Abstract
本发明公开一种低温脱硝MnOx-CuO-TiO2-Al2O3催化剂及制备方法和应用，所述低温脱硝MnOx-CuO-TiO2-Al2O3催化剂由载体和活性组分两部分组成，所述载体为TiO2和Al2O3，活性组分为MnOx和CuO，所述低温脱硝MnOx-CuO-TiO2-Al2O3催化剂中按金属元素Mn、Ti、Al、Cu的摩尔比计算，其中Cu：Ti：Al：Mn为0.2-0.4:1：1：0.4-1.2。其制备方法即以硫酸钛、硝酸铝、硝酸锰、硝酸铜为前驱体，使用共沉淀法制得的MnOx-CuO-TiO2-Al2O3催化剂，其制备成本低，便于工业化推广，在150-250℃的烟气中具有较好的脱硝效果。The invention discloses a low-temperature denitrification MnOx-CuO-TiO 2 -Al 2 O 3 catalyst and its preparation method and application. The low-temperature denitration MnOx-CuO-TiO 2 -Al 2 O 3 catalyst is composed of a carrier and an active component. , the carrier is TiO 2 and Al 2 O 3 , the active components are MnOx and CuO, the low-temperature denitrification MnOx-CuO-TiO 2 -Al 2 O 3 catalyst is based on the moles of metal elements Mn, Ti, Al, Cu Ratio calculation, where Cu:Ti:Al:Mn is 0.2-0.4:1:1:0.4-1.2. The preparation method is to use titanium sulfate, aluminum nitrate, manganese nitrate, and copper nitrate as precursors, and use the co-precipitation method to prepare the MnOx-CuO-TiO 2 -Al 2 O 3 catalyst. The preparation cost is low, and it is convenient for industrialization. It has a good denitrification effect in flue gas at -250°C.
Description
Technical field
The present invention relates to low-temperature denitration of flue gas field, be specifically related to a kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalysts and its preparation method and application.
Background technology
NOx is one of important atmosphere pollution of coal fired thermal power plant discharge, is the important origin cause of formation of acid rain and photochemical fog.Initial estimate, the NO of domestic thermal power industry during " 12 "
xdischarge capacity will reach 1,200 ten thousand tons of left and right.Due to China's acid rain type, oneself transfers nitric acid, sulfuric acid based mixed type acid rain to from sulfuric acid based acid rain, and environment and health have been caused to great harm.Therefore, NO
ximprovement become country " the 12 " focus that atmosphere pollution is administered in the works.
With NH
3for the selective catalytic reduction (SCR technology) of reducing agent is to control the effective means that the NOx of thermal power plant pollutes.The method is normally in the scope of 350-400 ℃, with V
2o
5+ WO
3(MoO
3)/TiO
2for catalyst carrys out NO_x removal.The operating temperature range of catalyst has determined that SCR Benitration reactor must be arranged between the economizer and air preheater of boiler, so, because flue gas does not pass through desulfurization and dedusting, the SO in flue gas
2be easy to and NH
3react and generation NH
4hSO
4(NH
4)
2sO
4and flying dust and cause the pore plugging of catalyst.In addition, owing to entering the flue gas of SCR reactor, do not pass through dedusting, contained K in flying dust
2o, CaO and AS
2o
3deng easily, cause the poisoning of catalyst, can reduce its service life.In addition, for some old power plant, due to the limitation of space and pipeline, the improvement expenses of building the SCR reactor between boiler economizer and air preheater is very high.
If can develop efficient SCR low temperature catalyst, can well address the above problem.With existing SCR technology, compare, low-temperature SCR can't increase extra equipment, on the contrary due to after it is positioned at electrostatic precipitator and wet method fume desulfurizing system, the characteristic by the flue gas of reactor with low temperature, low-sulfur and low dirt, to the steel construction of reactor and soot blower, and can reduce costs to a certain extent.Owing to need not flue gas being carried out to preheating, a large amount of energy consumptions and plant modification expense have been saved simultaneously.
Summary of the invention
One of object of the present invention is to provide a kind of low-temperature denitration MnOx-CuO-TiO in order to solve above-mentioned technical problem
2-Al
2o
3catalyst.
Two of object of the present invention is a kind of low-temperature denitration MnOx-CuO-TiO that provides above-mentioned
2-Al
2o
3the preparation method of catalyst.
Three of object of the present invention is above-mentioned low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst is applied in denitrating flue gas.
know-why of the present invention
SCR (SCR) technology is under catalyst action, reducing agent NH
3nO in (liquefied ammonia, ammoniacal liquor, urea etc.) and flue gas
xreaction, by the NO in flue gas
xbe reduced to the N of nontoxic pollution-free
2and H
2o.SCR method denitration technology is the current denitration technology of mature and reliable both at home and abroad, and denitration efficiency is high, and security of system is stable.Reaction principle is as follows:
Key reaction under the condition of aerobic:
4NH
3+4NO+O
2→4N
2+6H
2O
4NH
3+2NO
2+O
2→3N
2+6H
2O
NO+NO
2+2NH
3→2N
2+3H
2O。
technical scheme of the present invention
A kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst, is comprised of carrier and active component two parts;
Described carrier is that particle diameter is the Al of 20～40nm
2o
3tiO with 10～30nm
2;
Described active component is MnOx and CuO, and wherein MnOx is MnO
2, Mn
3o
4, Mn
2o
3in the mixture of one or more compositions;
Described low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3in catalyst, by the mol ratio of contained metallic element Mn, Ti, Al, Cu, calculate, wherein Cu:Ti:Al:Mn is 0.2-0.4:1:1:0.4-1.2.
Above-mentioned a kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the preparation method of catalyst, adopts coprecipitation preparation, specifically comprises the steps:
(1), soluble manganese salt, soluble copper salt, solubility titanium salt, aluminum soluble salt are dissolved in deionized water, at room temperature adopt polytetrafluoroethylene (PTFE) paddle, controlling stir speed (S.S.) is 200-600rpm stirring and dissolving, and the ammoniacal liquor that adds 3mol/L in backward solution adjusts pH to stir 1-3h after 5-11, quiescent setting, by gained sedimentation and filtration, the filter cake of gained with deionized water rinsing extremely
till the pH of eluate is neutrality;
Described soluble copper salt is Cu(NO
3)
23H
2o;
Soluble manganese salt is Mn(NO
3)
26H
2o;
Solubility titanium salt is Ti(SO
4)
28H
2o;
Aluminum soluble salt is Al(NO
3)
39H
2o;
The amount of soluble copper salt, soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water used in above-mentioned preparation process, calculate in molar ratio, be the copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is 1:2.5～5:2.5～5:1～6:84～168, is preferably 1:2.5:2.5:2～3:84;
(2), by the filter cake of step (1) gained dry 12-24h at 80-105 ℃, obtain dry filter cake;
(3), dry filter cake that step (2) is obtained is placed in tubular type Muffle furnace, under air atmosphere, with the heating rate of 10 ℃/min, is warming up to 450-650 ℃, insulation 5h, finally naturally cools to room temperature with stove, obtains low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst.
Above-mentioned low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the application of catalyst in denitrating flue gas process, specifically comprises the steps:
(1), denitration starts the front argon purge low-temperature denitration MnOx-CuO-TiO that first passes into
2-Al
2o
3catalyst allows low-temperature denitration MnOx-CuO-TiO simultaneously
2-Al
2o
3catalyst reaches the condition temperature of denitration requirement;
(2), with the NO in simulated flue gas, pass into the about 0.5-1h of fixed bed reactors, allow low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst absorption NO reaches capacity, and avoids because of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the absorption of catalyst causes the minimizing of NO;
Described simulated flue gas forms: NO is 600ppm, NH
3for 600ppm and O
2be 5%, remaining gas Ar is as Balance Air;
(3), low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3after catalyst absorption NO reaches capacity, the mixed flue gas for the treatment of denitration is sent into fixed bed micro anti-evaluation device and control reaction temperature at 150-250 ℃, flow velocity is 1000ml/min, space velocity 20000-30000h
-1, at low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3under the effect of catalyst, the NH in flue gas
3at low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3under the effect of catalyst, NO is reduced to N
2gas;
(4), flue gas is through low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the front and back of catalyst denitration reaction are carried out record by flue gas analyzer (Thermo) to various compositions in flue gas, thereby calculate the denitration efficiency to flue gas;
(5), reacted gaseous mixture absorbs unreacted NH through phosphoric acid solution
3by blast pipe, enter atmosphere.
beneficial effect of the present invention
A kind of MnOx-CuO-TiO of the present invention
2-Al
2o
3catalyst, due to adding of CuO, can improve the activity of denitrating catalyst, and at 150～250 ℃ of low temperature, particularly, in the time of 200 ℃, its denitration efficiency can reach 100%, therefore MnOx-CuO-TiO of the present invention
2-Al
2o
3catalyst is suitable for SCR denitrification apparatus and is arranged in thermal power plant's back-end ductwork, further can reduce waste heat loss, improves thermal power plant's performance driving economy.
Further, a kind of MnOx-CuO-TiO of the present invention
2-Al
2o
3catalyst, due to the valence state that can enrich MnOx that adds of CuO, thereby improves the water-resistance of denitrating catalyst, effectively extending catalyst service life.
Further, by coprecipitation, prepare MnOx-CuO-TiO
2-Al
2o
3catalyst, its preparation technology is simple, and easy operating is compared with vanadium series catalyst, and several elements of employing are all non-toxic, and raw materials used soluble manganese salt, soluble copper salt, solubility titanium salt, aluminum soluble salt easily obtains, so MnOx-CuO-TiO
2-Al
2o
3catalyst preparation cost is low, is convenient to industrialization promotion.
In sum, this kind of MnOx-CuO-TiO of the present invention
2-Al
2o
3the production cost of catalyst is low, and at 150～250 ℃ of low temperature, particularly, in the time of 200 ℃, its denitration efficiency is high, and catalyst is nontoxic, long service life, is suitable for industrialization promotion and uses.
It is the 4100 type fixed bed micro anti-evaluation devices of 16mm, length: 480mm that catalytic reactor used in embodiments of the invention adopts the external diameter purchased from Zhejiang Fan Tai Instrument Ltd., unstripped gas enters reactor through preheating, reaction temperature is at 125-300 ℃, flow velocity is 1000ml/min, space velocity 26000h
-1.
Simulated flue gas forms: NO is 600ppm, NH
3for 600ppm and O
2be 5%, remaining gas Ar is as Balance Air, and gas flow is controlled by the CS200 type mass flowmenter purchased from Beijing Co., Ltd of Sevenstar Huachuang Electronic.
NO, NH that the present invention is used
3molar concentration is 1%, and surplus is Ar, purchased from Shanghai Wei Chuan calibrating gas Co., Ltd;
O
2, Ar purity is 99.99%, purchased from south of the River mist Co., Ltd;
Reagent or raw material used in various embodiments of the present invention: the Al(NO that purity is 99%
3)
39H
2o, Ti(SO
4)
28H
2o, Cu(NO
3)
23H
2o, ammoniacal liquor, the Mn(NO that mass percent concentration is 50%
3)
26H
2o solution is all purchased from Aladdin.
The specific embodiment
Below by specific embodiment, the present invention is further set forth, but do not limit the present invention.
embodiment 1
A kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst A, calculates by the mol ratio of contained metallic element Mn, Ti, Al, Cu, and wherein Cu:Ti:Al:Mn is 0.2:1:1:0.4.
Above-mentioned a kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the preparation method of catalyst A, specifically comprises the steps:
(1), 8ml soluble manganese salt, 2.416g soluble copper salt, 20.107g solubility titanium salt, 18.757 aluminum soluble salts are dissolved in 300ml deionized water, under room temperature, adopt polytetrafluoroethylene (PTFE) paddle, controlling stir speed (S.S.) is 200rpm stirring and dissolving, and add the ammoniacal liquor tune pH of 3mol/L in backward solution, be 10 rear stirring 1h, carry out quiescent setting, till being neutrality by gained sedimentation and filtration and with deionized water rinsing to the pH of eluate;
Described soluble copper salt is Cu(NO
3)
23H
2o;
Aluminum soluble salt is Al(NO
3)
39H
2o;
Solubility titanium salt is Ti(SO
4)
28H
2o;
Soluble manganese salt is that mass percent concentration is 50% Mn(NO
3)
26H
2the O aqueous solution;
The amount of soluble copper salt, soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water used in above-mentioned preparation process, calculate in molar ratio, i.e. copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is: 1:5:5:2:168;
(2), by the filter cake of step (1) gained dry 12h at 105 ℃, obtain dry filter cake;
(3), dry filter cake that step (2) is obtained is placed in tubular type Muffle furnace, under air atmosphere, with the heating rate of 10 ℃/min, is warming up to 450 ℃, insulation 5h, is finally cooled to room temperature with furnace temperature, obtains 10g low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst A.
Through MAX2200VX x ray diffraction analysis x instrument (Rigaku company), analyze, can draw the MnOx-CuO-TiO of above-mentioned gained
2-Al
2o
3catalyst A is for to be comprised of carrier and active component two parts, and described carrier is that particle diameter is the Al of 20～40nm
2o
3tiO with 10～30nm
2, active component is MnOx and CuO, wherein MnOx is MnO
2, Mn
3o
4and Mn
2o
3the mixture forming.
embodiment 2
A kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst B, calculates by the mol ratio of contained metallic element Mn, Ti, Al, Cu, and wherein Cu:Ti:Al:Mn is 0.4:1:1:0.8.
Above-mentioned a kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the preparation method of catalyst B, step is as follows:
(1), 16ml soluble manganese salt, 4.832g soluble copper salt, 20.107g solubility titanium salt, 18.757g aluminum soluble salt are dissolved in 400ml deionized water, under room temperature, adopt polytetrafluoroethylene (PTFE) paddle, controlling stir speed (S.S.) is 200rpm stirring and dissolving, and add the ammoniacal liquor tune pH of 3mol/L in backward solution, be 10 rear stirring 1h, carry out quiescent setting, till being neutrality by gained sedimentation and filtration and with deionized water rinsing to the pH of eluate;
Described soluble copper salt is Cu(NO
3)
23H
2o;
Aluminum soluble salt is Al(NO
3)
39H
2o;
Solubility titanium salt is Ti(SO
4)
28H
2o;
Soluble manganese salt is that mass percent concentration is 50% Mn(NO
3)
26H
2the O aqueous solution;
The amount of soluble copper salt, soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water used in above-mentioned preparation process, calculate in molar ratio, i.e. copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is: 1:2.5:2.5:2:84;
(2), by the filter cake of step (1) gained dry 12h at 105 ℃, obtain dry filter cake;
(3), dry filter cake that step (2) is obtained is placed in tubular type Muffle furnace, under air atmosphere, with the heating rate of 10 ℃/min, is warming up to 450 ℃, insulation 5h, is finally cooled to room temperature with furnace temperature, obtains 12g low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst B.
Through MAX2200VX x ray diffraction analysis x instrument (Rigaku company), analyze, can draw the MnOx-CuO-TiO of above-mentioned gained
2-Al
2o
3catalyst B is for to be comprised of carrier and active component two parts, and described carrier is that particle diameter is the Al of 20～40nm
2o
3tiO with 10～30nm
2, active component is MnOx and CuO, wherein MnOx is MnO
2, Mn
3o
4and Mn
2o
3the mixture forming.
embodiment 3
A kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst C, calculates by the mol ratio of contained metallic element Mn, Ti, Al, Cu, and wherein Cu:Ti:Al:Mn is 0.4:1:1:1.2.
Above-mentioned a kind of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the preparation method of catalyst C, step is as follows:
(1), 24ml soluble manganese salt, 4.832g soluble copper salt, 20.107g solubility titanium salt, 18.757 aluminum soluble salts are dissolved in 500ml deionized water, under room temperature, adopt polytetrafluoroethylene (PTFE) paddle, controlling stir speed (S.S.) is 200rpm stirring and dissolving, and add the ammoniacal liquor tune pH of 3mol/L in backward solution, be 10 rear stirring 1h, carry out quiescent setting, till being neutrality by gained sedimentation and filtration and with deionized water rinsing to the pH of eluate;
Described soluble copper salt is Cu(NO
3)
23H
2o;
Aluminum soluble salt is Al(NO
3)
39H
2o;
Solubility titanium salt is Ti(SO
4)
28H
2o;
Soluble manganese salt is that mass percent concentration is 50% Mn(NO
3)
26H
2the O aqueous solution;
The amount of soluble copper salt, soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water used in above-mentioned preparation process, calculate in molar ratio, i.e. copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is: 1:2.5:2.5:3:126;
(2), by the filter cake of step (1) gained dry 12h at 105 ℃, obtain dry filter cake;
(3), dry filter cake that step (2) is obtained is placed in tubular type Muffle furnace, under air atmosphere, with the heating rate of 10 ℃/min, is warming up to 450 ℃, insulation 5h, is finally cooled to room temperature with furnace temperature, obtains 15g low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst C.
Through MAX2200VX x ray diffraction analysis x instrument (Rigaku company), analyze, can draw the MnOx-CuO-TiO of above-mentioned gained
2-Al
2o
3catalyst C is for to be comprised of carrier and active component two parts, and described carrier is that particle diameter is the Al of 20～40nm
2o
3tiO with 10～30nm
2, active component is MnOx and CuO, wherein MnOx is MnO
2, Mn
3o
4and Mn
2o
3the mixture forming.
application Example 1
By the low-temperature denitration MnOx-CuO-TiO of embodiment 1,2,3 gained
2-Al
2o
3catalyst A, B, C and typical catalyst are that east, Chengdu Kytril company produces, and the denitrating catalyst being comprised of tungstic acid, nano titanium oxide and vanadic anhydride carries out respectively denitration reaction experiment at 150 ℃, 200 ℃ and 250 ℃.
Experiment test starts the front argon purge low-temperature denitration MnOx-CuO-TiO that first passes into
2-Al
2o
3catalyst allows low-temperature denitration MnOx-CuO-TiO simultaneously
2-Al
2o
3catalyst meets the requirements of condition temperature, then with the NO in simulated flue gas, passes into fixed bed micro anti-evaluation device 0.5-1h, allows low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst and typical catalyst absorption NO are saturated, avoid because of low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the absorption of catalyst and typical catalyst causes the minimizing of NO;
(flue gas flow rate 1000ml/min, gas concentration: NO is 600ppm to analog gas, NH
3for 600ppm and O
2be 5%, remaining gas is Ar) in gas mixed box, after mixing, then send into fixed bed micro anti-evaluation device at low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3under the effect of catalyst and typical catalyst (volume 4ml), NH
3nO is reduced to N
2, reacted gaseous mixture absorbs unreacted NH through phosphoric acid solution
3by blast pipe, enter atmosphere, the NO concentration of import and export adopts the model60i flue gas analyzer of U.S.'s thermoelectricity to detect, its denitration the results are shown in following table:
In upper table, denitration efficiency computing formula is as follows:
;
As can be seen from the above table, adopt low-temperature denitration MnOx-CuO-TiO of the present invention
2-Al
2o
3catalyst A, low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst B, low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst C and typical catalyst are carried out denitrating flue gas under identical condition, low-temperature denitration MnOx-CuO-TiO of the present invention
2-Al
2o
3catalyst A, low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst B, low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst C is all high than typical catalyst denitration efficiency, when denitration temperature is 150～250 ℃, and low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst B, low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the denitration efficiency of catalyst C reaches 89～100%, particularly in the time of 200 ℃, and low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst B and low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3the denitration efficiency of catalyst C reaches 100%, shows thus low-temperature denitration MnOx-CuO-TiO of the present invention
2-Al
2o
3in catalyst, by the mol ratio of contained metallic element Mn, Ti, Al, Cu, calculate, wherein Cu:Ti:Al:Mn is preferably 0.4:1:1:1.2 or 0.4:1:1:0.8.
In sum, low-temperature denitration MnOx-CuO-TiO of the present invention
2-Al
2o
3catalyst, at 150～250 ℃ of low temperature, particularly has very high denitration efficiency at 200 ℃, so it has wider active window, is more conducive to make SCR denitrification apparatus to be arranged in thermal power plant's back-end ductwork, to reduce waste heat loss, improves thermal power plant's performance driving economy.
Above said content is only the basic explanation of the present invention under conceiving, and any equivalent transformation that technical scheme according to the present invention is done all belongs to the scope of protection of the invention.
Claims (10)
1. a low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst, is comprised of carrier and active component two parts, it is characterized in that described carrier is that particle diameter is the Al of 20～40nm
2o
3tiO with 10～30nm
2;
Described active component is MnOx and CuO, and wherein MnOx is MnO
2, Mn
3o
4, Mn
2o
3in the mixture of one or more compositions;
Described low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3in catalyst, by the mol ratio of contained metallic element Mn, Ti, Al, Cu, calculate, wherein Cu:Ti:Al:Mn is 0.2-0.4:1:1:0.4-1.2.
2. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 1
2-Al
2o
3catalyst, is characterized in that described low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst, calculates by the mol ratio of contained metallic element Mn, Ti, Al, Cu, and wherein Cu:Ti:Al:Mn is 0.4:1:1:0.8-1.2.
3. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 2
2-Al
2o
3catalyst, is characterized in that described low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst, calculates by the mol ratio of contained metallic element Mn, Ti, Al, Cu, and wherein Cu:Ti:Al:Mn is 0.4:1:1:0.8;
Wherein MnOx is MnO
2, Mn
3o
4and Mn
2o
3the mixture forming.
4. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 2
2-Al
2o
3the preparation method of catalyst, is characterized in that described low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst, calculates by the mol ratio of contained metallic element Mn, Ti, Al, Cu, and wherein Cu:Ti:Al:Mn is 0.4:1:1:1.2;
Wherein MnOx is MnO
2, Mn
3o
4and Mn
2o
3the mixture forming.
5. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 1
2-Al
2o
3the preparation method of catalyst, is characterized in that specifically comprising the steps:
(1), soluble manganese salt, soluble copper salt, solubility titanium salt, aluminum soluble salt are dissolved in deionized water, at room temperature adopt polytetrafluoroethylene (PTFE) paddle, controlling stir speed (S.S.) is 200-600rpm stirring and dissolving, and the ammoniacal liquor that adds 3mol/L in backward solution adjusts pH to stir 1-3h after 5-11, quiescent setting, by gained sedimentation and filtration, till the filter cake of gained is neutrality with deionized water rinsing to the pH of eluate;
The amount of soluble copper salt, soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water used in above-mentioned preparation process, calculate in molar ratio, i.e. copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is 1:2.5～5:2.5～5:1～6:84～168;
Described soluble copper salt is Cu(NO
3)
23H
2o;
Soluble manganese salt is Mn(NO
3)
26H
2o;
Solubility titanium salt is Ti(SO
4)
28H
2o;
Aluminum soluble salt is Al(NO
3)
39H
2o;
(2), by the filter cake of step (1) gained dry 12-24h at 80-105 ℃, obtain dry filter cake;
(3), dry filter cake that step (2) is obtained is placed in tubular type Muffle furnace, under air atmosphere, with the heating rate of 10 ℃/min, is warming up to 450-650 ℃, insulation 5h, finally naturally cools to room temperature with stove, obtains low-temperature denitration MnOx-CuO-TiO
2-Al
2o
3catalyst.
6. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 5
2-Al
2o
3the preparation method of catalyst, it is characterized in that soluble copper salt used in (1), soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water, calculate in molar ratio, i.e. copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is 1:2.5:2.5:2-3:84-126.
7. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 5
2-Al
2o
3the preparation method of catalyst, it is characterized in that soluble copper salt used in (1), soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water, calculate in molar ratio, i.e. copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is 1:2.5:2.5:2:84.
8. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 5
2-Al
2o
3the preparation method of catalyst, it is characterized in that soluble copper salt used in (1), soluble manganese salt, solubility titanium salt, aluminum soluble salt and deionized water, calculate in molar ratio, i.e. copper in soluble copper salt: the titanium in solubility titanium salt: the aluminium in aluminum soluble salt: the manganese in soluble manganese salt: deionized water is 1:2.5:2.5:3:126.
9. a kind of low-temperature denitration MnOx-CuO-TiO as described in claim 1,2,3 or 4
2-Al
2o
3the application of catalyst in denitrating flue gas, is characterized in that it is 150～250 ℃ that denitrification process temperature is controlled.
10. a kind of low-temperature denitration MnOx-CuO-TiO as claimed in claim 9
2-Al
2o
3the application of catalyst in denitrating flue gas, is characterized in that it is 200 ℃ that denitrification process temperature is controlled.
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|---|---|---|---|---|
| CN108686647A (en) * | 2017-04-10 | 2018-10-23 | 北京林业大学 | A kind of low temperature sulfur resistive Mn base SCR catalysts and preparation method thereof |
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2013
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| CN108686647A (en) * | 2017-04-10 | 2018-10-23 | 北京林业大学 | A kind of low temperature sulfur resistive Mn base SCR catalysts and preparation method thereof |
| CN108686647B (en) * | 2017-04-10 | 2020-10-09 | 北京林业大学 | A kind of low-temperature sulfur-resistant Mn-based SCR catalyst and preparation method thereof |
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