CN102773098B - Preparation process of nanometer titanium-dioxide denitration catalyst - Google Patents

Preparation process of nanometer titanium-dioxide denitration catalyst Download PDF

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CN102773098B
CN102773098B CN201210307469.0A CN201210307469A CN102773098B CN 102773098 B CN102773098 B CN 102773098B CN 201210307469 A CN201210307469 A CN 201210307469A CN 102773098 B CN102773098 B CN 102773098B
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张千
张建平
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HEBEI MILSON TITANIUM DIOXIDE CO Ltd
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HEBEI MILSON TITANIUM DIOXIDE CO Ltd
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Abstract

The invention relates to a preparation process of a nanometer titanium-dioxide denitration catalyst, which ensures that the titanium-dioxide denitration catalyst has better photocatalysis while the heat stability of the catalyst is improved. The process comprises the procedure of doping metallic elements in titanium dioxide, and is characterized in that the procedure of doping the metallic elements in the titanium dioxide comprises the steps of doping lanthanum and loading gold. The preparation process adopts the key technology that the procedure of doping the lanthanum and loading the gold is implemented during the preparation of the titanium dioxide; by loading the gold, the photocatalysis of the catalyst can be improved, and by doping the lanthanum, the heat stability of the catalyst can be improved; and therefore, a remarkable effect is achieved through the combination of the steps of doping the lanthanum and loading the gold. Through experimental processes and test results, an anticipated purpose is finally achieved, and thus the preparation process has great significance on the production field of the denitration catalyst.

Description

A kind of preparation technology of nano titanium oxide denitrating catalyst
Technical field
The invention belongs to the production technical field of titanium dioxide, relate to a kind of nano titanium oxide denitrating catalyst of using in production process of titanium pigment, particularly a kind of preparation technology of titanium dioxide denitrating catalyst of simultaneously adulterate lanthanum and gold-supported.
Background technology
TiO 2a kind of very rising NO xthe pollution control material of waste gas, but because light-catalyzed reaction speed is low, limited its application in industry, and therefore, noble metal (Pt, Ru, Au) doping vario-property is current generally acknowledged raising TiO 2a kind of more effective mode of light-catalyzed reaction performance.Gold Au has good catalytic effect as active component, and its price is comparatively cheap with respect to noble metals such as platinum, palladiums, can reduce to a certain extent raw-material cost; And to there is the semiconductor titanium dioxide TiO of multiphase photocatalysis performance 2for carrier, will have the advantage of the two concurrently, produce cooperative effect with active component., Au/TiO 2the major defect of catalyst is exactly poor heat stability, and generally at more than 300 ℃ inactivation partly or completely during roasting, because the working environment of denitrating catalyst is at 320-450 ℃, this just makes to improve Au/TiO 2the heat endurance of catalyst becomes the problem that must solve.
Research through us is found, lanthanum sesquioxide La 2o 3as a kind of structural promoter, the noble metal of effects on surface high dispersive has heat endurance preferably, to TiO 2the La that middle doping is a small amount of 3+can improve TiO 2heat endurance, improve catalytic activity.Therefore we consider, if lanthanum La can be entrained in titanium dioxide together with golden Au, effect is highly significant.。
Summary of the invention
Object of the present invention is exactly when having better photocatalysis performance, to improve the technical barrier of heat endurance in order to solve titanium dioxide denitrating catalyst, designed a kind of preparation technology of nano titanium oxide denitrating catalyst, make to adulterate lanthanum with golden in titanium dioxide simultaneously, finally reach the object that improves heat endurance.
The present invention is that the technical scheme that realizes goal of the invention employing is, a kind of preparation technology of nano titanium oxide denitrating catalyst, be included in the process of doped metallic elements in titanium dioxide, key is: in titanium dioxide, the operation of doped metallic elements comprises the step of doping lanthanum and gold-supported, and concrete steps comprise:
A, allotment microemulsion, prepare oleic acid C 18h 34o 2, n-butanol C 4h 10o, a NaOH solution, volume ratio is C 18h 34o 2: C 4h 10o:NaOH=1:(1.5-2.5): (3-5), standby after mixing;
B, configuration TiCl 4oil solution, with TiCl 4for solute, with oleic acid C 18h 34o 2with n-butanol C 4h 10o is solvent, then adds surfactant c-SAA, and the liquor capacity of above each material is than being TiCl 4: C 18h 34o 2: C 4h 10o:c-SAA=1:(3-3.5): (3-3.5): (0.01-0.02), and add tributyl phosphate in above formed miscella solution, the volume of interpolation is the 4%-6% of miscella solution, form TiCl 4oil solution, standby;
C, the microemulsion in a step is put into agitator, prepare lanthanum nitrate La(NO 3) 36H 2o, is dissolved in the TiCl configuring in b step 4in oil solution, form mixed solution, above mixed solution is slowly joined in agitator, at room temperature rapid stirring 1-1.5 hour, obtains H 2tiO 3precipitation, wherein lanthanum nitrate, TiCl 4the mass ratio of oil solution, microemulsion is controlled at 100:(3-5): (9-15);
D, above-mentioned precipitation is first used to acetone and absolute ethanol washing, at 100-150 ℃, be dried again 2.5-3.5 hour, obtain pressed powder, after grinding, with distilled water, wash, at 100-150 ℃, be dried again 0.5-1.5 hour, in 550-650 ℃ of high temperature furnace, calcine 2-2.5 hour again, obtain mixing the titania support of lanthanum, be denoted as La-TiO 2;
The HAuCl that d, preparation concentration are 1-1.2mol/L 4solution, using the 2nd NaOH solution as precipitating reagent;
E, with the 2nd NaOH solution by HAuCl 4the pH value of solution is adjusted to 8, then by the La-TiO obtaining in c step 2powder is added to HAuCl 4in solution, La-TiO 2powder and HAuCl 4mass ratio be (110-120): 1, continue afterwards to add NaOH solution that pH value is adjusted to 8;
F, by the suspension forming in step e vigorous stirring 1.5-2.5 hour at 80-90 ℃, be cooled to room temperature, through washing, filter, dry after, then through high-temperature roasting 12-18 hour, obtain the La-TiO of load Au 2, be denoted as Au/La-TiO 2.
Key technology of the present invention is when preparing titanium dioxide, the production process of adulterate lanthanum and gold-supported, and gold-supported can improve photocatalysis performance, and doping lanthanum can improve heat endurance, the two is in conjunction with the effect that has reached highly significant.And add c-SAA as surfactant, for improving titanium dioxide surface activity, play booster action, through experimentation and test result, finally reached the object of expection, the production field of denitrating catalyst is significant.
Accompanying drawing explanation
Fig. 1 is the Au/La-TiO that preparation technology of the present invention produces 2thermally-stabilised curve synoptic diagram.
The specific embodiment
A preparation technology for nano titanium oxide denitrating catalyst, is included in the process of doped metallic elements in titanium dioxide, and key is: in titanium dioxide, the operation of doped metallic elements comprises the step of doping lanthanum and gold-supported, and concrete steps comprise:
A, allotment microemulsion, prepare oleic acid C 18h 34o 2, n-butanol C 4h 10o, a NaOH solution, volume ratio is C 18h 34o 2: C 4h 10o:NaOH=1:(1.5-2.5): (3-5), standby after mixing;
B, configuration TiCl 4oil solution, with TiCl 4for solute, with oleic acid C 18h 34o 2with n-butanol C 4h 10o is solvent, then adds surfactant c-SAA, and the liquor capacity of above each material is than being TiCl 4: C 18h 34o 2: C 4h 10o:c-SAA=1:(3-3.5): (3-3.5): (0.01-0.02), and add tributyl phosphate in above formed miscella solution, the volume of interpolation is the 4%-6% of miscella solution, form TiCl 4oil solution, standby;
C, the microemulsion in a step is put into agitator, prepare lanthanum nitrate La(NO 3) 36H 2o, is dissolved in the TiCl configuring in b step 4in oil solution, form mixed solution, above mixed solution is slowly joined in agitator, at room temperature rapid stirring 1-1.5 hour, obtains H 2tiO 3precipitation, wherein lanthanum nitrate, TiCl 4the mass ratio of oil solution, microemulsion is controlled at 100:(3-5): (9-15);
D, above-mentioned precipitation is first used to acetone and absolute ethanol washing, at 100-150 ℃, be dried again 2.5-3.5 hour, obtain pressed powder, after grinding, with distilled water, wash, at 100-150 ℃, be dried again 0.5-1.5 hour, in 550-650 ℃ of high temperature furnace, calcine 2-2.5 hour again, obtain mixing the titania support of lanthanum, be denoted as La-TiO 2;
The HAuCl that d, preparation concentration are 1-1.2mol/L 4solution, using the 2nd NaOH solution as precipitating reagent;
E, with the 2nd NaOH solution by HAuCl 4the pH value of solution is adjusted to 8, then by the La-TiO obtaining in c step 2powder is added to HAuCl 4in solution, La-TiO 2powder and HAuCl 4mass ratio be (110-120): 1, continue afterwards to add NaOH solution that pH value is adjusted to 8;
F, by the suspension forming in step e vigorous stirring 1.5-2.5 hour at 80-90 ℃, be cooled to room temperature, through washing, filter, dry after, then through high-temperature roasting 12-18 hour, obtain the La-TiO of load Au 2, be denoted as Au/La-TiO 2.
In described step a, a NaOH solution concentration is 2-4mol/L.When being 2 mol/L, it is more that volume parts will add relatively, and when being 4mol/L, volume parts can add relatively less.
In described step e, NaOH solution concentration is 0.8-1.2mol/L.
In described step c, stir speed (S.S.) is 1250-1300r/min.
In described step f, stir speed (S.S.) is 1250-1300r/min.
In described step f, roasting process is divided into three phases roasting: in temperature, be roasting 4-6 hour at 350-360 ℃; Then roasting 4-6 hour at 480-495 ℃; Last roasting 4-6 hour at 500-510 ℃.
The present invention in the specific implementation, is below 6 groups of experimental datas that we enumerate,
Table 1:
Figure 2012103074690100002DEST_PATH_IMAGE002
Au/La-TiO of the present invention 2the experimental data of catalyst with the results are shown in Table 1.Can find out the Au/La-TiO producing by this technique 2demonstrate good activity and heat endurance.Au/La-TiO 2catalytic activity be better than the titanium dioxide of a gold-supported.Photocatalytic activity obtains so large raising, is because Au 3+more easily catch light induced electron, on the one hand electronics and hole are obtained effective separated, on the other hand Au 3+promote the generation of catalyst surface hydroxyl radical free radical, accelerated degradation reaction speed.Visible, the doping of La can make Au catalyst when temperature raises, also keep higher activity.Heat endurance curve is shown in Fig. 1.
Denitrification test carries out in stainless steel tubular type fixed bed SCR reactor, and internal diameter is 10 mm.Catalytic reactor is external electric, with the thermocouple measuring temperature that inserts catalyst layer.Temperature controller is controlled reaction temperature, and precision is ± 1 ℃.
Test employing standard steel cylinder gas simulative power plant flue gas.Because NO in typical flue gas NOx accounts for more than 95%, NO 2impact very little, can ignore, so the NOx in test adopts NO to replace.Air inlet consists of ψ (NO)=l 000 μ L/L, ψ (O 2)=5%, N 2for Balance Air, reducing agent adopts steel cylinder ψ (NH3)==l 000 μ L/L, total exhaust gas volumn 72 L/h.Getting respectively 3 g particle diameters and be the different catalysts of 0.3-1 m tests.Air speed compares n sv=2.4x10 4/ h.Each road gas enters gas mixer mixing and enters NH again after mass flowmenter 3blender.NH 3directly pass through NH 3blender passes into reactor.
Each operating mode is stablized 10 min.Gas component adopts Rosemount NGA 2000 flue gas analyzers to measure, and this instrument can on-line measurement NO removal efficiency.For avoiding NH 3to NO, the impact of test, flue gas removed NH with phosphoric acid solution washing before entering NGA 2000 3, pipeline complete stroke thermal insulating.
Known according to test, La doping can make the photocatalytic activity of nano titanium oxide load gold catalyst improve, and improves NO removal efficiency, and the tools such as smoke gas treatment are had very great significance.

Claims (6)

1. the preparation technology of a nano titanium oxide denitrating catalyst, be included in the process of doped metallic elements in titanium dioxide, it is characterized in that: in titanium dioxide, the operation of doped metallic elements comprises the step of doping lanthanum and gold-supported, and concrete steps comprise:
A, allotment microemulsion, prepare oleic acid C 18h 34o 2, n-butanol C 4h 10o, a NaOH solution, volume ratio is C 18h 34o 2: C 4h 10o:NaOH=1:(1.5-2.5): (3-5), standby after mixing;
B, configuration TiCl 4oil solution, with TiCl 4for solute, with oleic acid C 18h 34o 2with n-butanol C 4h 10o is solvent, then adds surfactant c-SAA, the liquor capacity ratio of above each material: TiCl 4: C 18h 34o 2: C 4h 10o:c-SAA=1:(3-3.5): (3-3.5): (0.01-0.02), and add tributyl phosphate in above formed miscella solution, the volume of interpolation is the 4%-6% of miscella solution, form TiCl 4oil solution, standby;
C, the microemulsion in a step is put into agitator, prepare lanthanum nitrate La(NO 3) 36H 2o, is dissolved in the TiCl configuring in b step 4in oil solution, form mixed solution, above mixed solution is slowly joined in agitator, at room temperature rapid stirring 1-1.5 hour, obtains H 2tiO 3precipitation, wherein lanthanum nitrate, TiCl 4the mass ratio of oil solution, microemulsion is controlled at 100:(3-5): (9-15);
D, above-mentioned precipitation is first used to acetone and absolute ethanol washing, at 100-150 ℃, be dried again 2.5-3.5 hour, obtain pressed powder, after grinding, with distilled water, wash, at 100-150 ℃, be dried again 0.5-1.5 hour, in 550-650 ℃ of high temperature furnace, calcine 2-2.5 hour again, obtain mixing the titania support of lanthanum, be denoted as La-TiO 2;
The HAuCl that e, preparation concentration are 1-1.2mol/L 4solution, using the 2nd NaOH solution as precipitating reagent;
F, with the 2nd NaOH solution by HAuCl 4the pH value of solution is adjusted to 8, then by the La-TiO obtaining in d step 2powder is added to HAuCl 4in solution, La-TiO 2powder and HAuCl 4mass ratio be (110-120): 1, continue afterwards to add NaOH solution by pH value be adjusted to 8 suspension;
G, by the suspension forming in step f vigorous stirring 1.5-2.5 hour at 80-90 ℃, be cooled to room temperature, through washing, filter, dry after, then through high-temperature roasting 12-18 hour, obtain the La-TiO of load Au 2, be denoted as Au/La-TiO 2.
2. the preparation technology of a kind of nano titanium oxide denitrating catalyst according to claim 1, is characterized in that: in described step a, a NaOH solution concentration is 2-4mol/L.
3. the preparation technology of a kind of nano titanium oxide denitrating catalyst according to claim 1, is characterized in that: in described step e, the 2nd NaOH solution concentration is 0.8-1.2mol/L.
4. the preparation technology of a kind of nano titanium oxide denitrating catalyst according to claim 1, is characterized in that: in described step c, stir speed (S.S.) is 1250-1300r/min.
5. the preparation technology of a kind of nano titanium oxide denitrating catalyst according to claim 1, is characterized in that: in described step g, stir speed (S.S.) is 1250-1300r/min.
6. the preparation technology of a kind of nano titanium oxide denitrating catalyst according to claim 1, is characterized in that: in described step g, roasting process is divided into three phases roasting: in temperature, be roasting 4-6 hour at 350-360 ℃; Then roasting 4-6 hour at 480-495 ℃; Last roasting 4-6 hour at 500-510 ℃.
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侯凯军等.掺杂La3+对纳米Au/TiO2催化剂结构和性能的影响.《无机化学学报》.2007,第23卷(第9期),1538-1544.
掺杂La3+对纳米Au/TiO2催化剂结构和性能的影响;侯凯军等;《无机化学学报》;20070930;第23卷(第9期);1538-1544 *

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