CN102773098A - Preparation process of nanometer titanium-dioxide denitration catalyst - Google Patents
Preparation process of nanometer titanium-dioxide denitration catalyst Download PDFInfo
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- CN102773098A CN102773098A CN2012103074690A CN201210307469A CN102773098A CN 102773098 A CN102773098 A CN 102773098A CN 2012103074690 A CN2012103074690 A CN 2012103074690A CN 201210307469 A CN201210307469 A CN 201210307469A CN 102773098 A CN102773098 A CN 102773098A
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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
Technical field
The invention belongs to the production technical field of titanium white powder, relate to a kind of nano titanium oxide denitrating catalyst of using in the production process of titanium pigment, particularly a kind of preparation technology of titanium dioxide denitrating catalyst of mix simultaneously lanthanum and load gold.
Background technology
TiO
2Be a kind of very rising NO
XThe pollution control material of waste gas, but because light-catalyzed reaction speed is low, limited it in Industrial Application, and therefore, noble metal (Pt, Ru, Au) doping vario-property is the raising TiO that generally acknowledges at present
2Light-catalyzed reaction performance a kind of than effective and efficient manner.Gold Au has catalytic effect preferably as active component, and its price is comparatively cheap with respect to noble metals such as platinum, palladiums, can reduce raw-material cost to a certain extent; And to have the semiconductor titanium dioxide TiO of multiphase photocatalysis performance
2Be carrier, advantage that will both produces cooperative effect with active component., Au/TiO
2The major defect of catalyst is exactly a poor heat stability, and generally at inactivation partly or completely during roasting more than 300 ℃, because the working environment of denitrating catalyst is at 320-450 ℃, this just makes and improves Au/TiO
2The heat endurance of catalyst becomes the problem that must solve.
That passes through us discovers lanthanum sesquioxide La
2O
3As a kind of structural promoter, the noble metal of surperficial high dispersive had heat endurance preferably, to TiO
2Middle a spot of La that mixes
3+Can improve TiO
2Heat endurance, improve catalytic activity.Therefore we consider, if can lanthanum La and golden Au be entrained in the titanium dioxide together, effect is highly significant then.。
Summary of the invention
The object of the invention is exactly in order to solve the titanium dioxide denitrating catalyst improves heat endurance when having better photocatalysis performance technical barrier; Designed a kind of preparation technology of nano titanium oxide denitrating catalyst; Make mix simultaneously in the titanium dioxide lanthanum and gold, finally reach the purpose that improves heat endurance.
The present invention for realizing the technical scheme that goal of the invention adopts is; A kind of preparation technology of nano titanium oxide denitrating catalyst; Be included in the process of doped metallic elements in the titanium dioxide; Key is: the operation of doped metallic elements comprises the step of doping lanthanum and load gold in titanium dioxide, and concrete steps comprise:
A, allotment microemulsion are prepared 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), subsequent use after mixing;
B, configuration TiCl
4Oil solution is with TiCl
4Be solute, with oleic acid C
18H
34O
2With n-butanol C
4H
10O is a solvent, adds surfactant c-SAA again, more than the liquor capacity of each material than for TiCl
4: C
18H
34O
2: C
4H
10O:c-SAA=1: (3-3.5): (3-3.5): (0.01-0.02), and in above formed miscella solution, add tributyl phosphate, the volume of interpolation is the 4%-6% of miscella solution, forms TiCl
4Oil solution, subsequent use;
C, the microemulsion in a step is put into agitator, prepare lanthanum nitrate La (NO
3)
36H
2O is dissolved in the TiCl that disposes in the b step
4Form mixed solution in the oil solution, above mixed solution is slowly joined in the agitator, at room temperature stirred fast 1-1.5 hour, obtain H
2TiO
3Deposition, wherein lanthanum nitrate, TiCl
4The mass ratio of oil solution, microemulsion is controlled at 100: (3-5): (9-15);
D, above-mentioned deposition is first with acetone and absolute ethanol washing; Descended dry 2.5-3.5 hour at 100-150 ℃ again, obtain pressed powder, grind the back and washs with distilled water; Descended dry 0.5-1.5 hour at 100-150 ℃ again; In 550-650 ℃ of high temperature furnace, calcined 2-2.5 hour, obtain mixing the titania support of lanthanum, note is made La-TiO
2
D, preparation concentration are the HAuCl of 1-1.2mol/L
4Solution, with the 2nd NaOH solution as precipitating reagent;
E, with the 2nd NaOH solution with HAuCl
4The pH value of solution is adjusted to 8, then with the La-TiO that obtains in the c step
2Powder is added to HAuCl
4In the solution, La-TiO
2Powder and HAuCl
4Mass ratio be (110-120): 1, continue to add NaOH solution afterwards pH value be adjusted to 8;
F, with the suspension that forms among the step e at 80-90 ℃ of following vigorous stirring 1.5-2.5 hour, be cooled to room temperature, after washing, filtration, drying, obtained the La-TiO of load Au again through high-temperature roasting 12-18 hour
2, note is made Au/La-TiO
2
Key technology of the present invention is when preparation titanium dioxide, the production process of lanthanum and the load gold that mixes, and the load gold can improve photocatalysis performance, and the doping lanthanum can improve heat endurance, the two combination has reached the effect of highly significant.And add c-SAA as surfactant, play booster action,, finally reached its intended purposes, the production field of denitrating catalyst is significant through experimentation and test result for improving the titanium dioxide surface activity.
Description of drawings
Fig. 1 is the Au/La-TiO that preparation technology of the present invention produces
2Thermally-stabilised curve synoptic diagram.
The specific embodiment
A kind of preparation technology of nano titanium oxide denitrating catalyst is included in the process of doped metallic elements in the titanium dioxide, and key is: the operation of doped metallic elements comprises the step of doping lanthanum and load gold in titanium dioxide, and concrete steps comprise:
A, allotment microemulsion are prepared 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), subsequent use after mixing;
B, configuration TiCl
4Oil solution is with TiCl
4Be solute, with oleic acid C
18H
34O
2With n-butanol C
4H
10O is a solvent, adds surfactant c-SAA again, more than the liquor capacity of each material than for TiCl
4: C
18H
34O
2: C
4H
10O:c-SAA=1: (3-3.5): (3-3.5): (0.01-0.02), and in above formed miscella solution, add tributyl phosphate, the volume of interpolation is the 4%-6% of miscella solution, forms TiCl
4Oil solution, subsequent use;
C, the microemulsion in a step is put into agitator, prepare lanthanum nitrate La (NO
3)
36H
2O is dissolved in the TiCl that disposes in the b step
4Form mixed solution in the oil solution, above mixed solution is slowly joined in the agitator, at room temperature stirred fast 1-1.5 hour, obtain H
2TiO
3Deposition, wherein lanthanum nitrate, TiCl
4The mass ratio of oil solution, microemulsion is controlled at 100: (3-5): (9-15);
D, above-mentioned deposition is first with acetone and absolute ethanol washing; Descended dry 2.5-3.5 hour at 100-150 ℃ again, obtain pressed powder, grind the back and washs with distilled water; Descended dry 0.5-1.5 hour at 100-150 ℃ again; In 550-650 ℃ of high temperature furnace, calcined 2-2.5 hour, obtain mixing the titania support of lanthanum, note is made La-TiO
2
D, preparation concentration are the HAuCl of 1-1.2mol/L
4Solution, with the 2nd NaOH solution as precipitating reagent;
E, with the 2nd NaOH solution with HAuCl
4The pH value of solution is adjusted to 8, then with the La-TiO that obtains in the c step
2Powder is added to HAuCl
4In the solution, La-TiO
2Powder and HAuCl
4Mass ratio be (110-120): 1, continue to add NaOH solution afterwards pH value be adjusted to 8;
F, with the suspension that forms among the step e at 80-90 ℃ of following vigorous stirring 1.5-2.5 hour, be cooled to room temperature, after washing, filtration, drying, obtained the La-TiO of load Au again through high-temperature roasting 12-18 hour
2, note is made Au/La-TiO
2
Among the 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.
Among the described step e, the NaOH solution concentration is 0.8-1.2mol/L.
Among the described step c, stir speed (S.S.) is 1250-1300r/min.
Among the described step f, stir speed (S.S.) is 1250-1300r/min.
Among the described step f, roasting process is divided into the three phases roasting: in temperature is 350-360 ℃ of following roasting 4-6 hour; Then at 480-495 ℃ of following roasting 4-6 hour; At last at 500-510 ℃ of following roasting 4-6 hour.
The present invention below is 6 groups of experimental datas that we enumerate in the specific implementation,
Table 1:
Au/La-TiO of the present invention
2The experimental data and the result of catalyst see table 1.Can find out the Au/La-TiO that uses this technology to produce
2Demonstrate activity and heat endurance preferably.Au/La-TiO
2Catalytic activity be better than the titanium dioxide of load gold.Photocatalytic activity obtains so big raising, is because Au
3+More be prone to catch light induced electron, on the one hand electronics effectively separated with the hole, on the other hand Au
3+Promote the generation of catalyst surface hydroxyl radical free radical, accelerated degradation reaction speed.It is thus clear that the doping of La can make Au catalyst when temperature raises, also keep higher activity.The heat endurance curve is seen Fig. 1.
Denitrification test carries out in stainless steel tubular type fixed bed SCR reactor, and internal diameter is 10 mm.Catalytic reactor is an external electric, with the thermocouple measuring temperature that inserts catalyst layer.Temperature controller control reaction temperature, precision is ± 1 ℃.
Test employing standard steel cylinder gas simulation power-plant flue gas.Because NO accounts for more than 95% NO in the typical flue gas NOx
2Influence very little, can ignore, so the NOx in the test adopts NO to replace.Air inlet consists of ψ (NO)=l 000 μ L/L, ψ (O
2)=5%, N
2Be balance gas, reducing agent employing steel cylinder ψ (NH3)==l 000 μ L/L, total exhaust gas volumn 72 L/h.Getting 3 g particle diameters respectively and be the different catalysts of 0.3-1 m tests.Air speed compares n
Sv=2.4x10
4/ h.Each road gas gets into the gas mixer mixing and gets into NH again behind mass flowmenter
3Blender.NH
3Directly pass through NH
3Blender feeds reactor.
Each operating mode is stablized 10 min.Gas component adopts Rosemount NGA 2000 flue gas analyzers to measure, but this instrument on-line measurement NO removal efficiency.For avoiding NH
3To NO, the influence of test, flue gas removed NH with the phosphoric acid solution washing before getting into NGA 2000
3, the pipeline complete stroke thermal insulating.
Can know that based on test the La photocatalytic activity can make the nano titanium oxide load gold catalyst that mixes improves, and improves the NO removal efficiency, smoke gas treatment etc. is had very significant meaning.
Claims (6)
1. the preparation technology of a nano titanium oxide denitrating catalyst; Be included in the process of doped metallic elements in the titanium dioxide; It is characterized in that: the operation of doped metallic elements comprises the step of doping lanthanum and load gold in titanium dioxide, and concrete steps comprise:
A, allotment microemulsion are prepared 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), subsequent use after mixing;
B, configuration TiCl
4Oil solution is with TiCl
4Be solute, with oleic acid C
18H
34O
2With n-butanol C
4H
10O is a solvent, adds surfactant c-SAA again, more than the liquor capacity ratio of 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 in above formed miscella solution, add tributyl phosphate, the volume of interpolation is the 4%-6% of miscella solution, forms TiCl
4Oil solution, subsequent use;
C, the microemulsion in a step is put into agitator, prepare lanthanum nitrate La (NO
3)
36H
2O is dissolved in the TiCl that disposes in the b step
4Form mixed solution in the oil solution, above mixed solution is slowly joined in the agitator, at room temperature stirred fast 1-1.5 hour, obtain H
2TiO
3Deposition, wherein lanthanum nitrate, TiCl
4The mass ratio of oil solution, microemulsion is controlled at 100: (3-5): (9-15);
D, above-mentioned deposition is first with acetone and absolute ethanol washing; Descended dry 2.5-3.5 hour at 100-150 ℃ again, obtain pressed powder, grind the back and washs with distilled water; Descended dry 0.5-1.5 hour at 100-150 ℃ again; In 550-650 ℃ of high temperature furnace, calcined 2-2.5 hour, obtain mixing the titania support of lanthanum, note is made La-TiO
2
D, preparation concentration are the HAuCl of 1-1.2mol/L
4Solution, with the 2nd NaOH solution as precipitating reagent;
E, with the 2nd NaOH solution with HAuCl
4The pH value of solution is adjusted to 8, then with the La-TiO that obtains in the c step
2Powder is added to HAuCl
4In the solution, La-TiO
2Powder and HAuCl
4Mass ratio be (110-120): 1, continue to add NaOH solution afterwards pH value be adjusted to 8;
F, with the suspension that forms among the step e at 80-90 ℃ of following vigorous stirring 1.5-2.5 hour, be cooled to room temperature, after washing, filtration, drying, obtained the La-TiO of load Au again through high-temperature roasting 12-18 hour
2, note is made 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: among the 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: among the 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: among the 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: among the described step f, 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: among the described step f, roasting process is divided into the three phases roasting: in temperature is 350-360 ℃ of following roasting 4-6 hour; Then at 480-495 ℃ of following roasting 4-6 hour; At last at 500-510 ℃ of following roasting 4-6 hour.
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|---|---|---|---|---|
| US11697109B2 (en) * | 2017-07-19 | 2023-07-11 | Lg Hausys, Ltd. | Catalyst particles for treating vehicle exhaust gas, preparation method therefor, and method for treating vehicle exhaust gas by using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306357A (en) * | 2007-05-16 | 2008-11-19 | 北京化工大学 | Binary nano composite photo-catalyst preparation method |
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| CN101306357A (en) * | 2007-05-16 | 2008-11-19 | 北京化工大学 | Binary nano composite photo-catalyst preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 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》, vol. 23, no. 9, 30 September 2007 (2007-09-30), pages 1538 - 1544 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11697109B2 (en) * | 2017-07-19 | 2023-07-11 | Lg Hausys, Ltd. | Catalyst particles for treating vehicle exhaust gas, preparation method therefor, and method for treating vehicle exhaust gas by using same |
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