CN101773832A - Method for preparing BaFeO3 perovskite catalyst with excellent sulfur resistance for storing nitrogen oxide - Google Patents
Method for preparing BaFeO3 perovskite catalyst with excellent sulfur resistance for storing nitrogen oxide Download PDFInfo
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- CN101773832A CN101773832A CN200910228920A CN200910228920A CN101773832A CN 101773832 A CN101773832 A CN 101773832A CN 200910228920 A CN200910228920 A CN 200910228920A CN 200910228920 A CN200910228920 A CN 200910228920A CN 101773832 A CN101773832 A CN 101773832A
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Abstract
The invention relates to a method for preparing a BaFeO3 perovskite catalyst with excellent sulfur resistance for storing nitrogen oxide, and belongs to a catalyst technique for removing NOx in exhaust gas produced by the combustion of automobile fuel. The method comprises the following steps: mixing nitrates of Ba and Fe; using citric acid and EDTA as complex agents; adjusting pH to between 8.0 and 10.0 to obtain a sol; drying and baking the sol to obtain a perovskite sample; and grinding and screening the perovskite sample to obtain the catalyst. The method has the advantages that: a preparation process is simple; a complete perovskite structure can be obtained by accurately controlling a pH value in a sample preparation process; and the perovskite catalyst has excellent sulfur resistance and regeneration performance, and is a non-noble metal NOx storing reducing catalyst with a good development prospect.
Description
Technical field
The present invention relates to the good nitrogen oxide of a kind of anti-sulphur and store BaFeO
3The preparation method of perovskite catalyst belongs to the catalyst technology of removing the NOx in the vehicle fuel burning and gas-exhausting.
Background technology
In order to improve the economy of fuel oil, reduce CO
2Discharging, Lean Burning Technique has obtained broad development.The NO that Toyota Company at first proposes
xStorage and reduction (NSR) technology obtains practical application in the lean-combustion engine car of low sulfur content fuel.Li Xin has just waited the Ba-Fe-O catalyst of people at report in 2004, and adopting citric acid is the Prepared by Sol Gel Method of complexing agent, wherein Ba: Fe: the ratio of citric acid is 1: 2: 1.This catalyst has the excellent storage reducing property, and 400 ℃ of its storage capacitys are 340.1 μ mol/g; But its anti-sulphur is relatively poor, and sulfuration back storage capacity only is 50.9 μ mol/g, and storage capacity has descended 85.0%.The sulfur poisoning-resistant ability that improves catalyst on the basis that keeps NOx catalysis elimination activity is main from now on research direction.
Summary of the invention
The object of the invention provides the good nitrogen oxide of a kind of anti-sulphur and stores BaFeO
3The preparation method of perovskite catalyst, this procedure is simple, the BaFeO that makes with the method
3Perovskite catalyst is used for store nitrogen oxides and has good sulfur resistance, and regeneration reducing is good, long service life.
The present invention is realized by following technical proposals, the good store nitrogen oxides BaFeO of a kind of anti-sulphur
3The preparation method of perovskite catalyst is characterized in that comprising following process:
1.Ba (NO
3)
2And Fe (NO
3)
3Be dissolved in respectively in the deionized water, being mixed with concentration is the Ba (NO of 0.1～0.2mol/L
3)
2And Fe (NO
3)
3Solution, by Ba in the solution: the Fe mol ratio is 1: 1～2 with Ba (NO
3)
2And Fe (NO
3)
3Two solution mix also after ultrasonic 0.5～1 hour, under 70～90 ℃ of holding temperatures and stirring condition, mol ratio by barium in the mixed solution and citric acid is 1: 2～3, go into the citric acid solution that concentration is 0.4～0.6mol/L to mixed solution and dripping, and be 8.0～10.0 with the pH of ammonia spirit regulator solution in process, continue stirring reaction after 4～6 hours, make thick thing.
2, the thick thing that step 1 is made is in 110～130 ℃ of temperature down after 10～14 hours dryings of oven dry, again in 400～450 ℃ of roastings of temperature two hours, heating rate with 4～6 ℃/min rises to 750～950 ℃ of following roasting 6h of temperature in tube furnace then, obtains the sample of roasting.
3, sieving after the sample of the roasting that step 2 is made grinds and obtaining particle is 40～60 purpose store nitrogen oxides BaFeO
3Perovskite catalyst.
The invention has the advantages that preparation process is simple, the preparation raw material need not adopt noble metal, greatly reduces preparation cost.Prepared BaFeO
3Perovskite catalyst has store nitrogen oxides amount height, and anti-sulphur property can be good, is easy to the characteristics of regeneration reducing and long service life.
The specific embodiment
Embodiment 1
Prepare Ba (NO respectively
3)
2And Fe (NO
3)
30.1mol/L solution, according to Ba: the Fe mol ratio is that 1: 1 ratio is respectively got 100ml and evenly mixed, the citric acid solution 40ml (mol ratio is Ba: Fe: CA=1: 1: 2) that dropwise adds 0.5mol/L after ultrasonic half an hour, temperature maintenance is at 80 ℃, whole process is 9.0 with the pH of ammonia spirit control solution, prevents to produce in the solution precipitation, continues to stir with the electronics agitator, evaporation, and form thick material; Be placed in the baking oven 120 ℃ down after dry 13 hours, 400 ℃ of roastings two hours that organic compound combustion is complete earlier, then in tube furnace with heating rate to the 750 ℃ following roasting 6h of 4 ℃/min.
The sample specific area that makes is 6.5m
2/ g.Sample is carried out NOx storge quality test, and test is carried out in internal diameter is the quartz tube type fixed bed reactors of 8mm.Get the 500mg sample at 800ppm NO, 5%O
2, N
2Be balance gas, air speed 2.52 * 10
4h
-1Under the condition, 400 ℃ of following constant temperature NOx adsorption.Gas flow rate is controlled by mass flowmenter, and the NO flow velocity is 0.17mL/min, O
2Flow velocity is 11mL/min, N
2Flow velocity is 197mL/min.The concentration of NOx is with the variation in reaction time in the continuous monitoring tail gas.Absorption NO
xConcentration adopts Model 42i-HL nitrogen-oxide analyzer, (Thermo Scientific, chemiluminescence detector) to detect.Testing result is: the NOx storage capacity is 333.5 μ mol/g, the utilization rate 4.0% of barium.
Sample is vulcanized, and amount of samples is 200mg, and at 400 ℃ of following constant temperature sulfuration 1h, gas composition is 380ppm SO
2, 5%O
2, N
2Be balance gas, SO
2/ N
2The mist flow velocity is 100mL/min, O
2Flow velocity is 5mL/min.With the sulfuration after sample at 400 ℃ of following 5%H
2/ N
2Reduction 30min eliminates the nitrate that stores, H in the atmosphere
2/ N
2The flow velocity of gaseous mixture is 30mL/min, gets the 100mg catalyst and investigates the power of regeneration that catalyst roasting 1h in 400 ℃ of air atmospheres investigates sample.For 400 ℃ of sulfuration rear catalysts, use H under synthermal
2Power of regeneration behind the reduction elimination nitrate in air atmosphere can reach 90.5%.
Embodiment 2
Prepare Ba (NO respectively
3)
2And Fe (NO
3)
30.1mol/L solution, according to Ba: the Fe mol ratio is that 1: 1 ratio is respectively got 100ml and evenly mixed, the citric acid solution 40ml (mol ratio is Ba: Fe: CA=1: 1: 2) that dropwise adds 0.5mol/L after ultrasonic half an hour, temperature maintenance is at 80 ℃, whole process is 9.0 with the pH of ammonia spirit control solution, prevents to produce in the solution precipitation, continues to stir with the electronics agitator, evaporation, and form thick material; Be placed in the baking oven 120 ℃ down after dry 13 hours, 400 ℃ of roastings two hours that organic compound combustion is complete earlier, then in tube furnace with heating rate to the 850 ℃ following roasting 6h of 4 ℃/min.
The sample specific area that makes is 5.9m
2/ g.Get the 500mg sample at 800ppm NO, 5%O
2, N
2Be balance gas, air speed 2.52 * 10
4h
-1Under the condition, 400 ℃ of following constant temperature NOx adsorption.The NOx storage capacity is 747.7 μ mol/g, and the utilization rate 8.9% of barium for 400 ℃ of sulfuration rear catalysts, is used H under synthermal
2Power of regeneration behind the reduction elimination nitrate in air atmosphere can reach 70.2%.
Embodiment 3
Prepare Ba (NO respectively
3)
2And Fe (NO
3)
30.1mol/L solution, according to Ba: the Fe mol ratio is that 1: 1 ratio is respectively got 100ml and evenly mixed, the citric acid solution 40ml (mol ratio n/n is Ba: Fe: CA=1: 1: 2) that dropwise adds 0.5mol/L after ultrasonic half an hour, temperature maintenance is at 80 ℃, whole process is 9.0 with the pH of ammonia spirit control solution, prevents to produce in the solution precipitation, continues to stir with the electronics agitator, evaporation, and form thick material; Be placed in the baking oven 120 ℃ down after dry 13 hours, 400 ℃ of roastings two hours that organic compound combustion is complete earlier, then in tube furnace with heating rate to the 950 ℃ following roasting 6h of 4 ℃/min.
The sample specific area that makes is 2.6m
2/ g.Get the 500mg sample at 800ppm NO, 5%O
2, N
2Be balance gas, air speed 2.52 * 10
4h
-1Under the condition, 400 ℃ of following constant temperature NOx adsorption.The NOx storage capacity is 199.8 μ mol/g, and the utilization rate 2.4% of barium for 400 ℃ of sulfuration rear catalysts, is used H under synthermal
2Power of regeneration behind the reduction elimination nitrate in air atmosphere can reach 93.4%.
Comparative Examples 1
Get the Ba (NO of 0.25mol/L
3)
2, Fe (NO
3)
3Each 100ml of solution, ultrasonic assisting allows solution mix, the citric acid 50ml (mol ratio n/n is Ba: Fe: CA=1: 1: 1) that adds 0.5mol/L, solution continues to continue stirring and heating evaporation down to thick material at 80 ℃, 120 ℃ dry 13 hours down, in tube furnace with heating rate to the 750 ℃ roasting 6h of 4 ℃/min.This catalyst is designated as the CA sample.The used identified as samples of the present invention is designated as the pH sample.
CA sample and pH sample are vulcanized, and amount of samples is 200mg, and at 400 ℃ of following constant temperature sulfuration 1h, gas composition is 380ppm SO
2, 5%O
2, N
2Be balance gas, SO
2/ N
2The mist flow velocity is 100mL/min, O
2Flow velocity is 5mL/min.
CA sample storage capacity reaches 1271 μ mol/g, the utilization rate of barium is 15.3%, pH sample storage capacity is 333.5 μ mol/g, the utilization rate of barium is 4.0%, from the NOx storage capacity of sample after 400 ℃ of partial vulcanizations, though the NSC of CA sample is still big than the pH sample, but compare with fresh sample, descended 30.8%, and the pH sample has only descended 19.4%, and the utilization rate suppression ratio pH sample of CA sample barium after sulfuration descends also big, has descended 4.7%, though this explanation pH sample NOx storage capacity is little than the CA sample, its sulfur resistance is better.
Comparative Examples 2
With EDTA-CA as complexing agent.By citric acid and the synthetic perovskite sample of EDTA complexometry, under agitation be 0.25mol/L Ba (NO with 100ml concentration
3)
2It is 0.5mol/LEDTA-NH that solution adds 100ml concentration
3In the solution, adding 100ml concentration then is the Fe (NO of 0.25mol/L
3)
3Solution, behind the stirring 30min, adding 150ml concentration is in the 0.5mol/L citric acid solution, mol ratio EDTA: CA: Metals=1: 1.5: 1.May produce precipitation after adding citric acid, regulate pH=6, the solution clarification that becomes immediately, EDTA-NH with ammonia spirit
3Form cushioning liquid with citric acid, the pH value of system maintains 6,80 ℃ of following water-baths to forming colloidal sol, forms gel down in dry 12 hours at 120 ℃, earlier organic compound combustion is complete at 400 ℃ of roasting 2h, then sample in tube furnace with heating rate to the 750 ℃ following roasting 6h of 4 ℃/min.This catalyst is designated as the EDTA sample.
It is 242.6 μ mol/g that the storage capacity of EDTA sample has only, the utilization rate of barium only is 2.9%, pH sample storage capacity is 333.5 μ mol/g, the utilization rate of barium is 4.0%, from the NOx storage capacity of sample after 400 ℃ of partial vulcanizations, though the NSC of EDTA sample has only descended 16.4%, compare with pH sample NSC value will be low many, illustrate that the storge quality of pH sample wants better.
Claims (1)
1. the good nitrogen oxide of anti-sulphur stores BaFeO
3The preparation method of perovskite catalyst is characterized in that comprising following process:
1) Ba (NO
3)
2And Fe (NO
3)
3Be dissolved in respectively in the deionized water, being mixed with concentration is the Ba (NO of 0.1～0.2mol/L
3)
2And Fe (NO
3)
3Solution, by Ba in the solution: the Fe mol ratio is 1: 1～2 with Ba (NO
3)
2And Fe (NO
3)
3Two solution mix also after ultrasonic 0.5～1 hour, under 70～90 ℃ of holding temperatures and stirring condition, mol ratio by barium in the mixed solution and citric acid is 1: 2～3, go into the citric acid solution that concentration is 0.4～0.6mol/L to mixed solution and dripping, and be 8.0～10.0 with the pH of ammonia spirit regulator solution in process, continue stirring reaction after 4～6 hours, make thick thing;
2) the thick thing that step 1) is made is in 110～130 ℃ of temperature down after 10～14 hours dryings of oven dry, again in 400～450 ℃ of roastings of temperature two hours, heating rate with 4～6 ℃/min rises to 750～950 ℃ of following roasting 6h of temperature in tube furnace then, obtains the sample of roasting;
3) with step 2) sample of the roasting that makes sieves after grinding, and to obtain particle be that 40～60 purposes store nitride BaFeO
3Perovskite catalyst.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007994A (en) * | 2012-12-13 | 2013-04-03 | 天津大学 | BaFeO3-x/Cu-ZSM-5 coupled catalyst and application thereof |
| CN110422882A (en) * | 2019-07-17 | 2019-11-08 | 兰溪泛翌精细陶瓷有限公司 | A kind of novel ferroelectric material and preparation method thereof |
| CN113134352A (en) * | 2020-01-19 | 2021-07-20 | 天津大学 | Composite metal oxide catalyst for catalyzing direct decomposition of nitrogen oxide and preparation method thereof |
-
2009
- 2009-12-02 CN CN200910228920A patent/CN101773832A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007994A (en) * | 2012-12-13 | 2013-04-03 | 天津大学 | BaFeO3-x/Cu-ZSM-5 coupled catalyst and application thereof |
| CN110422882A (en) * | 2019-07-17 | 2019-11-08 | 兰溪泛翌精细陶瓷有限公司 | A kind of novel ferroelectric material and preparation method thereof |
| CN113134352A (en) * | 2020-01-19 | 2021-07-20 | 天津大学 | Composite metal oxide catalyst for catalyzing direct decomposition of nitrogen oxide and preparation method thereof |
| CN113134352B (en) * | 2020-01-19 | 2022-12-27 | 天津大学 | Composite metal oxide catalyst for catalyzing direct decomposition of nitrogen oxide and preparation method thereof |
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Open date: 20100714 |