Enhancing low-temperature NOx storage and reduction performance of a Pt-based lean NOx trap catalyst
School of Automotive and Traffic Engineering, Jiangsu University
Wuxi Weifu Environmental Catalysts Co. Ltd
作者简介:*Jia-Ming Wang e-mail:wxt5409@126.com;
收稿日期:1 July 2018
基金:financially supported by the National Key R&D Program of China (No. 2017YFC0211100);
Enhancing low-temperature NOx storage and reduction performance of a Pt-based lean NOx trap catalyst
Tong Wang Li-Wei Jia Xiu-Ting Wang Gang Wang Fu-Qiang Luo Jia-Ming Wang
School of Automotive and Traffic Engineering, Jiangsu University
Wuxi Weifu Environmental Catalysts Co. Ltd
Abstract:
Two lean NOx trap(LNT) catalysts, Pt/BaO/CeO2 + Al2O3 and Pt/BaO/CeO2-Al2O3, were prepared and compared for low-temperature(< 250℃) NOx storage and reduction performance. The influence of the form of ceria on low-temperature NOx storage and reduction performance of LNT catalysts was investigated with the focus on NOx storage capacity, NOx reduction efficiency during lean/rich cycling, product selectivity and thermal stability.Inductively coupled plasma-atomic emission spectrometry(ICP-AES), Brunner-Emmet-T eller(BET), H2-pulse chemisorption and X-ray diffraction(XRD) were conducted to characterize the physical properties of LNT catalysts. NOx storage capacity and NOx conversion efficiency were measured to evaluate NOx storage and reduction performance of LNT catalysts. Pt/BaO/CeO2-Al2O3 catalyst exhibits higher NOx storage capacity than Pt/BaO/CeO2 + Al2O3 catalyst in the temperature range of 150-250 ℃. Meanwhile, Pt/BaO/CeO2-Al2O3 catalyst shows better NOx conversion efficiency and N2 selectivity. XRD results indicate that the thermal stability of CeO2-Al2O3 complex oxide is superior to that of pure CeO2. H2-pulse chemisorption results show that Pt/BaO/CeO2-Al2O3 catalyst has higher Pt dispersion than Pt/BaO/CeO2 + Al2O3 catalyst over fresh and aged samples. The improved physical properties of Pt/BaO/CeO2-Al2O3 catalyst are attributed to enhance the NOx storage and reduction performance over Pt/BaO/CeO2 + Al2O3 catalyst.
Keyword:
NOx storage and reduction; Low temperature; Ceria; Ceria-alumina; LNT;
Received: 1 July 2018
1 Introduction
To meet the stringent China Stage-VI light-duty diesel vehicles’NOx emission regulations,a promising approach has been explored by a combination of lean NOx trap(LNT) and selective catalytic reduction (SCR) catalysts
LNT catalysts operate under cyclic lean/rich conditions
In the present work,the goal was to study the effects of the form of ceria on low-temperature NOx storage and reduction performance through surface/bulk analysis and activity tests.The first catalyst of Pt/BaO/CeO2+Al2O3used ceria as a support material as well as alumina,and the second catalyst of Pt/BaO/CeO2-Al2O3 used complex ceria-alumina as a new support material.The low-temperature NOx storage capacity (NSC),NOx reduction efficiency,NH3 production and N2O emissions were measured.Thermal stability of LNT catalysts was also investigated after aging for 20 h at 800℃.
2 Experimental
2.1 Catalyst preparation
Catalysts were prepared by incipient wetness impregnation technique,using aqueous solutions of Ba(CH3COO)2 and Pt(NO3)2.In the preparation of Pt/BaO/CeO2+Al2O3(1wt%Pt and 9 wt%BaO),CeO2 (specific surface area152 m2·g-1) andγ-Al2O3 (150 m2·g-1) were mechanically mixed at the weight ratio of 3:7.The impregnation was carried out in a sequential manner:The well-mixed CeO2+Al2O3 support was firstly impregnated with the Ba acetate solution followed by Pt nitrate solution.On the other hand,Pt/BaO/CeO2-Al2O3 (1 wt%Pt and 9 wt%BaO) was prepared similarly,but using a CeO2-Al2O3complex oxide (30 wt%CeO2 and 70 wt%Al2O3,154 m2·g-1) as the support.After each impregnation step,the catalyst was dried at 100℃in air for overnight and then calcined in air at 500℃for 5 h.The obtained fresh catalysts were denoted as F-1 and F-2,respectively.In order to compare their thermal stability,the catalysts were further calcined in air at 800℃for 20 h.The aged catalysts were denoted as A-1 and A-2.
2.2 Catalyst characterization
The actual elemental compositions of catalysts were analyzed by inductively coupled plasma-atomic emission spectrometry (ICP-AES,Optima 2100 DV,PerkinElmer).The Brunner-Emmet-Teller (BET) specific surface areas were measured by N2 adsorption-desorption at-196℃on a Micromeritics ASAP 2000 analyzer.Prior to measurements,the samples were pre-treated at 150℃under vacuum for 3 h to eliminate the adsorbed species.The Pt dispersions were determined by H2-pulse chemisorption at-80℃by a Micromeritics AutoChemⅡAnalyzer.The crystalline phases of the catalysts were characterized by X-ray diffractometer (XRD,XRD-600,Shimadzu) with a Cu Kαradiation (λ=0.154056 nm) at 36 kV with a graphite monochromator.
2.3 Activity measurements
In NOx storage capacity (NSC) and NOxconversion efficiency measurements,0.25 g Pt/BaO/Al2O3 catalyst was mixed with 0.75 g quartz sand.The total flow rate is 1L·min-1,corresponding to a space velocity of 60,000 h-1.Before each experiment,the sample was oxidized in 10%O2/N2 balance at 350℃for 30 min,and then reduced in5%H2/N2 balance at 450℃for 20 min.The reactor was then cooled in N2 to the target test temperatures at 150,200and 250℃.The outlet gas of the reactor was maintained at140℃to avoid condensation and NH3 hold-up.A MKS MultiGas 2030 FT-IR analyzer was used to monitor NO,NO2,N2O,NH3,CO,C3H6,CO2 and H2O concentrations of the outlet gas.
NOx storage capacity (NSC) tests were conducted by exposing the catalyst to the flowing gas containing250×10-6 NO.8%O2.5%H2O,5%CO2 at 150,200 and250℃.The storage time was 10 min at each temperature during NSC measurement.NOx conversion efficiency tests were also measured at 150,200 and 250℃,and LNT performance was evaluated in a lean/rich (100 s/17 s)cycle under the gas composition detailed in Table 1.The average value of the last 5 cycles was calculated after 15lean/rich cycles.
3 Results and discussion
3.1 Catalyst characterization
The contents of Pt,Ba,Ce and A1 in catalysts are summarized in Table 2.F-1 and F-2 samples have similar Pt and Ba contents.Ce content in F-1 is slightly lower than that in F-2 (26.24 wt%vs.27.54 wt%).
BET specific surface areas and Pt dispersions of catalysts are listed in Table 3.The specific surface areas of F-1and F-2 samples are 117 and 122 m2.g-1,respectively.Pt dispersion of F-1 is 60%,slightly lower than 62%of F-2.After thermal aging at 800℃for 20 h,their surface areas decrease to 99 and 103 m2.g-1,respectively.The Pt dispersions reach significantly low values,only 12%for A-1and 19%for A-2,indicating that the sintering of Pt particles occurs during aging due to the mobility of Pt crystallites and eventually merged to form larger particles
Figure 1 shows XRD patterns of fresh and aged catalysts.The results show that Pt-related phases in all four samples were not detected because of either the low loading ratio or its small size.The main crystallite phases detected are CeO2,BaCO3 andγ-Al2O3 in all samples.The BaAl2O4 peak only appears after aging
Table 1 NOx conversion efficiency measurement:gas composition
Table 2 Elemental composition of fresh catalysts (wt%)
F-1—fresh Pt/BaO/CeO2+Al2O3 catalyst;F-2—fresh Pt/BaO/CeO2—Al2O3 catalyst
Table 3 BET specific surface areas and Pt dispersions of catalysts
3.2 NOx storage capacity (NSC)
The results of NOx storage capacity tests are reported in Table 4.All samples’NSCs increase substantially as the test temperature increases from 150 to 250℃due to enhancing NO oxidation activity to produce NO2 which is known to be more effective than NO to be adsorbed on LNT catalysts
Table 4 NOx storage capacity (250×10-6 NO,8%O2,5%H2O,5%CO2,N2 bal.,GHSV=60,000 h-1) of catalysts (μmol·g-1)
3.3 NOx conversion efficiency
NOx concentration profiles during the last 5 lean/rich cycles are shown in Fig.2.Average NOx conversions during the last 5 cycles are presented in Table 5.For F-1sample,NOx breakthrough is immediately observed after the feed gas switched into lean condition at 150℃,and the outlet NOx concentration decreases with time and gradually approaches the inlet NOx concentration.When the feed gas is subsequently switched to the rich condition,a sharp and intense NOx release peak appears and then intensity quickly decreases.The similar profile was also observed in a previous study
Fig.1 XRD patterns of fresh and aged catalysts:a F-1 and F-2 catalysts and b A-1 and A-2 catalysts
Fig.2 NOx concentration profiles during last 5 lean/rich cycles:a F-1 catalyst,b F-2 catalyst,c A-1 catalyst,and d A-2 catalyst
Table 5 NOx conversion and selectivity of N-containing products during last 5 lean/rich cycles
In the case of F-2 sample,NOx evolutions at three temperatures are similar to those of F-1 sample,but F-2sample has slightly higher average NOx conversions,14.6%at 150℃,73.4%at 200℃,and 76.1%at 250℃,in accordance with the results of NSC measurements.
After thermal aging,the amount of NOxtrapped on the aged catalyst at lean phase at 150℃becomes smaller in comparison with fresh catalysts and the outlet NOxconcentrations gradually reach a constant level (around240×10-6) for both aged catalysts.Higher NOxslip is observed during rich phase,and average NOxxconversions of A-1 and A-2 samples are only 6.6%and 9.0%,respectively.At 200℃,NOx-spill-out over A-1 is relatively larger in comparison with that over A-2 during switching to the rich condition,leading to a lower NOx conversion for A-1 (49.0%vs.58.9%for A-2).NOx release still appears over aged samples at 250℃,resulting in that NOx conversion decreases to some extent.Average NOx conversion sharply declines at 150 and 200℃.Pt is known to have impacts on NO oxidation under lean conditions,NOx storage under rich/lean conditions and NOx reduction under rich conditions
Fig.3 Evolution of NH3 and N2O concentrations during lean/rich cycles at 200℃:a fresh samples and b aged samples
From the perspective of study on the law and production of NH3 and N2O,their concentrations evolution at 200℃during lean/rich cycles is taken as an example and shown in Fig.3.For fresh and aged samples,NH3 and N2O are both formed in lean and rich phases.During lean phase,NH3and N2O are subsequently formed,NH3 intensity sharply decreases to below 10×10-6 at the initial lean phase,while a small N2O peak appears,and then the N2O intensity gradually becomes stabilized.A sharp N2O peak is immediately observed at the beginning of rich phase,and NH3 peak delays about 2 s.In comparison with the results obtained over fresh samples,the amount of NH3 and N2O formation decreases over aged samples.In the lean and rich phase,NH3 is mainly formed via the reduction in NOx by surface hydrogen,although NH3 is also a product of isocyanate hydrolysis reaction
N2O formation in lean phase is related to the reactions between surface-deposited reductants/intermediates (CO,HC,NH3,isocyanate) and gaseous NO/O2,and N2O release peak during rich phase may be attributed to that NOx partially reduced over platinum group metal (PGM)sites
Concerning the product selectivity,N2O is the main product at 150℃.At 200℃,selectivity of NH3,N2O and N2 is similar for fresh samples,but NH3 and N2O become the main products for aged samples.By increasing the temperature to 250℃,N2 selectivity of all samples shows a substantial enhancement.Moreover,N2O selectivity decreases as the temperature increases from 150 to 250℃.N2 selectivity decreases in the following order:F-2>F-1>A-2>A-1.Thermal aging results are in an increase in NH3 and N2O selectivity,except NH3 selectivity at 150℃.Compared to fresh samples,the higher NH3 selectivity over aged LNT catalysts above 200℃was also found by Chatterjee et al.
4 Conclusion
The influence of the form of ceria on low-temperature NOx storage and reduction performance of LNT catalysts was investigated,using CeO2-Al2O33 complex oxide or CeO2+Al2O3 mixed oxide as the support for BaO and Pt.CeO2-Al2O3 support exhibits the improvements on NOx storage capacity,NOx conversion efficiency (especially for aged samples at 200℃) and N2 selectivity in comparison with CeO2+Al2O3 support in the temperature range of150-250℃.After aging for 20 h at 800℃,Pt/BaO/CeO2-Al2O3 catalyst exhibits better thermal stability and chemical distribution than Pt/BaO/CeO2+Al2O3 catalyst.Overall,CeO2-Al2O3-based catalysts show superior NOx storage and regeneration performance over CeO2+Al2O3-based catalyst at low temperatures.
Concerning NH3 and N2O selectivity of NOx reduction,N2O is the main product at 150℃,and its selectivity decreases as the temperature increases from 150 to 250℃.Thermal aging results are in an increase in the NH3 and N2O selectivity at 200 and 250℃.
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