Low-temperature VOCs oxidation performance of Pt/zeolites catalysts with hierarchical pore structure

Different zeolites supported Pt catalysts with micro-mesoporous structure were prepared by organic base tetrapropylammonium hydroxide (TPAOH) treatment and their catalytic oxidation activity for various volatile organic compounds (VOCs) were evaluated. The results reveal that the synergistic effect between Pt nanoparticles and surface acid sites plays an important role in VOCs low-temperature removal. The small size and high dispersion of Pt nanoparticles on the surface of the zeolites would promote the catalytic oxidation of aromatics and alkanes over the Pt/zeolite catalysts, while strong acidity and abundant acid sites of catalysts are in favour of the oxidation of the VOCs containing N and O heteroatoms. In addition, it was found that Pt/ZSM-5 catalyst exhibits the highest oxidation activity for various VOCs low-temperature removal amongst all the catalysts due to the balance of both Pt dispersion and abundant acid sites in the catalyst. This comprehensive consideration should be very helpful when designing and preparing novel catalysts for the low-temperature removal of VOCs.     

硅铝比和NiO对ZSM-5协同低温等离子体降解甲苯的影响

研究了不同硅铝比的ZSM-5与Ni/ZSM-5分子筛协同低温等离子体技术对甲苯降解性能的影响.以Ni O(Nickel Oxide)为活性组分,采用浸渍法对ZSM-5分子筛进行改性,利用氮气吸附脱附(BET)、X射线衍射仪(XRD)、X射线光电子能谱分析(XPS)、H_2程序升温还原(H_2-TPR)、NH_3程序升温脱附(NH_3-TPD)、Toluene程序升温脱附(Toluene-TPD)等技术表征样品的物理化学性质.考察了硅铝比对ZSM-5与Ni/ZSM-5分子筛体系中甲苯的吸附性能,研究了不同放电电压下硅铝比对甲苯降解率、碳平衡及二氧化碳选择性的影响,并采用气相色谱-质谱联用仪(GC-MS)分析了催化剂表面的有机产物.结果表明:硅铝比不但影响分子筛本身的物理化学特性(比表面积、氧化还原性能、表面酸性、疏水性等),还会影响Ni的负载形态和方式,更高的硅铝比与Ni O的负载能促进甲苯深度氧化,减少副产物,提高碳平衡和二氧化碳选择性.     

不同硅铝比Fe-ZSM-5催化剂对氧化亚氮催化分解性能的研究

以不同硅铝比的H-ZSM-5分子筛为载体,采用离子交换法和化学气相沉积法制备Fe-ZSM-5催化剂,并用XRD、BET、TEM、UV-vis和NH3-TPD等表征手段对催化剂进行分析,研究催化剂中铁的存在状态.结果表明,分子筛的硅铝比影响铁在分子筛中的分布形态,化学气相沉积法和热离子交换法制得硅铝比为25的Fe-ZSM-5-25分子筛催化剂上均匀地分布着粒径为8 nm左右的纳米氧化铁颗粒,并且Fe-ZSM-5-25分子筛催化剂比Fe-ZSM-5-300更容易形成Fe3+x O y团簇.制得的Fe-ZSM-5分子筛催化剂催化分解氧化亚氮(N2O),结果表明,相同的制备方法,硅铝比小的Fe-ZSM-5-25催化剂对N2O分解活性更好;相同硅铝比的Fe-ZSM-5催化剂,采用化学气相沉积法制得的对N2O分解活性最好.另外,O2的存在对Fe-ZSM-5上N2O催化分解活性有抑制作用,而NO对N2O催化分解活性展示了一定的正效应.最后,经过100 h的连续反应,Fe-ZSM-5催化剂依然能够保持催化活性.     

Effect of Mo contents on properties of Mo/ZSM-5 zeolite catalyst for NOx reduction

Mo/ZSM-5 catalysts with different Mo content were prepared by impregnation method. The effect of Mo content on the property of Mo/ZSM-5 catalysts and their performance for selective catalytic reduction(SCR) of NO with ammonia was investigated by XRD, ICP,XPS and NO-TPD respectively. The results showed that the catalytic activity of Mo/ZSM-5 for SCR of NO is strongly influenced by the Mo loading in HZSM-5 zeolites. The NOx conversion reached the highest value of 64.2% at 375℃ when Mo content is about 10.9%, and the temperatures at which the maximum of NOx conversion obtained were declined with the increase of Mo content. From XRD results, it can be seen that it exhibits the distinct interaction between Mo and HZSM-5 when Mo content is about 10.9%. This may result in a suitable phase structure in Mo/ZSM-5 catalyst, which is advantageous for NO reduction. XPS and NO-TPD results also showed that the catalytic activity of Mo/ZSM-5 may be related to the Mo percent on the surface.     

CuO/ZSM-5系列催化剂的脱硫脱硝性能研究

采用浸渍法制备了不同质量分数的催化剂x％ CuO/ZSM-5 (x =2、4、6、8、10、12、50),并考察了其在CH4为还原剂条件下的脱硫脱硝性能.同时,采用X射线衍射(XRD)、H2-程序升温还原(H2-TPR)、NH3-程序升温脱附(NH3-TPD)、比表面积(BET)、扫描电子显微镜与能谱分析(SEM-EDS)等测试手段对催化剂进行表征.实验结果表明:10％ CuO/ZSM-5催化剂的活性组分具有较好的晶型结构,且高度分散在ZSM-5骨架中.在CH4+NO+ SO2反应中,10％ CuO/ZSM-5催化剂具有最好的脱硫脱硝活性,最高脱硫率和脱硝率分别为97.4％和94.6％.     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Characterization and performance of Pt/SBA-15 for low-temperature SCR of NO by C3H6

Pt supported on mesoporous silica SBA-15 was investigated as a catalyst for low temperature selective catalytic reduction(SCR) of NO by C 3 H 6 in the presence of excess oxygen.The prepared catalysts were characterized by means of XRD,BET surface area,TEM,NO-TPD,NO/C 3 H 6-TPO,NH 3-TPD,XPS and 27 Al MAS NMR.The effects of Pt loading amount,O 2 /C 3 H 6 concentration,and incorporation of Al into SBA-15 have been studied.It was found that the removal efficiency increased significantly after Pt loading,but an optimal loading amount was observed.In particular,under an atmosphere of 150 ppm NO,150 ppm C 3 H 6,and 18 vol.% O 2,0.5% Pt/SBA-15 showed remarkably high catalytic performance giving 80.1% NOx reduction and 87.04% C 3 H 6 conversion simultaneously at 140°C.The enhanced SCR activity of Pt/SBA-15 is associated with its outstanding oxidation activities of NO to NO 2 and C 3 H 6 to CO 2 in low temperature range.The research results also suggested that higher concentration of O 2 and higher concentration of C 3 H 6 favored NO removal.The incorporation of Al into SBA-15 improved catalytic performance,which could be ascribed to the enhancement of catalyst surface acidity caused by tetrahedrally coordinated AlO 4.Moreover,the catalysts could be easily reused and possessed good stability.     

铂、钯蜂窝催化剂高温老化对甲醇深度氧化的影响

本研究对铂、钯蜂窝催化剂及分别添加助化剂CeO_2或WO_3,并于500℃、700℃、900℃或1100℃下经受热老化4h后,考察催化剂比表面、晶相结构及其对甲醇深度氧化活性、产物分布及反应动力学网络变化的情况。实验证明,添加CeO_2后,降低了铂催化剂的耐高温性能,但对钯催化剂无明显影响。添加WO_3,降低了钯催化剂对甲醇的氧化活性。经X-线衍射分析证明,在1100℃高温下,WO_3与堇青石载体中的氧化镁和氧化钙发生强相互作用,生成了相应的钨酸盐。甲醇氧化反应动力学研究表明,甲醇在新鲜和高温热老化的铂催化剂上,反应动力学网络表示式是有区别的。     

Pt/CeO2催化氧化甲苯反应机制研究

采用浸渍法制备了Pt/CeO_2和Pt/Al2O_3催化剂,并通过XRD、BET、ICP-OES、H2-TPR、XPS等手段表征其物理化学性质.结果发现,Pt/CeO_2和Pt/Al2O_3催化剂上Pt负载量约为0.6%,Al2O_3载体上Pt颗粒尺寸更小,Pt/CeO_2的可还原性更强.甲苯催化氧化活性评价结果表明,Pt/CeO_2催化剂表现出更好的催化活性,T50=170℃,T90=190℃.通过UV-Raman、甲苯TPD、GC/MS、In-situ FTIR等手段进一步研究发现,Pt/CeO_2活化甲苯及反应供氧的机制与Pt/Al2O_3存在区别,其活性更好是因为:(1)负载在CeO_2表面存在高电子密度的Pt原子,具有更强的活化甲苯能力,可以直接使苯基和甲基间的C—C链发生断裂;(2)Pt的负载促进了CeO_2氧空位形成,进一步提高了CeO_2的储氧性能,加速氧循环.除了Pt解离气相氧之外,CeO_2还可以提供活性氧物种参与催化氧化甲苯的反应,进一步提高甲苯催化氧化效率.     

δ-MnO2 decorated layered double oxides in-situ grown on nickel foam towards electrothermal catalysis of n-heptane

Energy-saving and efficient monolithic catalysts are hotspots of catalytic purification of industrial gaseous pollutants. Here, we have developed an electrothermal catalytic mode, in which the ignition temperature required for the reaction is provided by Joule heat generated when the current flows through the catalyst. In this paper, Mn/NiAl/NF, Mn/NiFe/NF and Mn/NF metal-based monolithic catalysts were prepared using nickel foam (NF) as the carrier for thermal and electrothermal catalysis of n-heptane. The results indicated that Mn-based monolithic catalysts exhibit high activity in thermal and electrothermal catalysis. Mn/NiFe/NF achieve conversion of n-heptane more than 99% in electrothermal catalysis under a direct-current (DC) power of 6 W, and energy-saving is 54% compared with thermal catalysis. In addition, the results indicated that the introduction of NiAl (or NiFe) greatly enhanced the catalytic activity of Mn/NF, which attributed to the higher specific surface area, Mn³⁺/Mn⁴⁺, Ni³⁺/Ni²⁺, adsorbed oxygen species (O_ads)/lattice oxygen species (O_latt), redox performance of the catalyst. Electrothermal catalytic activity was significantly higher than thermal catalytic activity before complete conversion, which may be related to electronic effects. Besides, Mn/NiFe/NF has good cyclic and long-term stability in electrothermal catalysis. This paper provided a theoretical basis for applying electrothermal catalysis in the field of VOCs elimination.     

整体式分子筛基催化剂制备及其微波催化燃烧VOCs

以整体式蜂窝状分子筛为载体,制备铜锰铈负载型催化剂,研究其微波辐照下对VOCs （甲苯、丙酮、乙酸乙酯）的催化活性及其稳定性,探究影响催化剂活性的因素,并通过测试床层温度分布进行分析.研究表明,微波功率1.3kW、催化剂体积300mm×300mm×300mm,固定床温度>300℃条件下,催化剂对初始浓度200~2000mg/m³的5m³/h VOCs气体的降解效率为80%~92%.温度是VOCs氧化降解的条件,但当床层温度超过了300℃（VOCs完全燃烧温度）之后,升温对VOCs降解效率的影响不再明显.表征可知,尖晶石态铜锰铈单金属氧化物及其复合氧化物是主要的催化活性组分.VOCs在催化剂表面进行准一级反应而被催化氧化;高温对催化剂结构有一定影响,但重复性试验证实了催化剂的高活性和良好的稳定性.     

整体式分子筛基催化剂制备及其微波催化燃烧VOCs

以整体式蜂窝状分子筛为载体,制备铜锰铈负载型催化剂,研究其微波辐照下对VOCs （甲苯、丙酮、乙酸乙酯）的催化活性及其稳定性,探究影响催化剂活性的因素,并通过测试床层温度分布进行分析.研究表明,微波功率1.3kW、催化剂体积300mm×300mm×300mm,固定床温度>300℃条件下,催化剂对初始浓度200~2000mg/m³的5m³/h VOCs气体的降解效率为80%~92%.温度是VOCs氧化降解的条件,但当床层温度超过了300℃（VOCs完全燃烧温度）之后,升温对VOCs降解效率的影响不再明显.表征可知,尖晶石态铜锰铈单金属氧化物及其复合氧化物是主要的催化活性组分.VOCs在催化剂表面进行准一级反应而被催化氧化;高温对催化剂结构有一定影响,但重复性试验证实了催化剂的高活性和良好的稳定性.     

Effect of preparation parameters on catalytic properties of Pt/graphite

Catalytic ozonation of aqueous solutions of oxalic acid was examined in the presence of graphite-supported platinum catalysts. The catalytic activity of graphite was significantly enhanced by loading platinum. The removal efficiency of oxalic acid was 3.0%, 47.6% and 99.3% for ozonation alone, graphite catalytic ozonation and Pt/graphite catalytic ozonation in 30 min under the experimental condition, respectively. The influence of support pretreatment, solvent, impregnation time, platinum loading amount and reduction temperature on the activity of Pt/graphite catalyst was investigated. The pretreatment of graphite support had no effect on activity improvement of Pt/graphite catalyst. Solvent and impregnation time also no great effect on the activity. Platinum loading amount and reduction temperature influenced the catalyst activity significantly. The optimal catalytic performance of Pt/graphite was obtained when 1.0% platinum loading and 623 K of reduction temperature was adopted. The Pt/graphite catalyst was used for five times with no significant decrease in its activity and more than 90% oxalic acid removal was obtained. __________ Translated from Environmental Science, 2007, 28(6): 1258–1263 [译自: 环境科学]     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

Efficient degradation of chlorobenzene in a non-thermal plasma catalytic reactor supported on CeO2/HZSM-5 catalysts

Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO₂/HZSM-5 catalysts. The performance of catalysts was evaluated in terms of removal and energy efficiency. The decomposition products of chlorobenzene were analyzed. The results show that CeO₂/HZSM-5 exhibited a good catalytic activity, which resulted in enhancements of chlorobenzene removal, energy efficiency, and the formation of lower amounts of by-products. With regards to CO₂ selectivity, the presence of catalysts favors the oxidation of by-products, leading to a higher CO₂ selectivity. With respect to ozone, which is considered as an unavoidable by-product in air plasma reactors, a noticeable decrease in its concentration was observed in the presence of catalysts. Furthermore, the stability of the catalyst was investigated by analyzing the evolution of conversion in time. The experiment results indicated that CeO₂/HZSM-5 catalysts have excellent stability: chlorobenzene conversion only decreased from 78% to 60% after 75 hr, which means that the CeO₂/HZSM-5 suffered a slight deactivation. Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS) analyses of the catalyst before and after the reaction, revealing the cause of catalyst deactivation.     

Preparation of MnO2 decorated Co3Fe1Ox powder/monolithic catalyst with improved catalytic activity for toluene oxidation

In this paper, KMnO₄ was used to pre-treat Co₃Fe-layered double hydroxides (LDH) precursor to prepare MnO₂ decorated Co₃Fe₁O_x catalyst. The toluene oxidation performance of the catalyst was investigated systematically. The optimized 0.1MnCF-LDO catalyst exhibited the best catalytic performance, and the temperatures of 50% and 90% toluene conversion (T₅₀ and T₉₀) were 218 and 243°C, respectively. The apparent activation energy (E_a) was 31.6 kJ/mol. The characterization results showed that the pre-redox reaction by KMnO₄ could increase the specific surface area, Co³⁺ species amount and oxygen defect concentration of the catalyst, which are the main reason of the improved toluene catalytic activity. Besides, this method was also applied to enhance toluene oxidation of iron mesh based monolithic catalyst. The 0.1MnCF-LDO/Iron mesh (IM) catalyst showed a 90% toluene conversion at around 316°C which was much lower than that of without MnO₂ addition (359°C). In addition, the water resistant of all the catalysts was studied as well, all the samples showed relatively good water resistance. The toluene conversion still remained to be over >80% even in the presence of 10 vol.% water vapor.     

N/Ce doped graphene supported Pt nanoparticles for the catalytic oxidation of formaldehyde at room temperature

Pt catalysts with nitrogen-doped graphene oxide (GO) as support and CeO₂ as promoter were prepared by impregnation method,and their catalytic oxidation of formaldehyde (HCHO) at room temperature was tested.The Pt-CeO₂/N-rGO (reduced GO) with a mass fraction of 0.7% Pt and 0.8%CeO₂ exhibited an excellent catalytic performance with the 100% conversion of HCHO at room temperature.Physicochemical characterization demonstrated that nitrogendoping greatly increased the...     

One-pot synthesis of Fe/Cu-SSZ-13 catalyst and its highly efficient performance for the selective catalytic reduction of nitrogen oxide with ammonia

Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy. The obtained catalysts were subjected to selective catalytic reduction (SCR) of NO_x with NH₃ and were characterized by various techniques. The results show that Fe_0.63/Cu_1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580°C, excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13, signifying its great potential for practical applications. Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite (CHA) structure with good crystallinity, while isolated Cu²⁺ and monomeric Fe³⁺ are revealed as the predominant copper and iron species. At low temperatures, isolated Cu²⁺ species act as primary active sites for SCR reaction, while monomeric Fe³⁺ species provide sufficient active sites for sustain the SCR activity at high temperature. Moreover, Fe over doping would lead to the damage of zeolite structure, destruction of isolated Cu²⁺ site, as well as the formation of highly oxidizing Fe₂O₃, thus causing deterioration of catalytic performances.     

Highly catalytic activity of Mn/SBA-15 catalysts for toluene combustion improved by adjusting the morphology of supports

Rod-like, hexagonal and fiber-like SBA-15 mesoporous silicas were synthesized to support MnO_x for toluene oxidation. This study showed that the morphology of the supports greatly influenced the catalytic activity in toluene oxidation. MnO_x supported on rod-like SBA-15(R-SBA-15) displayed the best catalytic activity and the conversion at 230°C reached more than 90%, which was higher than the other two catalysts. MnO_x species consisted of coexisting MnO_2 and Mn_2O_3 on the three kinds of SBA-15 samples. Large amounts of Mn_2O_3 species were formed on the surface and high oxygen mobility was obtained on MnO_x supported on R-SBA-15, according to the H_2 temperature programmed reduction(H_2-TPR)and X-ray photoelectron spectroscopy(XPS) results. The Mn/R-SBA-15 catalyst with greater amounts of Mn_2O_3 species possessed a large amount of surface lattice oxygen, which accelerated the catalytic reaction rate. Therefore, the surface lattice oxygen and high oxygen mobility were critical factors on the catalytic activity of the Mn/R-SBA-15 catalyst.     

载体平衡离子对MnOx/ZSM-5催化NH3-SCR性能影响

采用不同平衡离子（H⁺、Na⁺和NH₄⁺）的ZSM-5改性分子筛制备MnO_x/ZSM-5催化剂,研究平衡离子对氨选择催化还原（NH₃-SCR）反应活性的影响.NH₃-SCR反应结果表明,NH₄-ZSM-5为载体时,催化剂表现出优异的低温SCR活性,而H-ZSM-5为载体的催化剂则在高温范围对NO_x具有较高的转化率.XRD、TEM、BET、Raman、H₂-TPR、XPS等表征结果显示,平衡离子可明显影响MnO_x在催化剂中的分散位置以及氧化还原性质.MZ-NH₄催化剂中活性组分MnO_x分散在载体外表面,颗粒尺寸较大,主要以Mn³⁺形式存在,对NO具有较强的氧化能力,进而促进“快速SCR”反应的进行.而H-ZSM-5为载体时,MnO_x主要被限域在载体孔道内形成限域催化剂,主要以Mn⁴⁺形式存在.活性研究和表征结果证明,活性组分分散在催化剂外表面,更有利于低温SCR反应的进行.