Zeolite-NaY-supported Ir/Sn catalysts derived from single- and dual-source organometallic precursors. Preparation and characterization of highly selective dehydrogenation catalysts

Zeolite-NaY-supported Ir/Sn catalysts (1 wt% Ir, 0.6 wt% Sn; 1:1 molar ratio) were prepared by adsorption of the organometallic precursors Ir(CO)₂(acac) and SnMe₃OH or (COD)₂Ir–SnMe₃ {COD= 1,5-cyclooctadiene) from hexane solutions followed by activation in H₂ up to 773 K. The Ir/Sn/NaY catalysts displayed high selectivity for the dehydrogenation of propane to propene at ca. 773 K and, in the presence of H₂, maintained thermodynamic conversion levels for up to 24 h. After activation, the catalyst derived from the dual-source precursors ({Ir+Sn/NaY) appeared homogeneous in composition, whereas the catalyst derived from the single-source precursor (Ir–Sn/NaY) appeared heterogeneous with distinct regions of visible particles. Scanning transmission electron microscopy revealed that the nanoscale metal particles present were small and uniform in size (ca. 1 nm) in the Ir + Sn/NaY catalyst but ranged in size from 1 to 10 nm in the Ir–Sn/NaY catalyst. Energy-dispersive X-ray analysis showed that bimetallic particles were formed for both catalysts. Temperature-programmed reaction of chemiosorbed carbon monoxide indicated that the Ir/Sn/NaY catalysts were electronically modified by the presence of tin in comparison with analogously prepared Ir/NaY catalysts. This revised version was published online in July 2006 with corrections to the Cover Date.     

Deactivation characteristics inn-heptane reforming reaction catalyzed over small Pt,Ir and Pt-Ir bimetallic clusters in NaY

The deactivation characteristics of highly dispersed (about 1 nm) Pt, Ir and Pt-Ir bimetallic clusters in NaY were studied by hydrogen chemisorption, coke analysis and temperature programmed oxidation of used catalyst inn-heptane reforming reaction. As the Ir content was increased, the amount of coke decreased. Most of coke was located around the metal cluster and this coke decreased the selectivity of dehydrocyclization inn-heptane reaction. The higher activity and more improved activity maintenance of Pt-Ir/NaY bimetallic catalysts than those of Pt/NaY are related to the less amount of coke formation.     

Intrazeolite Pd clusters: particle location

A chemical vapour deposition (CVD) procedure has been adopted for the preparation of Pd/NaY, resulting in a high dispersion of the metal phase, characterised by a bimodal distribution of particle size. The most abundant particles (80%) are about 25 Å in size, corresponding to almost twice the dimension of the zeolitic supercages. To identify their location inside or outside the zeolite matrix, the IR spectra of adsorbed CO, obtained before and after admission of NH₃, have been compared. The results obtained are in sharp contrast with those for a Pd/SiO₂ system, where Pd particles of comparable size are exclusively located on the external surface of the carrier. These differences support the conclusion that Pd particles in Pd/NaY are indeed located in the zeolitic cavities.     

催化裂化催化剂生产过程中分子筛粉碎技术的应用

在催化裂化催化剂生产过程中为了提高超稳分子筛的有效利用率,提升产品质量,使用了一系列超稳分子筛粉碎技术。对超稳分子筛聚集的原因及粉碎技术进行了对比分析,重点分析了介质超细研磨粉碎技术对催化剂质量指标的影响。造成超稳分子筛粒子聚集的主要原因是NaY分子筛合成过程中粒子间相互吸附,后续分子筛交换改性工序对分子筛粒度分布影响较小。介质超细研磨机和干磨粉碎技术对粉碎超稳分子筛效果明显,能够有效降低分子筛粒径,在催化裂化催化剂生产过程中介质超细研磨机的应用效果较好。经粉碎后的超稳分子筛能够明显降低催化裂化催化剂的磨损指数,提高微反活性。     

高硅铝比小晶粒NaY分子筛/高岭土复合物的合成及其催化裂化性能

以两种不同粒径的高岭土为原料,采用水热法合成了高硅铝比小晶粒NaY分子筛/高岭土复合物,通过XRD、SEM、晶粒度分析和N₂物理吸附等表征手段对复合物进行了结构和形貌表征。结果表明,与商品NaY相比,高岭土合成样品的结构稳定性和水热稳定性显著提高,以细化高岭土为原料合成样品的晶粒尺寸达310 nm,比表面积达807 m²·g^-1。以改性NaY分子筛/高岭土复合物为活性组分制备了催化裂化催化剂,采用NH₃程序升温脱附(NH₃-TPD)技术对其酸性特征进行了分析,并在小型微反装置上对其重油催化裂化性能进行了评价。研究结果发现,随着骨架硅铝比增大,催化剂表面酸中心强度增加,而酸量下降。采用细化高岭土合成的NaY分子筛/高岭土复合物的分子筛晶粒更小,催化剂酸中心数量以及催化裂化性能均大幅度提升。随着高温焙烧高岭土/偏高岭土质量比的增加,合成产物中的高岭土基质含量增加,催化剂表面酸中心强度下降。以原料高温焙烧高岭土/偏高岭土质量比为0.5,骨架硅铝比为6.1(摩尔比)的样品制备的催化剂,去柴重油转化率高达85.4%,同时有高达64.2%的汽油收率,表现出优异的重油催化裂化性能。     

Pd/NaY催化苯甲醇无溶剂选择性氧化反应

采用离子交换法将[Pd(NH₃)₄]²⁺交换到NaY分子筛中,经焙烧和氢气还原制备金属钯粒径可调变的Pd/NaY催化剂。在(120~500) ℃改变焙烧温度,可以获得金属钯粒径(1.3~11.9) nm的Pd/NaY催化剂。Pd/NaY催化剂能够催化苯甲醇的无溶剂选择性氧化反应,对含不同钯粒径的Pd/NaY催化剂上醇选择性氧化研究发现,在1.6%Pd/NaY催化剂用量0.1 g、反应温度100 ℃、苯甲醇用量48.5 mmol和O₂流速3 mL·min^-1条件下,苯甲醇转化的真实转化频率随粒径变化在3.2 nm处呈最大值,该反应为结构敏感反应。     

Fluidizable catalyst for methane reforming

Fluidizable catalysts are developed in this study for advancing an integral approach towards a new methane reforming process. With this end, catalysts constituted by nickel supported on -alumina, NaY, and USY were developed using the incipient wetness technique producing bulk nickel loadings in the 0–20 wt.% range. These catalysts were also tested under relevant conditions for industrial operation in a novel Riser Simulator. It was found that, for the case of ‘dry’ reforming of methane, nickel deposited in zeolites is a promising catalyst given that it allows for close control of metal dispersion–redispersion process. In fact, when this catalyst was exposed to repeated oxidation and reduction cycles, nickel dispersions remained stable at 25% for NaY zeolite and at 15% for USY zeolite. This catalyst offers, however, limited application for steam reforming of methane given the potential collapse of the zeolite structure under steam atmosphere. As an alternative and for cases where steam reforming of methane is preferred, nickel on -alumina catalyst was considered. In these cases, optimum catalytic activity was achieved with 2.5 wt.% of nickel on -alumina with 3–6% nickel dispersion.     

超微NaY分子筛的合成和催化芳烃转化性能

进行了超微NaY分子筛的合成。以工业化为基础,系统研究了导向剂的老化时间、分子筛的成胶温度、凝胶的老化温度和时间、以及晶化温度和时间等因素对NaY分子筛细化的影响,合成出n(SiO₂)/n(Al₂O₃)≥5,粒度分布范围小,平均粒径小于300 nm 的超微NaY分子筛。测定表明,BET比表面积大于890 m2·g^-1。分别采用合成的分子筛与常规分子筛作为催化剂载体,以甲苯作为模型化合物考察了催化剂的催化脱芳烃性能。结果表明,与常规微米分子筛相比,超微NaY分子筛负载的Pt催化剂的甲苯加氢活性相当,但在加氢产物分布中,环异构化产物的量明显增加,裂化产物则明显减少。     

Reducibility and CO hydrogenation over Pt and Pt-Co bimetallic catalysts encaged in NaY-zeolite

Temperature programmed techniques (TPR, TPD) and X-ray diffraction (XRD) have been used to study ion migration and location as well as reducibility of platinum and cobalt ions encapsulated in Pt/NaY, Co/NaY and Pt-Co/NaY zeolites prepared by ion exchange. The temperature required to reduce Co²⁺ in NaY was significantly lowered by the presence of Pt and dependent upon the relative locations of Pt and Co ions in zeolite cages. The exact location was controlled by the calcination condition and the metal contents. For bimetallic catalyst with low Pt content (0.5 wt% Pt and 0.9 wt% Co), the TPR results indicated that reduction of Co²⁺ ions in the vicinity of Pt shifted toward lower temperature, while that of Co²⁺ staying alone was not affected. With high Pt loading (4.5 wt% Pt, 0.7 and 2.6 wt% Co), however, most of the Co²⁺ ions were reduced by means of Pt at temperature below 723 K after calcination at 573 K. The temperature for Pt reduction in bimetallic catalysts was somewhat higher than Pt/NaY and increased with Co atomic fraction, indicating that mixed oxide, PtCo _x O _y , might be formed during calcination. After reduction in hydrogen at 723 K, highly dispersed metal particles were formed. These fine particles were most probably confined inside zeolite cages as indicated by the absence of XRD peak for all samples after calcination and reduction. Surface composition of the bimetallic particles may be different for catalysts with similar Pt content but different Co loading. Accordingly, H/Pt ratios of 1.0 and 0.72 for catalysts with low and high Co content, respectively, were shown by hydrogen chemisorption. It was further supported by the increase in TPD peak intensity with Co loading in the high temperature range, which was related to the reoxidation of Co in bimetallic particles by surface hydroxyl groups. Preliminary results on CO hydrogenation demonstrated that activity and methanol selectivity were higher on Pt-Co bimetallic catalysts than either over monometallic Pt or Co catalyst, which was consistent with the Pt enhanced Co reduction and formation of Pt-Co bimetallic particles.     

Oxidation catalysts prepared from biosorbents supported on zeolites

The catalytic oxidation of 1,2-dichlorobenzene was investigated over NaY and NaX zeolites, loaded with chromium through the action of a robust biosorption system consisting of a bacterial biofilm supported on the zeolites. The results of biosorption showed that the maximum metal removal efficiency was 20%, in both systems based on NaY or NaX, starting from solutions with chromium(VI) concentrations ranging from 50 to 250 mg_Cr/L. The bacterial biofilm, Arthrobacter viscosus, supported on the zeolite reduces Cr(VI) to Cr(III). The Cr(III) is retained in the zeolite by ion exchange. The new catalysts were characterized by spectroscopic methods (FTIR ), chemical analyses (ICP-AES), surface analysis (XRD) and thermal analysis (TGA). The various techniques of characterization show that this biosorption process does not modify the morphology and structure of the FAU-zeolites. These catalysts, Cr/FAU, prepared through this new procedure present good activity and selectivity for dichlorobenzene oxidation in wet air at 350 °C. The Cr₅₀-Y was selected as the most active, selective and stable catalyst for oxidation of 1,2-dichlorobenzene in wet air.     

Hydrogenation of carbon monoxide over nickel zeolite catalysts — effect of reduction and calcination

NiNaY zeolite catalysts were prepared by successive ion exchange of NaY. The catalysts were characterized for BET surface area, nickel metal area, nickel crystallite size and crystallinity. The methanation of carbon monoxide was studied in a fixed bed reactor in the temperature range of 523–673 K. Specific activities for methanation were found to vary with nickel concentration and crystallite size. The values of nickel metal area and specific methanation activity for the uncalcined catalysts were found to be higher compared to those of calcined catalysts. The effect of reduction at 723 K on the zeolite base structure and the effects of calcining the catalyst on metal area, crystallite size and activity are discussed.     

Non-oxidative methane transformations into higher hydrocarbons over bimetallic Pt–Co catalysts supported on Al2O3 and NaY

The methane conversion under non-oxidative conditions over Al₂O₃ and NaY supported cobalt, platinum and Pt–Co bimetallic catalysts in a flow system has been investigated. The two-step process was applied in the temperature range between 523 and 673 K and 1 bar pressure and the one-step process was carried out under the conditions of 1073 K and 10 bar pressure. Addition of platinum to NaY and alumina supported cobalt samples results in the formation of metallic Co particles and Pt–Co bimetallic particles. On bimetallic catalysts in the two-step process, the amount of C₂₊ products formed were higher than that on mono-metallic samples. The synergism shown by the bimetallic system can be explained by: (i) enhanced reducibility of cobalt, and (ii) the co-operation of two types of active components (Co facilitates the chain-growth of partially dehydrogenated species produced on Pt in Pt–Co bimetallic particles). The use of higher pressures and high temperature makes it possible to run the process to form primarily ethane (and ethylene) which is predicted from thermodynamic calculations. For NaY as support, significantly enhanced activity and C₂₊ selectivity are obtained compared with Al₂O₃ as support, which can be attributed to the structural differences of metal particles (location, dispersion and reducibility).     

Ce修饰Na Y分子筛负载PdO纳米晶催化剂用于苯的催化氧化反应

以CeO_2修饰多孔NaY分子筛作为载体,采用高温液相还原法制备纳米晶PdO催化剂,用于低浓度苯催化氧化反应。采用XRD、N2吸附-脱附、透射电镜-能谱(HRTEM-EDS)、H2程序升温还原(H_2-TPR)、O_2程序升温脱附(O_2-TPD)和程序升温表面反应(TPSR)等对载体和催化剂进行表征。结果表明,NaY分子筛结构稳定,比表面积651 m~2·g~(-1)和孔容0. 326 cm~3·g~(-1),纳米晶PdO能够较均匀地分散在NaY载体上,颗粒尺寸约(3～5) nm。加入一定量CeO_2后,Pd O以较小的纳米晶颗粒形式分散在CeO_2周围,活性组分与助剂协同作用促进了催化剂中晶格氧的流动性,明显改善了0. 2%Pd/NaY的氧化性能。0. 2%Pd/8%Ce/NaY表现出最佳催化活性和良好稳定性,250℃可完全催化降解1000×10~(-6)的苯,并且230℃连续反应100 h,催化剂转化率稳定在86%。     

由煤系高岭土合成小晶粒NaY分子筛及其应用

利用不同的方法分别合成了常规尺寸和纳米NaY分子筛,并采用XRD和TEM手段对合成样品进行了表征,小晶粒分子筛其粒径小于100 nm。催化裂化试验表明,纳米分子筛可提高大分子转化能力及改善产物选择性,比常规晶粒尺寸分子筛更为优越的性能。     

Dehydrogenation of methylcyclohexane over Pt supported on Mg–Al mixed oxides catalyst: The effect of promoter Ir

To enhance the hydrogen release during hydrogen storage, several Pt–Ir supported on Mg–Al mixed oxide catalysts were prepared and then applied into the dehydrogenation of methylcyclohexane (MCH) in this study. The effects of iridium content, reduction temperature on the activity and stability of the catalysts were studied in detail. In the presence of Ir, metal particle size was decreased and electron transfer between Ir and Pt was observed. High reduction temperature increased the metallic Ir content but enlarged the particle size of active sites. During the dehydrogenation reaction on Pt–Ir bimetallic catalyst, MCH was efficiently converted into toluene and PtIr-5/Mg–Al-275 exhibited the highest activity. After prolonging the residence time and raising the reaction temperature to 350 °C, the conversion and hydrogen evolution rate were increased to 99.9% and 578.7 mmol·(g Pt)⁻¹·min⁻¹, respectively. Moreover, no carbon deposition was observed in the spent catalyst, presenting a high anti-coking ability and good potential for industrial application.     

Dehydrogenation of methylcyclohexane over Pt supported on Mg-Al mixed oxides catalyst: The effect of promoter Ir

To enhance the hydrogen release during hydrogen storage, several Pt-Ir supported on Mg-Al mixed oxide catalysts were prepared and then applied into the dehydrogenation of methylcyclohexane (MCH) in this study. The effects of iridium content, reduction temperature on the activity and stability of the catalysts were studied in detail. In the presence of Ir, metal particle size was decreased and electron transfer between Ir and Pt was observed. High reduction temperature increased the metallic Ir content but enlarged the particle size of active sites. During the dehydrogenation reaction on Pt-Ir bimetallic catalyst, MCH was efficiently converted into toluene and PtIr-5/ Mg-Al-275 exhibited the highest activity. After prolonging the residence time and raising the reaction temperature to 350 °C, the conversion and hydrogen evolution rate were increased to 99.9% and 578.7 mmol·(g Pt)^-1·min^-1, respectively. Moreover, no carbon deposition was observed in the spent catalyst, presenting a high anti-coking ability and good potential for industrial application.     

SiW12/NaY固体杂多酸催化剂的微波合成及LAS降解性能研究

以微波辐射方法合成了NaY分子筛、二氧化锆和二氧化钛不同载体负载磷钨酸、磷钼酸、硅钨酸不同杂多酸的固体酸催化剂,用Hammett指示剂与紫外光谱相结合的方法测定固体杂多酸催化剂的酸度,发现SiW12/NaY酸性最强。单因子实验研究了制备条件对SiW12/NaY固体酸催化剂酸活性的影响,正交试验探讨了影响SiW12/NaY固载杂多酸活性四个因素的大小顺序为:烧结时间>烧结功率>浸泡浓度>浸泡时间,催化剂制备的优化条件为:硅钨酸水溶液浓度0.10 mol/L,浸泡时间30 h,微波功率750 W,烧结时间40 min,制得的催化剂酸度最高。应用0.050 g SiW12/NaY固载硅钨酸催化剂降解150 mg/L,pH值为3的十二烷基苯磺酸钠(LAS)溶液60 min,LAS降解率由76%提高到94.5%。固载硅钨酸催化剂对LAS的降解率明显提高。     

Catalytic activity of Co,Mo and CoMo supported on NaY zeolite: hydrodesulfurization of gas oil at high pressure

Three series of Co/NaY, Mo/NaY and CoMo/NaY zeolite catalysts with variable metal content, prepared by a conventional impregnation method, were characterized by XRD, IR spectroscopy (oxide state) and acidity measurements (sulfide state), and tested in hydrodesulfurization (HDS) of gas oil at high pressure in the temperature range 275–350°C. The combined results of surface area, XRD and IR showed that in the catalysts with high metal loading a small loss in crystallinity and a partial blockage of the zeolite supercages were produced by Mo oxide species. The number of acid sites, which was lower for the Co/NaY than for the Mo/NaY catalysts, increased with increasing Co or Mo loading, but the strength of the acid sites was stronger for the Co/NaY series. HDS specific activities of the Co/NaY and Mo/NaY monometallic catalysts reached a maximum at very low loadings of Co ( 0.10 at. nm^–2) or Mo ( 0.16 at. nm^–2) by the double action of the metal sulfide species and the strong acid sites generated on the zeolite by the Co or Mo incorporation. In the binary CoMo/NaY catalysts, the synergy between Co and Mo species was significant for high Mo contents only.     

Dispersive XAFS Study on Cu and Mo Species in Zeolites During the Catalyst Preparation

A time-resolved energy dispersive XAFS (DXAFS) technique is applied to elucidate the local structure of catalyst precursors and active species during the preparation of catalysts. The structure of ion-exchanged copper species in ZSM-5 zeolite during temperature-programmed reduction and the structure of molybdenum carbonyl species in NaY zeolite during temperature-programmed decarbonylation were investigated by the DXAFS technique. The way of the analysis of XAFS data during the dynamic processes is also discussed. The XANES spectra were analyzed to determine the ratio of different species involved in the system as a function of temperature as well as the curve-fitting analysis of the time-resolved EXAFS. The detailed analysis of the XANES and EXAFS shed light on the structural changes during the dynamic processes. In Cu-ZSM-5, a stepwise reduction process of Cu species and the subsequent growth of Cu particles during the reduction were elucidated. In Mo–NaY, the formation of Mo subcarbonyl monomer species as an intermediate of molybdenum oxycarbide dimer species was observed. This paper demonstrates that the DXAFS technique is useful to study the chemistry of catalyst preparation and can provide vital information that cannot be obtained by other techniques.     

Y型分子筛改性的研究进展

作为一种在石油催化裂化过程中常用的分子筛,Y型分子筛以其高稳定性、高活性、抗重金属污染能力和抗结焦能力成为FCC催化剂中主要的活性组分。目前,中国重质油加工工艺以催化裂化为主,2015年原油加工量超过5.0×108 t/a。在未来一段时间,催化裂化加工重质原料油仍然是中国国内炼油厂的工作重点。综述了近年来Y型分子筛的改性研究进展,为今后Y型分子筛的改性研究提供了一定的借鉴。