A novel catalyst system based on quadruple silicoaluminophosphate and aluminosilicate zeolites for FCC gasoline upgrading

To develop a novel catalyst system that has excellent olefin reduction capability for FCC gasoline without loss in octane number, different catalysts supported on multiple composite carriers consisting of SAPO-11, Hβ, HMOR and HZSM-5 were prepared and their catalytic performances for FCC gasoline upgrading were assessed in the present investigation. The pore structure and acidity of the catalysts were characterized by N₂ adsorption and pyridine adsorption FTIR, respectively. Based on the results obtained over the catalysts supported on binary-zeolite carriers (Hβ/HZSM-5, HMOR/HZSM-5 and SAPO-11/HZSM-5) using FCC gasoline as the feedstock, various multiple-zeolite supported catalysts were developed from different combinations of the binary-zeolite systems. It was found that the SAPO-11/HMOR/β/ZSM-5 quadruple composite zeolite supported catalyst gave higher liquid yield, improved gasoline RON, and lower coke deposit amount for the hydro-upgrading of FCC gasoline and thus can be considered as a potential catalyst system. A comprehensive analysis based on the catalytic activities and acidity measurements revealed that acid strength and acid type were two very important factors influencing hydroisomerization and aromatization activities, and the difference in catalyst acid strength determined which factor predominates.     

Pt/Pt-Ce/γ-Al2O3催化氧化甲苯研究

通过等体积浸渍法制备单贵金属Pt/γ-Al₂O₃和双金属Pt-Ce/γ-Al₂O₃催化剂,考察Ce对催化剂活性的影响,确定催化剂最优配比。结果表明,当Pt的负载量为质量分数0.5%时,Pt/γ-Al₂O₃催化活性最高;当Pt的负载量为质量分数0.2%,Ce的负载量为质量分数1.0%时,Pt-Ce/γ-Al₂O₃催化剂的催化活性最高。Pt-Ce/γ-Al₂O₃催化剂的甲苯转化率高于Pt/γ-Al₂O₃催化剂。随着Pt负载量增大,催化剂孔容、孔径减小。粉体式催化剂性能优于整体式催化剂,但差别不大;Ce的添加有助于催化剂活性的提升。     

Hβ/HZSM-5 Composite Carrier Supported Catalysts for Olefins Reduction of FCC Gasoline Via Hydroisomerization and Aromatization

In order to develop a novel catalyst system that has excellent olefin reduction ability for FCC gasoline without loss in research octane number (RON), different catalysts supported on single- and binary-zeolite carriers consisting of Hβ or/and HZSM-5 were prepared and their catalytic performances for FCC gasoline upgrading were assessed in the present investigation. Acidity measurements by pyridine-adsorbed Fourier transformed infrared spectroscopy (FTIR) showed that hydroisomerization and aromatization activities were closely related to the density of acid sites and the ratios of medium Lewis acidity and strong Br?nsted acidity to total acidity. Compared with the single HZSM-5 supported catalyst, the single Hβ supported catalyst was found to have much better olefin reduction performance, but the product RON still suffered from a loss of 1.6. Compared to the single-zeolite supported catalysts, the binary-zeolite Hβ/HZSM-5 supported catalysts with the mass ratio of Hβ to HZSM-5 at 6.6 offered much more stable activity and selectivity to arene, which played an important role in preserving gasoline RON.     

Performance and characterization of Ru/Al2O3 and Ru/SiO2 catalysts modified with Mn for Fischer–Tropsch synthesis

Mn effect and characterization on γ-Al₂O₃-, -Al₂O₃- and SiO₂-supported Ru catalysts were investigated for Fischer–Tropsch synthesis under pressurized conditions. In the slurry phase Fischer–Tropsch reaction, γ-Al₂O₃ catalysts showed higher performance on CO conversion and C₅⁺ selectivity than -Al₂O₃ and SiO₂ catalysts. Moreover, Ru/Mn/γ-Al₂O₃ exhibited high resistance to catalyst deactivation and other catalysts were deactivated during the reaction. From characterization results on XRD, TPR, TEM, XPS and pore distribution, Ru particles were clearly observed over the catalysts, and γ-Al₂O₃ catalysts showed a moderate pore and particle size such as 8 nm, where -Al₂O₃ and SiO₂ showed highly dispersed ruthenium particles. The addition of Mn to γ-Al₂O₃ enhanced the removal of chloride from RuCl₃, which can lead to the formation of metallic Ru with moderate particle size, which would be an active site for Fischer–Tropsch reaction. Concomitantly, manganese chloride is formed. These schemes can be assigned to the stable nature of Ru/Mn/γ-Al₂O₃ catalyst.     

Preparation of new solid superacid catalyst, zirconium sulfate supported on γ-alumina and activity for acid catalysis

Zirconium sulfate supported on γ-Al₂O₃ catalysts were prepared by impregnation of powdered γ-Al₂O₃ with zirconium sulfate aqueous solution followed by calcining in air at high temperature. For Zr(SO₄)₂/γ-Al₂O₃ samples, no diffraction line of zirconium sulfate was observed up to 50 wt.%, indicating good dispersion of Zr(SO₄)₂ on the surface of γ-Al₂O₃. The acidity of catalysts increased in proportion to the zirconium sulfate content up to 40 wt.% of Zr(SO₄)₂. 40-Zr(SO₄)₂/γ-Al₂O₃ calcined at 400 °C exhibited maximum catalytic activities for 2-propanol dehydration and cumene dealkylation. The catalytic activities for both reactions, 2-propanol dehydration and cumene dealkylation were correlated with the acidity of catalysts measured by ammonia chemisorption method.     

催化裂化重汽油临氢脱砷剂的研究与开发

针对催化汽油砷化物脱除需要,开发一种以大孔γ-Al_2O_3为载体的双金属催化裂化重汽油临氢脱砷剂,并采用XRD和全自动比表面积及孔隙度分析仪对脱砷剂进行表征。考察脱砷剂活性、原料适应性及反应温度、体积空速等工艺条件对脱砷性能的影响。结果表明,该临氢脱砷剂具有较高的脱砷活性(≮85%)和脱砷选择性(≮95%),烯烃基本不饱和;提高反应温度和降低空速有助于提高脱砷剂脱砷活性,烯烃饱和活性基本不受影响。     

Deactivation studies over NiO/γ-Al2O3 catalysts for partial oxidation of methane to syngas

Two types of NiO/γ-Al₂O₃ catalysts prepared by the impregnation and the sol–gel method were used for the partial oxidation of methane to syngas at 850°C (GHSV1.8×10⁵ lkg⁻¹ h⁻¹). The effects of the carbon deposition, the loss and sintering of nickel and the phase transformation of γ-Al₂O₃ support on the catalytic performance during 80 h POM reaction were investigated with a series of characterization such as XRD, BET, AAS, TG, and XPS. The results indicated that the carbon deposition and the loss and sintering of nickel could not cause the serious decrease of catalytic performance over NiO/γ-Al₂O₃ catalyst during the short-time reaction. However, the slow process of the support γ-Al₂O₃ phase transforming into -Al₂O₃ could slowly decrease the performance of NiO/γ-Al₂O₃ catalysts. Aimed at the reasons of the deactivation, an improved catalyst was obtained by the complexing agent-assisted sol–gel method.     

ZSM-5/γ-Al2O3质量比对FCC轻汽油异构化/芳构化性能影响

通过调变ZSM-5分子筛与γ-Al₂O₃质量比,采用等体积浸渍法制备系列FCC轻汽油异构化/芳构化催化剂。本文采用X射线衍射（XRD）、N₂吸附脱附、扫描电子显微镜（SEM）、氨气程序升温脱附（NH₃-TPD）、红外光谱（IR）和吡啶红外光谱（Py-IR）等手段对其进行表征,并以乌鲁木齐石化醚后C₅掺杂液化石油气（LPG）为原料对催化剂异构化/芳构化性能进行评价。实验结果表明,ZSM-5分子筛与γ-Al₂O₃质量比的调变可以改变催化剂的酸性质及孔结构性质。在反应温度380℃、反应压力1.0MPa、反应空速1.0h^-1、氢/油体积比100、LPG进量4.4g/h的条件下,ZnLa/ZSM-5/γ-Al₂O₃-1异构化/芳构化产物与反应原料相比,烯烃体积分数降低27.49%、异构烷烃体积分数增加15.87%、芳烃体积分数增加3.97%,辛烷值损失3.38个单位,产品收率高达89.90%,实现了异构化/芳构化大幅降烯烃保辛烷值的目标。     

复合氧化物催化剂催化氧化甲苯性能

以γ-Al2O3为催化剂载体,铜、锰为活性组分,稀土元素铈为助催化剂,采用浸渍法制备复合氧化物催化剂5%Cu/γ-Al2O3、5%Mn/γ-Al2O3、5%Cu-5%Mn/γ-Al2O3和5%Cu-5%Mn-1.6%Ce/γ-Al2O3,并考察其催化氧化甲苯性能。研究表明,复合氧化物催化剂催化氧化甲苯具有显著的效果,5%Cu-5%Mn/γ-Al2O3催化剂和5%Cu-5%Mn-1.6%Ce/γ-Al2O3催化剂表现出良好的低温活性和催化性能,对甲苯的完全燃烧温度分别为340℃和285℃。采用SEM和BET对催化剂进行表征,结果表明,催化剂的催化活性与活性组分在催化剂表面的分散度和催化剂的孔结构相关。     

Research progress of γ-alumina support

由于γ-Al₂O₃载体的孔结构、表面酸性等性质的可调性,γ-Al₂O₃载体被广泛应用于催化剂载体领域。催化剂的孔结构、表面性质均取决于γ-Al₂O₃载体,因此通过掌握γ-Al₂O₃载体性质的可调变规律就可制备出适合特定催化反应的高性能载体。本文以γ-Al₂O₃载体制备及γ-Al₂O₃载体后处理等过程为出发点,详细评述了近年来γ-Al₂O₃载体的孔结构、表面酸性和水热稳定性等性质调变的最新研究进展,并指明了γ-Al₂O₃载体今后研究重点和发展方向。     

Gas-phase dehydration of glycerol over commercial Pt/γ-Al2O3 catalysts

Gas-phase dehydration of glycerol to produce acrolein was investigated over commercial catalysts based onγ-Al2O3, viz. A-64, A-56, I-62, AP-10, AP-56, AP-64 and KR-104. To understand the effect of Cl?anions, HCl-impregnated sup-ports have been investigated in the dehydration reaction of glycerol at 375 °C. For comparison, various H-zeolites were also examined. It was found that the glycerol conversion over the solid acid catalysts was strongly dependent on their acidity and surface area. And the relationship between the catalytic activity and the acidity of the catalysts was discussed. The outstanding properties of Pt/γ-Al2O3 catalyst systems for the dehydration of glycerol were revealed. Pt/γ-Al2O3 catalyst (AP-64) showed the highest catalytic activity after 50 h of reaction with an acrolein selectivity of 65%at a conversion of glycerol of 90%. Based on these results, catalysts based onγ-Al2O3 appear to be most promising for gas phase dehydration of glycerol.     

Effect of La on the thermal stability of Pd/γ-Al2O3 catalytic membranes

Lanthanum-doped Pd/γ-Al₂O₃ and Pd/γ-Al₂O₃ membranes were prepared by sol-gel methods. The thermal stability of the unsupported Pd/γ-Al₂O₃ and La/Pd/γ-Al₂O₃ membranes was investigated with BET (including average pore size, pore volume and BET surface area), XRD, and DTA techniques. The average pore size of the Pd/γ-Al₂O₃ membranes increased sharply after sintering at temperatures higher than 1000°C. Addition of 3 mol% lanthanum can raise the temperature of the γ-Al₂O₃ to-Al₂O₃ phase transformation significantly. This improves the thermal stability of the Pd/γ-Al₂O₃ catalytic membranes.     

A novel method for enhancing on-stream stability of fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst: Post-treatment of HZSM-5 zeolite by combined steaming and citric acid leaching

This article describes a novel modification method consisting of steaming and subsequent citric acid leaching to finely tune acidity and pore structure of HZSM-5 zeolite and thereby to enhance the on-stream stability of the zeolite derived fluid catalytic cracking (FCC) gasoline hydro-upgrading catalyst. A series of dealuminated HZSM-5 zeolites and their derived catalysts were prepared and characterized by X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), ²⁷Al MAS NMR, nitrogen adsorption, temperature programmed desorption of ammonium (NH₃-TPD) and infrared (IR) spectroscopy of chemisorbed pyridine. The results showed that the citric acid leaching could preferentially remove the extra-framework Al (EFAl) species formed by steaming treatment and thus reopen the EFAl-blocked pore channels of the steamed zeolite. The steaming treatment at a suitable temperature and subsequent citric acid leaching not only decreased the strength of acid sites to a desirable degree but also increased the ratio of medium and strong Lewis acidity to medium and strong Brönsted acidity, both of which conferred the resulting catalyst with superior selectivity to aromatics, good hydroisomerization activity and gasoline research octane number (RON) preservability, as well as enhanced on-stream stability. The results fully demonstrated that the treatments by steaming and followed citric acid leaching can serve as an important method for adjusting the physicochemical properties of HZSM-5 zeolite.     

Carbon formation and its influence on ethanol steam reforming over Ni/Al2O3 catalysts

Ethanol steam reforming was studied over Ni/Al₂O₃ catalysts. The effect of support (- and γ-Al₂O₃), metal loading and a comparison between conventional H₂ reduction with an activation method employing a CH₄/O₂ mixture was investigated. The properties of catalysts were studied by N₂ physisorption, X-ray diffraction (XRD) and temperature programmed reduction (TPR). After activity tests, the catalysts were analyzed by scanning electron microscopy (SEM) and thermogravimetric analysis (TG/DTA). Ni supported on γ-Al₂O₃ was more active for H₂ production than the catalyst supported on -Al₂O₃. Metal loading did not affect the catalytic performance. The alternative activation method with CH₄/O₂ mixture affected differently the activity and stability of the Ni/γ-Al₂O₃ and the Ni/-Al₂O₃ catalyst. This activation method increased significantly the stability of Ni/-Al₂O₃ compared to H₂ reduction. SEM and TG/DTA analysis indicate the formation of filamentous carbon during the CH₄/O₂ activation step, which is associated with the increasing catalyst activity and stability. The effect of temperature on the type of carbon formed was investigated; indicating that filamentous coke increased activity while encapsulating coke promoted deactivation. A discussion about carbon formation and the influence on the activity is presented.     

Role of CeO2 in Ni/CeO2–Al2O3 catalysts for carbon dioxide reforming of methane

Ni catalysts supported on γ-Al₂O₃, CeO₂ and CeO₂–Al₂O₃ systems were tested for catalytic CO₂ reforming of methane into synthesis gas. Ni/CeO₂–Al₂O₃ catalysts showed much better catalytic performance than either CeO₂- or γ-Al₂O₃-supported Ni catalysts. CeO₂ as a support for Ni catalysts produced a strong metal–support interaction (SMSI), which reduced the catalytic activity and carbon deposition. However, CeO₂ had positive effect on catalytic activity, stability, and carbon suppression when used as a promoter in Ni/γ-Al₂O₃ catalysts for this reaction. A weight loading of 1–5 wt% CeO₂ was found to be the optimum. Ni catalysts with CeO₂ promoters reduced the chemical interaction between nickel and support, resulting in an increase in reducibility and stronger dispersion of nickel. The stability and less coking on CeO₂-promoted catalysts are attributed to the oxidative properties of CeO₂.     

A comparison between β- and USY-zeolite-based hydrocracking catalysts

Two series of zeolite-based hydrocracking catalysts were prepared to study the effects of the support type, preparation method and metal loading on catalyst properties and hydrocracking activity for hydrotreated vacuum gas oil (HT-VGO). The support used was γ-Al₂O₃ and β-zeolite in the first series and γ-Al₂O₃ and USY-zeolite in the second series. Nickel and tungsten were loaded as active metals on these supports. The prepared catalysts were characterized as to their surface area, pore volume, thermal stability, reducibility and acidity characteristics. The characterization results revealed that catalysts displayed significant differences in properties dependent on the preparation method and the type of support used. Catalysts from both series showed promising results for HT-VGO hydrocracking in the batch reactor. A correlation exists between the reducibility of oxidic form and the hydrogenation activity of the sulfided form of the catalysts. The higher the reducibility, the higher the hydrogenation activity. Catalysts prepared on mixed supports gave higher amounts of saturates.     

Study of Ag/La0.6Sr0.4MnO3 catalysts for complete oxidation of methanol and ethanol at low concentrations

Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure were prepared by using a citric acid sol–gel method, and their catalytic performance for complete oxidation of methanol and ethanol was evaluated and compared with that of the γ-Al₂O₃-supported catalysts, Ag/γ-Al₂O₃, Pt/γ-Al₂O₃, and Pd/γ-Al₂O₃. The results showed that the Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure displayed the activity significantly higher than that of the supported precious metal catalysts, 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ in the temperature range of 370–573 K. Over a 6%Ag/20%La_0.6Sr_0.4MnO₃/γ-Al₂O₃ catalyst, the T₉₅ temperature for methanol oxidation can be as low as 413 K. Even at such low reaction temperature, there were little HCHO and CO detected in the reaction exit-gas. However, for the 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ catalysts, the HCHO content in the reaction exit-gas reached 200 and 630 ppm at their T₉₅ temperatures. Over a 6%Ag/La_0.6Sr_0.4MnO₃ catalyst, the T₉₅ temperature for ethanol oxidation can be as low as 453 K, with a corresponding content of CH₃CHO in the exit-gas at 782 ppm; when ethanol oxidation is performed at 493 K, the content of acetaldehyde in the exit-gas can be below 1 ppm. Characterization of the catalysts by X-ray diffraction (XRD), TEM, XPS, laser Raman spectra (LRS), hydrogen temperature-programmed reduction (H₂-TPR) and oxygen temperature-programmed desorption (O₂-TPD) methods revealed that both the surface and the bulk phase of the perovskite La_0.6Sr_0.4MnO₃ played important roles in the catalytic oxidation of the alcohols, and that γ-Al₂O₃ as the bottom carrier could be beneficial in creating a large surface area of catalyst. Moreover, a small amount of Ag⁺ doped onto the surface of La_0.6Sr_0.4MnO₃ was able to partially occupy the positions of La³⁺ and Sr²⁺ due to their similar ionic radii, and thus, became stabilized by the perovskite lattice, which would be in favor of preventing the aggregation of the Ag species on the surface and enhancing the stability of the catalyst. On the other hand, modification of the Ag⁺ to the surface of La_0.6Sr_0.4MnO₃ resulted in an increase in relative content of the surface O₂²⁻/O⁻ species highly reactive toward the alcohols and aldehydes as well as CO. Besides, solution of low-valence metal oxides SrO and Ag₂O with proper amounts in the lattice of the trivalent metal perovskite-type oxide LaMnO₃ would also lead to an increase in the content of the reducible Mnⁿ⁺ and the formation of anionic vacancies, which would be favorable for the adsorption-activation of oxygen on the functioning catalyst and the transport of the lattice and surface oxygen species. All these factors would contribute to the pronounced improvement of the catalyst performance.     

Monodispersed gold nanoparticles supported on γ-Al2O3 for enhancement of low-temperature catalytic oxidation of CO

Monodispersed nano-Au/γ-Al₂O₃ catalysts for low-temperature oxidation of CO have been prepared via a modified colloidal deposition route, which involves the deposition of dodecanethiolate self-assembled monolayer (SAM)-protected gold nanoparticles (C₁₂ nano-Au) in hexane on γ-Al₂O₃ at room temperature. The diameter of the gold nanoparticles deposited on the support is 2.5 ± 0.8 nm after thermal treatment, and their valence states comprise both the metallic and oxidized states. It is found that the thermal treatment temperature affects significantly the catalytic activity of the catalysts in the processing steps. The catalyst treated at 190 °C exhibits considerably higher activity as compared to catalysts treated at 165 and 250 °C. A 2.0-wt.% nano-Au/γ-Al₂O₃ catalyst treated at 190 °C for 15 h maintains the catalytic activity at nearly 100% CO oxidation for at least 800 h at 15 °C, at least 600 h at 0 °C, and even longer than 450 h at −5 °C. Evidently, the catalysts obtained using this preparation route show high catalytic activity, particularly at low temperatures, and a good long-term stability.     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

CO偶联合成草酸二甲酯催化剂研究

采用浸渍法制备CO偶联制备草酸二甲酯用负载型Pd催化剂,考察载体、浸渍方法、Pd含量、助剂对Pd催化剂性能的影响。根据傅里叶变换红外光谱研究Pd/α-Al_2O_3负载型催化剂上CO偶联制草酸二甲酯的反应机理。结果表明,采用α-Al_2O_3载体,Pd质量分数4‰,掺杂助剂Cu的蛋壳型的Pd/α-Al_2O_3催化剂上,草酸二甲酯时空收率达到735.7 g·(L·h)~(-1)。