渣油加氢催化剂的研究和应用

渣油加氢处理技术是近年发展最快的技术领域。渣油加氢处理催化剂是此技术的关键。多种固定床渣油加氢处理催化剂在国外已进行了开发和工业应用。我国也开发了多种固定床渣油加氢处理催化剂，实践表明这种催化剂具有良好的活性和稳定性，产品质量良好，收率高，可为RFCC提供优质的原料。悬浮床渣油加氢处理催化剂也在开发之中，中试试验取得了良好的结果。     

Experimental investigation and prediction of the gas dynamic characteristics of commercial catalysts

Gas dynamic characteristics of commercial catalysts used in steam reforming and pollution-free catalysis have been investigated. Data that make it possible to predict the catalyst behavior under production conditions are represented. The optimal geometrical characteristics of the catalysts have been identified.     

甲醇脱氢制无水甲醛的研究进展

甲醇直接脱氢制无水甲醛是具有工业化前景的新工艺。介绍了该领域催化剂及相关工艺的研究现状。利用金属、金属氧化物、金属难熔盐和分子筛催化剂以及相关工艺技术制得定量的无水甲醛,该技术目前处于研发阶段,离工业化尚有一定距离,在催化剂的选择性、稳定性及使用寿命等方面有待于改进。     

Solventless Silane Alcoholysis Catalyzed by Recoverable Dirhodium(II) Perfluorocarboxylates

We have developed a novel reaction protocol for the highly efficient and sustainable catalysis of the silane alcoholysis reaction. The catalysts of choice are dirhodium(II) perfluorocarboxylates bearing long perfluoroalkyl chains, which are easily prepared in one step from commercial precursors. Under optimized reaction conditions, these catalysts exhibit up to about 50 times higher activity and 100 times higher productivity than analogous dirhodium(II) complexes described in the prior art. Furthermore, the reaction can be run in a completely solventless fashion. Finally, heterogenization of these catalysts has been accomplished through a novel strategy based on fluorous chemistry. Indeed, perfluorinated catalysts of this kind are easily adsorbed on silica which has been previously functionalized at its surface with perfluoroalkyl chains. Use of such supported catalysts (bonded fluorous phase catalysts) allows an easy and almost complete catalyst separation and recycling with improved catalytic performance.     

Hydroprocessing of shale oil using ruthenium-based catalysts

Retorted shale oils from the Rundle (Queensland) deposit have been hydrotreated in both batch and continuous modes. Two catalysts, a commercial NiMo system and a novel Ru-containing catalyst, have been employed. The new Ru catalyst displayed nitrogen removal and hydrocracking abilities far in excess of the commercial system. Chemical analyses of the products showed that when using the Ru-containing catalysts, the remaining polar materials were phenols, and aniline/pyridine homologues. By contrast, the remaining polar compounds from the NiMo system were predominantly pyrrole and benzopyrrole homologues.     

Supported foam-silver catalysts for alcohol partial oxidation

Structural, mechanical, gas-dynamic and catalytic properties of silver catalysts supported on foam ceramics have been studied. The foam catalysts have high gas permeability, mechanical strength, and low density. Catalytic activity and selectivity of the foam catalysts in the process of oxidation of methanol to formaldehyde exceed the characteristics of the commercial crystalline and granulated catalysts. Different electronic states (ions, charged cluster, crystals) of silver on the catalyst surface have been studied by the method of UV–visible spectroscopy.     

Comparison of mechanical strength of reforming catalysts of different geometry

Manufacturing of the first commercial lot of sphere-shaped reforming catalyst granules for units with a fixed catalyst bed and relevance of wide-scale application of sphere-shaped catalysts instead of extrudates made it necessary to compare mechanical crushing and attrition strengths of reforming catalysts having the form of cylinder-shaped extrudates and spherical granules. No such data have been published as of yet. The advantages of spherical catalysts for semi-regenerative reforming units, which is attributed to the absence of fines, the ability to form a dense bed, as well as practical convenience for the end users working with spherical catalysts are show. The results of the operation of the first test lot of RB-44U “Sh” spherical catalyst at a commercial unit which confirm high strength parameters and point to increased activity and selectivity are demonstrated. The presented collection of the data reveals advantages of sphere-shaped catalysts, namely their mechanical strength and some properties associated with catalyst utilization.     

Unifying Principles in Zeolite Chemistry and Catalysis

In recent years molecular sieve catalysts have assumed an increasingly important role in industrial catalysis, Applications of zeolite catalysts are expanding from the traditional petroleum refining to new and improved fuel processing applications, and to new roles in both the petrochemical and chemical industries. Up to the present, all commercial applications of zeolite catalysts have been carried out with aciaic zeolites. Recent investigations of zeolite chemistry revealed several important features which appear common to both alkali and acidic zeolites. This new chemical evidence raises the possibility that the underlying physicochemical features of both types of zeolites play a role in catalysis.     

Catalysts based on foam materials for neutralization of waste gases

Catalysts of new structural type – foam metals – have been tested in the process of complete oxidation of aromatic compounds and neutralization of gas emissions of furnaces for wire enameling. Foam catalysts have better hydrodynamic and mechanical characteristics as compared with commercial catalysts, high catalytic activity and life time in the processes of neutralization of waste gases exceeding the indices of the traditional granular and honeycomb catalysts.     

Nano-engineered PtVFe catalysts in proton exchange membrane fuel cells: Electrocatalytic performance

Proton exchange membrane fuel cells (PEMFCs) are attractive because of their high conversion efficiency, low pollution, lightweight, and high power density. A major area of challenges is the design and engineering of active, robust, and low-cost electrocatalysts. This report discusses recent findings of our investigations of the design and nano-engineering of platinum-vanadium-iron catalysts for use in PEMFC. The membrane electrode assembly was prepared using nano-engineered PtVFe nanoparticles with controlled composition and size supported on carbon as cathode electrocatalysts. The electrocatalytic activity and stability of the catalysts have been characterized by both rotating disk electrode and membrane electrode assembly measurements. The trimetallic catalysts have been shown to exhibit excellent electrocatalytic performance in PEMFC in comparison with commercial platinum catalysts. The results exhibited a good agreement between obtained these two types of measurements in terms of the dependence on particle size, composition, and thermal treatment condition. The catalysts also showed good stability, which are potentially useful for practical application in PEMFCs.     

On the Stability and Recyclability of Supported Metal–Ligand Complex Catalysts: Myths, Misconceptions and Critical Research Needs

Research on heterogenized metal complex catalysts has been carried out for 40 years. Despite thousands of published catalysts, there are only two significant commercial processes that utilize supported metal complex catalysts. Most academic papers are simply “demonstration of concept” studies reporting myriad ways to support various metal complex catalysts. Too few papers focus on rigorous studies of reaction kinetics, catalyst recycle, catalyst stability and deactivation pathways. Here, preliminary stability and deactivation studies of supported enantioselective Co-salen epoxide ring-opening catalysts and enantioselective Ru-salen olefin cyclopropanation catalysts are summarized. Insights with regard to catalyst deactivation suggest methodologies for catalyst stabilization, allowing for more effective catalyst recycle and enhanced catalyst turnover. Further examples where supported metal complex catalysts are applied in commercial processes will require the field to shift focus from “demonstration of concept” studies to more detailed investigations of catalyst stability and recyclability.     

在工业催化剂上水煤气变换反应宏观动力学

用内循环式无梯度反应器,在不同的反应条件下,测定了B106及B109两种型号的原粒度工业变换催化剂的宏观反应速率.根据实验数据关联出两种催化剂都适用的宏观动力学方程,求定了相应的模型参数.该式可用以模拟工业变换反应器.此外,并由实验数据计算了各种情况下的有效因子.整个实验及计算结果表明,这两种催化剂对气体的内扩散阻力都是相当大的.     

FHUDS系列催化剂在320万t/a柴油加氢装置的应用

天津石化320万t/a柴油加氢装置多次采用抚顺石油化工研究院开发的FHUDS系列催化剂进行了国V柴油的生产,该系列催化剂在生产中能够满足成品油质量升级到国V排放标准的需要。该装置工业应用结果表明,FHUDS系列催化剂是生产清洁柴油的理想催化剂,均能生产硫含量符合国Ⅴ排放标准的车用柴油组分,且在保证催化剂性能的前提下FHUDS-8催化剂堆比降低了20%。     

Unifying Principles in Zeolite Chemistry and Catalysis

Abstract

In recent years molecular sieve catalysts have assumed an increasingly important role in industrial catalysis, Applications of zeolite catalysts are expanding from the traditional petroleum refining to new and improved fuel processing applications, and to new roles in both the petrochemical and chemical industries. Up to the present, all commercial applications of zeolite catalysts have been carried out with aciaic zeolites. Recent investigations of zeolite chemistry revealed several important features which appear common to both alkali and acidic zeolites. This new chemical evidence raises the possibility that the underlying physicochemical features of both types of zeolites play a role in catalysis.     

重质油加氢脱硫和加氢脱氮催化剂的开发及工业应用

本文简要地介绍了重质油加氢脱硫、加氢脱氮催化剂的开发过程, 催化剂工业产品与国外同类催化剂的加氢活性对比情况, 以及催化剂在工业装置中的运行情况。工业使用表明, 所开发的催化剂具有良好的加氢处理活性和稳定性。     

MoS2 morphology and promoter segregation in commercial Type 2 Ni–Mo/Al2O3 and Co–Mo/Al2O3 hydroprocessing catalysts

A series of commercial liquid-phase-sulfided Type 2 Ni–Mo/Al₂O₃ and Co–Mo/Al₂O₃ catalysts used in different trickle-phase reactions has been characterized by (scanning) transmission electron microscopy combined with energy-dispersive X-ray analysis ((S)TEM-EDX) and X-ray diffraction (XRD) analysis. In contrast to what is reported for H₂S/H₂ sulfided Type 2 model catalysts, MoS₂ stacking is not prominent in liquid-phase sulfided Type 2 commercial catalysts. The presence or absence of MoS₂ stacking has been shown to be highly dependent on the sulfidation procedure applied. Although Type 2 commercial Ni–Mo catalysts have high MoS₂ dispersion, there is a significant Ni sulfide segregation. This is not the case for their Co-containing counterparts.     

Development of high performance catalysts for the production of vinyl acetate monomer

Two types of highly active and selective vinyl acetate monomer (VAM) catalysts have been developed in our lab via traditional lab preparation and high-pressure reactor performance test methods. Experimental results are presented here. Degussa is now engaged in high-throughput (HT) VAM catalyst powder preparation and HT (50 parallel reactor) testing to accelerate the development of new higher performing commercial catalysts. Our first results on HT are presented here. Though HT systems in both catalyst preparation and testing have existed for over a decade, HT heterogeneous catalyst preparation methods have been very slow to develop. The HT preparation system described here provides a versatile method of preparing commercially relevant catalysts as required by Degusssa. The HT reactor test system described here uses plant operating conditions and provides reliable STY and selectivity data on par with that obtained from conventional lab VAM test systems. Both the HT preparation and HT test systems combined allow for significant increases in the commercialization rate of new catalysts.     

合成气直接或间接制乙醇非铑基催化剂研究进展

乙醇作为一种清洁绿色能源,具有环境友好的特点,在能源领域显现了广阔的应用前景,研制高活性和选择性并适合工业化的合成乙醇催化剂具有重要的战略意义,非铑基催化剂具有相对较高的催化活性和选择性,并具有工业化的前景,近年来得到广泛的研究。本文介绍了国内外由合成气直接或者间接制乙醇的非铑基催化剂最新研究进展,分析了催化剂的活性组分、载体、助剂以及制备方法对催化活性和选择性的影响,指出了存在的问题,提出了高活性和选择性并且适合工业化的非铑基催化剂的研制是未来的发展趋势。     

Technological Applications of Zeolites in Catalysis

Zeolites have been used as catalysts in industry since the early 1960s. The great majority of commercial applications employ one of three zeolite types: zeolite Y (faujasite); mordenite; ZSM-5. By far the largest use of zeolites is in catalytic cracking, and to a lesser extent in hydrocracking. Table 1 presents some data showing the commercial importance of this field [1]. The data are for United States refineries only and must be multiplied by a factor to arrive at worldwide use. Better than 90% of free-world cracking units now use zeolite catalysts. For many years it had been assumed that crystalline aluminosilicates with their uniform pore structure would make inferior catalysts to amorphous silica-slumina with a rather wide pore size distribution. The tremendous acid activity of hydrogen zeolites also was not recognized. Rabo and co-workers [2] showed at the 2nd International Congress on Catalysis that hydrogen exchanged faujasites possessed good isomerization ability, but commercial application in catalytic cracking became feasible only after Plank and Rosinsky at Socony-Mobil Oil Co. succeeded in stabilizing zeolite Y against steam and heat sintering by exchange with rare earth ions and by separating zeolite crystallites by incorporating them into a silica-alumina matrix which provided a heat reservoir along with some synergistic cracking effects. Modern cracking catalysts comprise 10-40% rare earth exchanged H-Y zeolite dispersed in a matrix of silica-alumina, semisynthetic clay, or natural clay.     

AB-96型乙苯催化剂的试生产和工业应用

AB-96型苯与乙烯气相烷基化制乙苯分子筛催化剂成功地进行了试生产和工业应用,其性能完全达到了国外同类催化剂的水平,给工厂带来了显著的经济效益。