Lessening of the metal-support interaction by formation of bridged Al-O-Si sites

Significance 

Despite the increasing strict mitigation measures imposed on the use of fossil fuels, the petroleum industry will remain the main global source of energy for some time in the future. This is due to the underdeveloped alternative sources of energy which cannot meet the current global energy demand. Generally, light crude forms the cornerstone to the fossil fuels owing to their excellent properties such as low impurity contents and low viscosity. Unfortunately, the rapid reduction in the levels of the light crude oils has raised concern in the oil and gas industry. To this end, developing an alternative to substitute light crude oil is highly desirable. Recently, the focus has shifted to processing of heavy and extra heavy crude oils despite their high impurity content. However, more efficient processing method needs to be put in place considering their high carbon emission nature and the need for environmental protection.

Presently, several techniques have been developed for the processing of heavy crude oils. Among them, catalytic hydrotreating is widely preferred due to its ability to improve the quality of the final product through catalytic reactions. Recently, studies have shown that NiMo- and CoMo-based catalysts are highly favorable for catalytic hydrotreating processes. However, to ensure processing of complex feedstock and high-quality products, appropriate catalysts design criteria have been adopted. For instance, NiMo catalytic hydrotreating utilizes high availability and cost-effective γ-Al2O3. However, the catalytic activities are affected by the strong interaction between the alumina and metal surfaces. Therefore, researchers have been looking for alternative methods for reducing the interaction between the metals and alumina surface and have identified modification of the alumina with silicon as s promising solution.

To this note, Instituto Mexicano del Petróleo researchers: Patricia Rayo, Pablo Torres-Mancera, Guillermo Centeno, Fernando Alonso, José Antonio Muñoz and Jorge Ancheyta investigated the effects of silicon modifications on NiMo-based catalysts for hydrotreating reactions. Fundamentally, preparation of the NiMo catalysts supported on the Al-Si was based on: first incorporating the Si in alumina surface through drying and calcination and secondly structurally modifying the alumina. Additionally, Maya crude oil with high impurity content was used to prepare the feedstock to enable testing of the catalysis in the various reaction such as hydrodesulfurization and hydrodemetallization. Furthermore, various techniques including X-ray diffraction and nitrogen physisorption were used to analyze the supports and catalysts. The work is currently published in the journal, Fuel.

The authors observed higher conversion rates in the hydrotreating reactions due to the effects on the support surface properties that varied depending on the type of the preparation method. Consequently, incorporation of the silicon into Al2O3 support exhibited significant effects on the final properties of the catalysts including changes in the acidity and porosity. This was attributed to the weakening of the metal-surface interaction.

In summary, the research team demonstrated the effect of the Si-modified catalysts in the catalytic hydrotreating feedstock compound. The silicon incorporation method proved feasible for use in the catalytic hydrotreating of compounds with heavy crude oil fractions. The study will, therefore, ensure less-pollutant production of more energy for market demand.

Lessening of the metal-support interaction by formation of bridged Al-O-Si sites – Advances in Engineering

About the author

Patricia Rayo holds a doctorate in Materials Science from Research Center for Advanced Materials (CIMAV). She received her master’s degree in Catalysis from Metropolitan Autonomous University, Campus Iztapalapa (UAM-I) and her bachelor’s degree in Chemical from the National Autonomous University of Mexico (UNAM). She is currently a researcher at the Mexican Petroleum Institute (IMP), since 1991 where she coordinates several research projects. She has experience in Chemistry and Materials Science, focusing on synthesis, characterization and evaluation to different scale reactions of catalytic systems mainly supported catalysts for the Upgrading of Heavy Oils. She also has experience in preparing mass and supported catalysts for the Fischer-Tropsch to obtain synthetic crude oil and valuable compounds. One of its main objectives is to prepare new materials allowing the easy manipulation in the industry. She is member of the National System of Researchers of the National Council of Science and Technology of Mexico. She has authored/co-authored 26 papers in the international refereed journals and 7 patents.

About the author

Pablo Torres- Mancera is a researcher at the Mexican Petroleum Institute, where he carries out activities of design, validation and scaling up of products and catalytic systems for the processing of heavy crude oils and residua.

Pablo earned PhD from the National Autonomous University of Mexico, where he also studied undergraduate and master’s degrees in chemical engineering. He developed his thesis work in the area of catalysis in the Catalysis Research Unit of the School of Chemistry, where he was involved in the synthesis, characterization and evaluation of hydrotreatment catalyst prototypes.

Pablo has taught graduate and undergraduate courses at the postgraduate program of the Mexican Petroleum Institute and also at the School of Chemistry of the National Autonomous University of Mexico. He has participated in various courses, seminars and conferences at national and international level, and is member of the National System of Researchers of the National Council for Science and Technology of Mexico.

About the author

Guillermo Centeno graduated as a Petroleum Chemical Engineer in 1991 and a Master in Science in 1999 from Higher School of Chemical Engineering and Extractive Industries (ESIQIE). He earned Ph.D. in Chemical Engineering from Technological Institute of Madero City, (ITCM) Mexico, 2009. He is a researcher at the Mexican Petroleum Institute since 25 years where he has participated in different areas between those found: Petrochemical and Refining Processes, Research Program in Mayan Crude treatment.

He has experience in projects related to energy refining, lubricant schemes, and the process for obtaining the highest quality asphalt in various refineries of PEMEX. In the research area, he collaborated in the development of a process for the upgrading of heavy crude oils and waste testing its performance at semi-industrial level in the plant of the company. Headwaters Technology Innovation Group, Inc. in Lawrenceville, New Jersey USA in 2006 and 2008. He has been professor at the department of Petrochemical Chemical Engineering of the ESIQIE-IPN since 2011. He is member of the National System of Researchers and is reviewer of the research and technological development program of the National Council for Science and Technology (CONACyT).

He has published several technical articles in the area of the oil industry in different national and international journals, so it also counts with patents, which have been granted in different countries, including the USA, Canada and Japan. He has participated with various technical works in different national and international congresses. Currently, he collaborates in the Management of Products for Crude Transformation of the Product Technology Department.

About the author

Fernando Alonso

Researcher at the Mexican Petroleum Institute (IMP) since 1991, currently linked to the Direction of Product Technology. Skilled at experimental evaluations at micro-reaction and pilot plant scale, for the development of process technologies and IMP catalysts. Professor of the National Polytechnic Institute (IPN), in the Higher School of Chemical Engineering and Extractive Industries (ESIQIE) since 2011.

He studied the bachelor degree in Industrial Chemistry at the “Autonomous University of Puebla” (1992). He studied the Master of Science in Chemical Engineering at IPN-ESIQIE (2001). PhD in Chemical Engineering (2008). Member of the “Sistema Nacional de Investigadores” (SNI) and accredited reviewer of the “National council for Science and Technology” (CONACyT) since 2009.

He has published 24 scientific articles (more than 390 citations) and 4 articles in national journals; 13 patents granted in several countries, related to the development of catalysts and technologies for the hydroprocessing of heavy crude oils and residues; 22 papers in international congresses and 20 papers in national congresses.

He has received the awards “Highest note in PhD, generation 2003 – 2006”, First place in the “IMP Annual Research Prize 2005” and “Honorable Mention” in Bachelor (1992).

About the author

José Antonio D. Muñoz is a researcher at the Mexican Petroleum Institute (IMP) where he performs validation and scaling up activities related to crude oil transformation processes and their distillation fractions, mainly experienced in hydrotreatment thereof.

He earned PhD in the area of energy engineering and a master’s degree in chemical engineering at the National Autonomous University of Mexico. He is skilled at design and optimization of processes in the area of engineering at IMP and process operation in the Cadereyta refinery in Pemex. Has published 20 international papers, 5 patents, 6 copyright and has participated as a speaker of technical works in different national and international conferences.

He has also participated in different research projects in the area of processes and catalysts. He is a professor in Higher School of Chemical Engineering and Extractive Industries of the National Polytechnic Institute since 2012 teaching various subjects in the area of petroleum engineering, as well as a professor in the postgraduate studies and research in the master’s degree in petroleum engineering and its energetics, in the same academic institution. He is member of the National System of Researchers of the National Council of Science and Technology of Mexico.

About the author

Professor Jorge Ancheyta has worked for the Mexican Institute of Petroleum since 1989. His present position is Manager of Products for the Transformation of Crude Oil. He has also worked as professor at the School of Chemical Engineering at the National Polytechnic Institute of Mexico since 1992. He has been supervisor of more than one hundred BSc, MSc and PhD theses, as well as a number of postdoctoral and sabbatical year professors.

Dr. Ancheyta has been working in the development and application of petroleum refining catalysts, kinetic and reactor models, and process technologies for catalytic cracking, catalytic reforming, middle distillate hydrotreating and heavy oils upgrading. He is author and co-author of a number of patents, books and about 200 scientific papers.

Reference

Rayo, P., Torres-Mancera, P., Centeno, G., Alonso, F., Muñoz, J., & Ancheyta, J. (2019). Effect of silicon incorporation method in the supports of NiMo catalysts for hydrotreating reactions. Fuel, 239, 1293-1303.

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