Riazi, Eser, Agrawal, Pa Díez M R Riazi Dr M R Riazi is currently a Professor of Chemical Engineering at Kuwait University He was previously an Assistant Professor at Pennsylvania State University (USA), where he also received his MS and PhD He was also a visiting professor at various universities in the U.S., Canada, Europe and the Middle East He has been consultant and invited speaker to more than 50 oil companies and research institutions in Canada, the U.S., Europe, India, China, Malaysia, Australia, the Middle East and North Africa, including invited speaker to the World Economic Forum He is the author/co-author of more than 100 publications, including three books mainly in the areas of petroleum and chemical technology He is the founding and Editor-in-Chief of IJOGC and an associate editor of some other international journals He was awarded a Diploma of Honor from the National (American) Petroleum Engineering Society, as well as teaching and research awards from various universities He is a member of AIChE and the Research Society of North America (www.RiaziM.com) Semih Eser is a Professor of Energy and Geo-Environmental Engineering at Penn State University He received his B.S and M.S degrees in Chemical Engineering from Middle East Technical University in Ankara, Turkey and his Ph.D in Fuel Science from Penn State University Professor Eser teaches courses on petroleum refining and energy engineering at John and Willie Department of Energy and Mineral Engineering and directs the Carbon Materials Program at the EMS Energy Institute at Penn State He has served as Program Chair, Chair, and Councilor in the Fuel Chemistry Division of the American Chemical Society and as member of the Advisory Committee of the American Carbon Society Semih Eser José Luis Pa Díez is a consultant at the Technology Center at Repsol in Madrid, Spain His professional activity includes more than twenty years of experience leading and participating in research projects in upstream and downstream petroleum technologies Following his studies in chemical sciences at the Complutense University of Madrid, he collaborated with universities and academic institutions to coordinate activities in the areas of chemical engineering and special process simulation He is currently a part-time associate professor in chemical engineering at the Rey Juan Carlos University of Madrid José Luis Pa Díez Pa Díez is the author of forty technical articles and presentations at international conferences in the fields of petroleum fluids characterization, process engineering and control, and process simulation, areas in which his expertise contributed to this book www.astm.org ISBN: 978-0-8031-7022-3 Stock #: MNL58 Petroleum Refining and Natural Gas Processing Suresh S Agrawal Dr Suresh S Agrawal is founder and president of Offsite Management Systems LLC (www.globaloms.com) and has developed and installed innovative and technologically advanced automation software products, and integrated solutions for the automation of offsite operations of Chemical, Oil and Gas (COG) Industries Dr Agrawal has 25+ years of experience at senior positions with companies, including being Director of Refinery Offsite Operations at ABB Industrial Systems, Inc., Houston, Texas He worked earlier with reputable companies such as 3X Corporation and Exxon Corporation in New Jersey Dr Agrawal has successfully managed many advanced offsite refinery control projects in numerous countries He has a doctorate degree (Ph.D.) in Chemical Engineering from the Illinois Institute of Technology, Chicago, and a Bachelors Degree in Chemical Engineering from Indian Institute of Technology (I.I.T.), Mumbai, India He has published more than 20 technical papers in the area of refinery offsite automation Petroleum Refining and Natural Gas Processing M.R Riazi, S Eser, S.S Agrawal, J.L Pa Díez, editors Petroleum Refining and Natural Gas Processing M.R Riazi, Semih Eser, Suresh S Agrawal, and José Luis Pa Díez, Editors ASTM Stock Number: MNL58 ASTM International 100 Barr Harbor Drive PO Box C700 West Conshohocken, PA 19428-2959 Printed in U.S.A AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM ii Library of Congress Cataloging-in-Publication Data Petroleum refining and natural gas processing / M.R Riazi [et al.] p cm — ([ASTM manual series] ; MNL 58) Includes bibliographical references and index ISBN 978-0-8031-7022-3 (alk paper) Petroleum—Refining Natural gas I Riazi, M R TP690.P4728 2011 665.5’3—dc23 2011027593 Copyright © 2013 ASTM International, West Conshohocken, PA All rights reserved This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of the publisher ASTM Photocopy Rights Authorization to photocopy items for internal, personal, or educational classroom use of specific clients is granted by ASTM International provided that the appropriate fee is paid to ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959; Tel: 610-832-9634; online: http://www.astm.org/copyright/ ASTM International is not responsible, as a body, for the statements and opinions advanced in the publication ASTM International does not endorse any products represented in this publication Printed in 2013 AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM iii Foreword THIS PUBLICATION, Petroleum Refining and Natural Gas Processing, was sponsored by Committee D02 on Petroleum Products and Lubricants This is Manual 58 in ASTM International’s manual series AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM To Our families AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM v Preface Oil and gas have been the main sources of energy the world over for the past century and will remain important sources of energy for the first half of this century, and possibly beyond Currently, more than 60 % of the world’s energy is produced from oil and gas, and energy needs are increasing In addition, oil and gas provide the main feedstocks for the petrochemical industry World population is expected to increase to eight billion by 2030, which will demand an increase in energy of 40 % in the next two decades With these increases in energy consumption it is becoming necessary to consider unconventional types of oils Such oils, which are heavier, require more rigorous processing and treatment The evolution of petroleum refining began with the birth of modern oil production in Pennsylvania in the nineteenth century Current refineries are much more complex than those of a few decades ago and there is significant research concerning the development of more economical uses of available hydrocarbon resources In the past few decades there has been an increase in the number of publications that report advancements in the petroleum industry Petroleum Refining and Natural Gas Processing is a continuation of those efforts and attempts to bring together the most recent advances in various areas of petroleum downstream activities, with an emphasis on economic and environmental considerations, heavy-oil processing, and new developments in oil and gas processing The primary goal of this book is to provide a comprehensive reference that covers the latest developments in all aspects of petroleum and natural gas processing in the downstream sector of the petroleum industry It includes topics on economy and marketing, scheduling and planning, modeling and simulation, design and operation, inspection and maintenance, corrosion, environment, safety, storage and transportation, quality and process control, products specifications, management, biofuel processing and production, as well as other issues related to these topics Every attempt has been made to avoid overlap between chapters, however, there are some topics that have been included in more than one chapter when relevant to both chapters Another objective of this book is to describe the latest technology available to those working in the petroleum industry, especially designers, researchers, operators, managers, decision-makers, business people, and government officials The petroleum industry is a diverse and complex industry and it is almost impossible to include all aspects of it in a single book However, we tried to cover the most vital issues and we believe this is the most comprehensive resource published to date for use by people involved in this worldwide industry We hope this contribution will be useful to them In writing this book we benefited from the published works of many researchers, which are cited at the end of each chapter We welcome comments and suggestions from readers More than 40 scientists, experts, and professionals from both academia and industry have cooperated and contributed to the 33 chapters in this book Authors with years of experience made unique contributions not available in any similar publications We are grateful to all of them for their efforts in bringing this book to fruition We also thank the large number of anonymous reviewers who went through lengthy manuscripts and provided us with their constructive comments and suggestions, which greatly enhanced the quality of the manual Many publishers, organizations, and companies provided us with permission to use their published data, graphs, and figures and we thank them for their cooperation in supporting this publication effort We are also thankful to ASTM International for sponsoring publication of this book, especially to Kathy Dernoga, Monica Siperko, Marsha Firman, and other ASTM staff involved in this project Kathy Dernoga’s review and encouragement were essential to the completion of this work The support and encouragement of Dr George E Totten, ASTM’s Committee on Publications representative for this manual, is also appreciated The reviewing process was managed and conducted by Christine Urso of the American Institute of Physics (AIP) and she was extremely cooperative in uploading the manuscripts to the online reviewing site, inviting reviewers, and handling of all manuscripts submitted for this manual Also, many thanks to Rebecca L Edwards, senior project manager at Cenveo Publisher Services for copyediting and production Finally, and most importantly, we thank our families for their patience, understanding, cooperation, and moral support, which were essential throughout this process M R Riazi—Kuwait University, Kuwait Semih Eser—The Pennsylvania State University, University Park, PA, USA Suresh S Agrawal—Offsite Management Systems, Houston, TX, USA José Luis Peña Díez—Repsol, Madrid, Spain AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM vii Contents Preface v Chapter 1—Introduction M.R Riazi, Semih Eser, José Luis Pa Díez, and Suresh S Agrawal Chapter 2—Feedstocks and Products of Crude Oil and Natural Gas Refineries 21 M.R Riazi and Semih Eser Chapter 3—Worldwide Statistical Data on Proven Reserves, Production, and Refining Capacities of Crude Oil and Natural Gas ���������������������������������������������������������������������������������������������������������33 M.R Riazi, Mohan S Rana, and José Luis Pa Díez Chapter 4—Properties, Specifications, and Quality of Crude Oil and Petroleum Products 79 M.R Riazi and Semih Eser Chapter 5—Crude Oil Refining Processes 101 Semih Eser and M.R Riazi Chapter 6—Fluid Catalytic Cracking 127 Ravi Kumar Voolapalli, Chiranjeevi Thota, D.T Gokak, N.V Choudary, and M.A Siddiqui Chapter 7—Hydroisomerization of Paraffins in Light Naphthas and Lube Oils for Quality Improvement 159 B.L Newalkar, N.V Choudary, and M.A Siddiqui Chapter 8—Heavy-Oil Processing 177 Semih Eser and Jose Guitian Chapter 9—Advances in Petroleum Refining Processes 197 Isao Mochida, Ray Fletcher, Shigeto Hatanaka, Hiroshi Toshima, Jun Inomata, Makato Inomata, Shinichi Inoue, Kazuo Matsuda, Shigeki Nagamatsu, and Shinichi Shimizu Chapter 10—Advances in Catalysts for Refining Processes 223 Isao Mochida, Ray Fletcher, Shigeto Hatanaka, Hiroshi Toshima, Shikegi Nagamatsu, Makato Inomata, Rong He, Richard S Threlkel, Christopher J Dillon, Junko Ida, Toshio Matsuhisa, Shinichi Inoue, Shinichi Shimizu, and Kazuo Shoji Chapter 11—Natural Gas Conditioning and Processing 249 Calogero Migliore Chapter 12—Hydrogen Management 287 N Zhang and F Liu Chapter 13—Design Aspects of Separation Units and Processing Equipment 305 M.C Rodwell and M.R Riazi Chapter 14—Process Control and Instrumentation 355 L Raman and N.S Murthy Chapter 15—Modern Computer Process Control Refining Units 375 Ravi Jaisinghani Chapter 16—Refinery Inspection and Maintenance 393 A.L Kosta and Keshav Kishore Chapter 17—Corrosion Inspection and Control in Refineries 437 Jorge L Hau Chapter 18—Product Analysis and Quality Control 455 Pradeep Kumar and N.S Murthy AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM viii Contents Chapter 19—Fuel Blending Technology and Management 473 Suresh S Agrawal Chapter 20—Tank Farm Management 499 Suresh S Agrawal Chapter 21—Refinery Planning and Scheduling 531 Nan Zhang and Marc Valleur Chapter 22—Transportation of Crude Oil, Natural Gas, and Petroleum Products 549 Luis F Ayala H Chapter 23—Introduction to Trading, Pricing, and Valuation of Crude Oils and Petroleum Products 577 Cheng Seong Khor, Luis A Ricardez-Sandoval, Ali Elkamel, and Nilay Shah Chapter 24—A Review of Refinery Markets and Cost Estimation 597 Mark J Kaiser and James H Gary Chapter 25—Financial Risk Management in Refinery Operations Planning 631 Miguel Bagajewicz Chapter 26—Process Modeling and Simulation of Refineries 647 Maria J Guerra, Pablo Jiménez-Asenjo, Antonio López-Rodríguez, and José L Pa Díez Chapter 27—Maintenance Simulation and Optimization in Refineries and Process Plants 675 Miguel Bagajewicz Chapter 28—Roles of Computers in Petroleum Refineries 685 Cheng Seong Khor and Ali Elkamel Chapter 29—Environmental Issues Related to the Petroleum Refining Industry 701 Cheng Seong Khor and Ali Elkamel Chapter 30—Safety Issues Related to Petroleum Refineries 717 Joel M Haight Chapter 31—Refinery Management 729 Folkert J Herlyn Chapter 32—Biofuels and Biorefineries 747 José Baro Calle Chapter 33—Future Directions in Petroleum and Natural Gas Refining 769 Mohan S Rana, Jorge Ancheyta, M.R Riazi, and Meena Marafi Index 801 AST-MNL58-11-0801-FM.indd 13/03/13 4:29 PM Introduction M.R Riazi1, Semih Eser2, José Luis Pa Díez3, and Suresh S Agrawal4 Abbreviations APC API DAO DEG EIA EPA FCC FO GOR GTL H-Oil HDS LCO LPG MDEA MEA NGL OSHA PSA RON TEG ULSD VGO VRDS Advanced process control American Petroleum Institute Deasphalted oil Diethylene glycol Energy Information Administration U.S Environmental Protection Agency Fluid catalytic cracking Fuel oil Gas-to-oil ratio Gas-to-liquid Heavy oil Hydrodesulfurization Light cycle oil Liquefied petroleum gas Monodiethanol amine Monoethanol amine Natural gas liquid Occupational Safety and Health Administration Pressure sewing adsorption Research octane number Triethylene glycol Ultralow sulfur diesel Vacuum gas oil Vacuum residue desulfurization 1.1 Petroleum Fluids, Refinery Feedstocks, and Products Petroleum was first used in 1546 by the German mineralogist George Bauer and was reported as a naturally occurring flammable liquid found in rocks that contain various types of hydrocarbons Petroleum and natural gas play an important role in providing energy and the production of petrochemicals The word “petroleum” comes from the Latin words of petra (rock) and oleum, which refers to a special type of oil [1] Petroleum is a complex mixture of hundreds of hydrocarbons comprising mainly paraffins, naphthenes, and aromatics The lightest hydrocarbon component of petroleum is methane, which is the main element of natural gas, and the heaviest components include asphaltenes, with molecular weights higher than 1000 that are found in heavy oils These complex high-molecular-weight structures also contain heteroatoms such as nitrogen (N) and sulfur (S) In addition, small quantities of hydrogen and some metals are present in most crude oils as will be discussed later In today’s terminology, crude oil is referred to as the liquid type of petroleum that is processed in petroleum refineries, Kuwait University, Kuwait The Pennsylvania State University, University Park, PA, USA Repsol, Madrid, Spain Offsite Management Systems LLC, Sugar Land, TX, USA and natural gas is a mixture of light hydrocarbons produced from petroleum and gas reservoirs There are several theories on the formation process of petroleum and hydrocarbons It is generally believed that the petroleum is derived from aquatic plants and animals through conversion of organic compounds into hydrocarbons These organisms and plants under aquatic conditions have converted inorganic compounds dissolved in water (such as carbon dioxide) to organic compounds through the energy provided by the sun, 6CO2 + 6H 2O + energy → 6O2 + C H12O6 (1.1) in which C6H12O6 (a carbohydrate) is an organic compound Formed organic compounds may be decomposed into hydrocarbons under certain conditions of temperature and pressure, (CH O)n → xCO2 + yCH z (1.2) in which n, x, y and z are integer numbers and yCHz is the closed formula for the produced hydrocarbon compound Conversion of such organic materials to hydrocarbons occurs under heat (~210–250°F), pressure (~2500 psi), and radioactive rays Catalysts for such reactions are vanadium (V) and nickel (Ni), and for this reason some of these metals are found in small quantities in petroleum fluids A geologic time of approximately million years is required for completion of such reactions In some other theories it is suggested that calcium carbonate (CaCO3), an inorganic compound, can be converted to calcium carbide (CaC2), which reacts with water (H2O) to make acetylene (C2H2), a hydrocarbon Either way, an aquatic environment is required for the formation of petroleum and that could be a good reason why major oil reservoirs are located in the vicinity of seas and oceans, and major oil fields are found at the seabeds of the Gulf of Mexico or the Persian Gulf in the Middle East Hydrocarbons produced from organic materials gradually migrate through porous rocks and form a petroleum reservoir when a nonporous or seal rock is found A series of reservoirs within a common rock form an oil field Hydrocarbons found in different fields and reservoirs vary depending on their source and the maturity of the formation process, and this leads to the production of different kinds of reservoir fluids Figure 1.1 shows seven kinds of AST-MNL58-11-0801-001.indd 1 3/12/13 12:25 PM Chapter 31 n Refinery Management 743 Figure 31.13—Refinery BPM and longer term This includes interaction with corporate functions Products: The activities needed to meet the customer requirements in product volume, quality, and time The Operations and Technical functions provide sufficient data and models of the facilities for optimizing feedstock selection and production targets Develop feed and production schedules Feed includes the activities needed to schedule feed and products for individual units within the plant This schedule includes the calculation and definition of operations targets to generate optimum margins The operations and technical functions provide sufficient data and models of the facilities for optimizing the production schedule Manage inventories and dispositions This function ensures that there is a balanced inventory plan of raw materials and products meeting quality and shipping requirements 31.9.2.1.2 On-Sites Operation Plan and schedule operations Plan/Schedule: The function comprises the activities needed to plan/schedule the individual unit operations on the basis of the plant-wide operation schedules Those schedules cover, for example, feedstock changes, regenerations, turn-arounds and major repairs AST-MNL58-11-0801-031.indd 743 Operate on-site units The on-sites function is responsible for execution of the actual operation of the units according to agreed targets It includes keeping the production processes under control and also the delivery of the products according to specifications in quantity and quality at competitive cost at the required time Monitor performance This function captures all activities required to monitor process performance that is to compare actual and historical data (hourly, daily, monthly averages) with targets These data will include, for example, quality give-aways, utility consumptions, capacity utilization, efficiencies of equipment, and fouling trends Data reconciliation is performed on the actual plant data as required to ensure that the results of the comparisons are accurate Deviations from plan and violation of physical and/or technical constraints are highlighted for corrective action Equipment performance and historical data are available to take corrective actions 31.9.2.1.3 Off-Sites and Shared Operations Plan/schedule off-sites and shared unit operations The plant-wide daily scheduling application function provides the main targets for blending optimization, movements, inventory, and shipments 3/12/13 4:11 PM 744 Petroleum Refining and Natural Gas Processing Operate off-sites Determine/reconcile production and energy balances Blending: This function operates the blending facilities for all products that require blending to specifications This includes the selection of components from unit run-down lines or tankage and forwarding the products to shipment or tankage Feed and product movements: This function operates the movements that are necessary between on-site units and shipment Loading and shipment: This function schedules and executes the actual movements of all feed and product entering and leaving the plant via ships, trucks, rail cars, and pipeline facilities This includes the participation in the development of the plan for pier, station, and tank movements The function is responsible for the administration of all activities related to the receipt, dispatch, and storage of feed and products This includes the documents for suppliers, customers, shipment, and authorities This function, called in some plants “product accounting,” monitors the production and energy consumption and prepares material balances to come to an overall calculation of the energy consumption, and oil/material accounts and any losses This includes reconciliation and preparation of data for accounting and stewardship purposes Performance indicators are available for comparison to targets and plans 31.9.2.1.4 Operate Utilities This function is responsible for execution of the actual operation of the utility units (e.g., steam, power, air, inert gas, hydrogen purification units or facilities) according to agreed targets It includes keeping the production process under control and delivering the utilities to required specifications as needed and at competitive cost This includes scheduling and coordinating the supporting resources such as maintenance and technical for trouble shooting and repair Operate environmental units This function is responsible for monitoring of the environmental units (e.g., waste water treatment) and their operation to agreed targets to meet regulatory requirements 31.9.2.1.5 Operations Support Perform technical support This includes both the determination and guidance functions for all operations improvements Determine: This function monitors all production processes to derive an overall performance measure of the operation of the units It also includes analyzing production performance, losses, quality, give-away for the assessment of utilization and deviation reporting Guide: This function is responsible for all activities pertaining to the analysis and the troubleshooting of the production process by anticipating and reacting to process status and events These activities finally result in guiding and recommending technical settings for the production processes Provide advanced process control This function develops advanced process controls (APC), trains the operators, and maintains any APC applications This function includes the monitoring of application cost/benefits and the support of the console operator for assisting him in achieving safe and optimum production results Manage laboratory operations This function operates the laboratory facilities for the purpose of tracking and analyzing samples to support operations and quality assurance functions It includes management of the resources within the lab, the scheduling, transportation, receipt and disposal of the samples, and the assistance in monitoring quality assurance AST-MNL58-11-0801-031.indd 744 31.9.2.1.6 Manage Maintenance Plan maintenance Plan maintenance comprises the development of resource plans to ensure the integrity of the facilities and equipment over their planned life cycle based on requirements of operating plans (T/A, regenerations, etc.), equipment inspection, and preventive maintenance needs Part of this function is the development of maintenance budgets and overall control, issuing and maintaining up-to-date maintenance guidelines and manuals, and training of the personnel on any changes The systems will permit prioritization and sufficient input to perform work scheduling as the next step of work preparations The planning frequency is continuous but has formal planning outputs at monthly, quarterly, and yearly intervals Turnaround planning is part of this function Schedule maintenance Schedule maintenance comprises all activities pertaining to the scheduling of resources for maintenance jobs including in-house personnel, contractors, material, documentation for repairs, and the equipment and tools to execute the job It also includes reconciliation after completion to ensure continuous improvement of scheduling Execute and control maintenance The execute and control maintenance function comprises the physical execution and control of tasks outlined in the maintenance schedules This includes scheduling of daily activities and taking corrective action on backlog of jobs The function ensures that documentation, material, and tools provided as part of the scheduling activities is correct before use Finally, the function is responsible for recording of tasks performed, materials used, and services and man-hours consumed for later analysis by the individual equipment such as the pump, the exchanger, and the system of piping Analyze and reconcile maintenance This function consists of monitoring the maintenance activities and cost to come to an overall assessment of the maintenance services provided This includes analyzing efficiency and effectiveness using indicators for comparison to plans and analyzing backlog of work and the effectiveness of preventive and predictive maintenance 31.9.2.1.7 Warehouse and Procurement Operate materials warehouse This function ensures that there are sufficient parts and tools available at optimum cost to satisfy the refinery’s (maintenance) requirements It includes: Materials cataloging Movement tracking Procurement as an integral part of warehousing management 3/12/13 4:11 PM Chapter 31 n Refinery Management The function makes required information accessible at plant technician level around the clock Plant personnel can access materials information, request materials to be routed to work locations, and initiate reorders for larger repair work (turnaround) Reserved stock material information is available to those who are planning, scheduling, and performing work at the plant site This function also includes the analysis and optimization of warehouse stock levels and reorder frequency 31.9.2.1.9 Facilities Modification and Expansions Plan and schedule projects Manage materials and contract services Design and engineer facilities This function includes all activities required to develop a legal agreement between the supplier and the plant on services and materials which will allow the various plant departments to purchase services and equipment from the supplier This includes processing purchase requests, bid development, evaluation, contract negotiations, contract documentation, and approval 31.9.2.1.8 Manage Engineering and Technical Services Engineering and technical services management comprises all functions and entities that develop and implement projects and provide technical service and expertise on facilities to operations, maintenance and project functions Facilities engineering and maintenance services Provide inspection services: This includes all activities that are needed for carrying out quality assurance of all facilities in operation and also those at the design and implementation stage It includes the translation of statutory regulations into preventive maintenance services and operational constraints Provide instrumentation services: The instrumentation service function concerns all activities related to instrumentation, analyzer, and control systems This covers the activities over the full life cycle (design, engineering, maintenance) of equipment and software Provide electrical services: The electrical service function comprises all activities related to the electrical equipment and supply of electricity to the plant over its life cycle Provide machinery services: The machinery (rotating equipment) services function includes all activities related to machinery (rotating equipment) over its life cycle This includes monitoring of the performance of the equipment, the planning, design, and implementation of replacements and new projects Mechanical services: The mechanical services function is responsible for all activities related to the refinery’s mechanical equipment over its full life cycle This includes monitoring of the performance of the equipment and the planning, design, and implementation of replacements and new projects Provide civil services: This function comprises all activities related to the buildings, roads, and similar base infrastructure installations This includes monitoring the adequacy of those in place and the planning, design, and implementation of replacements and new projects AST-MNL58-11-0801-031.indd 745 745 The project planning and scheduling function includes all activities pertaining to the planning and scheduling of overall resource allocations for the projects within the plant It includes the consideration of constraints, synergies, and priorities Additionally, the detailed project planning and scheduling for each project is covered by this function The facilities design and engineering function supports the design, engineering, and estimating of facilities Execute and control projects The project execution and control function comprises all activities needed to make the facilities physically available and acceptable to the operating functions Part of this function is the requisitioning and purchasing of goods and services, the control of costs, the coordination of quality assurance of equipment received, the installation, the scheduling of daily activities, and the taking corrective actions on backlogs of jobs Provide cost estimating and controls The cost estimating and controls function includes all activities needed to support the project management from inception to completion Cost estimating is performed at an early stage of project planning to understand the cost implications Cost estimating will be updated as the project develops Cost control will be performed to ensure the project is on budget and plans Facilities process development/evaluate process opportunities This function comprises all activities that have the objective to evaluate opportunities to improve plant performance through modifications to the existing process and plant Among others, it includes surveying new technologies, technical and economic feasibilities, and preparing design proposals Design projects The function is responsible for all design and engineering activities needed for the reviews of appropriations and proposals 31.9.2.1.10 Manage Business Support Some of the business support processes below are functionally linked to the headquarters processes (business practices) and are needed to focus on meeting functional strategies (e.g., reliability) Business planning/performance monitoring/consolidate and reconcile business plans Business planning involves the preparation of medium and longer term plans, including major investments, and the budgeting for capital expenditures, expenses, and costs Finally, it includes the activities that are needed to effectively measure business performance and to adjust business targets where needed Business planning is performed at the plant level and will, therefore, impact every organizational unit in the complex 3/12/13 4:11 PM 746 Petroleum Refining and Natural Gas Processing Determine plant performance This function evaluates how the plant has performed by comparing planned versus actual business characteristics and identifying reasons for discrepancies both internal and external to the plant information This includes developing, integrating, and maintaining information applications Manage library and data stores: Operating and maintaining the storehouse of information that the company requires to function Manage business practices/compliance Manage reliability This function translates the corporate goals and governmental rules into a working set of policies, guidelines, and standards This includes, for example, the business controls, ethics requirements, and engineering standards Each business function has its own details that relate to the plant master set Perform target management Target management translates the business goals (including balanced scorecards management) and objectives into a working set of policies, guidelines, and standards This includes the planning, implementation, and control of achievements against these goals and objectives Manage safety Safety management comprises the development and implementation of programs designed to prevent the occurrence of incidents that would adversely affect the plant business assets, human resources, and the public This includes the effective and efficient implementation of action plans to control incidents Manage security Security management is the development and implementation of programs designed to ensure plant access control and asset control and to perform some investigative tasks to prevent the occurrence of incidents and losses that would adversely affect the plant business assets, human resources, and the public Regulations and plant management have to know which people are on site at any time The security task includes the effective and efficient implementation of action plans to control incidents Manage environmental activities This function includes the development and implementation of programs designed to ensure compliance with environmental regulations, those determined both internally and externally to the site or company This includes the effective and efficient implementation of action plans to avoid or to control environmental incidents Furthermore, the control of waste handling is included in case it is not covered by the operating unit Manage industrial hygiene The function covers the development and implementation of programs designed to comply with industrial hygiene practices and procedures Manage information systems Manage Information Architectures: planning, developing, implementing and maintaining the three architectures of information, systems, and technology Manage information applications: Managing the technology which provides the required views of the refinery’s AST-MNL58-11-0801-031.indd 746 The function develops and monitors programs designed to improve the integrity and reliability of equipment and processes This includes the effective and efficient implementation of action plans to avoid equipment failure or process malfunctions and related incidents This function may act as a consulting service to maintenance, process operations, engineering services, and management Manage human resources Plan: Development of an all-encompassing human resource plan that will provide the right people for the site It includes managing position planning, the appraisal program, and organizational redesign programs Acquire employees: Managing the process which will legally obtain employees for the refinery including recruitment, selection, and orientation of new employees Provide employee services: Maintenance of the contractual relationship between the employee and the company including areas of compensation, benefits, transfers, service awards, and retirement Manage employee development: Developing and implementing the plan which will continuously balance the variables of employee interests and needs, employee skills and abilities, and the company’s needs This includes management of the employee career development program Manage external relations Interpret government relations: Accumulating, interpreting, and complying with the laws and regulations set forth by all forms of government which may have an impact on the operations of the refinery Manage public relations: The management of all activities whereby the refinery interfaces with the general public including the interpretation of public opinion, providing public relations advice on external communications, and enhancing the refinery’s public image References [1] Birol, F., “Challenges Facing the Global Refinery Industry,” Oil Gas Process, Rev., 2006, http://www.touchbriefings.com/ pdf/1713/Birol.pdf [2] Herlyn, F J., and Starr, S., “The Six Significant Steps in Moving Towards a More Profitable Operating Environment,” NPRA Plant Automation, NPRA, San Antonio, TX, 2003 [3] Keese, G., Apple, J E., and Herlyn, F J., “Benchmarking Information Systems,” Chem Eng., June, 1998 [4] Herlyn, F. J , Plant Best Practices, http://www.herlyn.com/ index.php?option=com_content&task=view&id=5&Itemid=9 (accessed on August 16, 2008) [5] Herlyn, F J., “A Roadmap to Best Performance Indicators,” Hydrocarbon Eng., Vol 5, July, 2000 [6] The CALDER-MOIR IT Governance Framework, http://www itgovernance.co.uk/calder_moir.aspx: http://www.itgovernance co.uk/calder_moir.aspx (accessed on August 25, 2008) [7] CSB Investigation Information Page, http://www.csb.gov/index cfm?folder=completed_investigations&page=info&INV_ID=52 (accessed August 19, 2008) 3/12/13 4:11 PM 32 Biofuels and Biorefineries José Baro Calle1 Acronyms A/F BOB BTL CCS CDM CFPP CONCAWE CTL DME DOE EISA ETBE EtOH EUCAR FAEE FAME FT GHG GMO GTL HDS HV HVO IEA JRC LCA LCFS LHV LPG MON NOx PVO R&D RON SOS SRA VP WTL XTL WTW Air-fuel rate Blendstock for oxygen blending Biomass to liquid Carbon capture and sequestration Clean development mechanism Cold filter plugging point Conservation of Clean Air and Water in Europe Coal to liquid Dimethyl ether U.S Department of Energy Energy Independence and Security Act Ethyl terc butyl ether Ethanol European Council for Automotive R & D Fatty acid ethyl ester Fatty acid methyl ester Fischer-Tropsch Greenhouse gases Genetically modified organism Gas to liquid Hydrodesulfurization Heating value Hydrogenated vegetable oil International Energy Agency Joint Research Centre Life cycle analysis Low carbon fuel standard Low heating value Liquefied petroleum gas Motor octane number Nitrogen oxides Pure vegetable oils Research and development Research octane number Security of supply Strategic research agenda Vapour pressure Waste to liquid Something to liquid Well to wheel Nomenclature Gtoe BG Giga tons of equivalent oil Billion gallons 32.1 Introduction Karl Benz built the first automobile in 1885 Since then, the automobile industry has undergone constant technological evolution, involving improvements in a wide variety of areas Fuels, lubricants, and the processes associated with their production have always been one of the main focuses for technology development The continuous demand for innovation implies the existence of future unsolved technological needs The automobile industry has constantly raced against time to solve these technological issues successfully For instance, the oil industry has supplied sulfur-free fuels to satisfy environmental regulations, and this change also needs low-sulfur lubricants or gasoline with redesigned volatility These technology solutions need to be also economically competitive to become widely accepted by the industry The evolution of the automobile industry is continuing with no signs of slowing down Moreover, it is currently facing probable revolutionary changes in the vehicle concept The most important current challenge for the industry is to increase the energy efficiency of transportation without increasing the associated pollutant emissions, including greenhouse gas (GHG) emissions Fossil fuel reserves are finite and not fully available to all market economy countries The estimated global oil reserves are 335 Gtoe (equivalent to about 70 years at current rate of consumption), and the estimated natural gas reserves are similar At a glance, fossil fuels were formed over millions of years but have been largely consumed in only one century This massive consumption of fossil fuels has altered the carbon equilibrium on our planet by releasing large amounts of carbon dioxide (CO2) into the atmosphere CO2 is considered one of the most important GHGs and has direct implications in environmental regulations related to climate change These supply and environmental drivers are forcing a change in the conventional distribution of energy sources, as discussed in Chapter 3, and increasing the share of renewable sources in the production of fuels for transportation 32.2 The Need of Biofuels for Transportation Over the past decades, scientists around the world have foreseen serious threats for human life in the near future and have identified sustainable energy as a target for the 21st century However, what exactly does sustainable energy mean? Sustainable energy must fully satisfy global energy demands, produced at the same rate at which it is consumed, and with an economic cost that guarantees availability in every country and social strata Although this might be considered a utopia, the need is evident and has been one of the main legislation focuses in different world areas during the last decades Repsol S.A., Madrid, Spain 747 AST-MNL58-11-0801-032.indd 747 3/12/13 4:15 PM 748 Petroleum Refining and Natural Gas Processing In 2000, the European Commission released a “Green Paper” proposing a European strategy for the security of energy supply [1] This Green Paper highlighted and provided evidences on Europe’s dependence on energy supply and the narrow available margins, anticipating the challenges to accomplish the targets mandated by the Kyoto Protocol and starting to consider the use of more biofuels for transport This concern was further developed by a White Paper on a common transport policy [2], suggesting an action plan with a target of substituting 20 % of fossil fuels consumed in transportation with alternative fuels in 2020 This approach should provide: • Improvement in security of energy supply (SOS) by source diversification • Reduction of GHG emissions In November 2001, the Commission presented a communication on alternative fuels for road transportation [3], identifying biofuels, natural gas, and hydrogen as possible future energy sources for transport Each of these options was proposed to potentially cover at least % of total transportation fuel consumption in 2020 and to be implemented in the following order: biofuels for the short term, natural gas for the medium term, and hydrogen for the long term In the same document, the Commission presented proposals for directives on the promotion of the use of biofuels for transport and opening the possibility for the state members to introduce reduced tax duties on mixtures of biofuels with mineral oils This approach was confirmed by a stakeholder Contact Group on Alternative Fuels, established by the Commission, which presented a comprehensive report outlining a detailed strategy on market development for these alternative fuels [4] The report confirmed the technical feasibility of reaching the 20 % market share target defined by the Commission for 2020 and was mainly based on a well-to-wheel (WTW) analysis for the different alternative fuels In 2003 the European Union adopted Directive 2003/30 EC [5] on the promotion of the use of biofuels and other renewable fuels for transport Under this biofuels directive, the European Union established the goal for member states to set indicative targets for a minimum proportion of biofuels to be placed on the market of % in 2005 and 5.75 % in 2010 Due to the difference in prices with conventional fuels, the European Union allowed member states to apply a total or partial tax exemption for biofuels, as competitiveness was identified as one of the major barriers [6] During 2007, the European Union proposed a new energy strategy with several improvements to be attained by 2020 An updated roadmap [7] demonstrated that a target of 20 % for overall share of renewable energies and a 10 % target in transport would be feasible objectives These targets, together with improvement in energy efficiency, were endorsed by the European Council and by the European Parliament [8] and included in the updated and broader Directive 2009/28/EC [9] on the use of energy from renewable sources The confirmed targets included 20 % reduction in GHG emissions (versus 1990), 20 % of the total energy from renewable sources (10 % in transport), and 20 % reduction in primary energy consumption At the beginning of 2009, a revision of the Fuel Directive (Directive 2009/30/EC, [10]) was approved, allowing the addition of ethanol (EtOH) to gasoline up to 10 % and AST-MNL58-11-0801-032.indd 748 the addition of fatty acid methyl ester (FAME) (biodiesel) to diesel up to % The directive also sets targets to reduce fuel’s life cycle GHG emissions, placing the responsibility of reducing these emissions on fuel suppliers The most important commitment is the reduction of GHG emissions to 90 % of the 2010 level by 2020 The targets, which could be reviewed in 2014, include: • A mandatory reduction of fuel GHG emissions of % by 2020 Member states may increase this reduction up to 10 % and establish intermediate targets (2 % by 2014 and % by 2017) • An indicative % target subject to a Commission assessment by the end of 2012 to be delivered through alternative vehicles (e.g., electric or hydrogen vehicles, etc.) and the application of carbon capture and sequestration (CCS) • An indicative % target by 2020 to be achieved by the purchase of credits through clean development mechanism (CDM) under the Kyoto Protocol The main current consequence from these regulations related to biofuels is that the European transport sector is required to source 10 % of its energy needs from renewable energies, including sustainable biofuels and others While these steps were given in Europe, regulation activities related to biofuels were also taking place in the United States Legislations like the Clean Air Act Amendments (1990) and the Energy Policy Act of 1992 opened possibilities for alternative fuels that could be produced from internal resources Although the main biofuels focus was EtOH from corn, activities were also starting in bioethanol from other sources and biodiesel [11] In 2007, the U.S Government introduced the Energy Independence and Security Act (EISA) [12], increasing and expanding the Energy Policy Act of 2005 with the objective to improve vehicle fuel economy and reduce U.S dependence on petroleum EISA proposed a target to replace 30 % of transportation fuel consumption with alternative fuels by 2030 This reduction should be obtained through an increase of the percentage of renewable fuel blended with conventional fuels for transportation The new regulation defined seven categories of “advanced biofuels” (other than cornderived EtOH) that could be grouped in: • Cellulosic biofuels, including EtOH derived from cellulose, hemicellulose or lignin • Biomass-based biodiesel • Other advanced biofuels: EtOH from sugar, non-corn starch or waste material; biogas, butanol and other alcohols from renewable biomass This legislation proposed a calendar of renewable volume obligations (RVO) Some of the targets proposed for different biofuels with significant GHG emissions reduction include: • Renewable fuels: billion gallons (BG) in 2008, rising to 36 BG in 2022 • Advanced biofuels: 0.6 BG in 2009 to 21 BG in 2022 • Cellulosic biofuels: 0.1 BG in 2010 to 16 BG in 2022 • Biomass-based biodiesel: 0.5 BG in 2009 to BG in 2012 In another initiative, California issued the executive order S-01-07 [13], which proposed the development of “Low Carbon Fuel Standard” (LCFS), which aims to reduce the GHG footprint of transportation fuels by at least 20 % in 2020 This target would be met largely by the introduction 3/12/13 4:15 PM Chapter 32 n Biofuels and Biorefineries of biofuels, mainly through the addition of EtOH to gasoline at a rate beyond the federal mandate (possibly requiring a 50 to 100 % higher penetration of biofuels by 2020) Similar legislations have appeared in other areas around the world, including countries like Brazil, Argentina, South Africa, Thailand, India, and China Taking into account these actions, the market for biofuels seems to be enormous, at least until 2020 The International Energy Agency (IEA) [14] has forecasted in the reference scenario that biofuel use will continue rising until 2030 After a strong increase from 2006–2008, mainly in North America and Europe, reaching 1.7 % of total road-transport fuels, economic downturn and concerns about effects on food prices related to crop dedication to biofuels reduced the growth rate However, the projected scenario for 2030 (Figure 32.1) considers a significant growth in all world areas in 2030, when it will meet about % of worldwide transportation fuel consumption Nearly one quarter of this increase is expected to be produced using second generation technologies However, even with current exceptionally high fossil fuel prices, biofuels remain expensive to produce and are generally noncompetitive Thus, the question remains about the reason why biofuels have received major interest as alternative renewable fuels Probably the simplest answer would be “because they are here” (quoting Mallory, the mythic mountain climber), meaning that biofuels are the only renewable alternative for transportation fuels that is commercially available However, simply being here is not enough Public support schemes must justify the financial resources invested in biofuels The assumed benefits of biofuels are that they contribute to SOS and reduce GHG emissions Other benefits might include the reduction of crude oil consumption, and hence a slower depletion of proved reserves, and the support of rural areas, particularly in developing countries, preventing an exodus of the rural population as demonstrated in Brazil Depending on the objective and local resources, several biofuels and raw materials could be suitable However, although any biofuel may be a good response to GHG concerns, the selection between producing biofuels of bioenergy (biomass dedicated to generate electricity or heat) might be uncertain from the savings in GHG emissions point of view [15] 749 32.3 The Key Concept: Sustainability Plants use solar energy to convert CO2 and water into organic molecules, composed by carbon and hydrogen, allowing them to store energy through this process During the natural cycle of plant life, these organic molecules formed during crop growth are degraded, releasing CO2 back into the atmosphere Therefore, plants can be used not only as food but also to produce energy In this alternative application, CO2 returns to the atmosphere when biomass is burned, and the CO2 is captured again after a limited period of time that may range, depending on the plan, from year in oleaginous or cereal crops to decades for woods Under this concept, energy from biomass is renewable However, the level at which biomass can be considered a renewable energy source is determined by its energy content minus the necessary fossil energy required (if required) for its production In other words, not 100 % of the energy content in biomass is renewable, and therefore, only some of the CO2 emitted during biomass combustion is renewable There are other renewable energy sources (solar, wind, tides, etc.), but energy from biomass is unique in the sense that it is stored in molecules, making possible the conversion to other usable forms of energy or the production of chemicals In the past, an energy source only needed to be renewable to obtain social acceptance, but today renewable is an insufficient label, and it must be also sustainable The sustainability concept implies more than SOS or environmental concerns, and includes the global social impact It is not just “what” needs to be done but “how” it is done Conceptually, sustainable energy refers to energy that can be generated for long periods of time without compromising potential resources for future generations Climate change and its relationship with anthropogenic GHG emission promoted interest in sustainability certification Transportation is presumed to be the main contributor to GHG emissions, and transportation-related emissions will continue increasing over the next decades For this reason, the transportation sector was a pioneer in GHG control, and proposed some of the first rigorous WTW studies [16] However, after these analyses were carried out, it was already evident that this approach was insufficient In 2007, large-scale biofuel development started to raise concerns regarding competition with food and pressure on land resources [17,18] In some cases, it was even Figure 32.1—Forecast on biofuels demand for transportation Source: IEA [14] Note: On an energy-equivalent basis AST-MNL58-11-0801-032.indd 749 3/12/13 4:15 PM 750 Petroleum Refining and Natural Gas Processing feared that plowing land with high carbon content could produce enough additional CO2 emissions to negate any GHG emission benefits for several decades Society needs to be confident that the benefits of biofuels vastly exceed any undesirable effects Thus, the biofuel industry needs to apply an internationally recognized and accepted sustainability certification scheme and avoid a proliferation of local schemes, which would challenge the survival of a global market The scientific community has been working since that moment to define parameters and to create mechanisms to measure these parameters in a transparent and nonautocratic way The demands for the energy industry should also be comparable with other industries to maintain equilibrium in all economic activities The criteria for sustainability represent a very complex subject that requires not only technical knowledge but ethical and political aspects Figure 32.2 represents some of the main groups of sustainability pillars as proposed by IEA [19] There are currently several initiatives that have built some certification schemes for biofuels with certain degree of international recognition that cover the different sustainability legislations, mainly in Europe and the United States These schemes consider most of the following sustainability criteria, organized under these main pillar groups: • Environmental pillars: lifecycle GHG, soil quality, soil degradation, harvest levels, emission of non-GHG air pollutants, water use and efficiency, water quality, biological diversity, forest preservation, land use, and land use change • Social pillars: allocation and occupation of land, human food competition, local wealth, jobs in biofuels sector, access to modern energy services, human rights, worker rights, and indicators related to diseases, injuries, and mortality • Economic pillars: productivity, net energy balance, gross value, change in consumption of fossil fuels, workforce training, energy diversity, infrastructure, and logistics, capacity, and flexibility of bioenergy use IEA [19] identified near 70 worldwide initiatives to develop sustainability criteria and standards, including public and private initiatives Some of the most advanced international activities for sustainability criteria standards include: • ISO/TC 248, Sustainability Criteria for Bioenergy (international standard on preparation) • The European Standard EN 16214 from European Committee for Standardisation CEN/TC 383 on sustainably produced biomass for energy applications [20] • The Global Bioenergy Partnership (GEBP) Indicators [21] • Roundtable on Sustainable Biofuels (RSB), open and multi-stakeholder process that has developed certification systems recognized by the European Union under the Renewable Energy Directive [22] • The International Sustainability and Carbon Certification System (ISCC), with the first internationally recognized certification system for biomass Some of the main criteria from the previous standard proposals will be covered in this section It is expected that after biofuels, the certification scheme will be extended to include energetic biomass and, potentially, to other energy sources that could be certified under similar schemes, specifically adapted to each source Regarding land use change for biofuels, some theoretical calculations estimate that dedicating a small percentage of arable land (