Environmental, Health, and Safety Guidelines for Petroleum Refining
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The Chemistry of Sulfur in Fluid Catalytic Cracking
Catalytic Reduction of Sulfur in Fluid Catalytic Cracking Rick Wormsbecher Collaborators Grace Davison Laboratoire Catalyse et Spectrochimie, CNRS, Université de Caen Ruizhong Hu Michael Ziebarth Fabian Can Wu-Cheng Cheng Francoise Maugé Robert H. Harding Arnaud Travert Xinjin Zhao Terry Roberie Ranjit Kumar Thomas Albro Robert Gatte Outline • Review of fluid catalytic cracking. • Sulfur balance and sulfur cracking chemistry. • Catalytic reduction of sulfur by Zn aluminate/alumina. Fluid Catalytic Cracking • Refinery process that “cracks” high molecular weight hydrocarbons to lower molecular weight. • Refinery process that provides ~50 % of all transportation fuels indirectly. • Provides ~35 % of total gasoline pool directly from FCC produced naphtha. • ~80 % of the sulfur in gasolines comes from the FCC naphtha. Sulfur in Gasoline • Sulfur compounds reversibly poison the auto emission catalysts, increasing NOx and hydrocarbon emission. SOx emissions as well. • World-wide regulations to limit the sulfur content of transportation fuels. – 10 - 30 ppm gasoline. • Sulfur can be removed by hydrogenation chemistry. – Expensive. – Lowers fuel quality. Fluid Catalytic Cracking Unit Products Riser Flue Gas Reactor (~500 ºC) Regenerator (~725 ºC) Reaction is endothermic. 400 tons Catalyst circulates from catalyst Riser to Regenerator. inventory 50, 000 Air Feedstock barrels/day Carbon Distribution H2 ~0.05 % Flare C1 ~1.0 % Flare Petrochem Feed C2-C4 ~14-18 % Naphtha MW ~330 g/mole C5-C11 ~50 % C12-C22 ~15-25 % LCO C22+ ~5-15 % HCO Coke ~3-10 % -
Catalyst Precursors for Hydrodesulfurization Synthesized in Supercritical Fluids Manuel Théodet
New generation of ”bulk” catalyst precursors for hydrodesulfurization synthesized in supercritical fluids Manuel Théodet To cite this version: Manuel Théodet. New generation of ”bulk” catalyst precursors for hydrodesulfurization synthesized in supercritical fluids. Material chemistry. Université Sciences et Technologies - Bordeaux I,2010. English. NNT : 2010BOR14092. tel-00559113 HAL Id: tel-00559113 https://tel.archives-ouvertes.fr/tel-00559113 Submitted on 24 Jan 2011 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Distributed under a Creative Commons Attribution - NonCommercial - NoDerivatives| 4.0 International License N° d’ordre : 4092 THÈSE présentée à L’UNIVERSITÉ BORDEAUX I ÉCOLE DOCTORALE DES SCIENCES CHIMIQUES Par Manuel THEODET Ingénieur ENSCPB POUR OBTENIR LE GRADE DE DOCTEUR SPÉCIALITÉ : Physico-Chimie de la Matière Condensée ___________________ NOUVELLE GENERATION DE PRECURSEURS « BULK » DE CATALYSEUR D’HYDRODESULFURATION SYNTHETISES EN MILIEU FLUIDE SUPERCRITIQUE ___________________ NEW GENERATION OF « BULK » CATALYST PRECURSORS FOR HYDRODESULFURIZATION SYNTHESIZED IN SUPERCRITICAL FLUIDS ___________________ Co-superviseurs de recherche : Cristina Martínez & Cyril Aymonier Soutenue le 03 Novembre 2010 Après avis favorable de : M. E. PALOMARES, Professor, UPV, Valencia, Spain Rapporteurs M. M. TÜRK, Professor, KIT, Karlsruhe, Germany Devant la commission d’examen formée de : M. -
Oil Refinery Sector
Gujarat Cleaner Production Centre - ENVIS Centre CLEANER PRODUCTION OPPURTUNITIES IN OIL REFINERY SECTOR Gujarat Cleaner Production Centre - ENVIS Centre OIL REFINERY An oil refinery or petroleum refinery is an industrial process plant where crude oil is processed and refined into more useful products such as petroleum naphtha, gasoline, diesel fuel, asphalt base, heating oil, kerosene and liquefied petroleum gas. Oil refineries are typically large, sprawling industrial complexes with extensive piping running throughout, carrying streams of fluids between large chemical processing units. Common process units found in a refinery: • Desalter unit washes out salt from the crude oil before it enters the atmospheric distillation unit. • Atmospheric distillation unit distills crude oil into fractions. • Vacuum distillation unit further distills residual bottoms after atmospheric distillation. • Naphtha hydrotreater unit uses hydrogen to desulfurize naphtha from atmospheric distillation. Must hydrotreat the naphtha before sending to a Catalytic Reformer unit. • Catalytic reformer unit is used to conver t the naphtha-boiling range molecules into higher octane reformate (reformer product). The reformate has higher content of aromatics and cyclic hydrocarbons). An important byproduct of a r eformer is hydrogen released during the catalyst reaction. The hydrogen is used either in the hydrotreater or the hydrocracker. • Distillate hydrotreater unit desulfurizes distillates (such as diesel) after atmospheric distillation. • Fluid catalytic cracker (FCC) unit upgrades heavier fractions into lighter, more valuable products. • Hydrocracker unit uses hydrogen to upgrade heavier fractions into lighter, more valuable products. • Visbreaking unit upgrades heavy residual oils by thermally cracking them into li ghter, more valuable reduced viscosity products. • Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to organic disulfides. -
Exxonmobil Torrance Refinery Electrostatic Precipitator Explosion Torrance, California
InvestigationInvestigation Report Report ExxonMobil Torrance Refinery Electrostatic Precipitator Explosion Torrance, California Incident Date: February 18, 2015 On-Site Property Damage, Catalyst Particles Released to Community, Near Miss in MHF Alkylation Unit No. 2015-02-I-CA KEY ISSUES: • Lack of Safe Operating Limits and Operating Procedure • Safeguard Effectiveness • Operating Equipment Beyond Safe Operating Life • Re-use of Previous Procedure Variance Without Sufficient Hazard Analysis Published May 2017 CSB · ExxonMobil Torrance Refinery Investigation Report The U.S. Chemical Safety and Hazard Investigation Board (CSB) is an independent Federal agency whose mission is to drive chemical safety change through independent investigations to protect people and the environment. The CSB is a scientific investigative organization; it is not an enforcement or regulatory body. Established by the Clean Air Act Amendments of 1990, the CSB is responsible for determining accident causes, issuing safety recommendations, studying chemical safety issues, and evaluating the effectiveness of other government agencies involved in chemical safety. More information about the CSB is available at www.csb.gov. The CSB makes public its actions and decisions through investigative publications, all of which may include safety recommendations when appropriate. Examples of the types of publications include: CSB Investigation Reports: formal, detailed reports on significant chemical accidents and include key findings, root causes, and safety recommendations. CSB Investigation Digests: plain-language summaries of Investigation Reports. CSB Case Studies: examines fewer issues than a full investigative report, case studies present investigative information from specific accidents and include a discussion of relevant prevention practices. CSB Safety Bulletins: short, general-interest publications that provide new or timely information intended to facilitate the prevention of chemical accidents. -
Petroleum Coke
Report No. 72 PETROLEUM COKE by SAMUEL C. SPENCER October 1971 A private report by the 0 PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA I * CONTENTS 1 INTRODUCTION, . 1 2 SUMMARY . * . , . Economic Aspects ...................... 6 Technical Aspects ..................... 10 3 INDUSTRY STATUS . , . , , . 17 Trends . .................... 17 Applications . , . .................... 29 Fuel . .................... 31 Aluminum (anodes) .................... 32 MetallurgicalCoke .................... 36 Chemicals . .................... 37 Formed Shapes . .................... 38 Other Uses . , .................... 39 4 DEVELOPMENTOF COKING PROCESSES . , , , , . , . 41 5 CHEMISTRY ......................... 47 Composition ........................ 47 Basic Chemistry ...................... 52 6 DELAYED COKING. ...................... 59 Review of Process ..................... 59 Process Description .................... 68 Materials of COnStrUctiOn ................. 83 Process Discussion ..................... 84 Process Variations and Innovations ............. 93 Cost Estimates ....................... 95 Capital Costs ...................... 96 Production Costs ..................... 100 Needle Coke Economics ................... 112 V CONTENTS 7 FLUID COKING ........................ 119 Review of Process ..................... 119 Process Description .................... 129 Materials of Construction ................. 133 Process Discussion ..................... 140 Process Variations and Innovations ............. 144 Cost Estimates -
Burton Introduces Thermal Cracking for Refining Petroleum John Alfred Heitmann University of Dayton, [email protected]
University of Dayton eCommons History Faculty Publications Department of History 1991 Burton Introduces Thermal Cracking for Refining Petroleum John Alfred Heitmann University of Dayton, [email protected] Follow this and additional works at: https://ecommons.udayton.edu/hst_fac_pub Part of the History Commons eCommons Citation Heitmann, John Alfred, "Burton Introduces Thermal Cracking for Refining Petroleum" (1991). History Faculty Publications. 92. https://ecommons.udayton.edu/hst_fac_pub/92 This Encyclopedia Entry is brought to you for free and open access by the Department of History at eCommons. It has been accepted for inclusion in History Faculty Publications by an authorized administrator of eCommons. For more information, please contact [email protected], [email protected]. 573 BURTON INTRODUCES THERMAL CRACKING FOR REFINING PETROLEUM Category of event: Chemistry Time: January, 1913 Locale: Whiting, Indiana Employing high temperatures and pressures, Burton developed a large-scale chem ical cracking process, thus pioneering a method that met the need for more fuel Principal personages: WILLIAM MERRIAM BURTON (1865-1954), a chemist who developed a commercial method to convert high boiling petroleum fractions to gas oline by "cracking" large organic molecules into more useful and marketable smaller units ROBERT E. HUMPHREYS, a chemist who collaborated with Burton WILLIAM F. RODGERS, a chemist who collaborated with Burton EUGENE HOUDRY, an industrial scientist who developed a procedure us ing catalysts to speed the conversion process, which resulted in high octane gasoline Summary of Event In January, 1913, William Merriam Burton saw the first battery of twelve stills used in the thermal cracking of petroleum products go into operation at Standard Oil of Indiana's Whiting refinery. -
(HDS) Unit for Petroleum Naphtha at 3500 Barrels Per Day
Available online at www.worldscientificnews.com WSN 9 (2015) 88-100 EISSN 2392-2192 Design Parameters for a Hydro desulfurization (HDS) Unit for Petroleum Naphtha at 3500 Barrels per Day Debajyoti Bose University of Petroleum & Energy Studies, College of Engineering Studies, P.O. Bidholi via- Prem Nagar, Dehradun 248007, India E-mail address: [email protected] ABSTRACT The present work reviews the setting up of a hydrodesulphurization unit for petroleum naphtha. Estimating all the properties of the given petroleum fraction including its density, viscosity and other parameters. The process flow sheet which gives the idea of necessary equipment to be installed, then performing all material and energy balance calculations along with chemical and mechanical design for the entire setup taking into account every instrument considered. The purpose of this review paper takes involves an industrial process, a catalytic chemical process widely used to remove sulfur (S) from naphtha. Keywords: hydro desulfurization, naphtha, petroleum, sulfur Relevance to Design Practice - The purpose of removing the sulfur is to reduce the sulfur dioxide emissions that result from using those fuels in automotive vehicles, aircraft, railroad locomotives, gas or oil burning power plants, residential and industrial furnaces, and other forms of fuel combustion. World Scientific News 9 (2015) 88-100 1. INTRODUCTION Hydrodesulphurization (HDS) is a catalytic chemical process widely used to remove sulfur (S) from natural gas and from refined petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel fuel, and fuel oils. The purpose of removing the sulfur is to reduce the sulfur dioxide (SO2) emissions that result from various combustion practices. -
Screening-Level Hazard Characterization of Petroleum Coke
U.S. Environmental Protection Agency June 2011 Hazard Characterization Document SCREENING-LEVEL HAZARD CHARACTERIZATION Petroleum Coke Category SPONSORED CHEMICALS Petroleum coke, green CASRN 64741-79-3 Petroleum coke, calcined CASRN 64743-05-1 The High Production Volume (HPV) Challenge Program1was conceived as a voluntary initiative aimed at developing and making publicly available screening-level health and environmental effects information on chemicals manufactured in or imported into the United States in quantities greater than one million pounds per year. In the Challenge Program, producers and importers of HPV chemicals voluntarily sponsored chemicals; sponsorship entailed the identification and initial assessment of the adequacy of existing toxicity data/information, conducting new testing if adequate data did not exist, and making both new and existing data and information available to the public. Each complete data submission contains data on 18 internationally agreed to “SIDS” (Screening Information Data Set1,2) endpoints that are screening-level indicators of potential hazards (toxicity) for humans or the environment. The Environmental Protection Agency’s Office of Pollution Prevention and Toxics (OPPT) is evaluating the data submitted in the HPV Challenge Program on approximately 1400 sponsored chemicals by developing hazard characterizations (HCs). These HCs consist of an evaluation of the quality and completeness of the data set provided in the Challenge Program submissions. They are not intended to be definitive statements regarding the possibility of unreasonable risk of injury to health or the environment. The evaluation is performed according to established EPA guidance2,3 and is based primarily on hazard data provided by sponsors; however, in preparing the hazard characterization, EPA considered its own comments and public comments on the original submission as well as the sponsor’s responses to comments and revisions made to the submission. -
BENZENE Disclaimer
United States Office of Air Quality EPA-454/R-98-011 Environmental Protection Planning And Standards June 1998 Agency Research Triangle Park, NC 27711 AIR EPA LOCATING AND ESTIMATING AIR EMISSIONS FROM SOURCES OF BENZENE Disclaimer This report has been reviewed by the Office of Air Quality Planning and Standards, U.S. Environmental Protection Agency, and has been approved for publication. Mention of trade names and commercial products does not constitute endorsement or recommendation of use. EPA-454/R-98-011 ii TABLE OF CONTENTS Section Page LIST OF TABLES.....................................................x LIST OF FIGURES.................................................. xvi EXECUTIVE SUMMARY.............................................xx 1.0 PURPOSE OF DOCUMENT .......................................... 1-1 2.0 OVERVIEW OF DOCUMENT CONTENTS.............................. 2-1 3.0 BACKGROUND INFORMATION ...................................... 3-1 3.1 NATURE OF POLLUTANT..................................... 3-1 3.2 OVERVIEW OF PRODUCTION AND USE ......................... 3-4 3.3 OVERVIEW OF EMISSIONS.................................... 3-8 4.0 EMISSIONS FROM BENZENE PRODUCTION ........................... 4-1 4.1 CATALYTIC REFORMING/SEPARATION PROCESS................ 4-7 4.1.1 Process Description for Catalytic Reforming/Separation........... 4-7 4.1.2 Benzene Emissions from Catalytic Reforming/Separation .......... 4-9 4.2 TOLUENE DEALKYLATION AND TOLUENE DISPROPORTIONATION PROCESS ............................ 4-11 4.2.1 Toluene Dealkylation -
Converting Visbreakers to Delayed Cokers - an Opportunity for European Refiners
Converting Visbreakers to Delayed Cokers - An Opportunity for European Refiners European Coking.com Conference Sept. 30 - Oct. 2, 2008 Alex Broerse Lummus Technology a CB&I company © Lummus Technology Overview Introduction Delayed Coking Delayed Coking vs. Visbreaking Case Study Conclusions © Lummus Technology Converting Visbreakers to Delayed Cokers - 2 Fuel Oil Market General trend: reduction of sulfur content in fuel oil Typically 1.0-1.5 wt% S International Maritime Organization introduced SOx Emission Control Areas: . Sulfur content of fuel oil on board ships < 1.5 wt% . 1st SECA: Baltic Sea (effective 2006) . North Sea end of 2007 . More to follow Similar trend in other fuel oil application areas End of bunker fuel oil as sulfur sink? © Lummus Technology Converting Visbreakers to Delayed Cokers - 3 European Fuels Market Increased demand for ULS diesel Gradually decreasing fuel oil market Price gap between low sulfur crudes and opportunity crudes Re-evaluation of bottom-of-the-barrel strategy maximize diesel and minimize/eliminate fuel oil production What are the options? © Lummus Technology Converting Visbreakers to Delayed Cokers - 4 Bottom-of-the-Barrel Conversion Technologies Non Catalytic Catalytic Delayed coking Atm. / vac. resid hydrotreating Fluid / flexicoking Ebullated bed hydrocracking Gasification Resid FCC © Lummus Technology Converting Visbreakers to Delayed Cokers - 5 Lummus Capabilities for Bottom-of-the-Barrel Lummus Technology – Houston Delayed coking Resid FCC Chevron Lummus Global JV – Bloomfield Atmospheric/vacuum residue hydrotreating LC-FINING ebullated bed hydrocracking Lummus Technology – Bloomfield / The Hague Refinery planning studies (e.g., grassroots, revamps, processing of opportunity crudes) © Lummus TechnologyExtensive experience in heavy crude upgrade Converting Visbreakers to Delayed Cokers - 6 scenarios Overview Introduction Delayed Coking Delayed Coking vs. -
THE H-OIL PROCESS: a Worldwxide LEADER in VACUUM RESIDUE HYDROPROCESSING” \ ^
—t&CR I'd, D 3 YJj TT-097 CONEXPO ARPEL '96 . i ' 1 "THE H-OIL PROCESS: A WORLDWXiDE LEADER IN VACUUM RESIDUE HYDROPROCESSING” \ ^ J.J. Colyar1 L.I. Wisdom2 A. Koskas3 SUMMARY With the uncertainty of market trends, refiners will need to hedge their investment strategies in the future by adding processing units that provide them with flexibility to meet the changing market. The various process configurations involving the H-Oil® Process described in this paper have been tested commercially and provide the refiner with the latest state of the art technology. ABSTRACT The H-Oil® Process is a catalytic hydrocracking process, invented by HRI, Inc., a division of IFP Enterprises, Inc. which is used to convert and upgrade petroleum residua and heavy oils. Today the H-Oil Process accounts for more than 50 percent of the worldwide vacuum residue hydroprocessing market due to its unique flexibility to handle a wide variety of heavy crudes 'while producing clean transportation fuels. The process is also flexible in terms of changes in yield selectivity and product quality. The unconverted vacuum residue from the process can be utilized for fuel oil production, blended into asphalt, routed to resid catalytic cracking, directly combusted or gasified to produce hydrogen. This paper will discuss additional background information on the H-Oil Process, some of the key advances made to the process and applications for the Latin America market. The paper will also discuss the status of recent commercial plants which are in operation or which are under design or construction and which utilize these new advances. -
Optimization of Refining Alkylation Process Unit Using Response
Optimization of Refining Alkylation Process Unit using Response Surface Methods By Jose Bird, Darryl Seillier, Michael Teders, and Grant Jacobson - Valero Energy Corporation Abstract This paper illustrates a methodology to optimize the operations of an alkylation unit based on response surface methods. Trial based process optimization requires the unit to be operated across a wide range of conditions. This approach tends to be opposed by refinery operations as it can disrupt the normal operations of a process unit. Using the methods presented in this paper, the general direction of process improvement is first identified using a first order profit response surface built from available operating data. The performance of the unit is then evaluated at the refinery by making systematic changes to the key factors in the projected direction of process improvement. The operating results are then used to build a localized second order profit response surface to generate a revised set of optimum targets. Multiple linear regression models are used to predict alkylate yield, alkylate octane and Iso-stripper or De-Isobutanizer reboiler duty as a function of key process variables. These models are then used to generate a profit response surface for selection of an optimum target region for step testing at the refinery prior to implementation of the unit targets. 1. Introduction An alkylation unit takes a feed stream with a high olefin content, typically originating from a fluid catalytic cracking (FCC) unit, and adds isobutane (IC4) which reacts with the olefins to produce a high octane alkylate product. Either hydrofluoric or sulfuric acid is used as a catalyst for the alkylation reaction.