Refinery Process
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Sulfur Recovery
Sulfur Recovery Chapter 16 Based on presentation by Prof. Art Kidnay Plant Block Schematic Adapted from Figure 7.1, Fundamentals of Natural Gas Processing, 2nd ed. Kidnay, Parrish, & McCartney Updated: January 4, 2019 2 Copyright © 2019 John Jechura ([email protected]) Topics Introduction Properties of sulfur Sulfur recovery processes ▪ Claus Process ▪ Claus Tail Gas Cleanup Sulfur storage Safety and environmental considerations Updated: January 4, 2019 3 Copyright © 2019 John Jechura ([email protected]) Introduction & Properties of Sulfur Updated: January 4, 2019 Copyright © 2017 John Jechura ([email protected]) Sulfur Crystals http://www.irocks.com/minerals/specimen/34046 http://www.mccullagh.org/image/10d-5/sulfur.html Updated: January 4, 2019 5 Copyright © 2019 John Jechura ([email protected]) Molten Sulfur http://www.kamgroupltd.com/En/Post/7/Basic-info-on-elemental-Sulfur(HSE) Updated: January 4, 2019 6 Copyright © 2019 John Jechura ([email protected]) World Consumption of Sulfur Primary usage of sulfur to make sulfuric acid (90 – 95%) ▪ Other major uses are rubber processing, cosmetics, & pharmaceutical applications China primary market Ref: https://ihsmarkit.com/products/sulfur-chemical-economics-handbook.html Report published December 2017 Updated: January 4, 2019 7 Copyright © 2019 John Jechura ([email protected]) Sulfur Usage & Prices Natural gas & petroleum production accounts for the majority of sulfur production Primary consumption is agriculture & industry ▪ 65% for farm fertilizer: sulfur → sulfuric acid → phosphoric acid → fertilizer $50 per ton essentially disposal cost ▪ Chinese demand caused run- up in 2007-2008 Ref: http://ictulsa.com/energy/ “Cleaning up their act”, Gordon Cope, Updated December 24, 2018 Hydrocarbon Engineering, pp 24-27, March 2011 Updated: January 4, 2019 8 Copyright © 2019 John Jechura ([email protected]) U.S. -
Pump Product Catalog
Pump Division Pump Product Catalog Experience In Motion Pump Supplier to the World Flowserve is the driving force in the global Product Brands of Distinction industrial pump marketplace. No other pump ACEC™ Centrifugal Pumps company in the world has the depth or breadth of expertise in the successful application of Aldrich™ Pumps pre-engineered, engineered, and special purpose Byron Jackson ® Pumps pumps and systems. Calder™ Energy Recovery Devices Cameron™ Pumps Durco ® Process Pumps Flowserve ® Pumps IDP ® Pumps INNOMAG ® Sealless Pumps Lawrence Pumps ® Niigata Worthington™ Pumps Pacific ® Pumps Pleuger ® Pumps Scienco™ Pumps Sier-Bath ® Rotary Pumps TKL™ Pumps United Centrifugal ® Pumps Western Land Roller™ Irrigation Pumps Wilson-Snyder ® Pumps Worthington ® Pumps 2 Worthington Simpson™ Pumps flowserve.com Pump Designs Flowserve offers a wide range of complementary pump types, built to recognized global standards Committed to the Complete Pump and customer specification. These include: System Life Cycle • Single-stage process • Between bearings single-stage For more than two centuries, Flowserve has • Between bearings multistage served industries requiring solutions that add value and reduce costs throughout the life • Vertical cycle of a pumping system. • Submersible motor • Oil and gas • Positive displacement • Chemical • Nuclear • Power generation • Specialty • Water Available Configurations • General industry Flowserve partners • Sealed and sealless with customers to • Axially and radially split respond to the • Volute and diffuser dynamic business • Close coupled and spacer coupled conditions that • Single and double case affect them and to improve efficiency, maximize throughput and control process quality. Whether customer needs involve on-site technical assistance, equipment upgrades or broader project planning with full turnkey responsibility, Flowserve delivers professional, reliable results. -
APPENDIX M SUMMARY of MAJOR TYPES of Carfg2 REFINERY
APPENDIX M SUMMARY OF MAJOR TYPES OF CaRFG2 REFINERY MODIFICATIONS Appendix M: Summan/ of Major Types of CaRFG2 Refinery Modifications: Alkylation Units A process unit that combines small-molecule hydrocarbon gases produced in the FCCU with a branched chain hydrocarbon called isobutane, producing a material called alkylate, which is blended into gasoline to raise the octane rating. Alkylate is a high octane, low vapor pressure gasoline blending component that essentially contains no olefins, aromatics, or sulfur. This plant improves the ultimate gasoline-making ability of the FCC plant. Therefore, many California refineries built new or modified existing units to increase alkylate production to blend and to produce greater amounts of CaRFG2. Alkylate is produced by combining C3, C4, and C5 components with isobutane (nC4). The process of alkylation is the reverse of cracking. Olefins (such as butenes and propenes) and isobutane are used as feedstocks and combined to produce alkylate. This process enables refiners to utilize lighter components that otherwise could not be blended into gasoline due to their high vapor pressures. Feed to alkylation unit can include pentanes from light cracked gasoline treaters, isobutanes from butane isomerization unit, and C3/C4 streams from delayed coking units. Isomerization Units - C4/C5/C6 A refinery that has an alkylation plant is not likely to have exactly enough is-butane to match the proplylene and butylene (olefin) feeds. The refiner usually has two choices - buy iso-butane or make it in a butane isomerization (Bl) plant. Isomerization is the rearrangement of straight chain hydrocarbon molecules to form branched chain products or to convert normal paraffins to their isomer. -
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 % -
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. -
Olefins Recovery CRYO–PLUS ™ TECHNOLOGY 02
Olefins Recovery CRYO–PLUS ™ TECHNOLOGY 02 Refining & petrochemical experience. Linde Engineering North America Inc. (LENA) has constructed more than twenty (20) CRYO-PLUS™ units since 1984. Proprietary technology. Higher recovery with less energy. Refinery configuration. Designed to be used in low-pressure hydrogen-bearing Some of the principal crude oil conversion processes are off-gas applications, the patented CRYO-PLUS™ process fluid catalytic cracking and catalytic reforming. Both recovers approximately 98% of the propylene and heavier processes convert crude products (naphtha and gas oils) components with less energy required than traditional into high-octane unleaded gasoline blending components liquid recovery processes. (reformate and FCC gasoline). Cracking and reforming processes produce large quantities of both saturated and Higher product yields. unsaturated gases. The resulting incremental recovery of the olefins such as propylene and butylene by the CRYO-PLUS™ process means Excess fuel gas in refineries. that more feedstock is available for alkylation and polym- The additional gas that is produced overloads refinery erization. The result is an overall increase in production of gas recovery processes. As a result, large quantities of high-octane, zero sulfur, gasoline. propylene and propane (C3’s), and butylenes and butanes (C4’s) are being lost to the fuel system. Many refineries Our advanced design for ethylene recovery. produce more fuel gas than they use and flaring of the ™ The CRYO-PLUS C2= technology was specifically excess gas is all too frequently the result. designed to recover ethylene and heavier hydrocarbons from low-pressure hydrogen-bearing refinery off-gas streams. Our patented design has eliminated many of the problems associated with technologies that predate the CRYO-PLUS C2=™ technology. -
Hydrocarbon Processing®
HYDROCARBON PROCESSING® 2012 Gas Processes Handbook HOME PROCESSES INDEX COMPANY INDEX Sponsors: SRTTA HYDROCARBON PROCESSING® 2012 Gas Processes Handbook HOME PROCESSES INDEX COMPANY INDEX Sponsors: Hydrocarbon Processing’s Gas Processes 2012 handbook showcases recent advances in licensed technologies for gas processing, particularly in the area of liquefied natural gas (LNG). The LNG industry is poised to expand worldwide as new natural gas discoveries and production technologies compliment increasing demand for gas as a low-emissions fuel. With the discovery of new reserves come new challenges, such as how to treat gas produced from shale rock—a topic of particular interest for the growing shale gas industry in the US. The Gas Processes 2012 handbook addresses this technology topic and updates many others. The handbook includes new technologies for shale gas treating, synthesis gas production and treating, LNG and NGL production, hydrogen generation, and others. Additional technology topics covered include drying, gas treating, liquid treating, effluent cleanup and sulfur removal. To maintain as complete a listing as possible, the Gas Processes 2012 handbook is available on CD-ROM and at our website for paid subscribers. Additional copies may be ordered from our website. Photo: Lurgi’s synthesis gas complex in Malaysia. Photo courtesy of Air Liquide Global E&C Solutions. Please read the TERMS AND CONDITIONS carefully before using this interactive CD-ROM. Using the CD-ROM or the enclosed files indicates your acceptance of the terms and conditions. www.HydrocarbonProcessing.com HYDROCARBON PROCESSING® 2012 Gas Processes Handbook HOME PROCESSES INDEX COMPANY INDEX Sponsors: Terms and Conditions Gulf Publishing Company provides this program and licenses its use throughout the Some states do not allow the exclusion of implied warranties, so the above exclu- world. -
Natural Gas Acid Gas Removal and Sulfur Recovery Process Economics Program Report 216A
` IHS CHEMICAL Natural Gas Acid Gas Removal and Sulfur Recovery Process Economics Program Report 216A December 2016 ihs.com PEP Report 216A Natural Gas Acid Gas Removal and Sulfur Recovery Anshuman Agrawal Principal Analyst, Technologies Analysis Downloaded 3 January 2017 10:20 AM UTC by Anandpadman Vijayakumar, IHS ([email protected]) IHS Chemical | PEP Report 216A Natural Gas Acid Gas Removal and Sulfur Recovery PEP Report 216A Natural Gas Acid Gas Removal and Sulfur Recovery Anshuman Agrawal, Principal Analyst Abstract Natural gas is generally defined as a naturally occurring mixture of gases containing both hydrocarbon and nonhydrocarbon gases. The hydrocarbon components are methane and a small amount of higher hydrocarbons. The nonhydrocarbon components are mainly the acid gases hydrogen sulfide (H2S) and carbon dioxide (CO2) along with other sulfur species such as mercaptans (RSH), organic sulfides (RSR), and carbonyl sulfide (COS). Nitrogen (N2) and helium (He) can also be found in some natural gas fields. Natural gas must be purified before it is liquefied, sold, or transported to commercial gas pipelines due to toxicity and corrosion-forming components. H2S is highly toxic in nature. The acid gases H2S and CO2 both form weak corrosive acids in the presence of small amounts of water that can lead to first corrosion and later rupture and fire in pipelines. CO2 is usually a burden during transportation of natural gas over long distances. CO2 removal from natural gas increases the heating value of the natural gas as well as reduces its greenhouse gas content. Separation of methane from other major components contributes to significant savings in the transport of raw materials over long distances, as well as savings from technical difficulties such as corrosion and potential pipeline rupture. -
Reactions of Benzene & Its Derivatives
Organic Lecture Series ReactionsReactions ofof BenzeneBenzene && ItsIts DerivativesDerivatives Chapter 22 1 Organic Lecture Series Reactions of Benzene The most characteristic reaction of aromatic compounds is substitution at a ring carbon: Halogenation: FeCl3 H + Cl2 Cl + HCl Chlorobenzene Nitration: H2 SO4 HNO+ HNO3 2 + H2 O Nitrobenzene 2 Organic Lecture Series Reactions of Benzene Sulfonation: H 2 SO4 HSO+ SO3 3 H Benzenesulfonic acid Alkylation: AlX3 H + RX R + HX An alkylbenzene Acylation: O O AlX H + RCX 3 CR + HX An acylbenzene 3 Organic Lecture Series Carbon-Carbon Bond Formations: R RCl AlCl3 Arenes Alkylbenzenes 4 Organic Lecture Series Electrophilic Aromatic Substitution • Electrophilic aromatic substitution: a reaction in which a hydrogen atom of an aromatic ring is replaced by an electrophile H E + + + E + H • In this section: – several common types of electrophiles – how each is generated – the mechanism by which each replaces hydrogen 5 Organic Lecture Series EAS: General Mechanism • A general mechanism slow, rate + determining H Step 1: H + E+ E El e ctro - Resonance-stabilized phile cation intermediate + H fast Step 2: E + H+ E • Key question: What is the electrophile and how is it generated? 6 Organic Lecture Series + + 7 Organic Lecture Series Chlorination Step 1: formation of a chloronium ion Cl Cl + + - - Cl Cl+ Fe Cl Cl Cl Fe Cl Cl Fe Cl4 Cl Cl Chlorine Ferric chloride A molecular complex An ion pair (a Lewis (a Lewis with a positive charge containing a base) acid) on ch lorine ch loronium ion Step 2: attack of -
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.