Olefins from Conventional and Heavy Feedstocks: Energy Use in Steam Cracking and Alternative Processes
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Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture 2005)**
NOBEL LECTURES DOI: 10.1002/adsc.200600523 Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture 2005)** Robert H. Grubbsa,* a Victor and Elizabeth Atkins Professor of Chemistry Arnold and Mabel Beckman Laboratories of Chemical Synthesis California Institute of Technology, Pasadena, CA 91125, USA Fax : (+1)-626–564–9297 [**] Copyright The Nobel Foundation 2005. We thank the Nobel Foundation, Stockholm, for permission to print this lecture Received: February 21, 2006 This is a story of our exploration of the olefin-meta- ly added to this reaction, 1-butene was again ob- thesis reaction, a reaction that has been the major served. This discovery has since served as the founda- emphasis of my independent research. As with all sto- tion for an amazing array of nickel chemistry and cat- ries of scientific discovery, there are three compo- alysis. In addition, as nickel had been found to possess nents: the discoveries, the resulting applications, and, unexpected reactivity, other metal salts were also in- perhaps the most important of all, the people in- vestigated. In particular, when titanium and zirconium volved. Starting from observations made from seem- halides were used in combination with alkyl alumi- ingly unrelated work, our investigations into the fun- num compounds, a new form of polyethylene was ob- damental chemistry of this transformation have been tained. Natta further demonstrated that similar cata- an exciting journey, with major advances often result- lysts could promote the formation of stereoregular ing from complete surprises, mistakes, and simple in- polymers from propylene. The 1963 Nobel Prize in tuition. Ultimately, these efforts have contributed to Chemistry was awarded to Ziegler and Natta for this olefin metathesis becoming the indispensable synthet- work. -
Part I: Carbonyl-Olefin Metathesis of Norbornene
Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Graduate School of Arts and Sciences COLUMBIA UNIVERSITY 2016 1 © 2016 Zara Maxine Seibel All Rights Reserved 2 ABSTRACT Part I: Carbonyl-Olefin Metathesis of Norbornene Part II: Cyclopropenimine-Catalyzed Asymmetric Michael Reactions Zara Maxine Seibel This thesis details progress towards the development of an organocatalytic carbonyl- olefin metathesis of norbornene. This transformation has not previously been done catalytically and has not been done in practical manner with stepwise or stoichiometric processes. Building on the previous work of the Lambert lab on the metathesis of cyclopropene and an aldehyde using a hydrazine catalyst, this work discusses efforts to expand to the less stained norbornene. Computational and experimental studies on the catalytic cycle are discussed, including detailed experimental work on how various factors affect the difficult cycloreversion step. The second portion of this thesis details the use of chiral cyclopropenimine bases as catalysts for asymmetric Michael reactions. The Lambert lab has previously developed chiral cyclopropenimine bases for glycine imine nucleophiles. The scope of these catalysts was expanded to include glycine imine derivatives in which the nitrogen atom was replaced with a carbon atom, and to include imines derived from other amino acids. i Table of Contents List of Abbreviations…………………………………………………………………………..iv Part I: Carbonyl-Olefin Metathesis…………………………………………………………… 1 Chapter 1 – Metathesis Reactions of Double Bonds………………………………………….. 1 Introduction………………………………………………………………………………. 1 Olefin Metathesis………………………………………………………………………… 2 Wittig Reaction…………………………………………………………………………... 6 Tebbe Olefination………………………………………………………………………... 9 Carbonyl-Olefin Metathesis……………………………………………………………. -
Naphtha Catalytic Cracking Process Economics Program Report 29K
` IHS CHEMICAL Naphtha Catalytic Cracking Process Economics Program Report 29K December 2017 ihs.com PEP Report 29K Naphtha Catalytic Cracking Michael Arne Research Director, Emerging Technologies IHS Chemical | PEP Report 29K Naphtha Catalytic Cracking PEP Report 29K Naphtha Catalytic Cracking Michael Arne, Research Director, Emerging Technologies Abstract Ethylene is the world’s most important petrochemical, and steam cracking is by far the dominant method of production. In recent years, several economic trends have arisen that have motivated producers to examine alternative means for the cracking of hydrocarbons. Propylene demand is growing faster than ethylene demand, a trend that is expected to continue for the foreseeable future. Hydraulic fracturing in the United States has led to an oversupply of liquefied petroleum gas (LPG) which, in turn, has led to low ethane prices and a shift in olefin feedstock from naphtha to ethane. This shift to ethane has led to a relative reduction in the production of propylene. Conventional steam cracking of naphtha is limited by the kinetic behavior of the pyrolysis reactions to a propylene-to-ethylene ratio of 0.6–0.7. These trends have led producers to search for alternative ways to produce propylene. Several of these— propane dehydrogenation and metathesis, for example—have seen large numbers of newly constructed plants in recent years. Another avenue producers have examined is fluid catalytic cracking (FCC). FCC is the world’s second largest source of propylene. This propylene is essentially a byproduct of refinery gasoline production. However, in recent years, an effort has been made to increase ethylene and propylene yields to the point that these light olefins become the primary products. -
Wacker Oxidation ~Anti-Markovnikov~
Anti-Markovnikov Olefin Functionalization ~Prof. Robert H. Grubbs’ Work~ 4th Literature Seminar July 5, 2014 Soichi Ito (D1) Contents 1. Introduction • Flow of Prof. Grubbs’ Research • Markovnikov’s Rule • Wacker Oxidation 2. Grubbs’ Work • Substrate-Controlled Wacker Oxidation • Catalyst-Controlled Wacker-Type Oxidation 2 Introduction ~Flow of Research~ Olefin Metathesis Anti-Markovnikov Wacker Oxidation of Terminal Olefin Substrate-Controlled Wacker Oxidation of Internal Olefin Z-Selective Metathesis Hydration Ethenolysis + Reduction Hydroamination Z-Selective Ethenolysis Catalyst-Controlled Decarbonylative Dehydration Hydrophosphonation Production of Terminal Olefin Functionalization of Terminal Olefin 3 Introduction ~Markovnikov’s Rule~ Two-Step Two-Step (+1C) 4 Robert H. Grubbs et al. Science, 2011, 333, 1609. Anti-Markovnikov Hydration of Olefins • One-Step William C. Trogler et al. Science 1986, 233, 1069. This work was difficult to reproduce. Inorg. Chem. 1988, 27, 3151. • One-Step with Activated Olefins Robert G. Bergman and F. Dean Toste et al. J. Am. Chem. Soc. 2003, 125, 8696. Ben L. Feringa and Gerard Roelfes et al. Nat. Chem. 2010, 2, 991. • Three-Step 5 Shannon S. Stahl et al. J. Am. Chem. Soc. 2010, 132, 15116. Anti-Markovnikov Wacker Oxidation / Reduction Strategy Oxidation cycle must be compatible with the reduction cycle. aldehyde-selective Wacker Oxidation 6 Robert H. Grubbs et al. Science, 2011, 333, 1609. Introduction ~Wacker-Tsuji Oxidation~ • 1894 F. C. Phillips reported stoichiometric reaction. • 1959 J. Smidt et al. reported the Wacker process. (oxidation of ethylene to acetaldehyde) Investigations for convenient laboratory methods • 1976 J. Tsuji et al. reported PdCl2, CuCl / DMF, H2O method. “Terminal alkenes may be viewed as masked ketones.” 7 Jacques Muzart Tetrahedron 2007, 63, 7505. -
Self-Metathesis of 1-Octene Using Alumina-Supported Re2o7 in Supercritical CO2
Top Catal DOI 10.1007/s11244-008-9154-4 ORIGINAL PAPER Self-Metathesis of 1-Octene Using Alumina-Supported Re2O7 in Supercritical CO2 Massimo Fabris Æ Cindy Aquino Æ Antony J. Ward Æ Alvise Perosa Æ Thomas Maschmeyer Æ Maurizio Selva Ó Springer Science+Business Media, LLC 2009 Abstract In this contribution we describe the use of basic science has been applied for the benefit of man, heterogeneous catalysts for the liquid-phase self-metathesis society and the environment’’.1 Their contribution was of 1-octene in supercritical CO2. Our work aims at recognized for understanding the mechanism, and for addressing the mass-transfer problems associated with such developing very efficient and selective discrete metal- reaction systems. By coupling a heterogeneous supported based catalysts. Re2O7 catalyst with the use of scCO2, the self-metathesis Nonetheless, one should not forget that the metathesis of 1-octene takes place by and large much more rapidly reaction using heterogeneous catalysis has been an estab- than in traditional solvent media, and furthermore, by using lished industrial process since 1966, based on the use of scCO2 the overall efficiency and sustainability of the supported (usually on silica and alumina) metal oxides transformation can be improved. such as tungsten, nickel, cobalt, rhenium, and molybde- num. Three significant examples come to mind and are Keywords Metathesis Á 1-Octene Á Supercritical CO2 Á here recalled briefly. [1]. Re/Al O 2 3 1. The historic Phillips triolefin process for the produc- tion of ethene and 2-butene from propene using a WO /SiO catalyst, [2] that was shut down in 1972 1 Introduction 3 2 after 6 years of operation due to increased demand for propene, and later reutilized in the reverse direction to The metathesis of olefins is a very elegant and widely produce propene. -
Introduction
1 Chapter 1 INTRODUCTION Significant research efforts in the field of transition metal catalysis have led to the development of powerful methods for the formation of C–C and C–heteroatom bonds. Appropriate design of the catalyst and reaction conditions, along with careful choice of the substrate, can enable new and challenging transformations to proceed in high yield and selectivity. In this thesis, three categories of such transformations are presented: cross- coupling reactions to form carbon–silicon bonds, aldehyde-selective Wacker oxidations of fluorinated olefins, and olefin metathesis catalyzed by aminophosphine-ligated ruthenium complexes. Nickel-catalyzed cross-coupling has proven to be a very effective strategy for the addition of organometallic reagents to unactivated alkyl electrophiles. In particular, secondary alkyl halides are useful coupling partners, despite previously being considered to exhibit poor reactivity in comparison to aryl and alkenyl electrophiles, due to challenging oxidative addition and competitive b-hydride elimination. While this class of reactions has predominantly been applied to the formation of C–C bonds, the extension of this strategy to the formation of C–B bonds presented by Fu and coworkers inspired the work presented in the second chapter of this thesis, which details the development of a nickel-catalyzed cross- coupling reaction of unactivated alkyl bromides and silylzinc nucleophiles, resulting in C–Si bond formation. A brief overview of established strategies to form C–Si bonds, as well as some of the current challenges, is discussed. The palladium-catalyzed Wacker oxidation is a powerful tool for the oxidation of terminal olefins. However, controlling the regioselectivity of this process (i.e. -
Manipulating Selectivity and Reactivity in Palladium-Catalyzed Oxidation Reactions
Manipulating Selectivity and Reactivity in Palladium-Catalyzed Oxidation Reactions Thesis by Zachary Kimble Wickens In Partial Fulfillment of the Requirements for the degree of Doctor of Philosophy CALIFORNIA INSTITUTE OF TECHNOLOGY Pasadena, California 2015 (Defended June 2nd, 2015) © 2015 Zachary Kimble Wickens All Rights Reserved 1 Dedicated to my parents for never pushing me to become a scientist 2 Acknowledgments The work I have the pleasure of sharing with you in this thesis would have been completely impossible without the help (both emotional and intellectual) of a tremendously large number of people. First, I want to thank my advisor, Bob Grubbs. I truly could not have asked for a more incredible thesis advisor. Since the beginning of my time at Caltech, you have subtly guided me towards the water but never forced me to drink. You have given me independence in choosing which projects to pursue and the directions these projects go, but always provided suggestions and hints along the way that have kept me on track. I know you will continue to provide great advice and strong support even long after I've left Caltech. Thanks for being my invisible safety net over the last five years. I would have never even considered pursuing a Ph.D in chemistry in the first place if it weren't for the fantastic chemistry faculty at Macalester College. Rebecca Hoye, Ronald Brisbois, Paul Fischer, Keith Kuwata, Thomas Varberg and Katherine Splan, you were all tremendously influential in my life. You taught me how to see the exciting puzzles that are scattered throughout the field of chemistry. -
Cracking (Chemistry)
Cracking (chemistry) In petrochemistry, petroleum geology and organic chemistry, cracking is the process whereby complex organic molecules such as kerogens or long-chain hydrocarbons are broken down into simpler molecules such as light hydrocarbons, by the breaking of carbon-carbon bonds in the precursors. The rate of cracking and the end products are strongly dependent on the temperature and presence of catalysts. Cracking is the breakdown of a large alkane into smaller, more useful alkenes. Simply put, hydrocarbon cracking is the process of breaking a long chain of hydrocarbons into short ones. This process requires high temperatures.[1] More loosely, outside the field of petroleum chemistry, the term "cracking" is used to describe any type of splitting of molecules under the influence of heat, catalysts and solvents, such as in processes of destructive distillation or pyrolysis. Fluid catalytic cracking produces a high yield of petrol and LPG, while hydrocracking is a major source of jet fuel, Diesel fuel, naphtha, and again yields LPG. Contents History and patents Cracking methodologies Thermal cracking Steam cracking Fluid Catalytic cracking Hydrocracking Fundamentals See also Refinery using the Shukhov cracking References process, Baku, Soviet Union, 1934. External links History and patents Among several variants of thermal cracking methods (variously known as the "Shukhov cracking process", "Burton cracking process", "Burton-Humphreys cracking process", and "Dubbs cracking process") Vladimir Shukhov, a Russian engineer, invented and patented the first in 1891 (Russian Empire, patent no. 12926, November 7, 1891).[2] One installation was used to a limited extent in Russia, but development was not followed up. In the first decade of the 20th century the American engineers William Merriam Burton and Robert E. -
Ruthenium-Based Olefin Metathesis Catalysts Coordinated with N-Heterocyclic
Ruthenium-Based Olefin Metathesis Catalysts Coordinated with N-Heterocyclic Carbene Ligands: Synthesis and Applications Thesis by John Philip Morgan In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy California Institute of Technology Pasadena, California 2002 (Submitted September 12, 2002) ii 2002 John Philip Morgan All Rights Reserved iii To my family and my friends, I’d never be here if you weren’t there. iv “No matter where you go, there you are.” — Buckaroo Banzai, as told to Earl Mac Rausch [The Hitchhiker’s Guide to the Galaxy is superior to this thesis in two respects.] “First, it is slightly cheaper; and second, it has the words DON’T PANIC inscribed in large, friendly letters on its cover.” — Douglas Adams v Chapter 0: A Concise Synthesis of the Cocktail “Peter’s Catalyst” Experimental Section. General. All materials were used as obtained from the Athenaeum, Vons, or Ralph’s. “Cranberry juice” may refer to any “cocktail” preparation. “Grapefruit juice” may also be a “cocktail” preparation, but not a “sour mix.” Visual spectroscopy is used to estimate color of final preparation. Synthesis of “Peter’s Catalyst” (Compound 1). A clean, dry whisky glass is charged with ice (3-5 cubes), grapefruit juice (1 oz., 1 equiv.), cranberry juice (4 shots, approximately 2 equiv.), blue curacaó (0.5 shot, 0.25 equiv.), and vodka (1- 2 shots, 0.5-1.0 eq. to taste). The reaction mixture is stirred briefly until the color is homogeneous (5 s). An additional aliquot of cranberry juice is added until the reaction mixture has achieved a dark purplish color. -
Polycyclic Aromatic Hydrocarbons and Petroleum Industry
View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Columbia University Academic Commons 76905_ch81 p1236-1246.qxd 10/4/06 9:32 PM Page 1236 MARKED SET 81 Polycyclic Aromatic Hydrocarbons and Petroleum Industry Steven Stellman, PhD, MPH Tee L. Guidotti, MD, MPH, DABT CHEMISTRY AND STRUCTURES chrysene, dibenz(a,h)anthracene, fluoranthene, fluo- rene, indeno(1,2,3-cd)pyrene, naphthalene, phenan- The term polycyclic aromatic hydrocarbons (PAHs) threne, pyrene) that includes a group of seven PAHs (in generally refers to a group of chemical compounds bold) that are probable human carcinogens. Figure 81.1 consisting of carbon and hydrogen atoms arranged as illustrates structures of key PAHs. The best-known PAH is planar compounds whose principal structural feature benzo(a)pyrene (BaP), due to its early identification in is fused rings. Their nomenclature has evolved over coal tar and later use as a model compound for investigat- many decades and is complex. A comprehensive listing, ing the carcinogenic properties of tobacco smoke. including traditional synonyms and chemical struc- tures, is given by Sander and Wise (1). PAHs are produced during the incomplete combustion SOURCES OF POLYCYCLIC of organic material and are among the most ubiquitous AROMATIC HYDROCARBONS environmental pollutants. The combustion processes that IN THE ENVIRONMENT release PAHs invariably produce a variety of compounds, and in fact, it is difficult or impossible to ascribe health PAHs enter the environment through both natural and effects in humans to particular members of the PAH manmade processes. The principal natural sources of family. -
Catalytic Dehydrogenation of Ethane: a Mini Review of Recent Advances and Perspective of Chemical Looping Technology
catalysts Review Catalytic Dehydrogenation of Ethane: A Mini Review of Recent Advances and Perspective of Chemical Looping Technology Danis Fairuzov, Ilias Gerzeliev, Anton Maximov and Evgeny Naranov * Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskiy Prospect, 29, 119991 Moscow, Russia; [email protected] (D.F.); [email protected] (I.G.); [email protected] (A.M.) * Correspondence: [email protected] Abstract: Dehydrogenation processes play an important role in the petrochemical industry. High selectivity towards olefins is usually hindered by numerous side reactions in a conventional crack- ing/pyrolysis technology. Herein, we show recent studies devoted to selective ethylene production via oxidative and non-oxidative reactions. This review summarizes the progress that has been achieved with ethane conversion in terms of the process effectivity. Briefly, steam cracking, catalytic dehydrogenation, oxidative dehydrogenation (with CO2/O2), membrane technology, and chemical looping are reviewed. Keywords: ethylene; ethane; dehydrogenation; cracking; membrane technology; chemical looping 1. Introduction Citation: Fairuzov, D.; Gerzeliev, I.; Ethylene is one of the most critical intermediates in the petrochemical industry and Maximov, A.; Naranov, E. Catalytic the global demand for this chemical is shown in Figure1; it is currently produced through Dehydrogenation of Ethane: A Mini the steam cracking of light hydrocarbon derivatives, mainly ethane and naphtha [1–3]. Review of Recent Advances and Ethylene complexes operate in 57 countries of the world. There are 215 ethylene producing Perspective of Chemical Looping facilities operating in the world. The operators of these complexes are about 100 companies, Technology. Catalysts 2021, 11, 833. and the largest are ExxonMobil, SABIC, DowDuPont [4–6]. -
Steam Cracking: Chemical Engineering
Steam Cracking: Kinetics and Feed Characterisation João Pedro Vilhena de Freitas Moreira Thesis to obtain the Master of Science Degree in Chemical Engineering Supervisors: Professor Doctor Henrique Aníbal Santos de Matos Doctor Štepánˇ Špatenka Examination Committee Chairperson: Professor Doctor Carlos Manuel Faria de Barros Henriques Supervisor: Professor Doctor Henrique Aníbal Santos de Matos Member of the Committee: Specialist Engineer André Alexandre Bravo Ferreira Vilelas November 2015 ii The roots of education are bitter, but the fruit is sweet. – Aristotle All I am I owe to my mother. – George Washington iii iv Acknowledgments To begin with, my deepest thanks to Professor Carla Pinheiro, Professor Henrique Matos and Pro- fessor Costas Pantelides for allowing me to take this internship at Process Systems Enterprise Ltd., London, a seven-month truly worthy experience for both my professional and personal life which I will certainly never forget. I would also like to thank my PSE and IST supervisors, who help me to go through this final journey as a Chemical Engineering student. To Stˇ epˇ an´ and Sreekumar from PSE, thank you so much for your patience, for helping and encouraging me to always keep a positive attitude, even when harder problems arose. To Prof. Henrique who always showed availability to answer my questions and to meet in person whenever possible. Gostaria tambem´ de agradecer aos meus colegas de casa e de curso Andre,´ Frederico, Joana e Miguel, com quem partilhei casa. Foi uma experienciaˆ inesquec´ıvel que atravessamos´ juntos e cer- tamente que a vossa presenc¸a diaria´ apos´ cada dia de trabalho ajudou imenso a aliviar as saudades de casa.