Handbook of Industrial Hydrocarbon Processes PDF
Preview Handbook of Industrial Hydrocarbon Processes
Handbook of INDUSTRIAL HYDROCARBON PROCESSES JAMES G. SPEIGHT PhD, DSc AMSTERDAM(cid:129)BOSTON(cid:129)HEIDELBERG(cid:129)LONDON NEWYORK(cid:129)OXFORD(cid:129)PARIS(cid:129)SANDIEGO SANFRANCISCO(cid:129)SINGAPORE(cid:129)SYDNEY(cid:129)TOKYO GulfProfessionalPublishingisanimprintofElsevier Gulf Professional Publishing is an imprintof Elsevier The Boulevard,Langford Lane, Kidlington,Oxford OX5 1GB, UK 30 Corporate Drive,Suite 400, Burlington, MA 01803, USA Firstedition 2011 Copyright (cid:1) 2011 ElsevierInc. All rightsreserved Nopart of thispublication maybe reproduced,stored ina retrievalsystem or transmitted in anyform or byany means electronic, mechanical, photocopying, recordingorotherwisewithout the prior written permission of the publisher Permissionsmaybe sought directlyfrom Elsevier’sScience &Technology Rights Department in Oxford,UK:phone (+44) (0) 1865 843830; fax (+44) (0)1865 853333; email: [email protected]. Alternativelyyou can submityour requestonline byvisiting the Elsevierweb site at http://elsevier.com/locate/ permissions, and selecting Obtaining permissiontouse Elsevier material Notice Noresponsibility is assumed bythe publisherfor any injuryand/ordamage to persons or propertyasa matterof productsliability,negligence orotherwise, or fromanyuseoroperationofanymethods,products,instructionsorideascontained inthe material herein.Because of rapid advances inthemedicalsciences, in particular,independentverificationofdiagnosesanddrugdosagesshouldbemade British LibraryCataloguing in Publication Data A catalogue record for thisbook isavailablefrom the British Library LibraryofCongressCataloging-in-Publication Data A catalog record for thisbook isavailabefrom the Libraryof Congress ISBN–13: 978-0-7506-8632-7 For informationonallElsevier publications visit our web site at books.elsevier.com Printed and bound inthe UK 11 12 13 14 15 10 9 87 6 5 4 3 2 1 Gulf Professional Publishing is an imprintof Elsevier The Boulevard,Langford Lane, Kidlington,Oxford OX5 1GB, UK 30 Corporate Drive,Suite 400, Burlington, MA 01803, USA Firstedition 2011 Copyright (cid:1) 2011 ElsevierInc. All rightsreserved Nopart of thispublication maybe reproduced,stored ina retrievalsystem or transmitted in anyform or byany means electronic, mechanical, photocopying, recordingorotherwisewithout the prior written permission of the publisher Permissionsmaybe sought directlyfrom Elsevier’sScience &Technology Rights Department in Oxford,UK:phone (+44) (0) 1865 843830; fax (+44) (0)1865 853333; email: [email protected]. Alternativelyyou can submityour requestonline byvisiting the Elsevierweb site at http://elsevier.com/locate/ permissions, and selecting Obtaining permissiontouse Elsevier material Notice Noresponsibility is assumed bythe publisherfor any injuryand/ordamage to persons or propertyasa matterof productsliability,negligence orotherwise, or fromanyuseoroperationofanymethods,products,instructionsorideascontained inthe material herein.Because of rapid advances inthemedicalsciences, in particular,independentverificationofdiagnosesanddrugdosagesshouldbemade British LibraryCataloguing in Publication Data A catalogue record for thisbook isavailablefrom the British Library LibraryofCongressCataloging-in-Publication Data A catalog record for thisbook isavailabefrom the Libraryof Congress ISBN–13: 978-0-7506-8632-7 For informationonallElsevier publications visit our web site at books.elsevier.com Printed and bound inthe USA 11 12 13 14 15 10 9 87 6 5 4 3 2 1 PREFACE This book presents an analysis of the process steps that are required to produce hydrocarbons from various raw materials. The book will demon- strate the means by which hydrocarbons are produced from different raw materials and aims at helping the reader develop an instinct for process development strategy. This book emphasizes conversions, which may be defined as chemical reactions applied to industrial processing. The basic chemistry will be set forth along with easy-to-understand descriptions since the nature of the chemicalreactionwillbeemphasizedinordertoassistintheunderstandingof reactor type and design. In addition, the book contains chapters on the Physical and Chemical Properties of Hydrocarbons; Combustion of Hydrocarbons; Thermal Decomposition of Hydrocarbons; Petrochemicals; Monomers, Polymers, and Plastics; Pharmaceuticals; and finishes with a chapter on the Environ- mental Effects of Hydrocarbons. Thisbookisarrangedinanorganized,easy-to-read,andunderstandable mannerandpresentstheprocessstepsthatarerequiredtoproducechemicals from various raw materials. It will also assist chemists, engineers, and all manufacturing personnel, even specialists, as it is often possible to translate such general procedures from one discipline to another. For the growing number of chemical engineers and scientists who enter sales, executive, or management positions, a broader acquaintance with the chemical industry initsentiretyisessential.Forallthese,thespecialist,thesalesperson,andthe manager, the information is presented in a connected logical manner with an overall viewpoint of many processes. James G.Speight PhD,DSc Laramie,Wyoming June2010 j xiii 11 CHAPTER Chemistry and Chemical Technology Contents 1. Introduction 2 2. Organicchemistry 3 2.1.Thechemicalbond 3 2.2.Bondingincarbon-basedsystems 4 3. Chemicalengineering 7 3.1.Conservationofmass 8 3.2.Conservationofenergy 9 3.3.Conservationofmomentum 9 4. Chemicaltechnology 9 4.1.Historicalaspects 10 4.2.Technologyandhumanculture 11 5. Hydrocarbons 13 5.1.Bondinginhydrocarbons 15 5.2.Nomenclatureofhydrocarbons 16 5.2.1. Alkanes 16 5.2.2. Alkenes 18 5.2.3. Alkynes 19 5.2.4. Cycloalkanes 19 5.2.5.Aromatichydrocarbons 20 5.3.Isomers 24 6. Non-hydrocarbons 25 6.1.Alcohols 26 6.2.Ethers 27 6.3.Aldehydes 27 6.4.Ketones 28 6.5.Organicacids 28 6.6.Esters 28 6.7.Amines 29 6.8.Alkylhalides 30 6.9.Amides 30 7. Propertiesofhydrocarbons 31 7.1.Density 33 7.2.Heatofcombustion(energycontent) 34 7.3.Volatility,flammability,andexplosiveproperties 35 7.4.Behavior 37 HandbookofIndustrialHydrocarbonProcesses (cid:1)2011ElsevierInc. j ISBN978-0-7506-8632-7,doi:10.1016/B978-0-7506-8632-7.10001-5 Allrightsreserved. 1 2 ChemistryandChemicalTechnology 7.5.Liquefiednaturalgas 38 7.6.Environmentalproperties 39 References 41 1. INTRODUCTION Chemistry (from the Arabic al khymia) is the science of matter and is concerned with the composition, behavior, structure, and properties of matter, as well as the changes matter undergoes during chemical reactions. Chemistry is a physical science and is used for the investigation of atoms, molecules,crystals,andotherassemblagesofmatter,whether inisolationor combination, which incorporates the concepts of energy and entropy in relation to the spontaneity or initiation of chemical reactions or chemical processes. Disciplines within chemistry are traditionally grouped by the type of matter being studied or the kind of study and include (alphabetically): (1) analytical chemistry, which is the analysis of material samples to gain an understanding of their chemical composition and structure; (2) biochem- istry, which is the study of substances found in biological organisms; (3) inorganic chemistry, which is the study of inorganic matter (inorganic chemicals, such as minerals); (4) organic chemistry, which is the study of organic matter (organic chemicals, such as hydrocarbons); and (5) physical chemistry,whichis thestudyof theenergyrelations ofchemical systemsat macro, molecular and sub-molecular scales. In fact, the history of human culture can be viewed as the progressive developmentofchemicaltechnologythroughevolutionofthescientificand engineering disciplines in which chemistryand chemical engineering have played major roles in producing a wide variety of industrial chemicals, especially industrial organic chemicals (Ali et al., 2005). Chemical tech- nology, in the context of the present book, relies on chemical bonds of hydrocarbons. Nature has favored the storage of solar energy in the hydrocarbon bonds of plants and animals, and the evolution of chemical technology has exploited this hydrocarbon energy profitably. Thefocusofthisbookishydrocarbonsandthechemistryassociatedwith hydrocarbonsinorganicchemistry,whichwillbeusedtoexplaintheaspects of hydrocarbon properties, structure, and manufacture. The book will provide information relating to the structure and prop- ertiesof hydrocarbonsandtheir productionthroughprocesschemistryand chemical technology to their conversion into commercial products. ChemistryandChemicalTechnology 3 2. ORGANIC CHEMISTRY Organic chemistry is a discipline within chemistry that involves study of the structure, properties, composition, reactions, and preparation (by synthesis or by other means) of carbon-based compounds (in this context – hydrocarbons). On the other hand, inorganic chemistry is the branch of chemistry con- cernedwiththepropertiesandbehaviorofinorganiccompounds.Thisfield covers all chemical compounds except the myriad of carbon-based compounds, such as the hydrocarbons, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, and there is much overlap, most importantly in the sub-discipline of organ- ometallicchemistryinwhichorganiccompoundsandmetalsformdistinctand stable products. An example is tetraethyl lead, which was formerly used in gasoline(untilitwasbannedbyvariousnationalenvironmentalagencies)as an octane enhancer to prevent engine knockingor pinging during operation. Other than this clarification and brief mention here, neither inorganic chemistry nor organometallic chemistry will be described further in this text. Organic compounds are structurally diverse, and the range of applica- tions of organic compounds is enormous. In addition, organic compounds may contain any number of other elements, including nitrogen, oxygen, sulfur, halogens, phosphorus, and silicon. They form the basis of, or are important constituents of, many products (such as plastics, drugs, petro- chemicals,food,explosives,andpaints)and,withveryfewexceptions,they form the basis of all life processes and many industrial processes. 2.1. The chemical bond The most basic concept in all of chemistry is the chemical bond. The chemical bond is essentially the sharing of electrons between two atoms, a sharing which holds or bonds the atoms together. Atoms have three components: protons, neutrons, and electrons. Protonshaveapositivechargeofþ1,neutronshave0charge,andelectrons have a negative charge of –1. The protons and neutrons occupy the center oftheatomasapieceofsolidmattercalledthenucleus.Theelectronsexist in orbitals surrounding the nucleus. In reality, it is impossible to tell the precise trajectory of an electron and the best that can be achieved is to describe the probabilityof locating the electron in a region of space. Thesimplestcaseiswhenthenucleusissurroundedbyjustoneelectron (forexample,thehydrogenatom).Inthiscase,theprobabilityoffindingan 4 ChemistryandChemicalTechnology electron in its lowest energy, or most stable, state is distributed in a spheri- cally symmetric way around the nucleus. The probability of finding the electron is highest at the nucleus and decreases as the distance from the nucleus increases. This lowest energy, spherically symmetric orbital is called the 1s orbital, which is the lowest energy orbital that an electron can occupy, but several higherenergyorbitals aresignificant in organic chemistry. The next lowest energyorbitalthatanelectroncanoccupyisthe2sorbital,whichlooksmuch likethe1sorbitalexcept thattheelectron ismorelikelytobefoundfarther fromthenucleus.Thethirdlowestenergyorbitalisthe2porbital.Themajor and highly important difference between a p orbital and an s orbital is that theporbitalisnotsphericallysymmetricandisorientedalongaspecificaxis in space. There are three p orbitals, which are oriented along the x, y, and z axes. 2.2. Bonding in carbon-based systems A chemicalbond isessentially thesharingof electrons betweentwo atoms. Since electrons are negatively charged and exert an attractive force on nuclei,theyservetoholdtheatomstogetheriftheyarelocatedbetweentwo nuclei. When two atoms approach each other, their atomic orbitals overlap. The overlappedatomicorbitalscanaddtogethertoformamolecularorbital(linear combination of atomic orbitals, LCAO). The area of greatest overlap between the original atomic orbitals represents the chemical bond that is formed between them. Since the sharing of electrons is the basis of the chemical bond, the molecular orbitals formed represent chemical bonds. Forexample,inthecaseofhydrogen,thetwo1sorbitalsgraduallycome closer together until there is a good deal of overlap between them. At this point,theareainspaceofgreatestelectrondensitywillbebetweenthetwo nuclei,which themselveswere atthecenterof theoriginalatomicorbitals. This electron density, now part of a new molecular orbital, represents the chemical bond. When the area of greatest overlap occurs directly between the two nuclei on an axis containing the nuclei of both atoms (internuclear s axis), the bond is a sigma bond ( bond) (Figure 1.1). More than one atomic orbital from a single atom can be used to form newmolecularorbitals.Forexample,a2sorbitalanda2porbitalfromone atom might add together and overlap with one or more orbitals from asecondatomtoformnewmolecularorbitals.Second,partsoforbitalscan ChemistryandChemicalTechnology 5 Figure 1.1 Two hydrogen 1s atomic orbitals overlap to form a hydrogen molecular orbital possessasign(þor–).Thesorbitalhasthesamesignthroughout,whilein theporbitals,onelobeisþandtheotherlobeis–.Signsdonotmatterwith respect to electron density, but they must be taken into account when orbitals are added or subtracted. If two orbitals of the same sign are added, electron density will increase, while if two orbitals of opposite signs are added, the shared electron density will cancel out. Carbonhassixelectrons–onlytwoelectronscanoccupyansorbitalat atime.Thefirsttwoelectronsincarbonoccupythe1sorbitalandthenext twooccupythehigher-energy,butsimilarlyshaped2sorbitalwhilethefinal two electrons occupy the 2p orbitals. In carbon, the electrons in the 1s orbital are too low in energy to form bonds. Thus, electrons used to form bonds must come from the 2s and 2p orbitals. Carbon very often makes four bonds by redistribution of the 2p electrons: Whenitdoesso,thesebondsarearrangedsothattheyareasfarawayfrom each other as possible. This arrangement is referred to as a tetrahedral bond (Figure 1.2). The individual 2s orbital and the 2p orbital cannot form bonds in this arrangementduetotheirgeometry.The2sorbitaliscompletelysymmetric, whilethe2porbitalsarealignedalongspecificaxes.Noneoftheseorbitalsis well-equipped to form bonds in the tetrahedral geometry alone. Since a chemical bond does not have to be formed from individual atomic orbitals, but can be formed from a combination of several atomic orbitals from the same atom, each bond that is made in the tetrahedral geometry, a part of the 2s and a part of each of the 2p orbitals will 6 ChemistryandChemicalTechnology Figure1.2 Tetrahedralgeometryasexhibitedbythecarbonatomsurroundedbyfour hydrogenatoms(methane) (cid:2) contribute,resultinginatetrahedralarrangementandthereisa109.5 angle betweeneachofthebonds(Figure1.2).Toachievethisgeometry,boththe 2s and all three of the 2p orbitals (2p , 2p, and 2p ) must contribute. The x y z new bonds that are formed are called sp3 bonds, since one s orbital and 3 p orbitals were used to form the bonds. Carbonsometimesmakesthreebondsinsteadoffour.Inthiscase,notallof the 2p orbitals combine with the 2s orbital to form bonds. Instead, a combination of the 2s orbital and two of the 2p orbitals make three sp2 bonds,whiletheotherporbitaldoesnotparticipateinthiscombinationand can make a fourth bond on its own. Like the sp3 bonds, the sp2 bonds are oriented such that they are as far away from each other as possible (trigonal planar geometry). Each of the bonds points to one of the vertices of a triangle, but all three bonds are locatedinthesameplane.Theother2porbital,theonewhichdidnotadd to make sp2 bonds, exists perpendicular to the plane in which the sp2 bonds form. It too is able to form bonds, and it does so independently of the sp2 bonds. When two carbon atoms with sp2 orbitals form a bond to each other using their sp2 orbitals, a s bond is formed between them. Moreover, the extraporbitals,whichexistaboveandbeloweachcarbonatom,alsooverlap with each other. This overlap between p orbitals leads to the formation of a second bond in addition to the s bond formed between the sp2 orbitals. Thissecondbondwhichdoesnotoccurdirectlybetweenthenucleionthe p internuclear axis but above and below the internuclear axis is a bond s p (pibond).Whena bondanda bondformtogetherbetweentwoatoms, a double bond is said to have formed (Figure 1.3).
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