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Über dieses Buch

This handbook provides a comprehensive but concise reference resource for the vast field of petroleum technology. Built on the successful book "Practical Advances in Petroleum Processing" published in 2006, it has been extensively revised and expanded to include upstream technologies. The book is divided into four parts: The first part on petroleum characterization offers an in-depth review of the chemical composition and physical properties of petroleum, which determine the possible uses and the quality of the products. The second part provides a brief overview of petroleum geology and upstream practices. The third part exhaustively discusses established and emerging refining technologies from a practical perspective, while the final part describes the production of various refining products, including fuels and lubricants, as well as petrochemicals, such as olefins and polymers. It also covers process automation and real-time refinery-wide process optimization. Two key chapters provide an integrated view of petroleum technology, including environmental and safety issues.Written by international experts from academia, industry and research institutions, including integrated oil companies, catalyst suppliers, licensors, and consultants, it is an invaluable resource for researchers and graduate students as well as practitioners and professionals.

Inhaltsverzeichnis

1. Introduction to Petroleum Technology

When people consider petroleum, they first think of energy. Petroleum and other fossil fuels now provide more than 86% of the energy consumed by mankind. In addition, fossil resources, especially petroleum and natural gas, serve as the organic source of tens of thousands of consumer products, which enrich our daily lives.To understand petroleum and the petroleum industry, one must be familiar with the technology used to find and recover crude oil and natural gas and transform them into useful products. These technologies can also be applied to gases and liquids from coal, shale, and renewable biomass. Research and development aimed at improving or modifying existing technologies and developing new ones usually require physical testing and chemical characterization.Three-dimensional imaging exhibits geological formations most likely to contain oil and gas. Rigorous basin modeling optimizes exploration and production. Modern production technology includes enhancements in horizontal drilling and offshore platform design. The application of hydraulic fracturing to previously unrecoverable oil and gas from tight reservoirs has transformed the United States into the world's leading producer of oil and gas.Midstream technology includes trading, shipping, and transportation, along with processing prior to transportation. Midstream processing includes froth treatment for upgrading bitumen from steam-assisted gravity drainage (SAGDsteam-assisted gravity drainage (SAGD)) into synthetic crude oil (syncrudesynthetic crude (syncrude)). Sophisticated planning models enable global energy companies to quickly decide logistics: which oils to buy, how to allocate them between numerous processing plants, and whether to resell them.Crude oil goes to refineries, which use distillation, treating, conversion, extraction and blending processes to produce fuels, hydrogen, lubricants, waxes, coke products, asphalt, and sulfur. Some refinery streams are sent to petrochemical plants.Ever-improving mathematical models enhance all aspects of petroleum technology. Model-predictive control (MPCmodel-predictive control (MPC)) stabilizes operations and reduces product-quality giveaway, increasing profitability at relatively low cost. The simple return on investment for an MPC project can be 3–4 months. Process engineers rely on rigorous equipment and piping models to optimize designs, not just in the oil and chemical businesses, but in all process industries. With such models, energy consumption in processing plants has been reduced by up to 70% since the 1980s. Rigorous reaction models, based on molecular characterization, serve as the foundation for real-time online economic optimization, in some cases for entire refineries. Economic optimization uses an objective function to find the most profitable balance between equipment constraints, feed quality, product yields, product properties, and utilities costs.One cannot over-emphasize the importance of safety and protection of the environment. Failure to understand technology fundamentals and process details is the root cause of many infamous industrial catastrophes. Lack of understanding of technology fundamentals occurs at all levels, from the control board to the board room. Corporate executives who insist that safety is Number One must invest in safety-enhancing infrastructure. They must ensure that operators are well-trained and equipment is well-maintained.Petroleum will remain significant for decades to come. Hopefully, ever-advancing technology will continue to supply energy and raw materials while protecting workers and the environment.

Paul R. Robinson, Chang Samuel Hsu

2. Safety and the Environment

Safety, reliability, and protecting the environment are inextricably linked. In modern industry, they are prerequisites to profit. Company executives frequently tout their strong commitment to worker health and safety. Their commitment derives to a large extent from strict legislation. Health and safety rules address personal protection equipment, toxic substances, equipment maintenance, worker training, and compliance monitoring. Environmental regulations fall into five main categories: air pollution, waste water, solid wastes, spills, and fugitive emissions. Harm from chronic exposure to pollutants accumulates with time. Harm from major accidents causes tremendous short-term destruction, which often is followed by damage that lingers for years. Many of the worst industrial incidents occur in the coal, oil, and chemical industries. This chapter describes and analyzes numerous examples, many of which are infamous. In most, human misbehavior is the root cause. Misbehavior by unit engineers and operators includes ignoring safety rules, changing procedures without proper management of change, and sabotage. Misbehavior by management includes failing to provide proper training, postponing maintenance, approving substandard equipment, distracting workers (sometimes just with their presence) during safety-sensitive tasks, and understaffing turnarounds with exhausted personnel. Accidents can teach hard lessons. But not everyone learns such lessons, and those who do learn sometimes forget. Others choose to ignore the lessons, because they got away with ignoring them before. Things have gotten better – in developed countries, coal mining companies no longer employ children – but there's still room for improvement.

Paul R. Robinson

3. Molecular Science, Engineering and Management

All organic materials, living and nonliving are made of molecules. Hence, the composition and structuremolecularstructure of the organic molecules, either in pure compounds or different in complex mixtures, determine the properties, behavior, and reactivityreactivity of the compounds and mixtures. Chemistry is a science to study the changes of molecules and the relationship of those changes with physics, mathematics, biology, geology, and other disciplines. Chemistry controls how molecules can be used in exploration/production, refining engineering/processing, chemical production, drug discovery, disease controls, etc.Molecular engineeringmolecularengineering is the science of manufacturing molecules through transformation and/or combination of molecules by engineering processes. It is especially valuable in petroleumpetroleumengineering, where it impacts chemical engineeringchemicalengineering (downstreamdownstream) and petroleum engineering (upstreamupstream), the two major disciplines in which molecules are handled in large scales. Molecular engineering can be guided, controlled, or predicted through molecular-basedmolecular-based modeling modeling.Through knowledge of chemistry and the understanding of chemicalchemicalprocess processes, we can manage molecules more economically, while minimizing harm to life and the environmentenvironmental. Waste molecules must be properly handled and disposed. Hence, science, engineering, and managementmolecularmanagement should be an integral part of handling molecules from the beginning to the end of all chemical and biochemical processesbiochemicalprocess.Detailed information on molecules often requires the use of sophisticated analytical instrumentationanalytical instrumentation. Analytical devices and instruments play key roles in providing information of existing, unknown, or new molecules for the design and control of chemical processes. Analytical research and development have been driven by business needs, market demands, and governmental regulations.In the oiloilindustry sector industry, regardless of sector – upstream, downstream, petrochemical, environmental or modeling, molecular understanding of petroleum and upgrading processesupgrading process is important for science and technology development and the improvement of processes and products.

Chang Samuel Hsu

4. Petroinformatics

Studies on petroleomics have been focused on advanced molecular-level characterization of compounds that could not be analyzed by conventional techniques. The next stage of the development would be more discussions on the information obtained and relationships with the properties and functions. The relationship between molecular composition and bulk properties or functions can be explicitly expressed by petroinformatics, which utilizes statistics, mathematics, and computational visualization technology to interpret or correlate analytical results with bulk properties and experimental data. This provides explicit or implicit information for underlying science and engineering.In this chapter, several examples of petroinformatics are presented. Statistical methods, such as principle component analysis (PCAprincipal componentanalysis (PCA)) for dimensionality reduction in multivariate analysis, and hierarchical clustering analysis (HCAhierarchical clustering analysis (HCA)), have been applied to interpret complex petroleum mass spectra obtained by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MSFourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS)). The mass spectral peaks were statistically analyzed by Spearman's rank correlation, and by correlation diagrams showing relationships between composition and bulk properties. Additionally, the chapter demonstrates quantitative analyses for petroleum samples by PCA for multivariate analysis and t-tests for univariate analysis. Volcano plots are utilized to visualize the quantitative change or difference between samples in detail.The software platform, which integrates data from many samples obtained from different analytical instruments, is a very important tool to achieve more comprehensive understanding of complex analytes such as crude oils. The learnings from other research fields, such as metabolomics, genomics, and proteomics, are important and valuable for the next steps of petroinformatics development, i. e., standardization of data and retrieval of its metadata information.

Manhoi Hur, Sunghwan Kim, Chang Samuel Hsu

5. Separations in the Sample Preparation for Sulfur Compound Analysis

Analytical chemists have been interested in the sulfur compounds found in petroleum for over 100 years. They have developed an impressive array of methods for separating the sulfur compounds from the matrix and for separating the several functional groups from each other. These separations greatly aid in molecular characterization of these materials, which is of fundamental importance in areas such as desulfurization, catalyst development, geochemical studies, etc. Here, such methods are reviewed from the methodological perspective. Chemical transformations have a prominent place in this area and can reversibly or irreversibly change the compounds. Chromatographic separations are shown to have contributed greatly to our knowledge of the composition of petroleum. Areas where current methods fail are also pointed out.

6. Asphaltenes

Asphaltenes are the most enigmatic component of crude oil, and resolution of fundamentals such as asphaltene molecular weight and predominant molecular architecture has been required for the field to advance. Application of many sophisticated analytical methods to asphaltenes has recently given rise to a broad understanding. This chapter reviews many of the most important and recent studies of asphaltene molecular and nanocolloidal structures that have been codified in the Yen–Mullins model. Broad consistency across wide-ranging disciplines has been achieved, yielding robust interpretations. The result that a simple nanoscience model applies to chemically diverse asphaltenes is placed within the context of related similar findings of the gas and liquid components of crude oil. Implications are discussed for thermodynamic modeling of asphaltenes that are specifically treated in the next chapter. In addition to describing measurements of average molecular parameters, this chapter deals with the characterization of the width of certain asphaltene distributions, including molecular weight and the range of asphaltene polycyclic aromatic hydrocarbons (PAHpolycyclic aromatic (PCA)hydrocarbon (PAH)s). The unique role of the asphaltene PAHs in intermolecular interaction is discussed within the context of structure–function relations, for example, for interfacial properties. With these advances, the concept of petroleomics, predictive petroleum science, is realized, even for the most complex fraction of petroleum.

Oliver C. Mullins, Andrew E. Pomerantz, A. Ballard Andrews, Rudraksha Dutta Majumdar, Paul Hazendonk, Yosadara Ruiz-Morales, Lamia Goual, Richard N. Zare

7. Reservoir Evaluation by DFA Measurements and Thermodynamic Analysis

Downhole fluid analysis (DFAdownhole fluid analysis (DFA)) has enabled the cost-effective measurement in oil wells of a variety of chemical properties of reservoir crude oils. An immediate benefit of DFA is the improvement of the sample quality of the reservoir fluid in the subsurface environment. In addition, this early feedback on the nature of the reservoir fluid aids in understanding key reservoir challenges. DFA also enables the accurate determination of fluid gradients in the reservoir in both vertical and lateral directions. These gradients can then be analyzed in a thermodynamic equation of state (EoSequation of state (EoS)) context; the gas-liquid properties can be modeled with the cubic EoS and the asphaltene gradients equilibrium can be modeled with the Flory–Huggins–Zuo (FHZFlory–Huggins–Zuo (FHZ)equation of state (EoS)Flory–Huggins–Zuo (FHZ)) EoS with its reliance on the Yen–Mullins model of asphaltenes. Time-dependent processes in geologic time can be modeled by adding appropriate dynamic terms to the EoS. Simple thermodynamic models can then be used to understand distributions of key fluid properties for reservoir crude oils and aid in simulating production. This thermodynamic analysis of the geodynamics of reservoir fluids fills a gap in the industry's modeling of reservoir fluids. Traditional basin modeling predicts what fluids enter the reservoir. This new geodynamic modeling coupled with DFA measurements determines what transpired in geologic time in regards to fluid distributions within the reservoir. The output of this fluid geodynamic modeling can then be used as input for traditional reservoir simulation for production. This new understanding of reservoir fluid geodynamics is made possible by new DFA measurements coupled with new FHZ EoS with the Yen–Mullins model.

Go Fujisawa, Oliver C. Mullins

8. Phase Behavior and Properties of Heavy Oils

The phase behaviors and thermophysical and transport properties of heavy oilsheavy oil not only share numerous features with light oils and reservoir fluids, but also exhibit substantial differences because of their more complex chemistry and fluid physics associated with this chemistry. As a consequence, conventional understanding, experimental methods, and property/phase behavior computation tools are stretched to their limits. They often fail to provide needed data and insights for process development, design, and operation for production, transport, or refining applications. Heavy oils are inherently multiphase and exhibit time-dependent and polymorphic behaviors that depend not only on temperature and pressure, but also on thermal and shear history as well. Simple properties such as density at fixed temperature and pressure have irreducible uncertainty, and one must think in terms of rheological response rather than viscosity, particularly at low temperatures. Heavy oil characterization poses challenges as well because available analytical tools can provide composition information for less than 50 wt% of typical heavy oils and there is much guess work and correlation needed even to generate composition/property estimates with significant – and hard to quantify uncertainties. In this chapter, we draw upon our diverse experiences to survey the current state of the experimental and computational landscapes related to heavy oil thermophysical and transport properties and phase behavior. Differing and occasionally opposing approaches are presented. Limitations of experimental and computational methods and knowledge needs are discussed, and practical recommendations for specific calculations are noted, typically with caveats. There caveats arise because the landscape is changing rapidly and best practices are evolving continuously, even though we have been producing hydrocarbon resources, transporting, and refining them into diverse products at an industrial scale worldwide for more than a century.

John M. Shaw, Marco A. Satyro, Harvey W. Yarranton

9. Fundamentals of Petroleum Geology

This chapter provides an overview of the fundamental concepts, processes, and theories associated with petroleum exploration and exploitation. The content of this chapter is structured into four main topics. The first topic provides a brief history of the modern petroleum industry and the role that petroleum plays in the society today. The second topic covers the geological basis, and discusses the material, processes, time span, and conditions under which petroleum forms and migrates in rocks. The third topic discusses how petroleum accumulates and concentrates in economic quantities in rocks to warrant exploitation, and the last topic describes the sophisticated methods and techniques that are used in finding, locating, and extracting the petroleum that is found deep in the subsurface. Modern prospecting uses methods of exploration such as three-dimensional seismic surveying and geophysical well logging that have revolutionized how we explore and locate new petroleum reservoirs in the subsurface, to fuel today's fossil fuel addiction. Although petroleum and fossil fuel derivatives have been around for thousands of years, the dominance of petroleum as a global source of energy and petrochemicals products, only developed in the last couple of centuries. Extensive research has led to detailed understanding of the geological and geochemical processes that generate, migrate, and accumulate economic quantities of this essential resource. Additional studies on the source, nature, and composition of petroleum will continue to improve our ability to find, produce, refine, and utilize petroleum products. The chapter concludes with a look at the future of petroleum and its exploration in the world.

Hendratta N. Ali

10. Origin of Petroleum

Theories concerning the origin of oiloilorigin of on Earth fall into two camps: biogenic, where oiloilbiogenicoilabiogenic is generated by the thermal conversion of sedimentary organic matter derived from living organisms, and abiogenic, where oil is formed from mineral catalyzed reactions of nonbiological carbon deep within the Earth. Most geochemists believe that there are multiple and overwhelming lines of evidence supporting biogenic origins for petroleum. While there are known occurrences of abiogenic methane generated by geologic processes, these contribute little to petroleum resources. Economic reserves require all specific elements and processes occur within a sedimentary basin. The Petroleum System must contain: (1) at least one formation of organic-rich sediments (source rock) that has been buried to a sufficient depth by overburden rock such that petroleum is generated and expelled, (2) pathways (permeable strata and faults) that allow the petroleum to migrate, (3) reservoir rocks with sufficient porosity and permeability to accumulate economically significant quantities of petroleum, and (4) seal rock (low permeability) and structures that retain migrated petroleum within the reservoir rock. In the case of many unconventional resources, the source rock itself serves as source, reservoir, and seal.petroleomicsPetroleum, composed of hydrocarbons and heteroatomic molecules, is the most complex mixture occurring in nature. The composition ofpetroleumoriginpetroleumsystem petroleum generated within its source rocksource rock is influenced by the type of organisms that contributed organic matter, the environment of depositiondepositional environment, and thermal exposure. Most of the deposited biomolecules are chemically altered, broken apart, and reassembled into an insoluble carbonaceous material termed kerogen. Upon burial and heating, the kerogen reacts producing mostly compounds that have lost their biochemical signature; however, some of these generated molecules, termed biomarkersbiomarker, preserve enough of their chemical structure that their original biological precursor can be identified. Expulsion from the source rock chemically fractionates the generated petroleum, with the expelled product enriched in gases and hydrocarbons, and retained bitumen enriched in heteroatomic polar species and asphaltenes. Petroleum composition can be further altered as it migrates and resides in reservoir rocks by physical, chemical, and biological processes. Collectively, these processes result in petroleum accumulations with a diverse range of compositions and physical properties.

Clifford C. Walters

11. Basin and Petroleum System Modeling

Since the early 1970s, basin and petroleum system modeling (BPSMbasin and petroleum system modeling (BPSM)) has evolved from a simple tool, used mainly to predict regional source rock thermal maturity, to become a critical component in the worldwide exploration programs of many national and international oil companies for both conventional and unconventional resources. The selection of one-dimensional 1-D, 2-D or 3-D BPSM depends on available input data and project objectives. Organic richness and rock properties must be reconstructed to original values prior to burial. For example, in geohistory analysis each unit is decompacted to original thickness and corrected for paleobathymetry and eustasy. Boundary conditions for thermal evolution include heat flow and sediment-water interface temperature corrected for water depth through time. Default petroleum generation kinetics available in most software should be used only when suitable samples of the source rock organofacies are unavailable. Kinetic parameters are best measured using representative, thermally immature equivalents of the effective source rock. 3-D poroelastic and poroplastic rock stress modeling are significant advances over the 1-D Terzaghi method employed by most software. Calibration should start with the available pressure data, followed by thermal calibration (e. g., corrected borehole temperatures or vitrinite reflectance) and calibration to other measurements (e. g., petroleum composition). The dynamic petroleum system concept has proven to be a more reliable tool for exploration than static play fairway maps used in the past, partly because BPSM accounts for the timing of trap formation relative to generation-migration-accumulation. Tectonic activity and other processes can result in remigration or destruction of accumulations and more than one critical moment on the petroleum system event chart. Organoporosity within the kerogen and solid bitumen accounts for much of the petroleum in unconventional mudstone reservoirs, and secondary cracking of oil to gas is particularly important. Hybrid unconventional systems, which juxtapose ductile organic-rich and brittle, more permeable organic-lean intervals are typically the best producers.

Kenneth E. Peters, Oliver Schenk, Allegra Hosford Scheirer, Björn Wygrala, Thomas Hantschel

12. Seismic Explorations

Geophysics is an extremely diverse subject including fields of study with backgrounds in chemistry, geology, biology, and physics. This chapter attempts to show the reader a broad cross section of the geophysics of petroleum explorationpetroleumexploration. Three fundamental steps exist in the workflow of geophysical petroleum exploration. First, there is the acquisition of seismic data by using initiating acoustic energy into the Earth's subsurface and recording the reflected energy. Second, this raw acoustic data is processed using the physical and mathematical principles of wave propagation and continuum mechanics. Finally the processed seismic data is interpreted. Interpretation endeavors to create a pseudo-geological model from the geophysical data for verification or update by purely geological data. The model is then iteratively updated by both geologists and geophysicists to form a complete risk assessment of a prospective drill location.

Graham Ganssle

13. Formation Evaluation

Petrophysicists utilize laboratory and borehole geophysical measurements as input into petrophysical models to estimate reservoir hydrocarbon resources and recoverable reserves. Unlike surface and airborne geophysicists, who work with one to three scientific disciplines, petrophysicists comfortably work with eight or more scientific disciplines on a daily basis.

Donald G. Hill

14. Petroleum Production Engineering

Petroleum production engineering focuses on producing hydrocarbons from well bottom-hole to surface through the wellborewellbore. In this chapter, the terms inflow performance relationship, tubing performance relationship and choke performance relationship are firstly introduced, which relate the production rates with the in situ pressure along the flow path of the reservoir fluids in the wellbore. Different artificial lift techniques are then discussed to either resume production from a well where no flow is occurring or to achieve a higher production rate by lowering the well flowing bottom-hole pressure. Well stimulation methods, including matrix acidizing and hydraulic fracturing, are finally presented, which enhance the well production rate either by removing the skin from the well, or creating high conductive flow paths for the reservoir fluids to flow to the bottom-hole of the producers.

Shengnan Chen

15. Offshore Production

About 71% of the Earth's surface is under water. It is not surprising that exploration companies pay attention to the bedrock below oceans, treating it as a source of oil and gas. This chapter presents a brief overview of offshore drilling from oceanographic-meteorological, engineering, geological, legal, and historical perspectives. Some topics discussed are the types of rigs and platforms used for offshore drilling and effects of metocean conditions (such as currents, waves, and winds) on these structures and operations; the factors influencing the regions of hydrocarbon potential, and how the coastal state's ownership is defined; and finally, the history of offshore drilling, its current state, and prospects for the future are touched upon.

Ekaterina V. Maksimova, Cortis K. Cooper

16. Petroleum Distillation

Crude oils are complex mixtures of numerous molecules with different boiling points. After removing solid particulates and salts by a desalting process, fractional distillation is the primary means for refineries to separate the molecules into fractions (cuts) continuously. A crude distillation unit includes an atmospheric distillation tower, a vacuum distillation tower, and associated equipment. The cuts can be further processed or upgraded in downstream units – hydrotreaters, catalytic reformers, fluid catalytic cracking units etc. The products of upgrading units often require further separations, usually by distillation for lighter cuts and extraction for heavy cuts.

Chang Samuel Hsu, Paul R. Robinson

17. Gasoline Production and Blending

Gasoline is a volatile, flammable mixture of liquid hydrocarbons primarily obtained from refining petroleum. Most gasoline is consumed as a fuel in spark-ignition engines, primarily those which power automobiles and certain airplanes. For engine performance, important gasoline properties include volatility (Reid vapor pressure), octane number and heat content. Reid vapor pressure (RVP) is one of the gasoline specifications for performance in engine. Reformulated gasoline laws now protect the environment by limiting smog precursors, banning tetraethyl lead (TELtetraethyl lead (TEL)) and regulating concentrations of sulfur, olefins, benzene and oxygenates in gasoline. Refineries produce gasoline from blendstocks derived from various processes – crude oil distillation, catalytic reforming, fluid catalytic cracking (FCC), thermal cracking, hydrocracking, alkylation, isomerization and catalytic polymerization. Finished products sold in the market include additives, which inhibit oxidation, inhibit corrosion, passivate trace metals, reduce deposition of carbon on intake valves and combustion chambers, and minimize the formation of ice in cold weather. Relative gasoline demand is highest in North America, while automotive diesel is preferred in most of the rest of the world.

Chang Samuel Hsu, Paul R. Robinson

18. Catalytic Reforming

Since the early 1940s, dual function catalysts have been converting lower octane, naphtha-range hydrocarbons into aromatics and higher octane blend stock for petrochemical and gasoline production while producing valuable hydrogen as a by-product. Early on, the associated technology became known as catalytic naphtha reforming to acknowledge that the desired products resulted from molecular rearrangement, reforming, of the reactants without alteration of their carbon number. Numerous improvements in catalyst and process technology have been commercialized over the past seven plus decades. Catalytic naphtha reformers remain key units in essentially every refinery and petrochemical plant throughout the world.This chapter provides an overview of catalytic naphtha reforming with sections on the role of catalytic naphtha reforming in the refining and petrochemical industries, naphtha feedstock characteristics, reforming reactions, reforming catalysts, catalyst contaminants, process and catalyst evolution, and catalyst regeneration.

Pierre-Yves le Goff, William Kostka, Joseph Ross

19. Fluid-Bed Catalytic Cracking

Catalytic crackingcatalytic cracking is the thermal decomposition of petroleum constituents in the presence of a catalyst. Refineries use the process cracking to correct the imbalance between the market demand for gasoline and the excess of heavy, high boiling range products (as well as heavy oil and tar sand bitumen) resulting from the distillation of the crude oil. catalytic crackingcatalystcatalytic crackingchemistrycatalytic crackingfeedstockcatalytic crackingheavy oilcatalytic crackingprocess optionscatalytic crackingreactor designcatalytic crackingresidscatalytic crackingchemistryThe typical catalytic cracker that accepted a single-source gas oil feedstock is almost extinct and in the modern refinery is more inclined to be a blend of several high-boiling fractions – often with heavy oil and/or residuum as part of the blend, which has led to the development of residuum fluid catalytic cracking units. In addition to designing new units, as part of the evolutionary process many of the older catalytic cracking units were modified to accommodate more complex feedstocks as well as feedstock blends containing residua. Feedstocks to the modern units now range from blends of gas oil fractions (included in normal heavier feedstocks for upgrading) to residua (reduced crude), heavy oil, and even tar sand bitumen.Fluid catalytic cracking is the most important conversion process used in petroleum refineries to convert the high-boiling feedstock constituents to more valuable naphtha, olefin gases, as well as other products and is likely to remain predominant in the refining industry for at least another three-to-five decades.

James G. Speight

20. Sulfur Removal and Recovery

Petroleum, natural gas and other fossil fuels contain significant amounts of sulfur. When burned, the sulfur becomes sulfur oxides (SO x ), which can cause significant damage to the environment and human health. To minimize such damage and to ensure that finished products meet performance specifications, the sulfur is removed and transformed into useful chemicals, primarily sulfuric acid and fertilizers.About 57% of the world's sulfur is a byproduct of oil and gas processing. The sulfur in natural gas is primarily H2S, sometimes accompanied by mercaptans. The sulfur compounds in heavier fossil fuels include entrained H2S, inorganic sulfur compounds and organic sulfur compounds. For natural gas and petroleum, the predominant sulfur recovery strategy is:1.To convert all sulfur compounds into H2S2.To adsorb the H2S into a solution containing an alkanolamine3.To transport the H2S-laden amine to a sulfur plant4.To convert the H2S into elemental sulfur with the modified Claus process5.To employ Claus tail-gas treatment to increase overall recovery to > 99.5%.Sulfur removal and recovery protects the planet from pollution by sulfur oxides and acids, which continue to threaten our atmosphere, water, land, and inhabitants. The challenge is worldwide, and so must be the solution.

Paul R. Robinson

21. Modern Approaches to Hydrotreating Catalysis

Hydrotreatinghydrotreating (HDT) plays an important role in petroleumpetroleum refiningrefining. Crude oil contains contaminantscontaminant – sulfur, nitrogennitrogen, oxygenoxygen and trace elements – which must be removed to meet productproductspecification specifications. Most refineries include at least three hydrotreating units for upgrading naphtha, middle distillatesdistillate, gas oils, intermediate process streams, and/or residue. Hydrotreating catalysts are the core of the process.This chapter reviews current progress in tackling the issues found in upgrading distillates and residues by hydrotreating and focuses on the chemistry of hydrodesulfurization (HDShydrodesulfurization (HDS)), hydrodenitrogenation (HDNhydrodenitrogenation (HDN)), hydrodeoxygenation (HDOhydrodeoxygenation (HDO)) and hydrolytic demetalization (HDMhydrodemetalation (HDM)). We discuss the composition and functions of hydrotreating catalysts, and we highlight areas for further improvement. The distillate molecules are accessed by gas chromatography-atomic emission detection (GC-AEDgas chromatography (GC)-atomic emission detection (GC-AED)) and gas chromatography-time of flight (GC-TOFgas chromatography (GC)-time of flight (GC-TOF)) to identify and quantify all molecules in the feeds and hydrotreated products. Enhancement of reactivity and suppression of inhibition are discussed based on the molecular structure versus reactivity/inhibition correlations. A molecular approach towards the residue is progressed by applying ultrahigh-resolution Fourier-transform ion cyclotron resonance (FT-ICRFourier-transform ion cyclotron resonance (FT-ICR)asphaltene) mass spectroscopy. Nevertheless, target molecules in resid HDS and HDN are not defined yet due to the polymeric and agglomerated nature of the molecules. Molecular images of sulfur- and nitrogen-containing species are still major targets of hydrotreating. However, porphyrinic metal compounds in the resid, even the asphaltene, can now be detected by GC-AED, gas chromatography-iconductively coupled plasma-mass spectrometry (GC-ICP-MSgas chromatography (GC)-inductively coupled plasma-mass spectrometry (GC-ICP-MS)metalcapacityadsorption) as well as FT-ICR, indicating that the porphyrinic metal compounds can be isolated for observation from the resid and asphaltene matrix under the analytical conditions. The carbon deposit on the catalyst in the HDM is reviewed to show its important influence on capacity and distribution of metal on the catalyst. The carbon deposit is the major issue in hydrotreating. The reactivity of feed molecules for the carbon deposit includes the condensation and adsorption phase separation, which depend on reactivity and dissolution/antidissolution properties of surrounding species as well as the properties of particular molecules concerned. Further challenges in hydrotreating are also discussed concerning the issues picked up in the molecular structure reactivity/inhibition of distillates and residues.

Joo-Il Park, Isao Mochida, Abdulazeem M. J. Marafi, Adel Al-Mutairi

22. Hydrocracking

Hydrocrackinghydrocracking (HC) converts heavy petroleum fractions into lighter products by breaking C−C bonds in the presence of hydrogen. It is in fact a collection of processes which transform a variety of feedstocks into both finished products and streams for further upgrading by downstream units. Hydrocrackers with fixed-bed reactors process straight-run VGOvacuumgas oil (VGO) and/or streams with similar boiling ranges – FCCfluid catalytic cracking (FCC) (Fluid catalytic cracking) cycle oils, coker gas oils, deasphalted oils, etc. Hydrocrackers designed for residue conversion employ ebullated bed (e-bedebullated bed (e-bed)) reactors or slurry-phase reactors. All commercial units consume hydrogen at high pressure, typically 100−200 bar and generate considerable heat.Fixed-bed and e-bed hydrocrackersfixed-bedhydrocrackerhydrocracker (HYC)fixed-bed employ dual-function hydrocracking catalysts, which contain both acid sites and hydrogenation sites. Acidity comes from amorphous aluminosilicates (ASAamorphous silica alumina (ASA)), crystalline zeolites, and related materials such as silica-alumina phosphates (SAPOsilica-alumina phosphate (SAPO)). Hydrogenation activity comes either from noble metals (Pd or Pt) or metals sulfides (MoS2 or WS2). The acid sites catalyze C−C bond cleavage and the resulting fragments are stabilized by hydrogenation on the metal sites. In fixed-bed units, feed contaminants are removed first in a separate catalytic hydrotreating (pretreat) section. The most critical contaminant is organic nitrogen, which inhibits cracking by neutralizing cracking-catalyst acid sites.In slurry-phase processes, the cracking is thermal and the cracked fragments are hydrogenated on highly dispersed additives. Some slurry-phase processes use noncatalytic additives. Additives for other processes are infused with catalytic metal compounds to enhance the conversion. Conversion of vacuum residue can exceed 95 wt%.Products contain only ppm levels of nitrogen and sulfur and low amounts of olefins. Product aromatics are considerably lower than feed aromatics. From fixed-bed units, the heavy naphtha is a preferred feed for catalytic reformers. With some feedstocks under appropriate process conditions, middle distillates meet sales-quality specifications for jet and/or diesel fuels without further treatment. The unconverted oil (UCOunconverted oil (UCO)oilunconverted (UCO)) is a premium feedstock for FCC units. UCO also can go to olefin production plants or lube base stock plants. The UCOs from e-bed and slurry-phase units can go to FCC units, but they tend to contain high concentrations of poly-ring compounds, which makes them less suitable for producing olefins and lube base stocks.Safe operation requires tight control of reaction heat. This is achieved with proper design and effective training of operators, engineers, and managers. Poor decisions based on inadequate understanding of process dynamics and reaction chemistry have caused serious accidents, dozens of injuries, and at least one fatality.

Paul R. Robinson, Geoffrey E. Dolbear

23. Hydroprocessing Reactor Internals

As discussed in other chapters, catalytic hydrotreatingcatalytichydrotreatinghydrotreating (HDT)catalytic upgrades petroleum fractions by saturating olefins and aromatics with hydrogen, and by converting contaminants such as sulfur, nitrogen and sometimes oxygen into H2S, NH3, and H2O respectively. Hydrotreating also remove trace elements such as Ni, V, Fe, Si, As and Hg. Catalytic hydrocracking converts heavy hydrocarbons into lighter material by breaking carbon-carbon bonds.The hydroprocessing process is exothermic, and thus produces heat as the process stream and treat gas are reacted in the catalyst bed. Controlling temperature rise is a major concern during design and operation. Flow distribution is also important. Inside reactors during normal operation, fluid flow is the only significant way to remove process heat. Uneven fluid flow can impair performance. It can lead to hot spot formation, which can jeopardize process safety and catalyst life.While proper catalyst loading and grading is very important, reactor design, specifically the internals, is the key to controlling both the exotherm and fluid flow.This chapter provides an overview of essential components of reactor internals, with emphasis on the relative performance of different designs.

F. Emmett Bingham, Douglas E. Nelson, Daniel Morton

24. Hydrogen Production

Many petroleum refining processes require hydrogen. Some is generated as a by-product from other units, such as catalytic reformers, but additional on-purpose production is required to meet increasing demands to process heavier feeds and meet tighter fuel and lubricant base oil specifications. In this chapter, we describe technology for on-purpose H2 production, which is accomplished by four different processes – steam methane reforming (SMRsteammethane reforming (SMR)), SMR with oxygen enrichment (SMR/O2R), autothermal reforming (ATRautothermal reforming (ATR)), and thermal partial oxidation (POXpartial oxidation (POX)). Designs can be adjusted to produce hydrogen, pure carbon monoxide, or mixtures of H2 and CO (synthesis gas). All aspects of SMR, SMR/O2R, and ATR are described: chemistry and thermodynamics, process design parameters and options, hydrogen purification, environmental protection, operation, process monitoring, processes improvements, safety, and economics.

M. Andrew Crews, B. Gregory Shumake

25. Hydrogen Network Optimization

Plantwide systems impact every process unit in a petroleum refinery. All units require electrical power, water, steam and instrument air. Units with fired heaters burn fuel oil or fuel gas from a common pool. Many units require hydrogen and most produce offgas streams, which are collected and treated in common facilities. In addition to methane and other light hydrocarbons, offgas may contain H2 and toxic H2S. Most modern refineries can benefit from hydrogen recovery and purification. Keeping hydrogen out of fuel gas is beneficial for many reasons. Recovery decreases the required amount of on-purpose hydrogen. Hydrogen burns hotter than other gases, so it raises the temperature of fuel gas combustion, which can limit fired heaters constrained by tube temperature limits. Hydrogen network optimization is more complex that other utility optimization efforts, because in addition to flow and pressure, one must consider the impact of gas composition on the units to which hydrogen gas might be sent. The benefits of hydrogen network optimization with the technology described in this chapter range from US$1 million per year for low- or no-cost recovery and purification projects to more than US$ 15 million per year for modest-investment projects, with payback times measured in months.

Nick Hallale, Ian Moore, Dennis Vauk, Paul R. Robinson

Model-predictive control (MPCmodel-predictive control (MPC)) improves the capability of process units by stabilizing operation, increasing throughput, improving fractionator performance, decreasing product quality giveaway, and reducing utility consumption. MPC provides real-time information to higher-level applications, such as planning models and process optimizers. MPC input comes from the distributed control system (DCSdistributed control system (DCS)), advanced regulatory controllers (ARCadvancedregulatory control (ARC)s), and laboratory data. A well-implemented MPC controller responds once per minute – or in some cases more frequently – to changes in feedstock, ambient temperature, and so on, by moving several variables simultaneously. For major process units, returns on investment for MPC can exceed $0.50 per barrel, not including collateral benefits, such as improving the efficiency of operators and engineers, and improving process safety. Paul R. Robinson, Dennis Cima 27. Modeling Refining Processes Conversion of petroleum fractions and crude oils involves a vast number of chemical species. Modeling of such large reaction systems has been and will continue to be an active research area. There has been an array of approaches bearing on the subject scattered throughout the literature in different contexts. This chapter provides a brief, coherent overview of several selected approaches. The emphasis is on model simplification and mechanism reduction via heuristic concepts and formal mathematical techniques. Among the topics discussed are: top-down and bottom-up kinetic modeling, graph/matrix representation of chemical reactions, mechanistic versus pathways models, quantitative structure–reactivity relationships, asymptotic and optimization methods of dimension reduction, tradeoff between kinetics and hydrodynamics, continuum approximation, collective behavior, and overall kinetics of a large number of reactions. Some common features of dimension reduction approaches are discussed. The areas requiring further investigation are suggested. Teh C. Ho 28. Refinery-Wide Optimization Refinery-wide optimization (RWOrefinery-wide optimization (RWO)) requires integration of several systems – regulatory control, the distributed control system (DCSdistributed control system (DCS)laboratory information management system (LIMS)linearprogram (LP)), the laboratory information management system (LIMS), model-predictive control, online optimization based on rigorous models of individual units and process areas, and refinery planning linear program (LP) software. Project implementation requires communication between refinery personnel – managers, engineers, and operators – and outside modeling experts.Starting in 1998, refinery-wide optimization was implemented at the Suncor refinery in Sarnia, Ontario, Canada. The model-predictive control system was DMCplus. The rigorous models were developed by Aspen Technology, Inc., using Aspen RT-Opt for conventional equipment, a rigorous hydrocracker model developed jointly by Sun Oil and AspenTech, and reactor models developed by AspenTech for the Houdry cracking unit (HCCHoudry cracking unit (HCC)) and a catalytic reformer. Benefits from implementation of an early version of the hydrocracker rigorous model exceeded US$ 3000 per day.

Dale R. Mudt, Clifford C. Pedersen, Maurice D. Jett, Sriganesh Karur, Blaine McIntyre, Paul R. Robinson

29. Rigorous Kinetics Modeling of Hydrogen Synthesis

Closed-loop real-time optimization (CLRTO)closed-loop real-time optimization (CLRTO) with rigorous models improves the profitability of scores of process units in refineries and chemical plants. In addition to optimizing operations, the models serve as the basis for effective process monitoring and the identification of revamp opportunities. Rigor in every part of the plant – equipment, feed definition and reaction kinetics – is the key to success. Equipment constraints define the plant's capability, so CLROT models must include these too. Hydrogen synthesis online optimizers are part of several plant-wide optimizers.This chapter describes the rigorous reaction kinetics employed for CLRTO in steam/hydrocarbon reforming plants. Kinetic relationships are shown for the core reactions, coking in different kinds of equipment, catalyst poisoning, heat transfer, and heat balances. Finally, comparisons are shown between model predictions and plant performance.

Milo D. Meixell

30. Delayed Coking

Thermal processing is the most common refining technique for heavy residues. Thermal processingthermalprocessing techniques include delayed coking, fluid cokingfluidcokingcokingfluid, flexicokingflexicokingcokingflexi-, and visbreakingvisbreaking; of these, delayed coking is by far the most common method of thermal processing, with the ability to produce motor fuels from vacuum tower bottoms with a minimum of capital expenditure. Delayed coking capacity has increased greatly in recent years, mostly due to the heavier crude slates being used in refineries. Although delayed coking is an old process, there are many challenges associated with it, especially as crude slates continue to change and greater throughput is required of delayed coking units.

Keith Wisecarver

31. Transitioning Refineries from Sweet to Extra Heavy Oil

A sweet–sour petroleum refinerysweet–sour petroleum refinery shifting to heavy crude processingheavycrude processing will face a number of challenges, many requiring investment to overcome. The difficulty in processing these feeds is related to the properties of extra-heavy oil, including a high aromatics content and a relatively high concentration of contaminants that pose a threat to reliability and product quality.In this chapter, the relationship between feed composition and unit design is explored, with unit revamp and new-build strategies discussed for process units to adapt to the new crudes. Among other investments, significant scope is likely to include fractionation upgrading for improved removal of asphaltenes, volatile metals, and salts, as well as hydrotreaters modifications to deal with contaminants and counter the hydrogen deficiency of the oil.

Martin R. Gonzalez

32. Carbon Dioxide Mitigation

Stringent regulations on carbon dioxide (CO2) emissions from industrial sources (in general) and petroleum refineries (in particular) are being enforced world wide. Low-sulfur clean fuels enhance the demand for petroleum refinery utility gases (e. g., hydrogen, H2), which in turn leads to an increase in carbon-emission-intensive processes. This will ultimately force refineries to start implementing CO2 mitigation measures, which are increasingly evident in the strategies of industrial countries. In this work, we describe the major processes that contribute to a typical petroleum refinery's global CO2 emissions. Typical sources include unit utilities (i. e., heaters, boilers, and furnaces), fluid catalytic cracking units, hydrogen production (HP) units, flaring, and acid gas removal. A case study for a mega refinery structure is also given detailing a methodology for estimating CO2 emissions from various processes. The carbon footprint and specific emissions of various sources being considered are also reported.

Sultan M. Al-Salem, Xiaoliang Ma, Mubarak M. Al-Mujaibel

33. Conventional Lube Base Stock

This chapter reviews the basic unit processes in modern conventional lube manufacturing. As this is a large subject area, this chapter will focus on giving the reader an overview of the major processes most frequently found in the lube-manufacturing plant. It will neither cover all technologies or processes nor will it discuss detailed plant design and operation as this would easily require another book. The reader should come away with a general understanding of the conventional lube-manufacturing process and key factors affecting the unit processes.

Brent E. Beasley

34. Premium Lubricant Base Stocks by Hydroprocessing

This chapter discusses the manufacture of premium lubricant base stocks using hydroprocessing technology. After a brief introduction about base stock demand and key base stock properties, we discuss the benefits of premium base stocks versus solvent-refined base stocks and how premium stocks help to meet the stringent specifications of automotive engine oils. The focus of this chapter is on the chemistry and processing of base stocks by modern refining technology, which includes hydrocracking, hydroisomerization, and hydrofinishing. Also included is a brief discussion of syngas-to-liquids (STLsyngas-to-liquids (STL)), also called gas-to-liquids (GTLgas-to-liquid (GTL)s).

Stephen K. Lee, John M. Rosenbaum, Yalin Hao, Guan-Dao Lei

35. Synthetic Lubricant Base Stock

Conventional lubricants are formulated using mineral base stocks, which are refined from petroleum and contain many chemical species. Although mineral base stocks serve general-purpose lubricants well, they cannot be optimized for specific performance features. Modern machines and equipment are increasingly designed to operate under more severe conditions, to require less maintenance, to have improved longevity and better energy efficiency. Sometimes, conventional lubricants based on mineral base stocks fail to meet these elevated performance requirements. Synthetic lubricants using tailored synthetic base stocks are designed to meet these higher performance needs and can provide superior performance and economic benefits over conventional lubricants.In this chapter, we briefly discuss the history of synthetic lubricant development to understand the fundamental driving forces behind the use of synthetic lubricants, which have synthetic base stocks as the main components. The major part of the chapter is devoted to discussing the key synthetic base stocks, polyalphaolefins (PAOpolyalphaolefin (PAO)), esters and polyalkyleneglycols (PAGpolyalkyleneglycol (PAG)) – their chemistries, manufacturing processes, product properties, performance features, major applications and advantages compared with mineral base stocks. Additional discussions on less widely used synthetic base stocks, such as alkylaromatics, polyisobutylene and phosphate esters, are briefly reviewed for completeness.

Margaret M. Wu, Suzzy C. Ho, Shuji Luo

36. Catalytic Processes for Light Olefin Production

Up to now, the major process for light olefin production has been thermal steam cracking. The diversification of feedstocks from heavy oil fractions to light hydrocarbons as well as methanol led to the development of catalytic processes. Differing from the radical mechanism for olefin formation by the thermal process, there are two reaction mechanisms for the description of olefin formation in the catalytic process: the carbocation mechanism for hydrocarbon cracking and the hydrocarbon pool mechanism for methanol to light olefin.Deep catalytic cracking (DCCdeepcatalytic cracking (DCC)catalytic crackingdeep (DCC)), developed by the Research Institute of Petroleum Processing (RIPP) of Sinopec, is a fluidized catalytic cracking process that uses a proprietary catalyst for the selective cracking of a wide variety of heavy feedstocks to produce light olefins. The catalytic pyrolysis process (CPPcatalyticpyrolysis process (CPP)pyrolysiscatalytic (CPP)), also developed by RIPP of Sinopec, is an extension of DCC that gives an increased ethylene yield while keeping propylene production at a reasonable rate. The commercial units run worldwide showing the success of the development of these processes.The key process features, the representative catalysts, and the performance of PetroFCC, Propylur, SuperFLEX, propylene catalytic cracking, olefins catalytic cracking, olefins conversion technology, propane dehydrogenation, and methanol-to-olefins are also briefly introduced.In future, for the production of light olefin, catalytic processing is the key step to integrate the refining and petrochemicals plants.

Genquan Zhu, Chaogang Xie, Zaiting Li, Xieqing Wang

37. Polyolefins

The petroleum refining industry produces small fractions of volatile olefins in addition to transportation fuels such as gasoline. In aggregate, these olefins represent very large quantities because of the huge scale of the primary refining industry. The availability of these olefins has given rise to a worldwide polyolefinpolyolefin industry which makes most of the common rubbers and plastics in use today. These olefins are converted to high polymers by the process of polymerization. The polymers span an unexpected range of thermal and mechanical properties. The introduction and the acceptance of these polymers arise from continuous innovation which improves the properties for use. The introduction of new fabrication processes allow the utilization of novel methods to produce forms with typical densities at or below 1.00 gm∕cc, leading to lightweight materials.

David Fiscus, Antonios Doufas, Sudhin Datta

38. Biomass to Liquid (BTL) Fuels

We introduce a strategy for biomass fractionation and refinerybiomassbiomassfractionationbiorefinery co-processing. Some of the leading conversion technologies areco-processing, biomass oil and petroleum oil reviewed, including pretreatment-hydrolysis (for 2nd-generationbiofuel2nd generationhydrolysispretreatment biofuels), gasification and Fischer–Tropsch (FT) synthesis, pyrolysis, and aqueous phase reforming (APR), along withpyrolysis some of the current challenges for commercialization. The main objective is to give an overview and recommendations in regard to the co-processing of biomass oil with crude oil that includes somebio-oil (biomass oil) of the developed technologies, as well as providing a new theoretical approach to the co-utilization of these raw materials. This new approach utilizes biomass to undergo 2nd-generation conversion processes where it is fractionated into relatively pure streams of soluble cellulosic/hemicellulosic sugars and residual solid ligninhemicelluloselignin (non-sugar) fractions. The cellulose/lignin fractionation would alsocellulose facilitate the development of new-generation characterization schemes to reduce interference between sugar and non-sugar components. Upgrading and reforming techniques such as gasificationgasification and Fischer–Tropsch (FT) synthesis, pyrolysis, or aqueous phaseFischer–Tropsch (FT)synthesis reforming (APR) can then be adopted for use with these fractions to generate feedstocks such as bio-oils that resemble those used within a petroleum refinery. If treated properly these biomass-derived oils have been shown to resemble crude-derived oil feeds and when supplemented in large quantities to process feeds can produce equivalent fuels and chemicals to that of petroleum crude oil. Consequently, dependence on fossil fuels will be reduced, among other advantages such as a reduction in greenhouse gas (GHG)greenhouse gas (GHG) emission, while still utilizing in-place technologies and with lower capital investments compared to earlier generations of biofuels.

Gary Brodeur, Subramanian Ramakrishnan, Chang Samuel Hsu

39. Renewable Diesel and Jet Fuels

Hydroprocessing offers great potential for producing renewable diesel compatible with existing infrastructure and engine technology. This chapter discusses the catalyst technology and the process technology required to convert renewable feed sources such as triglyceride-based vegetable oil, used cooking oil, animal tallow and algae oils into transportation fuels.

Henrik Rasmussen

40. Small Scale Catalytic Syngas Production with Plasma

The production of syngas has been desired for nearly a century as a starting point towards an effort to achieve the synthesis of higher-energy liquid fuels. Methods that are utilized for obtaining syngas have undergone profound technological transformations over the years. The formation of plasma is one such concept capable of energizing molecular chains through dielectric manipulation in order to excite electrons and form radicals. Many types of plasma configurations exist under a range of variable parameters such as pressure, temperature, current, power intensity, and physical structure. Nonthermal plasma in conjunction with catalysis is a relatively new concept that takes a more subtle approach that eliminates the intensive energy requirement while maintaining high conversion efficiency. The technology and process presented in this book chapter will encompass a hybrid plasma/catalysis (PRISM) system having the ability to ionize and reform any vapor phase species with a focus on short to long chain hydrocarbons. The apparatus promotes reactions that would otherwise be disadvantageous from either a high activation energy standpoint or from the yield of unfavorable side products. Catalytic partial oxidation (CPOXcatalyticpartial oxidation (CPOX)) using a low-energy, nonthermal plasma is capable of nearly perfect conversion of a carbonaceous starting material into clean, homogeneous, hydrogen-rich syngas.

Adam A. Gentile, Leslie Bromberg, Michael Carpenter

41. Hydrocarbon Processing by Plasma

Nonthermal plasma processes have been successfully utilized commercially in air pollution control, ozone generation, polymerization processes, and microelectronics processing. The addition of a liquid phase that contacts the plasma has given rise to a wide range of other potential applications in materials synthesis, biomedicine, and chemical synthesis. Applications in the petroleum and energy fields utilizing organic chemistry plasma processes have been investigated as well, for example, in hydrogen generation, gas reforming, and partial oxidation. Partial oxidation of hydrocarbons is a longstanding challenge in organic chemistry, and recent work with plasma and plasma contacting liquids have demonstrated the formation of alcohols and other oxygenated species from a range of hydrocarbons. This review focuses on the functionalizationfunctionalization of hydrocarbons with radical species produced by nonthermal plasma discharges primarily in oxygen and argon gases with liquid water. Since the types of chemical reactions that can be induced by plasma depend strongly on the composition of the gases utilized, the reactor configuration, and the plasma properties, we address two major ways of functionalizing hydrocarbons with plasma; 1) utilization of oxygen radicals from molecular oxygen and 2) utilization of hydroxyl radicals from liquid water. Both methods supply oxidants that lead to similar reaction product distributions and such plasma processesplasmaprocessing have the potential to produce value-added products efficiently and with reduced environmental impact.

Robert J. Wandell, Bruce R. Locke

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