PETROLEUM REFINERY ENGINEERING

Petroleum is a combustible oily liquid of reddish brown to almost black colour, produced from oil wells. It is a complex mixture of hydrocarbons and their derivatives containing oxygen, sulphur, nitrogen and minor quantities of some other materials. The importance of petroleum crude oil and natural gas has been realized with the development of its numerous applications as fuel and feedstock. The invention of the internal combustion engines in the last quarter of the nineteenth century gave an impetus to the development of petroleum processing. The most basic refining process is aimed at separating the crude oil into its various components. Crude oil is heated and put into a still -- a distillation column -- and different hydrocarbon components boil off and can be recovered as they condense at different temperatures. Additional processing follows crude distillation, changing the molecular structure of the input with chemical reactions, some through variations in heat and pressure, and some in the presence of a catalyst. The main constituents of petroleum _hydrocarbons _ may differ in the number of carbon and hydrogen atoms in the molecular structure. The hydrocarbons are present in the following groups or homologous series: paraffins (saturated st. chain hydrocarbons, alkanes), naphthenes (cycloalkanes), and benzene hydrocarbons (aromatics). In most grades of petroleum, paraffins and naphthenes prevail mostly. Based on the chemical

composition of the crude

(1) Paraffin-Base Crude Oils These contain higher molecular weight paraffins which are solid at room temperature, but little or no asphaltic (bituminous) matter. They can produce high-grade lubricating oils. (2) Asphaltic-Base Crude Oils Contain large proportions of asphaltic matter, and little or no paraffin. Some are predominantly naphthenes so yield lubricating oil that is more sensitive to temperature changes than the paraffin-base crudes. (3) Mixed-Base Crude Oils The "gray area" between the two types above. Both paraffins and naphthenes are present, as well as aromatic hydrocarbons. Most crude fit this category. CRUDE OIL PHYSICAL PROPERTIES The physical properties of crude are as follows Specific Gravity: 0.669 to 0.99 API Gravity: 10 50

Viscosity: 1 4 centipoises The American Petroleum Institute (API) has developed the term Degrees API Gravity (API) which is widely used as another general characterization of the density of crude oils. The relationship is as follows: API = (141.5/Specific Gravity at 60 degrees Fahrenheit) - 131.5 Specific Gravity at 60 degrees Fahrenheit is the density of the crude oil measured at 60F divided by the density of water at 60F. Therefore, when comparing two crude oils, the higher density crude (i.e., the one with the highest specific gravity) will have a correspondingly lower API. For example, the 34.5API West African crude oil Bonny Light is heavier than the 40.4API North Sea crude oil Forties.

Chemical composition
On an average crude oil is [ultimate analysis] made up of the following components: Carbon - 84% Hydrogen - 14% Sulphur - 1 to 3% (hydrogen sulfide, sulfides, disulfides, elemental sulfur) Nitrogen - less than 1% (basic compounds with amine groups) Oxygen - less than 1% (found in organic compounds such as carbon dioxide, phenols, ketones, carboxylic acids) Metals - less than 1% (nickel, iron, vanadium, copper, arsenic) Salts - less than 1% (sodium chloride, magnesium chloride, calcium chloride) Crude oils are complex mixtures containing many different Hydrocarbons compounds that vary in appearance and composition from one oil field to another. Crude oils are generally classified as paraffinic, napthenic or aromatic based on the predominant proportion of similar Hydrocarbons.

Hydrocarbons found in crude may be of the following types 1. Paraffins (Alkanes) General formula: CnH2n+2 (n is a whole number, usually from 1 to 20) These compounds are saturated hydrocarbons with all carbon bonds satisfied, that is, the hydrocarbon chain carries the full complement of hydrogen atoms. Consist of straight chain (normal)- or branched-chain ( isomers) atoms The lighter straight chain molecules are found in gases and heavier in paraffin waxes. The branched chain (isomer) parrafins are usually found in heavier fractions of crude oil and have higher octane numbers than normal parrafins. examples: methane, ethane, propane, butane, isobutane, pentane, hexane

2. Aromatics General formula: C6H5 - Y (Y is a longer, straight molecule that connects to the benzene ring) They are unsaturated ring type (cyclic) compounds which react because they have carbon atoms that are deficient in hydrogen. ringed structures with one or more rings. They have at least one benzene ring.

rings contain six carbon atoms, with alternating double and single bonds between the carbons typically liquids and are found in heavier fractions of crude oil. examples: benzene, naphthalene

3. Napthenes or Cycloalkanes General formula: CnH2n (n is a whole number usually from 1 to 20) ringed structures with closed rings (cyclic) Found in all fractions of crude except the very lightest. rings contain only single bonds between the carbon atoms typically liquids at room temperature examples: cyclohexane, methyl cyclopentane

Nonhydrocarbons.
1. Sulfur Compounds. Sulfur may be present in crude oil as hydrogen sulfide (H 2S), as compounds (e.g. mercaptans, sulfides, disulfides, thiophenes, etc.) or as elemental sulfur. Each crude oil has different amounts and types of sulfur compounds, but as a rule the proportion, stability, and complexity of the compounds are greater in heavier crude-oil fractions. Hydrogen sulfide is a primary contributor to corrosion in refinery processing units. Other corrosive substances are elemental sulfur and mercaptans. Moreover, the corrosive sulfur compounds have an obnoxious odor. 2. Oxygen Compounds. Oxygen compounds such as phenols, ketones, and carboxylic acids occur in crude oils in varying amounts. 3. Nitrogen Compounds. Nitrogen is found in lighter fractions of crude oil as basic compounds, and more often in heavier fractions of crude oil as non basic compounds that may also include trace metals such as copper, vanadium, and/or nickel. Nitrogen oxides can form in process furnaces. The decomposition of nitrogen compounds in catalytic cracking and hydrocracking processes forms ammonia and cyanides that can cause corrosion. 4. Trace Metals. Metals, including nickel, iron, and vanadium are often found in crude oils in small quantities and are removed during the refining process. Burning heavy fuel oils in refinery furnaces and boilers can leave deposits of vanadium oxide and nickel oxide in furnace boxes, ducts, and tubes. It is also desirable to remove trace amounts of arsenic, vanadium, and nickel prior to processing as they can poison certain catalysts.

Fractionation Processes:
Process name Atmospheric distillation Action separation Method thermal Purpose Separate fractions feedstocks Desalted Crude oil products Gas, Gas oil, distillate, residue Vacuum distillation separation thermal Separate w/o cracking Atm. tower residue Gas oil, lube stock, residue

An oil refinery is an industrial process plant where crude oil is processed and refined into more useful products. Oil refineries are quite large industrial complexes with extensive pipelines carrying streams of fluids between large chemical (thermal and catalytic) processes.
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(Petroleum Gas)

Temperature increases down the column

Petrol Naphtha Kerosene

Diesel

Lubricants

Bitumen

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Catalytic Reforming Although motor gasolines have numerous specifications that must be satisfied to provide the performance demanded by our high-performance motor vehicles, the most widely recognized gasoline specification is the octane number. Gasolines are typically retailed in grades of regular, mid-grade and premium, which are differentiated by the posted octane number. The Octane Number of a test fuel refers to the percentage by volume of
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isooctane in a mixture of isooctane and heptane in a reference fuel that when tested in a laboratory engine, matches the antiknock quality, as measured by a knockmeter, of the fuel being tested under the same conditions. The octane number posted at the gasoline pump is actually the average of the Research Octane Number (RON) and Motor Octane Number (MON), commonly referred to as (R+M)/2. RON and MON are two different test methods that quantify the antiknock qualities of a fuel. Since the MON is a test under more severe conditions than the RON test, for any given fuel, the RON is always higher than the MON. Unfortunately, the desulfurized light and heavy naphtha fractions of crude oils have very low octane numbers. The heavy naphtha fraction is roughly 50 (R+M)/2. Catalytic Reforming is the refinery process that reforms the molecular structure of the heavy naphtha to increase the percentage of high-octane components while reducing the percentage of low-octane components. The hydrocarbon compounds that constitute heavy naphtha are classified into four different categories: paraffins, olefins (a very low percentage of olefins occur in the heavy naphthas from crude), naphthenes and aromatics. In lieu of a complete course in organic chemistry, simplistically the paraffins and olefins are compounds with straight or branched carbon chains, whereas the naphthenes and aromatics are carbon rings. The paraffins and naphthenes are saturated hydrocarbons. Saturated means that they have the maximum number of hydrogen atoms attached to the carbon atoms. The olefins and aromatics, however, are unsaturated hydrocarbons because the compounds contain carbon atoms that are double bonded to other carbon atoms. The straight chain, saturated compounds exhibit very low octane numbers, the branched, saturated compounds exhibit progressively higher octane numbers, while the unsaturated compounds exhibit very high octane numbers. Catalytic Reforming uses a precious metal catalyst (platinum supported by an alumina base) in conjunction with very high temperatures to reform the paraffins and napthenes into high-octane components. Sulfur is a poison to the Catalytic Reforming catalyst, which requires that virtually all the sulfur must be removed from the heavy naphtha through Hydrotreating prior to Catalytic Reforming. Several different types of chemical reactions occur in the Catalytic Reforming reactors.olefins are converted to paraffins, paraffins are isomerized to branched chains and to a lesser extent to naphthenes, and naphthenes are converted to aromatics. Aromatic compounds are essentially unchanged. The resulting reformate product stream from Catalytic Reforming has a RON from 96102 depending on the reactor severity and feedstock quality. The dehydrogenation reactions which convert the saturated naphthenes into unsaturated aromatics produce hydrogen. This hydrogen is available for
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distribution to other refinery processes which consume hydrogen. The Catalytic Reforming process consists of a series of several spherical reactors which operate at temperatures of approximately 900F. The reforming reactions are .endothermic. meaning that the reactions cool the hydrocarbons. The hydrocarbons are re-heated by direct-fired furnaces in between the subsequent reforming reactors. As a result of the very high temperatures, the catalyst becomes deactivated by the formation of .coke. (i.e., essentially pure carbon) on the catalyst which reduces the surface area available to contact with the hydrocarbons. A simplified process flow for the Catalytic Reforming process is presented above.

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Fluidized Catalytic Cracking

The Fluidized Catalytic Cracking (FCC) process unit is considered by many refiners to be the heart of the petroleum refinery. This derives from the fact that the FCC is a key tool to correct the imbalance reflected by the markets demand for predominantly lighter, lower boiling petroleum products, whereas fractionated crude oils typically provide an excess of heavy, high boiling range oils. The FCC process converts heavy gas oils into lighter products which are then used as blend stocks for gasoline and diesel fuels. The olefinic FCC catalytic naphtha product exhibits a very high-octane value for gasoline blending. The FCC process cracks the heavy gas oils by breaking carbon-to-carbon bonds in the large molecules comprising the gas oils and splitting them into multiple smaller molecules which boil at a much lower temperatures. The FCC may achieve conversions of 70-80% of the feed hydrocarbons boiling above the gasoline range (i.e., 430F) to products boiling below 430F. The lower density of the FCC products relative to the gas oil feedstocks has the added benefit of producing a volume gain in which the combined volume of the liquid product streams is greater than the volume of the unit feed stream. Since most petroleum products are bought and sold on a volume basis, the volume gain aspect of the FCC process is a key aspect in how it enhances refinery profitability. The resulting FCC product hydrocarbons are highly olefinic (i.e., unsaturated). Virgin is a term used to distinguish straight-run (i.e., crude distillation and possibly hydrotreated only) hydrocarbons stocks from those that are products of conversion units such as the FCC. The FCC cracking reactions are catalytically promoted at very high temperatures of 950-1,020F. At these temperatures, coke (i.e., essentially pure carbon) formation deactivates the catalyst by blocking catalyst surface area which prevents intimate contact between the catalyst and the hydrocarbons. To retain catalyst activity, the FCC utilizes a very fine powdery, zeolite catalyst that behaves like a fluid (i.e., is able to flow). The fluidized catalyst is continuously circulated in the FCC from the reactor to a regenerator vessel and then returned to the reactor. Coke is removed from the catalyst in the regenerator vessel through the controlled incomplete combustion of the carbon with oxygen to form carbon monoxide and carbon dioxide.

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PETROLEUM REFINERY ENGINEERING

Books for Reference:

1. Petroleum Refinery Engineering, 4th Ed., 1958, W.L. Nelson, McGraw-Hill Book Company 2. Handbook of Petroleum Processes, 3rd Edition, R. A. Meyers McGraw-Hill 3. Fundamentals of Petroleum and Petrochemical Engineering. Uttam Ray Chaudhuri, CRC Press, 2010 4. Mcketta S. (Ed), Petroleum Processing Hbk, Marcell Dekker Inc. 1992. 5. Gary J., Handework G., Petroleum Refining Technology and Economics, Marcell Dekker Inc. 1984. 6. B. K. Bhaskara Rao, "Modern Petroleum Refining Processes",2nd Edn., Oxford and IBH Publishing Company, New Delhi, 1990. 7. G. D. Hobson and W. Pohl., Modern Petroleum Technology", Gulf Publishers, 2nd Ed., 1990 8. An Introduction to Industrial Organic Chemistry, 2nd ed., P. Wiseman, (1979), Applied Science Publishers, London.

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About Fundamentals of Petroleum and Petrochemical Engineering. BY Uttam Ray Chaudhuri, CRC Press, 2010:
The supply of petroleum continues to dwindle at an alarming rate, yet it is the source of a range of products - from gasoline and diesel to plastic, rubber, and synthetic fiber. Critical to the future of this commodity is that we learn to use it more judiciously and efficiently. Fundamentals of Petroleum and Petrochemical Engineering provides a holistic understanding of petroleum and petrochemical products manufacturing, presented in a step-by-step sequence of the entire supply chain. Filled with crucial information relevant to a range of applications, the book covers topics such as: The essential preliminaries for the exploration and production of crude petroleum oil and gas Analysis of crude oil and its petroleum products The processing of petroleum in refineries The fundamentals of lubricating oil and grease Petrochemicals - their raw materials and end products, and manufacturing principles of industrially important products Theories and problems of unit operations and the processes involved in refineries and petrochemical plants Automatic operations in plants Start up, shutdown, maintenance, fire, and safety operations Commercial and managerial activities are necessary for the ultimate success of a refining or manufacturing business. Due to the advancement of technology, new petrochemicals are being invented and will continue to be relevant to the petroleum industry in the near future.

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