• Introduction

• Distillation Processes

• Thermal Cracking Processes

• Catalytic Processes

• Treatment Processes

• History of Refining

• Basics of Crude Oil

• Typical Characteristics of various crudes

• Basics of Hydrocarbon Chemistry

• Principal Groups of Hydrocarbon

• Other Hydrocarbons

• Non-hydrocarbons

• Major Refinery Products

• Common Refinery Chemicals

Introduction

Petroleum refining has evolved continuously in response to changing consumer demand for better and different products. The original requirement was to produce kerosene as a cheaper and better source of light than whale oil. The development of the internal combustion engine led to the production of gasoline and diesel fuels. The evolution of the airplane created an initial need for high-octane aviation gasoline and then for jet fuel, a sophisticated form of the original product, kerosene. Present-day refineries produce a variety of products including many required as feedstock for the petrochemical industry.

Distillation Processes

The first refinery, opened in 1861, produced kerosene by simple atmospheric distillation. Its by-products included tar and naphtha. It was soon discovered that distilling petroleum under vacuum could produce high-quality lubricating oils. However, for the next 30 years kerosene was the product consumer wanted. Two significant events changed this situation. The invention of the electric light decreased the demand for kerosene and the invention of the internal combustion engine created a demand for diesel fuel and gasoline (naphtha).

Thermal Cracking Processes

With the advent of mass production and World War I, the number of gasoline-powered vehicles increased dramatically and the demand for gasoline grew accordingly. However, distillation processes produced only a certain amount of gasoline from crude oil. In 1913, the thermal cracking process was developed, which subjected heavy fuels to both pressure and intense heat, physically breaking the large molecules into smaller ones to produce additional gasoline and distillate fuels. Visbreaking, another form of thermal cracking, was developed in the late 1930's to produce more desirable and valuable products.

Catalytic Processes

Higher-compression gasoline engines required higher-octane gasoline with better antiknock characteristics. The introduction of catalytic cracking and polymerization processes in the mid- to late 1930's met the demand by providing improved gasoline yields and higher octane numbers.   Alkylation, another catalytic process developed in the early 1940's, produced more high-octane aviation gasoline and petrochemical feedstock for explosives and synthetic rubber. Subsequently, catalytic isomerization was developed to convert hydrocarbons to produce increased quantities of alkylation feedstock. Improved catalysts and process methods such as hydrocracking and reforming were developed throughout the 1960's to increase gasoline yields and improve antiknock characteristics. These catalytic processes also produced hydrocarbon molecules with a double bond (alkenes) and formed the basis of the modern petrochemical industry.

Treatment Processes

Throughout the history of refining, various treatment methods have been used to remove non-hydrocarbons, impurities, and other constituents that adversely affect the properties of finished products or reduce the efficiency of the conversion processes. Treating can involve chemical reaction and/or physical separation. Typical examples of treating are chemical sweetening, acid treating, clay contacting, caustic washing, hydrotreating, drying, solvent extraction, and solvent dewaxing. Sweetening compounds and acids desulfurize crude oil before processing and treat products during and after processing.

Following the Second World War, various reforming processes improved gasoline quality and yield and produced higher-quality products. Some of these involved the use of catalysts and/or hydrogen to change molecules and remove sulfur.

History of Refining

Basics of Crude Oil

Crude oils are complex mixtures containing many different hydrocarbon compounds that vary in appearance and composition from one oil field to another. Crude oils range in consistency from water to tar-like solids, and in color from clear to black. An "average" crude oil contains about 84% carbon, 14% hydrogen, 1%-3% sulfur, and less than 1% each of nitrogen, oxygen, metals, and salts. Crude oils are generally classified as paraffinic, naphthenic, or aromatic, based on the predominant proportion of similar hydrocarbon molecules. Mixed-base crudes have varying amounts of each type of hydrocarbon. Refinery crude base stocks usually consist of mixtures of two or more different crude oils.

Relatively simple crude oil assays are used to classify crude oils as paraffinic, naphthenic, aromatic, or mixed. One assay method (United States Bureau of Mines) is based on distillation, and another method (UOP "K" factor) is based on gravity and boiling points. More comprehensive crude assays determine the value of the crude (i.e., its yield and quality of useful products) and processing parameters. Crude oils are usually grouped according to yield structure.

Crude oils are also defined in terms of API (American Petroleum Institute) gravity. The higher the API gravity, the lighter is the crude. For example, light crude oils have high API gravities and low specific gravities. Crude oils with low carbon, high hydrogen, and high API gravity are usually rich in paraffins and tend to yield greater proportions of gasoline and light petroleum products; those with high carbon, low hydrogen, and low API gravities are usually rich in aromatics.

Crude oils that contain appreciable quantities of hydrogen sulfide or other reactive sulfur compounds are called "sour." Those with lower sulfur are called "sweet." Some exceptions to this rule are West Texas crudes, which are always considered "sour" regardless of their H₂S content and Arabian high-sulfur crudes, which are not considered "sour" because their sulfur compounds are not highly reactive.

Typical Characteristics of various crudes

Basics of Hydrocarbon Chemistry

Crude oil is a mixture of hydrocarbon molecules, which are organic compounds of carbon and hydrogen atoms that may include from one to 60 carbon atoms. The properties of hydrocarbons depend on the number and arrangement of the carbon and hydrogen atoms in the molecules. The simplest hydrocarbon molecule is one carbon atom linked with four hydrogen atoms: methane. All other variations of petroleum hydrocarbons evolve from this molecule.

Hydrocarbons containing up to four carbon atoms are usually gases, those with 5 to 19 carbon atoms are usually liquids and those with 20 or more are solids. The refining process uses chemicals, catalysts, heat, and pressure to separate and combine the basic types of hydrocarbon molecules naturally found in crude oil into groups of similar molecules. The refining process also rearranges their structures and bonding patterns into different hydrocarbon molecules and compounds. Therefore it is the type of hydrocarbon (paraffinic, naphthenic, or aromatic) rather than its specific chemical compounds that is significant in the refining process.

Principal Groups of Hydrocarbon

• Paraffins - The paraffinic series of hydrocarbon compounds found in crude oil have the general formula C_nH_2n+2 and can be either straight chains (normal) or branched chains (isomers) of carbon atoms. The lighter, straight chain paraffin molecules are found in gases and paraffin waxes. Examples of straight-chain molecules are methane, ethane, propane, and butane (gases containing from one to four carbon atoms), and pentane and hexane (liquids with five to six carbon atoms). The branched-chain (isomer) paraffins are usually found in heavier fractions of crude oil and have higher octane numbers than normal paraffins. These compounds are saturated hydrocarbons, with all carbon bonds satisfied, that is, the hydrocarbon chain carries the full complement of hydrogen atoms.

  • Example of simplest hydrocarbon molecule: Methane (CH₄), Examples of straight chain paraffin molecule (Butane) and branched paraffin molecule (Isobutane) with same chemical formula (C₄H₁₀)

• Aromatics - Aromatics are unsaturated ring-type (cyclic) compounds which react readily because they have carbon atoms that are deficient in hydrogen. All aromatics have at least one benzene ring (a single-ring compound characterized by three double bonds alternating with three single bonds between six carbon atoms) as part of their molecular structure. Naphthalenes are fused double-ring aromatic compounds. The most complex aromatics, polynuclears (three or more fused aromatic rings), are found in heavier fractions of crude oil.

  • Example of simple aromatic compound: Benzene (C₆H₆), Examples of simple double-ring aromatic compound: Naphthalene (C₁₀H₈)

• Naphthenes - Naphthenes are saturated hydrocarbon groupings with the general formula C_nH_2n, arranged in the form of closed rings (cyclic) and found in all fractions of crude oil except the very lightest. Single-ring naphthenes (monocycloparaffins) with five and six carbon atoms predominate, with two-ring naphthenes (dicycloparaffins) found in the heavier ends of naphtha.

  • Example of typical single-ring naphthene: Cyclohexane (C₆H₁₂), Examples of naphthene with same chemical formula (C₆H₁₂) but different molecular structure: Methyl cyclopentane (C₆H₁₂)

Other Hydrocarbons

• Alkenes - Alkenes are mono-olefins with the general formula C_nH_2n and contain only one carbon-carbon double bond in the chain. The simplest alkene is ethylene, with two carbon atoms joined by a double bond and four hydrogen atoms. Olefins are usually formed by thermal and catalytic cracking and rarely occur naturally in unprocessed crude oil.

  • Example of simples Alkene: Ethylene (C₂H₄), Typical Alkenes with the same chemical formula (C₄H₈) but different molecular structures: 1-Butene and Isobutene

• Dienes and Alkynes - Dienes, also known as diolefins, have two carbon-carbon double bonds. The alkynes, another class of unsaturated hydrocarbons, have a carbon-carbon triple bond within the molecule. Both these series of hydrocarbons have the general formula CnH2n-2. Diolefins such as 1,2-butadiene and 1,3-butadiene, and alkynes such as acetylene,occur in C5 and lighter fractions from cracking. The olefins, diolefins, and alkynes are said to be unsaturated because they contain less than the amount of hydrogen necessary to saturate all the valences of the carbon atoms. These compounds are more reactive than paraffins or naphthenes and readily combine with other elements such as hydrogen, chlorine, and bromine.

  • Example of simplest Alkyne: Acetylene (C₂H₂), Typical Diolefins with the same chemical formula (C₄H₆) but different molecular structures: 1,2-Butadiene and 1,3-Butadiene

Non-hydrocarbons

• Sulfur Compounds -  Sulfur may be present in crude oil as hydrogen sulfide (H₂S), as sulfur compounds such as 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.  Pyrophoric iron sulfide results from the corrosive action of sulfur compounds on the iron and steel used in refinery process equipment, piping, and tanks. The combustion of petroleum products containing sulfur compounds produces undesirables such as sulfuric acid and sulfur dioxide. Catalytic hydrotreating processes such as hydrodesulfurization remove sulfur compounds from refinery product streams. Sweetening processes either remove the obnoxious sulfur compounds or convert them to odorless disulfides, as in the case of mercaptans.

• Oxygen Compounds -  Oxygen compounds such as phenols, ketones, and carboxylic acids occur in crude oils in varying amounts.

• Nitrogen Compounds -  Nitrogen is found in lighter fractions of crude oil as basic compounds, and more often in heavier fractions of crude oil as nonbasic 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.

• 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.

• Salts -  Crude oils often contain inorganic salts such as sodium chloride, magnesium chloride, and calcium chloride in suspension or dissolved in entrained water (brine). These salts must be removed or neutralized before processing to prevent catalyst poisoning, equipment corrosion, and fouling. Salt corrosion is caused by the hydrolysis of some metal chlorides to hydrogen chloride (HCl) and the subsequent formation of hydrochloric acid when crude is heated. Hydrogen chloride may also combine with ammonia to form ammonium chloride (NH₄Cl), which causes fouling and corrosion.

• Carbon Dioxide -  Carbon dioxide may result from the decomposition of bicarbonates present in or added to crude, or from steam used in the distillation process.

• Naphthenic Acids -  Some crude oils contain naphthenic (organic) acids, which may become corrosive at temperatures above 450° F when the acid value of the crude is above a certain level.

 Major Refinery Products

• Gasoline. The most important refinery product is motor gasoline, a blend of hydrocarbons with boiling ranges from ambient temperatures to about 400 °F. The important qualities for gasoline are octane number (antiknock), volatility (starting and vapor lock), and vapor pressure (environmental control). Additives are often used to enhance performance and provide protection against oxidation and rust formation.
• Kerosene. Kerosene is a refined middle-distillate petroleum product that finds considerable use as a jet fuel and around the world in cooking and space heating. When used as a jet fuel, some of the critical qualities are freeze point, flash point, and smoke point. Commercial jet fuel has a boiling range of about 375°-525° F, and military jet fuel 130°-550° F. Kerosene, with less-critical specifications, is used for lighting, heating, solvents, and blending into diesel fuel.
• Liquified Petroleum Gas (LPG). LPG, which consists principally of propane and butane, is produced for use as fuel and is an intermediate material in the manufacture of petrochemicals. The important specifications for proper performance include vapor pressure and control of contaminants.
• Distillate Fuels. Diesel fuels and domestic heating oils have boiling ranges of about 400°-700° F. The desirable qualities required for distillate fuels include controlled flash and pour points, clean burning, no deposit formation in storage tanks, and a proper diesel fuel cetane rating for good starting and combustion.
• Residual Fuels. Many marine vessels, power plants, commercial buildings and industrial facilities use residual fuels or combinations of residual and distillate fuels for heating and processing. The two most critical specifications of residual fuels are viscosity and low sulfur content for environmental control.
• Coke and Asphalt. Coke is almost pure carbon with a variety of uses from electrodes to charcoal briquets. Asphalt, used for roads and roofing materials, must be inert to most chemicals and weather conditions.
• Solvents. A variety of products, whose boiling points and hydrocarbon composition are closely controlled, are produced for use as solvents. These include benzene, toluene, and xylene.
• Petrochemicals. Many products derived from crude oil refining, such as ethylene, propylene, butylene, and isobutylene, are primarily intended for use as petrochemical feedstock in the production of plastics, synthetic fibers, synthetic rubbers, and other products.
• Lubricants. Special refining processes produce lubricating oil base stocks. Additives such as demulsifiers, antioxidants, and viscosity improvers are blended into the base stocks to provide the characteristics required for motor oils, industrial greases, lubricants, and cutting oils. The most critical quality for lubricating-oil base stock is a high viscosity index, which provides for greater consistency under varying temperatures.

Common Refinery Chemicals

• Leaded Gasoline Additives. Tetraethyl lead (TEL) and tetramethyl lead (TML) are additives formerly used to improve gasoline octane ratings but are no longer in common use except in aviation gasoline.
• Oxygenates. Ethyl tertiary butyl ether (ETBE), methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME), and other oxygenates improve gasoline octane ratings and reduce carbon monoxide emissions.
• Caustics. Caustics are added to desalting water to neutralize acids and reduce corrosion. They are also added to desalted crude in order to reduce the amount of corrosive chlorides in the tower overheads. They are used in some refinery treating processes to remove contaminants from hydrocarbon streams.

• Sulfuric Acid and Hydrofluoric Acid. Sulfuric acid and hydrofluoric acid are used primarily as catalysts in alkylation processes. Sulfuric acid is also used in some treatment processes.