Indstrias Qumicas e Biolgicas

Petrleo Bruto. Extraco e refinao

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Petroleum Definitions

Petroleum is a complex mixture of hydrocarbons that occur in the sedimentary rocks in the form of gases (natural gas), liquids (crude oil), semisolids (bitumen), or solids (wax or asphaltite). An underground reservoir that contains hydrocarbons is called petroleum reservoir and its hydrocarbon contents that can be recovered through a producing well is called reservoir fluid.

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Petroleum Definitions

Paraffins
Generally, hydrocarbons are divided into four groups: paraffins, olefins, naphthenes and aromatics. Paraffins are also called alkanes and have the general formula of CnH2n+2, where n is the number of carbon atoms. Paraffins from C1 to C40 usually appear in crude oil and represent up to 20% of crude by volume. Since paraffins are fully saturated (no double bond), they are stable and remain unchanged over long periods of geological time.

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Petroleum Definitions

Olefins
Olefins are another series of noncyclic hydrocarbons but they are unsaturated and have at least one double bond between carbon-carbon atoms. Compounds with one double bond are called monoolefins or alkenes. Monoolefins have a general formula of CnH2n. Olefins are uncommon in crude oils due to their reactivity with hydrogen that makes them saturated; however, they can be produced in refineries through cracking reactions.

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Petroleum Definitions

Naphthenes
Naphthenes or cycloalkanes are ring or cyclic saturated hydrocarbons with the general formula of CnH2n. Cyclopentane (C5H10), cyclohexane (C6H12), and their derivatives such as n-alkylcyclopentanes are normally found in crude oils. Thermodynamic studies show that naphthene rings with five and six carbon atoms are the most stable naphthenic hydrocarbons. The content of cycloparaffins in petroleum may vary up to 60%.

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Petroleum Definitions

Aromatics
Aromatics are an important series of hydrocarbons found in almost every petroleum mixture from any part of the world. Aromatics are cyclic but unsaturated hydrocarbons that begin with benzene molecule (C6H6) and contain carbon-carbon double bonds. Some of the common aromatics found in petroleum and crude oils are benzene and its derivatives with attached methyl, ethyl, propyl, or higher alkyl groups. This series of aromatics is called alkylbenzenes and have a general formula of CnH2n-6 (where n 6).
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Petroleum Definitions

Sulfur content
Sulfur is the most important heteroatom in petroleum and it can be found in cyclic as well as noncyclic compounds such as mercaptanes (R-S-H) and sulfides (R-S-R), where R and R are alkyl groups. Sulfur in natural gas is usually found in the form of hydrogen sulfide (H2S). Some natural gas contain H2S as high as 30% by volume. The amount of sulfur in a crude may vary from 0.05 to 6% by weight.

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Destilao atmosfrica e em vcuo

A empresa que mais refinarias tem construdo no mundo a UOP (Universal Oil Products) pertencente Honeywell http://www.uop.com/.

Crude oil is a non-uniform material. The composition depends on its location.

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Destilao atmosfrica e em vcuo

The majority of crude oil is alkanes, cycloalkanes (naphthenes), aromatics, polycyclic aromatics, S-containing compounds, etc. Gasoline: branched alkanes Diesel: linear alkanes

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Destilao atmosfrica e em vcuo

Heavier crude contains more polycyclic aromatics Lead to carboneceous deposits called coke

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Destilao atmosfrica e em vcuo

Some crudes contain a lot of sulfur, which leads to processing considerations.

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Petroleum Definitions

Gas-to-Oil Ratio
The most important characteristic of a reservoir fluid in addition to specific gravity (or API gravity) is its gas-to-oil ratio (GOR), which represents the amount of gas produced at SC in standard cubic feet (scf) to the amount of liquid oil produced at the SC in stock tank barrel (stb). Generally, reservoir fluids are black oil, volatile oil, gas condensate, wet gas, and dry gas.

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Petroleum Definitions

Gas-to-Oil Ratio
The American Petroleum Institute gravity, or API gravity, is a measure of how heavy or light a petroleum liquid is compared to water. If its API gravity is greater than 10, it is lighter and floats on water; if less than 10, it is heavier and sinks. The API scale was designed so that most values would fall between 10 and 70 API gravity degrees.

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Petroleum Definitions

Crude Oil
The crude oil produced from the atmospheric separator has a composition different from the reservoir fluid from a producing well. Two important characteristics of a crude that determine its quality are the API gravity (specific gravity) and the sulfur content. Generally, a crude with the API gravity of less than 20-22 is called heavy crude and with API gravity of greater than 33-40 is called light crude. Similarly, if the sulfur content of a crude is less than 0.5 wt% it is called a sweet oil. Petroleum containing higher levels of sulfur is called sour crude oil.
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Petroleum Definitions

Crude Oil
Tipos de petroleo bruto: Leve doce: 0.10-0.40% S em peso 33-55 API Lece cido: 1-2.5% S em peso 30-45 API Pesado doce 0.20-0.80 % S em peso 19-29 API Pesado cido 1.70-2.80% S em peso 11-29 API

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Petroleum Standards

There are a number of international standard organizations that recommend specific characteristics or standard measuring techniques for various petroleum products. Some of these organizations are as follows: 1. ASTM (American Society for Testing and Materials) in the United States 2. ISO (International Organization for Standardization), which is at the international level 3. IP (Institute of Petroleum) in the United Kingdom 4. API (American Petroleum Institute) in the United States
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Petroleum Properties

Distillation curves
For a crude oil or a petroleum fraction of unknown composition, the boiling point may be presented by a curve of temperature versus vol% (or fraction) of mixture vaporized. There are several methods of measuring and reporting boiling points curves of crude oil and petroleum fractions: 1- ASTM D 86 2- True Boiling Point (TBP) 3- Simulated Distillation by GC (ASTM D 2887) 4- Equilibrium Flash Vaporization (EFV) 5- Distillation at Reduced Pressures (ASTM D 1160)
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Petroleum Properties

ASTM D 86
ASTM D 86 is one of the simplest and oldest methods of measuring and reporting boiling points of crude oil and petroleum fractions. The test is conducted at atmospheric pressure with 100 mL of sample and the result is shown as a distillation curve with temperatures at 0, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 95, and 100% volume vaporized. For crudes and heavy products, temperatures are reported at maximum of 90, 70, or even 50% volume vaporized. This is due to the cracking of heavy hydrocarbons at high temperatures. Mrio Eusbio (2012)

Petroleum Properties

ASTM D 86

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Petroleum Properties

True Boiling Point

ASTM D 86 distillation data do not represent actual boiling point of components in a petroleum fraction. Atmospheric true boiling point (TBP) data are obtained through distillation of a petroleum mixture using a distillation column with 15-100 theoretical plates at relatively high reflux ratios (1-5 or greater). The high degree of fractionation in these distillations gives accurate component distributions for mixtures. The lack of standardized apparatus and operational procedure is a disadvantage, but variations between TBP data reported by different laboratories for the same sample are small.
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Petroleum Properties

True Boiling Point

The IBP from TBP curve is less than the IBP from ASTM D 86 curve, while the FBP of TBP curve is higher than that of ASTM curve. Therefore, the boiling range based on ASTM D 86 is less than the actual true boiling range.

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Petroleum Properties

ASTM D 2887
A distillation curve produced by GC is called a simulated distillation (SD) and the method is described in ASTM D 2887 test method. Simulated distillation method is simple, consistent, and reproducible and can represent the boiling range of a petroleum mixture without any ambiguity. Distillation curves by SD are presented in terms of boiling point versus wt% of mixture vaporized because in gas chromatography composition is measured in terms of wt% or weight fraction. SD curves are very close to actual boiling points shown by TBP curves.
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Petroleum Properties

ASTM D 1160
For products such as heavy gas oils that contain heavy compounds and may undergo a cracking process during vaporization at atmospheric pressure, distillation data are measured at reduced pressures, 1, 2, 10, or 50 mmHg. The experimental procedure is described in ASTM D 1160 test method. ASTM D 1160 distillation data are measured more accurately than ASTM D 86 since it is conducted at low pressure. For this reason ASTM D 1160 curves are closer to TBP curves at the same pressure base.
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Petroleum Properties

The Watson characterization factor (Kw) is one of the oldest characterization factors originally defined by Watson et al. of the Universal Oil Products (UOP) in mid 1930s. For this reason the parameter is sometimes called UOP characterization factor and is defined as

Tb1/ 3 Kw = SG

where Tb = normal boiling point oR

The naphthenic hydrocarbons have Kw values between paraffinic and aromatic compounds. In general, aromatics have low Kw values while paraffins have high values.
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Petroleum Properties

Reid vapor pressure (RVP) is the absolute pressure exerted by a mixture at 100 oF and a vapor-to-liquid volume ratio of 4. The RVP is one of the important properties of gasolines and jet fuels. The standard test of RVP is ASTM D 323. For a pure compound the freezing point is the temperature at which liquid solidifies at 1 atm pressure. Similarly the melting point is the temperature that a solid substance liquefies at 1 atm. A pure substance has the same freezing and melting points; however, for petroleum mixtures, there are ranges of melting and freezing points versus percent of the mixture melted or frozen.
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Petroleum Properties

Pour point of a petroleum fraction is the lowest temperature at which the oil will pour or flow when it is cooled without stirring under standard cooling conditions. Pour point represents the lowest temperature at which an oil can be stored and still capable of flowing under gravity. When temperature is less than pour point of a petroleum product it cannot be stored or transferred through a pipeline. Test procedures for measuring pour points of petroleum fractions are given under ASTM D 97 and ASTM D 5985 methods.
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Petroleum Properties

Cloud point is the lowest temperature at which wax crystals begin to form by a gradual cooling under standard conditions. At this temperature the oil becomes cloudy and the first particles of wax crystals are observed. The standard procedure to measure the cloud point is ASTM D 2500. Low cloud point products are desirable under low-temperature conditions. Wax crystals can plug the fuel system lines and filters, which could lead to stalling aircraft and diesel engines under cold conditions. Cloud points are measured for oils that contain paraffins in the form of wax and therefore for light fractions (naphtha or gasoline) no cloud point data are reported.
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Petroleum Properties

Flash point for a hydrocarbon or a fuel is the minimum temperature at which vapor pressure of the hydrocarbon is sufficient to produce the vapor needed for spontaneous ignition of the hydrocarbon with the air with the presence of an external source, i.e., spark or flame. The standard procedure to measure the Flash point is ASTM D 93. Flash point is an important parameter for safety considerations, especially during storage and transportation of volatile petroleum products (i.e., LPG, light naphtha, gasoline). The surrounding temperature around a storage tank should always be less than the flash point of the fuel to avoid possibility of ignition.
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Petroleum Properties

Flash point should not be mistaken with fire point, which is defined as the minimum temperature at which the hydrocarbon will continue to burn for at least 5 s after being ignited by a flame. Autoignition temperature is the minimum temperature at which hydrocarbon vapor when mixed with air can spontaneously ignite without the presence of any external source. Values of autoignition temperature are generally higher than flash point. This is particularly important from a safety point of view when hydrocarbons are compressed. Standard test is ASTM D 2155.
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Petroleum Properties

To have a combustion, three elements are required: fuel (hydrocarbon vapor), oxygen (i.e., air), and a spark to initiate the combustion. One important parameter to have a good combustion is the ratio of air to hydrocarbon fuel. The combustion does not occur if there is too much air (little fuel) or too little air (too much fuel). This suggests that combustion occurs when hydrocarbon concentration in the air is within a certain range. This range is called flammability range and is usually expressed in terms of lower and upper volume percent in the mixture of hydrocarbon vapor and air.
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Petroleum Properties

Octane number is a parameter defined to characterize antiknock characteristic of a fuel (gasoline and jet fuel) for spark ignition engines. Octane number is a measure of fuel's ability to resist auto-ignition during compression and prior to ignition. Higher octane number fuels have better engine performance. The octane number of a fuel is measured based on two reference hydrocarbons of n-heptane with an assigned octane number of zero and isooctane (2,2,4trimethylpentane) with assigned octane number of 100.
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Petroleum Properties

There are two methods of measuring octane number of a fuel in the laboratory; motor octane number (MON) and research octane number (RON). The MON is indicative of high-speed performance (900 rpm) and is measured under heavy road conditions (ASTM D 357). The RON is indicative of normal road performance under low engine speed (600 rpm) city driving conditions (ASTM D 908). The arithmetic average value of RON and MON is known as posted octane number (PON). Isoparaffins and aromatics have high octane numbers while n-paraffins and olefins have low octane numbers.
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Petroleum Properties

Generally there are three kinds of gasolines: regular, intermediate, and premium with PON of 87, 90, and 93, respectively. Improving the octane number of fuel would result in reducing power loss of the engine, improving fuel economy, and a reduction in environmental pollutants and engine damage. There are a number of additives that can improve octane number of gasoline or jet fuels. These additives are tetra-ethyl lead (TEL), alcohols, and ethers.

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Petroleum Properties

For diesel engines, the fuel must have a characteristic that favors auto-ignition. The ignition delay period can be evaluated by the fuel characterization factor called cetane number (CN). The shorter the ignition delay period the higher CN value. The cetane number is defined as: CN = vol% n-cetane + 0.15(vo1% HMN) Where n-cetane (n-C16H34) has a CN of 100, and heptamethylnonane (HMN) has a CN of 15. The cetane number of a diesel fuel can be measured by the ASTM D 613 test method.
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Petroleum Properties

Higher cetane number fuels reduce combustion noise and permit improved control of combustion resulting in increased engine efficiency and power output. Higher cetane number fuels tend to result in easier starting and faster warm-up in cold weather and can cause reduction in air pollution. The product distributed in France and Europe have CN in the range of 48-55. In the United States and Canada the cetane number of diesel fuels are most often less than 50. Cetane number of diesel fuels can be improved by adding additives such as 2-ethyl-hexyl nitrate or other types of alkyl nitrates.
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Petroleum Properties

Aniline point for a hydrocarbon or a petroleum fraction is defined as the minimum temperature at which equal volumes of liquid hydrocarbon and aniline are miscible. The aniline point is important in characterization of petroleum fractions and analysis of molecular type. The aniline point is also used as a characterization parameter for the ignition quality of diesel fuels. It is measured by the ASTM D 611 test method. Aromatics have very low aniline points in comparison with paraffins, since aniline itself is an aromatic compound (C6H5-NH2) and it has better miscibility with aromatic hydrocarbons.
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Petroleum Properties

When a petroleum fraction is vaporized in the absence of air at atmospheric pressure, the nonvolatile compounds have a carbonaceous residue known as carbon residue (CR). Therefore, heavier fractions with more aromatic contents have higher carbon residues while volatile and light fractions such as naphthas and gasolines have no carbon residues. There are three different test methods to measure carbon residues, Ramsbottom (ASTM D 524), the Conradson (ASTM D 189) and microcarbon (ASTM D 4530). In most cases carbon residues are reported in wt%.
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Petroleum Properties

The smoke point (SP) is a maximum flame height at which a fuel can be burned in a standard wick-fed lamp without smoking. It is expressed in millimeters and a high smoke point indicates a fuel with low smoke-producing tendency. Measurement of smoke point is described under ASTM D 1322. Smoke point is a characteristic of aviation turbine fuels and kerosenes and indicates the tendency of a fuel to burn with a smoky flame. Higher amount of aromatics in a fuel causes a smoky characteristic for the flame and energy loss due to thermal radiation.
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Quality of Petroleum Products

The quality of a petroleum product depends on certain specifications or properties of the fuel to satisfy required criteria set by the market demand. These characteristics are specified for best use of a fuel (i.e., highest engine performance) or for cleaner environment. These specifications vary from one product to another and from one country to another. Standard organizations such as ASTM give such specifications for various products. For example: ASTM D 4814 for gasoline, ASTM D 975 for diesel fuel, ASTM D 3699 for kerosene and ASTM D 6615 for jet fuel.
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The Modern Refinery

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Destilao atmosfrica e em vcuo After desalting and dehydration, crude is separated into fractions by distillation. The distilled fractions can not be used directly. The reason for such a complex set of processes is the difference between the crude oil properties and the needs of the market. Another reason for complexity is environmental. Legislation demands cleaner products and is the major drive for process improvement and development of novel processes.

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Desalting/dehydration
Crude oil often contains water, inorganic salts, suspended solids, and water-soluble trace metals. Step 0 in the refining process is to remove these contaminants so as to reduce corrosion, plugging, and fouling of equipment and to prevent poisoning catalysts in processing units. The two most typical methods of crude-oil desalting are chemical and electrostatic separation, and both use hot water as the extraction agent. In chemical desalting, water and chemical surfactant (demulsifiers) are added to the crude, which is heated so that salts and other impurities dissolve or attach to the water, then held in a tank to settle out. Electrical desalting is the application of high-voltage electrostatic charges to concentrate suspended water globules in the bottom of the settling tank. Surfactants are added only when the crude has a large amount of suspended solids. A third (and rare) process filters hot crude using diatomaceous earth.
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Desalting/dehydration
The crude oil feedstock is heated to 65-180C to reduce viscosity and surface tension for easier mixing and separation of the water. The temperature is limited by the vapor pressure of the crude-oil feedstock. In both methods other chemicals may be added. Ammonia is often used to reduce corrosion. Caustic or acid may be added to adjust the pH of the water wash.

CHEE 2404: Industrial Chemistry

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43

Desalting/dehydration

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Crude distillation
Step 1 in the refining process is the separation of crude oil into various fractions or straight-run cuts by distillation in atmospheric and vacuum towers. The main fractions or "cuts" obtained have specific boiling-point ranges and can be classified in order of decreasing volatility into gases, light distillates, middle distillates, gas oils, and residuum. Atmospheric distillation The desalted crude feedstock is preheated using recovered process heat. The feedstock then flows to a direct-fired crude charge heater then into the vertical distillation column just above the bottom, at pressures slightly above atmospheric and at temperatures ranging from 340-370C (above these temperatures undesirable thermal cracking may occur). All but the heaviest fractions flash into vapor. As the hot vapor rises in the tower, its temperature is reduced. Heavy fuel oil or asphalt residue is taken from the bottom. At successively higher points on the tower, the various major products including lubricating oil, heating oil, kerosene, gasoline, and uncondensed gases (which condense at lower temperatures) are drawn off.
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Atmospheric distillation

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Simple crude distillation

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Vacuum distillation
To further distill the residuum or topped crude from the atmospheric tower without thermal cracking, reduced pressure is required. The process takes place in one or more vacuum distillation towers. The principles of vacuum distillation resemble those of fractional distillation except that larger diameter columns are used to maintain comparable vapor velocities at the reduced pressures. The internal designs of some vacuum towers are different from atmospheric towers in that random packing and demister pads are used instead of trays. A typical first-phase vacuum tower may produce gas oils, lubricatingoil base stocks, and heavy residual for propane deasphalting. A second-phase tower operating at lower vacuum may distill surplus residuum from the atmospheric tower, which is not used for lubestock processing, and surplus residuum from the first vacuum tower not used for deasphalting. Vacuum towers are typically used to separate catalytic cracking feedstock from surplus residuum.
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Vacuum distillation

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Modern crude distillation

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Gases: metano, etano, propano, butano

Nafta: C5 C9 componentes para gasolina automvel ou petroqumica Pontos de ebulio 65 180C

Jet fuel: C9 C12 gasolina de avio. Pontos de ebulio 145 230 C

Gasleo: C12 C18 Pontos de ebulio 230 375 C

Fuel: mais que C18 acima de 375C

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Petroleum Fractions

Some of the petroleum fractions produced from distillation columns with their boiling point ranges are given in Table below. These fractions may go through further processes to produce desired products.

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Destilao
As caldeiras para aquecimento por chama directa esto separadas das torres de destilao por motivos de segurana, pois os destilados ardem facilmente se entrarem em contacto com a chama. Os gases separam-se bem por destilao, pois tem pontos de ebulio suficientemente diferentes. O metano existe em muito pequena quantidade dissolvido no petrleo bruto. O metano encontra-se na natureza sobretudo em jazigos de gs natural, de que o metano o principal constituinte. Os restantes 4 destilados so lquidos constitudos por misturas de muitos hidrocarbonetos e alguns dos seus derivados. Cada destilado caracterizase pela temperatura inicial e final da destilao correspondente. No processo apresentado da empresa Total, as colunas 2 e 3 poderiam ser reduzidas a uma nica coluna, mas esta ficaria com um numero excessivo de pratos, e portanto uma altura excessiva. Na coluna 5 separa-se o jet (kerosene) e na coluna 6, que trabalha com vcuo, separa-se o gasleo, o fuel destilado para alimentao do FCC e fica um resduo. A separao faz-se com vcuo na coluna 6 porque sem vcuo a temperatura de ebulio seria to elevada que os hidrocarbonetos se decompunham.
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Destilao
Alis a decomposio a alta temperatura, com ou sem catalisadores, o processo usado para converter hidrocarbonetos de alta massa molecular em hidrocarbonetos de baixa massa molecular. No processo da Total refere-se a pinch technology, que consiste em reduzir o consumo de energia atravs da utilizao de permutadores que retiram calor s correntes quentes para transferir para as correntes frias. Por exemplo, fazer um pr-aquecimento da alimentao com as corrente quentes que saem da destilao. Outro processo usado para reduzir o consumo de energia a destilao de mltiplo efeito. Baseia-se no facto que separar dois lquidos por destilao em que o destilado fica no estado de vapor consome mais energia do que se o destilado ficar no estado liquido. Para conseguir que o destilado fique liquido e se aproveite a entalpia de vaporizao, usa-se o destilado em estado de vapor para aquecer a coluna de destilao seguinte. Para isso normalmente necessrio que cada coluna de destilao trabalhe a uma presso superior coluna de destilao seguinte.

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Petrleo
matria prima bsica para a qumica orgnica produto natural existente no subsolo em determinadas regies do globo, onde se acumularam residuos vegetais em grandes quantidades h milhes de anos. estes residuos transformaram-se em misturas de hidrocarbonetos contendo grupos funcionais com enxofre, azoto, fsforo e tambem compostos organo metlicos O petrleo bruto, tal como outros minrios, no poluente em si, no sentido que no poluente enquanto est no seu jazigo, passa a ser poluente se sair de l e for derramado no mar ou nos campos. O petrleo extraido por furos com centenas de metros, at 4 mil metros de profundidade. Sai espontaneamente do furo quando a presso suficiente no jazigo, seno bombeado para fora. Estes poos de petrleo existem em terra on shore, mas tambm no mar off shore.

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Tipos de petrleo bruto

Por serem produtos naturais obtidos a partir de plantas, os petrleos brutos so uma mistura de muitos compostos. A sua composio varia de furo para furo. A classificao mais usual baseia-se nos derivados que se podem obter por destilao:
Gases: metano, etano, propano, butano C5 C9: nafta para gasolina automvel ou petroqumica Pontos de ebulio 65 180C C9 C12: gasolina de avio jet fuel . Pontos de ebulio 145 230 C C12 C18: gasleo Pontos de ebulio 230 375 C Mais que C18: fuel acima de 375C

Estas fraces so definidas duma forma varivel de pas para pas e com a estao do ano, com base nos pontos de ebulio indicados.
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Tipos de petrleo bruto

No inverno usa-se uma gasolina com pontos de ebulio mais baixos que no vero. Como existem ismeros do mesmo hidrocarboneto com pontos de ebulio superiores a ismeros de hidrocarbonetos com mais tomos de carbono, a correspondncia entre a separao de fraces por pontos de ebulio no coincide com a separao de hidrocarbonetos pelo seu numero de tomos de carbono Os petrleos brutos classificam-se segundo:
a sua viscosidade o seu teor em hidrocarbonetos com menos ou mais tomos de carbono, respectivamente chamados leves e pesados
o seu teor em enxofre

O preo de cada tipo de petrleo varia segundo estas caractersticas. Cada refinaria escolhe por isso os seus petrleos brutos de acordo com o seu mercado de produtos refinados e de acordo com o seu preo.

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Tipos de petrleo bruto

Para alem disso, uma refinaria dimensionada em cada uma das suas unidades de acordo com os petrleos brutos que se prope refinar e de acordo com o seu mercado para produtos finais. Depois de construida uma refinaria, ela no tem flexibilidade para alterar a sua alimentao de petrleos brutos leves para petrleos brutos pesados, para alem de determinados limites. Para se adaptar ter que construir novas unidades de tratamento.

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Tipos de derivados primrios do petrleo

os gases metano, etano, propano, butano, usados quer como combustveis quer com matrias primas petroqumicas a gasolina automvel, que tem que satisfazer determinadas caractersticas de pontos de ebulio, teor de enxofre e comportamento num motor automvel. Este comportamento avaliado pelo ndice de octano. O ndice de octano medido num motor construdo segundo uma norma ISO, em que se mede a vibrao durante a exploso da gasolina, e se compara com o octano, que tem ndice de octano 100 e outro hidrocarboneto para o qual se arbitra na norma ISO um valor do ndice de octano. A gasolina com menor ndice de octano produz maior detonao nos cilindros, o que reduz a durao do motor e aumenta o rudo e a vibrao. A gasolina por isso obtida a partir da nafta resultante da destilao do petrleo, que se submete a operaes de dessulfurao e enriquecimento em hidrocarbonetos de elevado ndice de octano a gasolina de avio, tambm deve satisfazer especificaes apertadas definidas pelos construtores de turbinas

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Tipos de derivados primrios do petrleo

o gasleo, tem como propriedades mais importantes o ndice de cetano e o teor de enxofre. O ndice de cetano medido de acordo com a norma ISO 5165. uma medida emprica, realizada num motor construdo segundo esta norma, do tempo que decorre entre a injeco de gasleo no cilindro de combusto e a ignio. Como padro usa-se o cetano, que hexadecano com ndice 100 e o 2,2,3,3,6,8,8 heptametilnonano, um heptadecano, que tem ndice de cetano 15 . Os hidrocarbonetos lineares alifticos tem maior ndice de cetano do que os aromticos e os hidrocarbonetos cclicos. o fuel, a fraco mais pesada, cujas propriedades variam conforme o resduo duma destilao atmosfrica ou destilao em vcuo. O fuel de vcuo tem por isso hidrocarbonetos de maior ponto de ebulio. O fuel pode ser usado como combustvel directamente ou tambm como matria prima petroqumica. O asfalto constitudo por hidrocarbonetos pesados, parcialmente oxidados Os lubrificantes, constitudos por hidrocarbonetos com um numero de tomos de carbono semelhante ao do fuel a que se misturam aditivos especiais

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Motores
O motor de ignio tem cilindros com embolo e vlvulas para admisso de combustvel e ar e vlvulas para escape dos gases de combusto. O combustvel pode ser LPG ou gasolina, e misturado com ar. A mistura injectada no cilindro com o combustvel vaporizado. A ignio produzida por uma fasca elctrica numa vela. D-se uma exploso e os gases de escape saem do cilindro. A energia desenvolvida pela exploso acciona um embolo, cujo movimento de vai vem transformado em movimento rotativo das rodas do automvel.

Mrio Eusbio (2012)

Motores
O motor diesel tambm tem cilindros com embolo e vlvulas, mas o combustvel injectado sob a forma de gotas finas. A ignio no causada por uma fasca elctrica, mas sim pelo aumento de temperatura causado pela compresso da mistura de ar e combustvel. A taxa de compresso a relao entre a presso aps o embolo ter reduzido ao mnimo o espao ocupado pela mistura de ar e combustvel e a presso aps admisso dos gases no cilindro. Esta razo de compresso de 11 nos motores a gasolina e de 22 nos motores diesel. Esta diferena tem como consequncia que a temperatura da fonte quente no ciclo de Carnot correspondente ao motor mais elevada no motor diesel. O rendimento dum motor diesel por isso superior. Os construtores automveis procuram por isso actualmente construir motores diesel que usem gasolina como combustvel.
Mrio Eusbio (2012)

Motores
O terceiro tipo de motor a turbina. A mistura de combustvel e excesso de ar arde em regime continuo e ao arder aumenta a temperatura, o volume e a presso duma forma aproximadamente adiabtica. Esta expanso vai accionar uma turbina que no caso dos avies a jacto produz uma corrente de gases de combusto que empurram a turbina e o avio em sentido oposto ao da sada dos gases de combusto.

Mrio Eusbio (2012)

Destilao atmosfrica e em vcuo

A empresa que mais refinarias tem construdo no mundo a UOP (Universal Oil Products) pertencente Honeywell http://www.uop.com/.

Mrio Eusbio (2012)

Destilao atmosfrica e em vcuo

Major Chemical Classes of Compounds
Saturated linear hydrocarbons (alkanes or paraffins) Unsaturated linear hydrocarbons (alkenes or olefins, etc.) Saturated cyclic hydrocarbons (naphthenes or alicyclics) Unsaturated cyclic hydrocarbons (aromatic hydrocarbons) Heteroatomic compounds (linear and aromatic compounds containing C,H and N, S, O or metals) Inorganic compounds

Sources of Compositional Uniqueness, Complexity and Variability

Crude oil source Crude oil distillation temperature Further processing steps

Mrio Eusbio (2012)

Destilao atmosfrica e em vcuo

Major Chemical Classes of Compounds
Saturated linear hydrocarbons (alkanes or paraffins) Unsaturated linear hydrocarbons (alkenes or olefins, etc.) Saturated cyclic hydrocarbons (naphthenes or alicyclics) Unsaturated cyclic hydrocarbons (aromatic hydrocarbons) Heteroatomic compounds (linear and aromatic compounds containing C,H and N, S, O or metals) Inorganic compounds

Sources of Compositional Uniqueness, Complexity and Variability

Crude oil source Crude oil distillation temperature Further processing steps

Mrio Eusbio (2012)

Destilao atmosfrica e em vcuo

A empresa que mais refinarias tem construdo no mundo a UOP (Universal Oil Products) pertencente Honeywell http://www.uop.com/.

Mrio Eusbio (2012)

Crude Oil Distillation

Unfortunately, a practical crude oil distillation cannot be operated in quite the way shown in Figure (b), because: Extremely high temperature sources of heat would be required. Steam is usually not distributed for process heating at such high temperatures. High temperatures in the reboilers would result in significant fouling of the reboilers from decomposition of the hydrocarbons to form coke. Therefore, in practice, some or all of the reboiling is substituted by the direct injection of steam into the distillation. The steam is condensed in the overhead and is separated in a decanter from the hydrocarbons.
Mrio Eusbio (2012)

Crude Oil Distillation

Furnace
The crude oil entering the main column needs to be preheated to around 400 C. This is down by a furnace (fired heater). Note that this temperature is higher than decomposition limit, but a high temperature can be tolerated in the furnace if it is only for a short residence time. All of the material that needs to leave as product above the feed point must vaporize as it enters the column. In addition to this, some extra vapor over and above this flowrate must be created that will be condensed and flow back down through the column as reflux. This extra vaporization to create reflux is known as overflash.
Mrio Eusbio (2012)

Crude Oil Distillation

Ref: R. Smith, Chemical Process Design and Integration, Wiley, 2005.

In the first stage of processing crude oil, it is distilled under conditions slightly above atmospheric pressure. A range of petroleum fractions are taken from the crude oil distillation. Designs are normally thermally coupled. Most configurations follow the thermally coupled indirect sequence as shown in Figure (a). However, rather than build the configuration in Figure (a), the configuration of Figure (b) is the one normally constructed. Notice that the two arrangements are equivalent.
Mrio Eusbio (2012)