Petroleum process lecture one 111 .pptx

lecture one

1. Petroleum Prof. Dr. Eid M. Sayd Azzam

2. Petroleum Formation Petroleum formation  occurs by various hydrocarbons combining with certain minerals such as sulphur under extreme pressure. Modern day scientists have proven that most if not all  petroleum  fields were created by the remains of small animal and plant life being compressed on the sea bed by billions of tons of silt and sand several million years ago. When small sea plants and animals die they will sink, they will then lie on the sea bed where they will decompose and mix with sand and silt. During the decomposition process tiny bacteria will clean the remains of certain chemicals such as phosphorus, nitrogen and oxygen. This leaves the remains consisting of mainly carbon and hydrogen . At the bottom of the ocean there is insufficient oxygen for the corpse to decompose entirely. What we are left with is the raw materials for the  formation of petroleum . The partially decomposed remains will form a large, gelatinous mass , which will then slowly become covered by multiple layers of sand, silt and mud. This burying process takes millions of years, with layers piling up one atop another. As the depth of the sediment build up increases the weight of the sand and silt pressing down on the mass will compress it into a layer which is much thinner than the original .

3. Finally, when the depth of the buried decomposing layer reaches somewhere around 10,000 feet the natural heat of the earth and the intense pressure will combine to act upon the mass . The end result, over time, is the formation of petroleum . Effect of heat on petroleum formation : With petroleum formation the actual temperature applied to the original organic mass is critical in determining the overall properties of the resulting petroleum . Typically lower temperatures during petroleum formation will result in thicker, darker raw petroleum deposits , the most solid of which being a bitumen substance . If the heat applied during the formation of petroleum process fluctuates too much then gas will be produced , often separating from the petroleum, sometimes remaining mixed with the raw oil. If temperatures are too high , in the somewhere over 450 degrees Fahrenheit then the original biomass will be destroyed and no gas or petroleum is formed. As the mud and silt above the deposit become heavier and the forces placed upon the silt and mud begin to change the bottom layers of the compressing layer above the petroleum then it will turn into shale . As the shale forms the oil will be forced out of its original area of formation. The raw petroleum then moves to a new rock formation, usually termed a reservoir rock, and lays trapped until it is accessed in some way. As we can see, the formation of naturally occurring raw petroleum  takes millions of years , certainly far longer than can be deemed renewable, yet mankind has managed to almost complete deplete the world supply in little more than a century. It is important that people are educated and come to realize that burning such a precious fuel, which takes so long to form, at such a rate as we do now is nothing short of disastrous for the environment.

4. The Future of Petroleum Most experts seem to agree that if the world has not already reached peak petroleum production , then it will do so within the next 20 years. Elsewhere on the site it is explained that peak oil does not mean that petroleum reserves have run out, but that the maximum rate of petroleum extraction has been reached and that subsequent methods of extraction cannot increase the rate further . Over time, the total rate of petroleum output will decrease . This naturally leads people to question what the future will look like . Several scenarios are possible and it seems that all of them will come true to some degree or another, rather than any single one of them coming true alone . Heavy Oil and Oil Shale Efforts have already been made to extract oil that was once considered uneconomical to produce. As the world supplies of light, easily extractable crude oil continue to decrease and demand continues to increase, the price people are willing to pay for a barrel of crude will increase as well. As a result, heavier oil that was once uneconomical to extract due to high upfront costs has become profitable to produce .

5. Countries like Canada and Venezuela and United States all sit atop extremely large deposits of heavy oil and oil shale . In fact, it is estimated that there is more heavy oil in Venezuela then there is petroleum in the entirety of the Middle East. Canada is currently the world’s leading producer of heavy oil and it is estimated that the heavy crude in Canada is enough to supply the entire world at current demand for well over 200 years . Of course, the vastness of the supply is only one of the considerations of extracting heavy oil. Production methods for heavy oil are discussed elsewhere, but the two things they have in common are decreased energy returned on energy invested and it increased impact on the environment. While world demand for petroleum continues to rise, there has recently been competing interests from environmental lobbies concerned about the long-term impact of extracting heavy crude. Environmental concerns arise not just from the direct impact of the environments, but also from the fact that the decreased energy returned on energy invested for heavy oils means that they produce more greenhouse gases and other pollutants than do same quantities of lighter crudes. In other words, the extraction and use of heavy oil is expected to exacerbate the problem of carbon dioxide and greenhouse gas emissions throughout the world.

6. What is clear is that heavy oil production will be necessary in the near future unless there is a drastic decrease in demand for petroleum. While techniques are being developed to help reduce the impact of extracting heavy oil on the environment, there is little doubt that utilization of this resource will have substantial negative impact. For this reason, conservation has become more important than ever. The less oil the world uses, then the less the environment is impacted both from current and future oil production activities. Conservation efforts are less about concern over running out of oil than they are about concern of increasing use of oil. Environmentalists point out that time and money being spent on research and development for the extraction of heavy oil could be better invested into developing alternative energies.

7. Electricity Because the transportation industry is responsible for using 70% of all crude oil produced, there has been great effort in the last two decades to produce an electric vehicle capable of performance similar to that of petroleum powered vehicles. While there are major obstacles to overcome, recent advances have seen mileage ranges increased from less than 100 to well over 200 miles. The major factors holding back the mainstream production of electric vehicles are the cost of batteries, the production and recycling of batteries, and the time that it takes to charge a battery. In other words, the only thing holding back electric vehicles is how they store electricity when the vehicle is not in use. A cheap, efficient, reliable alternative to current batteries would make electric vehicles instantly practical. Many proponents of electric powered vehicles point to hybrid vehicles as the logical bridge between petroleum vehicles and vehicles that rely 100% upon electricity. Hybrid vehicles offer the benefits of unlimited mileage obtained from gasoline while increasing fuel economy through the employment of electric motors as well. These hybrid vehicles are slowly but surely progressing from a disproportionate amount of reliance on petroleum to increased reliance on electricity through techniques like adding solar panels, regenerative braking, and plug-in capabilities (allowing them to be charged through the electrical grid rather than by running their petrol motors). It is worth pointing out that while electric vehicles can reduce petroleum use, the source of electricity used to charge their batteries is of critical importance. If that energy does not come from clean, renewable resources, then the problem is simply being shifted from one location to another and is not being solved. Proponents are clear that the success of electric vehicles also depends upon the implementation of renewable resources for the generation of the majority of electricity. Technologies like solar, wind, hydro, and geothermal are all being investigated and have met with various levels of success throughout different regions of the world.

8. Conclusion What is clear about petroleum is that it will continue to play a large role in our lives in the near to medium term future. While technologies are being invented to reduce our dependence on fossil fuels, it will be several decades before they become commonplace and affordable. Some of the major car manufacturers across the world estimate that it will be at least 2025 before electric vehicles are competitive in terms of cost and performance with petroleum powered vehicles. Even if the world the world switched to an energy source independent of petroleum, one must not forget the fact that petroleum is an integral part of modern life in terms of the things it is used to make beyond a gasoline and other fuels. Objects as diverse as plastics, pharmaceuticals, and cosmetics use various aspects of petroleum as foundations in chemical reactions. In fact, our tremendous reliance on petroleum for manufacturing and not for fuel is all the more reason to be conservative about simply burning it to drive across town .

9. Other Uses of Petroleum When most people think of petroleum they think of gasoline and diesel fuel. They may even conjure up images of jet fuel, but most will rarely consider the other unexpected places that petroleum byproducts show up in modern life. Because crude oil contains a vast number of different hydrocarbons, various refined products have found their way into everything from plastics to pharmaceuticals . The industry that uses petroleum to produce other chemicals is referred to as the petrochemical industry. It is estimated that industrialized nations currently consume petrochemical products at a rate of three and a half gallons of oil per day. That means that, excluding fuel oil, modern life results in each citizen of an industrial nation using over 1,200 gallons of oil per year.

10. Agriculture One of the most important uses of petroleum is in the production of ammonia to be used as the nitrogen source in agricultural fertilizers. In the early 20th century, Fritz Haber invented a process that allowed for industrial scale production of ammonia. Prior to that, ammonia for fertilizer came only from manure and other biological processes. The Haber process works in two steps. First, methane from natural gas is cleaned to remove sulfur and hydrogen sulfide. It is then reacted with steam over a catalyst to produce hydrogen and carbon dioxide. In the next step, which is the actual Haber process, hydrogen and gaseous nitrogen are reacted at high heat and pressure to produce ammonia, which is siphoned off and added to chemical fertilizers. Agriculture also depends on the use of pesticides to ensure consistent, healthy crop yields. Pesticides are almost all produced from oil. In essence, from running farm machinery to fertilizing plants, agriculture is one of the largest users of petroleum based products. Plastics Plastic is a staple of modern life. From computer monitors to nylon to Styrofoam, plastics are integral aspects of many manufactured products. Polystyrene, from which Styrofoam is made, and polyvinyl chloride (PVC) were both products of post-World War II industrialization. Nylon, which is in everything from stockings to mechanical gears and even in car engines, is the most successful petroleum-based plastic to date. Most plastics come from olefins, which include ethylene and propylene.

11. Tires Tires are made of rubber. Until 1910 all rubber was produced from natural elastomers obtained from plants. The need for synthetic rubber was relatively small until World War II, which resulted in embargos on natural rubber from South America and the need to produce synthetic rubber on a large scale. Rubber is primarily a product of butadiene. Pharmaceuticals Mineral oil and petrolatum are petroleum byproducts used in many creams and topical pharmaceuticals. Tar, for psoriasis and dandruff, is also produced from petroleum. Most pharmaceuticals are complex organic molecules, which have their basis in smaller, simpler organic molecules. Most of these precursors are petroleum byproducts. Dyes, Detergents, and Other Petroleum distillates such as benzene, toluene, xylene, and others provide the raw material for products that include dyes, synthetic detergents, and fabrics. Benzene and toluene are the starting materials used to make polyurethanes, which are used in surfactants, oils, and even to varnish wood. Even sulfuric acid has its origins in the sulfur that is removed from petroleum.

12. Partial List of Unexpected Products Made from or Containing Petroleum Ink Upholstery CDs Vitamin Capsule Denture Adhesive Putty Guitar Strings Heart Valves Anesthetics Cortisone Toilet Seats Crayons Pillows Artificial Turf Deodorant Lipstick Hair Coloring Aspirin

13. Fuel from Crude The primary uses of crude oil to this point have been in the production of fuel. A single barrel of crude oil can produces the following components, which are listed by percent of the barrel they constitute. 42% Gasoline 22% Diesel 9% Jet Fuel 5% Fuel Oil 4% Liquefied Petroleum Gases 18% Other products

14. Refining Petroleum refining refers to the process of converting crude oil into useful products . Crude oil is composed of hundreds of different hydrocarbon molecules, which are separated through the process of refining.  The process is divided into three basic steps: separation, conversion, and treatment. Separation Separation refers to the process of distillation . Crude oil is heated in a furnace so that hydrocarbons can be separated via their boiling point.  Inside large towers, heated petroleum vapors are separated into fractions according to weight and boiling point.  The lightest fractions, which include gasoline, rise to the top of the tower before they condense back to liquids.  The heaviest fractions will settle at the bottom because they condense early. Conversion Conversion is simply the process of changing on kind of hydrocarbon into another. Of the, the desired product is gasoline.  Cracking is the process of taking heavier , less valuable fractions of crude and converting them into lighter products.  Cracking uses heat and pressure to break heavier elements into lighter ones.  Alkylation is another common process, which is basically the opposite of cracking.  In alkylation, small gaseous byproducts are combined to form larger hydrocarbons. Treatment Treatment is the final process of refining , and includes combining processed products to create various octane levels, vapor pressure properties, and special properties for products used in extreme environments. One common example of treatment is the removal of sulfur from diesel fuel, which is necessary for it to meet clean air guidelines. Treatment is highly technical and is the most time consuming step of refining.

15. Gasoline Gasoline is the most popular product derived from petroleum and constitutes the largest fraction of product obtained per barrel of crude oil. The hydrocarbons in gasoline have a chain length of between 4 and 12 carbons . Internal combustion engines burn gasoline in a controlled process called deflagration.   Of importance in this process is the timing of combustion, which can be adversely impacted by autoignition of gasoline. This leads to the phenomenon commonly referred to as “ engine knock .”  In fact, the resistance to autoignition is the largest difference between gasoline and jet fuel, jet fuel being highly resistant to autoignition .   A gasoline’s resistance to autoignition is expressed in its octane rating .  Octane levels are manipulated by the addition of a particular hydrocarbon called octane.  The higher the octane rating of the gasoline, the more the fuel can be compressed.  Higher compression means higher temperature and pressure can be achieved inside the engine, which translates to higher power output.

16. Diesel Diesel fuel consists of hydrocarbons of a chain length between 8 and 21 carbon atoms.  Diesel has higher energy content per volume than gasoline.  Because they hydrocarbons in diesel are larger, it is less volatile and therefore less prone to explosion, which is one reason it is preferred in military vehicles. Unlike gasoline engines, diesel engines do not rely upon electrically generated sparks to ignite the fuel. Diesel is compressed to high degree along with air, creating high temperatures within the cylinder that lead to combustion. This process makes diesel engines highly efficient, achieving up to 40% better fuel economy than gasoline powered vehicles. Until recently, diesel fuel contained a high degree of sulfur, which contributes to acid rain. Because of their similar distillation points, diesel and sulfur contaminants are removed from crude at the same time during refining. Government regulation now requires that additional steps be taken to remove the sulfur so that diesel fuel is more environmentally friendly. This is part of reason that diesel fuel costs more than gasoline

17. Heating Oil and Fuel Oil Fuel oil is one of the “left-over” products of crude refining. It is often less pure than other refined products, containing a broader range of hydrocarbons. Because of its contaminants, fuel oil has a high flash point and is more prone to autoignition . It also produces more pollutants when burned. Jet Fuel Jet fuel requires specific characteristics. Namely, it must have a low flammability and it must be able to experience the cold temperatures associated with high altitude without freezing. Jet fuel is based on kerosene, which is slightly heavier than gasoline. Additives help to ensure that it is highly compressible, has a low volatility, and will be free from freezing. Jet fuel comes in three main types: Jet A Used only in the United States. Flash point of 38 C (100 F) and autoiginition temperature of 210 C (410 F). This makes jet fuel safer than traditional gasoline. Jet A-1 Jet A-1 is similar to Jet A, but with a lower freezing point of 47 C. Jet B Jet B is designed for use in cold climates. It has a lower autoignition temperature, which makes it more dangerous than Jet A fuels.

18. Drilling Hydraulic fracturing is most often performed in horizontally drilled wells.  After a period of vertical drilling in order to reach shale deposits, a lateral extension of up to 5000 feet is drilled parallel to the rock layer containing the shale. Lateral drilling has many advantages, including reduce ground surface disruption. Fracturing In the next step, water is injected into the recently bored hole.  Occasionally, other substances such as gels, foams, compressed gases and even air are injected.  Chemical mixtures are usually included in the injection.  Chemicals are intended to increase the permeability of the rock by dissolving various components. The exact composition of the chemical injection is based on the geological composition of the area . Added chemicals include acids, biocides to kill bacteria, corrosion inhibitors, and surfactant. Specifics include hydrochloric acid, methanol, ammonium chloride, ethylene glycol (antifreeze), isopropanol (rubbing alcohol). Approximately 750 chemicals are listed as possible additives for hydraulic fracturing . The fluid is injected under high pressure with the intent of fracturing the soft shale.  Pressures can reach as high as 15,000 pounds per square inch (100 Mpa ) and injection rates can be as high as 265 liters per minute.  Injected fluid is recovered, to some degree, and stored in surface containers.  Do to the chemical additives, this material is often toxic.

19. Petroleum Reserves Petroleum reserves are any quantity of petroleum that is commercially recoverable. In order to be considered a reserve, a given deposit of petroleum must satisfy four criteria: Discovered through an exploratory well. In other words, drilling must be performed to prove recoverability. Must be recoverable using existing technology Must be commercially viable, meaning the petroleum can be extracted at a profit and not a loss Must still be in the ground

20. Proven Reserves A proven reserve is one in which there is 90% certainty that the petroleum is recoverable. To determine the “recoverability” of a given reserve geologic, economic, and political conditions are all taken into account. Such proven reserves are referred to as P90 in the industry, meaning they have a 90% chance of being produced. Proven reserves can be sub-classified as either “proven developed” (PD) or “proven undeveloped” (PUD). PD simply means that wells have already been drilled on these reserves or that little additional investment is needed. PUD reserves require more substantial investment in order to make them productive. The five largest proven oil reserves lie in Saudi Arabia, Canada, Iran, Iraq, and Kuwait. While the largest quantities of oil are found in the Middle East, when divided by country, Canada has the second largest number of proven reserves at roughly 19 to 20% of global total. The United States ranks fourteenth and the United Kingdom at thirty.

21. Unproven Reserves Unproven reserves are geologically equivalent to proven reserves. Their “unproven” status rests on technical, regulatory, or political issues. This is an example of the global criteria used to classify a reserve. If the reserve is producing oil, but is being used only internally by a country due to political or contractual issues, then it is classified as unproven. If that same well were to begin producing oil for global consumption, it would then be classified as proven. Unproven reserves fall into two categories: probable and possible. A probable reserve is the same as a P50 reserve in industry jargon, which simply means there is a 50% chance of recovering oil from the reserve. A possible reserve is also called a P10 reserve. P10 reserves generally receive their designation for technical or economic concerns and not for political reasons.

22. Petroleum Chemistry Petroleum Chemistry is made of a mixture of different hydrocarbons . The most prolific hydrocarbons found in the chemistry of petroleum are alkanes , these are also sometimes knows as branched or linear hydrocarbons . A significant percentage of the remaining chemical compound is the made up of aromatic hydrocarbons and cycloalkanes . Additionally petroleum chemistry contains several more complex hydrocarbons such as asphaltenes . Each geographical location and hence oil field will produce a raw petroleum with a different combination of molecules depending upon the overall percentage of each hydrocarbon it contains, this directly affects the colouration and viscosity of the petroleum chemistry. The primary form of hydrocarbons in the chemistry of petroleum are the alkanes, which are also often named paraffins . These are termed saturated hydrocarbons and the exhibit either branched or straight molecule chains. The paraffins are very pure hydrocarbons and contain only hydrogen and carbon; it is the alkanes which give petroleum chemistry its combustible nature. Depending upon the type of alkanes present in the raw petroleum chemistry it will be suitable for different applications.

23. For fuel purposes only the alkanes from the following groups will be used: Pentane and Octane will be refined into gasoline, hexadecane and nonane will be refined into kerosene or diesel or used as a component in the production of jet fuel, hexadecane will be refined into fuel oil or heating oil. When it comes to the chemistry of petroleum which does not contain a significant quantity of the kinds of paraffins required to produce a combustible fuel then things become simpler, as many non-fuel applications of petroleum are far more lenient in the chemical compound of the raw petroleum. The exception to this are the petroleum molecules which have less than five carbon atoms, these are a form of natural petroleum gas and will either be burned away or harvested and sold under pressure as LPG (Liquid Petroleum Gas). The cycloalkanes, which are also often referred too as the napthenes are classed as a saturated form of hydrocarbon. By saturated we mean the molecule contains either one or several carbon rings with atoms of hydrogen attached to them. These hydrocarbons display almost identical properties to paraffins but have a much higher point of combustion.

24. Lastly, the aromatic hydrocarbons are another form of unsaturated hydrocarbon . The specific difference between the other hydrocarbons in the  petroleum  molecule is that the aromatic hydrocarbons will contain benzene rings , with atoms of hydrogen attached to them. Aromatic hydrocarbons tend to produce far more emissions when combusted, many will have a sweet, sickly smell to them, hence the name aromatic hydrocarbons . The quantity and percentages of the specific types of hydrocarbons in raw petroleum chemistry can be determined by testing in a laboratory. The process involves extracting the, molecules using some form of solvent and then separating them using a gas chromatograph . Finally an instrument such as a mass spectrometer will be used to examine the separate molecules in the chemical compound of the sample.

25. The crude oil assay The crude oil assay is a compilation of laboratory and pilot plant data that define the properties of the specific crude oil. At a minimum the assay should contain a distillation curve for the crude and a specific gravity curve. Most assays however contain data on pour point (flowing criteria), sulfur content, viscosity, and many other properties . The assay is usually prepared by the company selling the crude oil, it is used extensively by refiners in their plant operation. Engineering companies use the assay data in preparing the process design of petroleum plants they are bidding on or, having been awarded the project, they are now building.

26. The true boiling point curve This is a plot of the boiling points of almost pure components, contained in the crude oil or fractions of the crude oil. In earlier times this curve was produced in the laboratory using complex batch distillation apparatus of a hundred or more equilibrium stages and a very high reflux ratio. Nowadays this curve is produced by mass spectrometry

27. The ASTM distillation curve American Society for Testing and Materials  ( ASTM ) While the TBP curve is not produced on a routine basis the ASTM distillation curves are. ASTM curve conducted on the whole crude . Is used however on a routine basis for plant and product quality control. This test is carried out on crude oil fractions using a simple apparatus designed to boil the test liquid and to condense the vapors as they are produced . Vapor temperatures are noted as the distillation proceeds and are plotted against the distillate recovered.

28. API (Ammerican Petroleum Institute) gravity This is an expression of the density of an oil. API gravity refers to the density at 60 o F (15.6 o C). Flash points The flash point of an oil is the temperature at which the vapor above the oil will momentarily flash or explode. This temperature is determined by laboratory testing using an apparatus consisting of a closed cup containing the oil, heating and stirring equipment, and a special adjustable flame. There are many empirical methods for determining flash points from the ASTM distillation curve. One such correlation is given by the expression

29. Octan numbers Ocatn numbers are a measure of a gasoline‘s resistance to knock or denation in cylinde of a gasoline engine. The higher of this resistance is the higher effeiciency of the fuel to produce work. The higher the octane rating of the fuel is the higher compression ratio of the engine . Octane number: is the % of the isoocatne in the bland of isooctane and the normal heptane e.g gasoline 90 containe 90 % isooctane and 10 % n-heptane . The knock characteristics are detemined in laboratory using a standerd single cylinder test engine equipped with a super sensitive knock meter.

30. Two octan numbers are usually determined. Research Octane number (RON) and Motor octane number (MON) . The difference between the two octane number is termed the (sensitivety of gasoline) .