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Chemical Engineering Design and Professional Skills A Assignment 1: Individual written report
Topic: Petrochemicals Diesel

Kingsley Wong 2011

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Contents page

Page number

Introduction Uses and applications Raw material Manufacturing process Transportation and storage of fuel Legislation Reference

3 4 5 6 9 9 10

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Introduction
This report will give information on the purposes of diesel fuel, the target market which requires the uses of the fuel, how it is manufactured and some legislation for the regulations of diesel. Petrochemicals can be defined as organic and inorganic compounds that can be made from crude oil and natural gas. Diesel or more specifically, petroleum diesel, was first discovered by German engineer Rudolf Diesel, the fuel is produced from fractional distillation of crude oil in oil refineries (Collins, 2007). The distillation process of diesel is slightly simpler than the distillation of gasoline, however, it requires more crude oil to produce one gallon of diesel. This means the energy density of diesel is higher than gasoline; the fuel efficiency of diesel is around 166,600BTU per gallon of fuel. BTU, short for British Thermal Unit, is a basic unit of measurement for the energy it takes to heat up one tenth of a gallon of water by one degree Fahrenheit from 39F to 40F. One unit of BTU is around 1055 joules (Business Dictionary, 2011). Typically, diesel is composed of around 75% of saturated hydrocarbons and 25% of aromatic hydrocarbons with most hydrocarbons containing 12 carbon atoms or more. Diesel is classified into different ratings by its cetane number. The cetane number represents how easily the diesel fuel ignites, the higher the cetane number, the higher the efficiency of the fuel is. The cetane number is measured by the amount of cetane, a branched alkane, mixed with 1-methylnapthalene, with cetane number 100 as the highest (Collins, 2005). Normal diesel used in vehicles has cetane number 45-50. Cetane number 50 and above are normally used in winter fuels and high performance fuel. Diesel has a higher mpg (miles per gallon) than gasoline and it also has a lower greenhouse gas emission per mile driven in the diesel vehicle. However diesel emits around 15% more greenhouse gases per gallon of fuel when compared to gasoline (Koerner, 2008), in the past when diesel technology was less advanced, the sulphur content was very high. The high emission of sulphurs and nitrous oxides caused photochemical smog to be produced. There was also a distinctive stench produced from the combustion of diesel fuel. Diesel fuel today contains a much lower content of sulphurs, meaning less soot is produced and technology is more advanced in treating the nitrous oxides in the exhaust pipe before it escapes into the atmosphere. Technology such as BlueTec reduces the carbon monoxide produced, filters out the soot and uses a nitrous oxide absorber catalyst to removes the nitrous oxides (Gold, 2007). The modern diesel technology has advanced hugely in the last few decades, meaning the reduction of the disadvantages listed above. As crude oil continues to deplete, the diesel industry is moving slowly towards biodiesel, rather than relying solely on petroleum diesel.

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Uses and Application Diesel is used heavily in the transportation industry; the most common use of diesel is to fuel the diesel engine. Diesel engines are a type of compression ignition engine; they are split into two classes of engines, two stroke engines or four stroke engines. Most engines in use are generally four stroke cycle engines, with some larger industrial diesel engines using the two stroke cycle. Most heavy road vehicles, a large majority of family vehicles as well as some ships, yachts and locomotives all use diesel engines. In the past, diesel was used to power some aircraft engines, but they were all eventually replaced by fuels based on kerosene. A vast majority of motorist uses diesel to run their vehicles, no specific training is needed to carry out processes such as refuelling a vehicle at a petrol station. However, special training will be needed for more specific processes such as the manufacturing and transportation of diesel to ensure health and safety regulations are followed and the product follows specification set by government legislation. Diesel is also used to fuel backup generators for emergency power if there was a power cut, such uses are common in the military and medical sector as diesel fuel is a more reliable source of fuel with lower volatility and lower flammability than gasoline, making it safer to be handled and stored. Diesel generators have a longer life span in comparison to petrol generators, lasting up to 30,000 hours compared to 5000 hours respectively (Anthony Isaac Palacios, 2010). The mining and extraction industry depends heavily on the supply on diesel, because around 72% of all machinery such as mining trucks, drills, shovels and more uses diesel as fuel. The higher reliability and safety is one of the biggest aspects for using diesel fuel in mining and extraction sector, as well as it being more economical. The reason why diesel is used as fuel is because of the high energy stored in the compounds, petroleum diesels are composed entirely of hydrocarbon compounds. When combusted, the hydrocarbon bonds are broken which releases high amount of energy that can be used to drive the piston of an engine or heat up water to form steam and etc. Diesel has a low volatility, which means it is more stable. Due to the low volatility, when diesel is spilt, it does not evaporate. It remains on the surface which is hazardous to vehicles on the road as it reduces friction between the tires of the vehicles and the road. The low volatility also means diesel is harder to ignite in cold weathers for vehicles using a diesel engine. Another important property of diesel to consider when using it is its viscosity; diesel fuels viscosity varies with temperature, so additives are added to the fuel to improve its viscosity index and to retain in as a liquid as temperature changes.

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Raw material The raw material used to produce petroleum diesel is crude oil. Crude oil is found underneath the surface of the earths crust and is extracted to produce a range of petrochemicals. Crude oil is made naturally over thousands of years from decaying plants and animals, formed by the high temperature and pressure underground. On average, crude oil is composed approximately of the following components:
Carbon, around 84% Hydrogen, around 14% Sulphur and sulphur compounds, around 1 to 3% Nitrogen compounds, less than 1% Oxygen in compounds, less than 1% Metals, less than 1% (nickel, iron, vanadium, copper, arsenic) Salts, less than 1% (sodium chloride, magnesium chloride, calcium chloride)

(Freudenrich, 2011) Crude oils hydrocarbons can be split into four major classes of molecules. Paraffins- straight or branched molecules with up to 20 carbon atoms Naphthenes- compounds with one or more ringed structures composed of single bonded carbons Aromatics- hydrocarbon compounds with benzene ring (alternating single-double carbon bonds in a ring structure) Alkenes- compounds with one or more carbon double bonds.

(Freudenrich, 2011) Crude oils can be found in different appearance in colour and viscosity, from clear to tar black in colour and from liquid phase to almost solid phase (Freudenrich, 2011). After locating the oil, it is extracted by drilling into the oil well and then it is pumped out and transported to the refinery plants.

Figure 1, Crude oil

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Manufacturing process Fractional distillation Crude oil can be separated by fraction distillation because the hydrocarbon compounds within the oil all have different boiling temperatures. So when heated, the crude oil can be separated into fractions, with the gases rising to the top of the distillation column and the liquid and solids going to the middle and bottom of the column. The middle distillate from which diesel is formed can be obtained between 250 C and 350 C at atmospheric pressure (Pearson Longman, 2008). After the fractions are obtained, it is further treated by either: Cracking- breaking large hydrocarbons down to smaller hydrocarbons Reforming- conversion to the desired hydrocarbons Isomerisation- conversion of linear hydrocarbons to branched hydrocarbons Alkylation- rearrangement of hydrocarbon molecules Polymerisation forming larger hydrocarbons

Figure 2, generic oil refinery flow diagram (Mbeychok, 2008)

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Petroleum diesel is formed by hydrotreating the middle distillate and can also be formed by hydrocracking the heavier oil fractions, bitumen. Hydrotreating and Hydrocrackings produces a cleaner fuel, both processes uses hydrogen as the feedstock and is recycled after the processes. Hydrotreating Hydrotreating is the most common method for producing petroleum diesel from the diesel oil of middle distillates; hydrotreating is a catalytic reaction which removes contaminants, which consists of sulphur, nitrogen, oxygen and metals. Hydrotreating also hydrogenates the olefins (alkenes) and aromatics to produce a cleaner product. (Colwell, 2009). Hydrotreating uses transition metal sulphides as the catalyst to increase the rate of the reactions. Noble metals such as palladium are also used as catalyst; however they are more sensitive to catalyst poisoning (Robinson and Dolbear, 2007). Hydrogen is mixed with the diesel oil feed, and then it is heated to temperatures of around 300C depending on the reactions desired. Next, it is passed into a hydrogenation reactor, lined with catalysts, where hydrogenation reactions occur to remove the contaminants from the aromatic and olefin molecules. The feed then enters a high pressure separator which separates the gases produced from the reactants. Pressure of the feed could be at around 4200 kPa (kilopascal) to 5600 kPa. The liquid hydrocarbons are then ready to be separated further and blended into the final product of petroleum diesel. (Robinson and Dolbear, 2007)

Figure 3, Process flow diagram of hydrotreating of diesel (R. Egeberg, 2009)

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Hydrocracking Hydrocracking is a process used to break down the bigger, heavier hydrocarbon molecules found in the bitumen from crude oil. Hydrocracking can be split into two different stages. Cracking and hydrogenation, the reactions all occur under the presence of different catalysts, very high temperature and very high pressure. In the first stage, the preheated feedstock is mixed with hydrogen and passed into a hydrogenation reactor like hydrotreating and the contaminants such as sulphur, nitrogen and metals are removed from the hydrocarbon compounds of the feedstock. In the next stage, the feed enters a separator where the liquid is removed from the gases formed during hydrogenation; it then undergoes cracking to break the larger hydrocarbon molecules down and gets separated once more to obtain the desired products such as diesel. (SET laboratories, 2008). Cracking occurs under temperature of between 400 C - 700 C, the larger molecules, for example decane is thermally decomposed to form octane and ethene. Cracking always produces alkane and alkene molecules, because there are not enough hydrogen molecules present to form all alkane molecules. Cracking occurs under presence of a catalyst such as aluminium oxide, AlO and zeolites to decrease the enthalpy needed to break the hydrocarbon bonds. (Cutler J. Cleveland, 2008)

Figure 4, Generic hydrocracking flow diagram (Honeywell Company, 2011)

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Transportation and storage Crude oil and diesel are mainly transported through networks of pipelines across the world. Crude oil can be transported straight from the oil well to the oil refinery plants pipelines underwater, underground and above ground. The liquid petroleum products can also be transported to the distributors through pipelines. Crude oil can be transported over sea in supertankers as well as pipelines. (Werner Slken, 2008) After refinery, diesel is transported to the consumers in cargo fuel tanks. Diesel is delivered to the consumers as a liquid. Small quantities of diesel can be stored in a plastic container (under 5 gallons), but larger quantities of diesel must be stored in a storage tank. Plastic tanks, steel tanks and bunded tanks are the most common storage tanks. Bunded tanks are tanks that are structured with an area to prevent any breaches or leakage of the content, the bunded tanks can resists corrosion and oxidation caused by the content if leaking occurs. Legislation Transportation and storage Transportation and storage of diesel are governed by the environmental agency and the department of transportation. Some regulations for storage are: Storage bays should be bunded to provide a minimum retention capacity of not less than 150 percent of the largest tank capacity Tanks should be labelled correctly with a reference number present Tanks should be inspected regularly Tanks must comply with regulations of hazardous substance and for flammable and combustible liquids

(Department of industry and resources, 1997) Some regulations for transportation are: Diesel must be transported in specialised containers that comply to regulations Vehicle transporting the fuel must be well maintained and must not contain any other flammable material Containers should be clearly labelled

(Department of industry and resources, 1997) Manufacturing As of 2007, most diesel fuel manufactured across Europe, USA and Canada are ultra-low sulphur diesel (USLD). The legislation specifies that diesel must contain less than 50ppm (parts per million) of sulphur in diesel fuel, and as of 2009 in Europe, it has further lowered to 10ppm of sulphur. The

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Page 10 of 11 significant reduction of sulphur lowers greenhouse gases emission; however it lowers the fuel economy due to the heavier processing that is required to remove the sulphur. (DieselNet, 2010)

References

Websites 1. http://www.fastcompany.com/magazine/120/the-evolution-of-diesel.html 2. Chris Collins (2007), Implementing Phytoremediation of Petroleum Hydrocarbons, Methods in Biotechnology 23:99-108 3. http://www.slate.com/articles/health_and_science/the_green_lantern/2008/04/will_diesel _save_the_world.html Brendan Koerner, April 1, 2008 4. http://cars.about.com/od/thingsyouneedtoknow/a/ag_BLUETEC.htm Aaron Gold, 2007 5. http://www.businessdictionary.com/definition/British-thermal-unit-Btu.html Business Dictionary, 2011 6. Collins Discovery Encyclopedia, 1st edition HarperCollins Publishers 2005 7. http://www.dieselserviceandsupply.com/industrial_industry_usage.aspx 8. http://ezinearticles.com/?Getting-the-Best-Fuel---The-Many-Uses-of-Diesel&id=1353220 Timothy Z. Tan, 2008 9. http://www.livestrong.com/article/176622-uses-for-diesel-oil Anthony Isaac Palacios, 2010 10. http://www.buzzle.com/articles/how-is-diesel-fuel-made.html Ningthoujam Sandhyarani, 2010 11. http://science.howstuffworks.com/environmental/energy/oil-refining1.htm Craig Freudenrich, 2011 12. http://www.aip.com.au/industry/fact_refine.htm 13. http://chentserver.uwaterloo.ca/aelkamel/che720/che735/lectures_che735_students/newbook-practical-advances-refinery/chapter7-hydrotreater-hydrocracker.pdf Paul Robinson, Geoffrey Dolbear, 2007 14. http://www.processengr.com/ppt_presentations/oil_refinery_processes.pdf Ronald Colwell, 2009 15. http://www.pearsonlongman.com/technicalenglish/pdf/level2/level2_unit8.pdf Pearson Longman, 2008 16. http://www.setlaboratories.com/hydrocra/tabid/105/Default.aspx SET laboratories, 2008 17. http://www.wermac.org/others/oil_and_gas_transportation.html Werner Slken, 2008 18. http://www.dmp.wa.gov.au/documents/Guidelines/MSH_G_DieselTransportStorageAndRef uellingUG.pdf Department of industry and resources, 1997

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Page 11 of 11 19. http://www.dieselnet.com/standards/eu/fuel_auto.php DieselNet, 2010 20. http://www.eoearth.org/article/Cracking Cutler J. Cleveland, 2008 Images 1. http://en.wikipedia.org/wiki/File:RefineryFlow.png Generic oil refinery flow diagram - Mbeychok, 2008 2. http://new.backoffice.euromoneydigital.com/images/22/25267/0902_Michaelsen_Con_fig1.gif Hydrotreating of diesel flow diagram- R. Egeberg, 2009 3. http://www.uop.com/wp-content/uploads/2011/08/HVGO-HCGO.jpg Generic hydrocracking flow diagram - Honeywell Company, 2011 4. http://www.sciencephoto.com/image/339795/530wm/T1100494-Fuel_oil-SPL.jpg Fuel oil

Word count - 2340

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