‘Worsthasst/) ee & oe Crude oil and cracking ei Crude oil is an invaluable source of organic compounds. About 95% of all synthesised organic ° compounds (e.g. plastics, polymer fibres, detergents, pharmaceuticals, agrochemicals etc.) are made from a number of key compounds that are produced in bulk from crude oil or natural gas. But, however important these compounds might be, we still use over 90% of our crude oil and natural gas as fuels. Petrol is one of those fuels. What is petrol? ‘The main source of petrol is the gasoline fraction obtained from the primary distillation of crude oil in 4 fractionating column, Usually this fraction accounts for 15-30% of the crude oil, It is a mixture of liquids with between five and ten carbon atoms, which boil in the range 20-180°C (see Question 3). The gasoline fraction is in great demand. Some goes to refineries to be used in producing motor fuels. The rest is used in the manufacture of organic chemicals ~ this part of the gasoline fraction is called naphtha. Supply and demand [Demand (summer) EB Supply Residue Diesel oll Kerosene (paraffin) Gasoline (naphtha} Gasoline (petrol) Refinery gas Seeders ne a er ae lee ot ee temic % by mass Figure 1 ‘As shown in Figure 1, the demand for the gasoline (petrol) fraction is much greater than the supply. Cracking is one of the most important processes in the petroleum industry because it allows the oil ‘companies to convert the kerosene and diesel oil fractions (for which supply is greater than demand) into petrol, thereby making up for the shortfall Cracking — how is it done? ‘There are two basic processes for splitting alkane chains: using heat, which is called thermal cracking: and using catalysts, which is called catalytic cracking (or cat cracking for short), Whichever process is used, sufficient energy must be supplied to break the very strong C-C and C-H bonds. Most of the ‘tacking carried out to produce petrol is done by cat cracking. The feedstock can be kerosene, diese! oi! or even the heavier fuel oils from the residue. The molecules in the feedstock can have 25-100 carbon atoms, although most will usually have 30-40 carbon atoms. Oo ‘ORGANIC CHEMISTRY 4 ® Filip Allan Updates“= mae IE ALKANES Wortksiheelf ee oe (Cracking reactions are quite varied. Some of the types of reactions are: a Sta Ces Hs HaC(CHa)0CHs ——* — He0—CH—CH,—CH—CHy + CH»=C—CH:CHs (2) alkanes > smaller alkanes + eycloalkanes (3) cycloalkanes > alkenes + branched allenes (4) alkenes — smaller alkenes In these reactions, carbon-carbon and carbon-hydrogen bonds are split homolytically in free radical reactions. The alkenes that are produced are important feedstocks for other parts of the petrochemicals industry. In a moder catalytic cracker, the cracking takes place in a 60-metre-high vertical tube about ‘2 metres in diameter (see Figure 2). It is called a riser reactor, because the hot vaporised hydrocarbons =~" and zeolife catalyst are fed into the bottom of the tube and forced upwards by steam, The mixture is called a fluidised bed, in which the solid particles flow like a liquid, Cracked products to fractionating — column Separator where products separate from catalyst ‘Waste gases: Regenerator where catalyst is cleaned (700°C) Stripping steam {to help separation) Riser reactor where the cracking reaction takes place (500°O) Air (to clean catalyst) Rogenerated catalyst (clean) roar NSCS Figure 2 How a cat cracker and steam noe It takes about 2 seconds for the mixture to flow from the bottom to the top of the tube — so the hydrocarbons are in contact with the catalyst for a short period of time. One of the problems with cat cracking is that, in addition to all the reactions that take place, coke (carbon from the decomposition of hydrocarbon molecules) forms on the catalyst surface so that the catalyst eventually becomes inactive. To overcome this, the powdery catalyst needs to be regenerated. After the riser reactor, the mixture passes into a separator, where jets of steam carry away the cracked products, leaving behind the solid catalyst. This then goes into the regenerator, where it takes Philp Aly Updates ORGANIC CHEMISTRY 1 oF aE ALKANES a s e about 10 minutes for the hot coke to bum off in the stream of air which is blown through the © regenerator. The catalyst is then reintroduced into the base of the reactor ready to repeat the cycle. © ‘The energy released from the burning coke heats up the catalyst. The catalyst transfers the energy @ to the feedstock so that cracking can occur without additional heating. s The catalyst Zeolites are a family of aluminium silicates often known as molecular sieves. Their silicon, oxygen and aluminium atoms provide a regular network of infinitesimally small (typically 3x 10" m to 1 x 10° m) pores and interconnecting channels, rather like a sponge (Figure 3). It is the size of the pores that is critical to the use of zeolites as catalysts. If the pore size is large enough, the zeolite can accommodate hydrocarbon molecules, which are cracked inside the structure. Zeolites have saved the oil industry billions of pounds because they are so efficient and produce more commercially desirable products than the previous clay catalysts. a Figure 3 Two types of zeolite Type B structure Cat crackers have been in operation since the Jate 1940s and have handled a wide range af different feedstocks. The conditions and catalyst can be varied to give the maximum amount of the desired product ~ in this case branched alkanes for blending in petrol. Other cat crackers are geared up to produce large amounts of ethene (CH_=CH.), an important raw material for the petrochemicals industry. (Adepeed from Making petvol ~ getting the right octane rating’ in Chemical Storylines, Salters Advanced Chemistry, Heinemann (1994) Questions ‘Many people believe that crude oil is too precious to be used simply as fuel. Why might they think this? Explain, in some detail, how crude oil is formed, Nabe € > oreanie CHEMISTRY 1s lip Alan UpeatesE ALKANES Using the table below, determine what fraction from the primary distillation of crude oil would be most * likely to contain the following hydrocarbons? e Name of Boiling % fraction. range/°C Composition crude oil Use Refinery <20 CHG 12 Gaseous fuels and blending gas with petrol feedstock for organic chemicals Gasoline/ 20-180 Cs-Cio 15-30 Petrol for cars (gasoline) naphtha Production of organic chemicals (naphtha) Kerosene 160-250 Co Cig 1015 Jet fuel ~ (paratfin) Heating fuel Diesel ofl 220-370 Cis-Crs 15-20 Diesel fuel Heating fuel Residue >370 >Os 40-50 Fuel oil (e.g. power stations) Lubricating oils and waxes Bitumen or asphalt for roads and roofing (a) Case (b) Cito (0) Cobley (@) CoHhe ‘The following molecules are all found in petrol. In each case, draw one possible structural formula. (@) CH (b) CiHs a (©) GBs Write balanced symbol equations to describe the following reactions: (2) Cio is cracked to produce decane and ethene. (©) Cube is cracked to produce ethene, hydrogen and one other compound, (©) CisHs is cracked to produce ethene and propene in 2 2:1 ratio and only one other compound. Name the fwo basic processes used in industry to break up alkane chains, Which process is used to produce petrol? ‘The catalytic cracking reaction is also very important because it can be used to produce alkenes. (a) Why are alkenes important feedstocks for the petrochemicals industry, whilst alkanes are less so? (b) Give an example of the use of an alkene in a commercially important reaction \cgoeld ‘Pili Alln Updaies ORGANIC CHEMISTRY 1 Wois 2 zs EB) gue aLkanes 2 : came e & (@) The demand for diesel oil and residue is greater in winter than in summer. Why? 8 ¢ (b) Why is the demand for petrol fairly constant in summer and in winter? ® (©) What could an oil company do to cope with the changing demand between summer and winter? @ {a) Cracking reactions are believed to be ‘free radical’ reactions. What is a free radical? (b) A variety of products are produced on cat cracking in the riser reactor. How are they separated? (c) When the crude oil is fractionally distilled, the fractional distillation is carried out under reduced pressure, i.e, vacuum distillation is carried out. Why? (@) Some of the compounds found in crude petroleum contain sulfur, Petrol is obtained by refining crude petroleum, State and explain two reasons why sulfur compounds are removed from petrol during its manufacture. Calculate the enthalpy chenge for the following reactic HoC—CHp—CHp—CHp—CHy— CHy— CHa —CH— Cy ~ CHa ~CHy CH (Re toe xB om poe ews Cs cH Ho oHe a xT as HgO—CH—CHp—CH—CHy + —clcHs ee ee r T given the following average bond enthalpies (in kJ mol) (a) What is a ‘zeolite’? (b) If you look at a packet of washing powder, you will probably find that more than a quarter of the powder is made from zeolites. What do you think might be the purpose of the zeolites in the washing powder? Suggest how the zeolite is able to achieve this function, ORGANIC CHEMISTRY 1 ‘ Pailip Allan Updates