REFINING OF PETROLEUM

Petroleum is a complex mixture of organic liquids called crude oil and natural gas, which occurs naturally in the ground and was formed millions of years ago. Crude oil varies from oilfield to oilfield in colour and composition, from a pale yellow low viscosity liquid to heavy black 'treacle' consistencies.

Crude oil and natural gas are extracted from the ground, on land or under the oceans, by sinking an oil well and are then transported by pipeline and/or ship to refineries where their components are processed into refined products. Crude oil and natural gas are of little use in their raw state; their value lies in what is created from them: fuels, lubricating oils, waxes, asphalt, petrochemicals and pipeline quality natural gas.

An oil refinery is an organised and coordinated arrangement of manufacturing processes designed to produce physical and chemical changes in crude oil to convert it into everyday products like petrol, diesel, lubricating oil, fuel oil and bitumen.

As crude oil comes from the well it contains a mixture of hydrocarbon compounds and relatively small quantities of other materials such as oxygen, nitrogen, sulphur, salt and water. In the refinery, most of these non - hydrocarbon substances are removed and the oil is broken down into its various components, and blended into useful products.

Natural gas from the well, while principally methane, contains quantities of other hydrocarbons - ethane, propane, butane, pentane and also carbon dioxide and water. These components are separated from the methane at a gas fractionation plant.

Petroleum hydrocarbon structures

Petroleum consists of three main hydrocarbon groups:

Paraffins

These consist of straight or branched carbon rings saturated with hydrogen atoms, the simplest of which is methane ($CH$4) the main ingredient of natural gas. Others in this group include ethane ($C$2H6), and propane ($C$3H8).

Hydrocarbons

With very few carbon atoms ($C$1 to $C$4) are light in density and are gases under normal atmospheric pressure. Chemically paraffins are very stable compounds.

Naphthenes

Naphthenes consist of carbon rings, sometimes with side chains, saturated with hydrogen atoms. Naphthenes are chemically stable, they occur naturally in crude oil and have properties similar to paraffins.

Aromatics

aromatic hydrocarbons are compounds that contain a ring of six carbon atoms with alternating double and single bonds and six attached hydrogen atoms. This type of structure is known as a benzene ring. They occur naturally in crude oil, and can also be created by the refining process.

The more carbon atoms a hydrocarbon molecule has, the "heavier" it is (the higher is its molecular weight) and the higher is its the boiling point.

Small quantities of a crude oil may be composed of compounds containing oxygen, nitrogen, sulphur and metals. Sulphur content ranges from traces to more than 5 per cent. If a crude oil contains appreciable quantities of sulphur it is called a sour crude; if it contains little or no sulphur it is called a sweet crude.

The refining process

Every refinery begins with the separation of crude oil into different fractions by distillation.

The fractions are further treated to convert them into mixtures of more useful saleable products by various methods such as cracking, reforming, alkylation, polymerisation and isomerisation. These mixtures of new compounds are then separated using methods such as fractionation and solvent extraction. Impurities are removed by various methods, e.g. dehydration, desalting, sulphur removal and hydrotreating.

Refinery processes have developed in response to changing market demands for certain products. With the advent of the internal combustion engine the main task of refineries became the production of petrol. The quantities of petrol available from distillation alone was insufficient to satisfy consumer demand. Refineries began to look for ways to produce more and better quality petrol. Two types of processes have been developed:

• breaking down large, heavy hydrocarbon molecules
• reshaping or rebuilding hydrocarbon molecules.

Distillation (Fractionation)

Because crude oil is a mixture of hydrocarbons with different boiling temperatures, it can be separated by distillation into groups of hydrocarbons that boil between two specified boiling points. Two types of distillation are performed: atmospheric and vacuum.

Atmospheric distillation takes place in a distilling column at or near atmospheric pressure. The crude oil is heated to $350 - 400oC$ and the vapour and liquid are piped into the distilling column. The liquid falls to the bottom and the vapour rises, passing through a series of perforated trays (sieve trays). Heavier hydrocarbons condense more quickly and settle on lower trays and lighter hydrocarbons remain as a vapour longer and condense on higher trays.

Liquid fractions are drawn from the trays and removed. In this way the light gases, methane, ethane, propane and butane pass out the top of the column, petrol is formed in the top trays, kerosene and gas oils in the middle, and fuel oils at the bottom. Residue drawn of the bottom may be burned as fuel, processed into lubricating oils, waxes and bitumen or used as feedstock for cracking units.

To recover additional heavy distillates from this residue, it may be piped to a second distillation column where the process is repeated under vacuum, called vacuum distillation. This allows heavy hydrocarbons with boiling points of $450oC$ and higher to be separated without them partly cracking into unwanted products such as coke and gas.

The heavy distillates recovered by vacuum distillation can be converted into lubricating oils by a variety of processes. The most common of these is called solvent extraction. In one version of this process the heavy distillate is washed with a liquid which does not dissolve in it but which dissolves (and so extracts) the non-lubricating oil components out of it. Another version uses a liquid which does not dissolve in it but which causes the non-lubricating oil components to precipitate (as an extract) from it. Other processes exist which remove impurities by adsorption onto a highly porous solid or which remove any waxes that may be present by causing them to crystallise and precipitate out.

Reforming

Reforming is a process which uses heat, pressure and a catalyst (usually containing platinum) to bring about chemical reactions which upgrade naphthas into high octane petrol and petrochemical feedstock. The naphthas are hydrocarbon mixtures containing many paraffins and naphthenes. In Australia, this naphtha feedstock comes from the crudes oil distillation or catalytic cracking processes, but overseas it also comes from thermal cracking and hydrocracking processes. Reforming converts a portion of these compounds to isoparaffins and aromatics, which are used to blend higher octane petrol.

• paraffins are converted to isoparaffins
• paraffins are converted to naphthenes
• naphthenes are converted to aromatics

e.g.

 catalyst heptane -> toluene + hydrogen  C7H16 -> C7H8 + 4H2
 catalyst cyclohexane -> benzene + hydrogen  C6H12 -> C6H6 + 3H2

Cracking

Cracking processes break down heavier hydrocarbon molecules (high boiling point oils) into lighter products such as petrol and diesel. These processes include catalytic cracking, thermal cracking and hydrocracking.

e.g.

A typical reaction:

 catalyst  C16H34 -> C8H18 + C8H16

Catalytic cracking is used to convert heavy hydrocarbon fractions obtained by vacuum distillation into a mixture of more useful products such as petrol and light fuel oil. In this process, the feedstock undergoes a chemical breakdown, under controlled heat ($450 - 500oC$) and pressure, in the presence of a catalyst - a substance which promotes the reaction without itself being chemically changed. Small pellets of silica - alumina or silica - magnesia have proved to be the most effective catalysts.

The cracking reaction yields petrol, LPG, unsaturated olefin compounds, cracked gas oils, a liquid residue called cycle oil, light gases and a solid coke residue. Cycle oil is recycled to cause further breakdown and the coke, which forms a layer on the catalyst, is removed by burning. The other products are passed through a fractionator to be separated and separately processed.

Fluid catalytic cracking uses a catalyst in the form of a very fine powder which flows like a liquid when agitated by steam, air or vapour. Feedstock entering the process immediately meets a stream of very hot catalyst and vaporises. The resulting vapours keep the catalyst fluidised as it passes into the reactor, where the cracking takes place and where it is fluidised by the hydrocarbon vapour. The catalyst next passes to a steam stripping section where most of the volatile hydrocarbons are removed. It then passes to a regenerator vessel where it is fluidised by a mixture of air and the products of combustion which are produced as the coke on the catalyst is burnt off. The catalyst then flows back to the reactor. The catalyst thus undergoes a continuous circulation between the reactor, stripper and regenerator sections.

The catalyst is usually a mixture of aluminium oxide and silica. Most recently, the introduction of synthetic zeolite catalysts has allowed much shorter reaction times and improved yields and octane numbers of the cracked gasolines.

Thermal cracking uses heat to break down the residue from vacuum distillation. The lighter elements produced from this process can be made into distillate fuels and petrol. Cracked gases are converted to petrol blending components by alkylation or polymerisation. Naphtha is upgraded to high quality petrol by reforming. Gas oil can be used as diesel fuel or can be converted to petrol by hydrocracking. The heavy residue is converted into residual oil or coke which is used in the manufacture of electrodes, graphite and carbides.

This process is the oldest technology and is not used in Australia.

Hydrocracking can increase the yield of petrol components, as well as being used to produce light distillates. It produces no residues, only light oils. Hydrocracking is catalytic cracking in the presence of hydrogen. The extra hydrogen saturates, or hydrogenates, the chemical bonds of the cracked hydrocarbons and creates isomers with the desired characteristics. Hydrocracking is also a treating process, because the hydrogen combines with contaminants such as sulphur and nitrogen, allowing them to be removed.

Gas oil feed is mixed with hydrogen, heated, and sent to a reactor vessel with a fixed bed catalyst, where cracking and hydrogenation take place. Products are sent to a fractionator to be separated. The hydrogen is recycled. Residue from this reaction is mixed again with hydrogen, reheated, and sent to a second reactor for further cracking under higher temperatures and pressures.

In addition to cracked naphtha for making petrol, hydrocracking yields light gases useful for refinery fuel, or alkylation as well as components for high quality fuel oils, lube oils and petrochemical feedstocks.

Following the cracking processes it is necessary to build or rearrange some of the lighter hydrocarbon molecules into high quality petrol or jet fuel blending components or into petrochemicals. The former can be achieved by several chemical process such as alkylation and isomerisation.

Alkylation

Olefins such as propylene and butylene are produced by catalytic and thermal cracking. Alkylation refers to the chemical bonding of these light molecules with isobutane to form larger branched-chain molecules (isoparaffins) that make high octane petrol.

Olefins and isobutane are mixed with an acid catalyst and cooled. They react to form alkylate, plus some normal butane, isobutane and propane. The resulting liquid is neutralised and separated in a series of distillation columns. Isobutane is recycled as feed and butane and propane sold as liquid petroleum gas (LPG).

e.g.

 catalyst isobutane + butylene -> isooctane  C4H10 + C4H8 -> C8H18

Isomerisation

Isomerisation refers to chemical rearrangement of straight-chain hydrocarbons (paraffins), so that they contain branches attached to the main chain (isoparaffins). This is done for two reasons:

• they create extra isobutane feed for alkylation

• they improve the octane of straight run pentanes and hexanes and hence make them into better petrol blending components.

Isomerisation is achieved by mixing normal butane with a little hydrogen and chloride and allowed to react in the presence of a catalyst to form isobutane, plus a small amount of normal butane and some lighter gases. Products are separated in a fractionator. The lighter gases are used as refinery fuel and the butane recycled as feed.

Pentanes and hexanes are the lighter components of petrol. Isomerisation can be used to improve petrol quality by converting these hydrocarbons to higher octane isomers. The process is the same as for butane isomerisation.

Polymerisation

Under pressure and temperature, over an acidic catalyst, light unsaturated hydrocarbon molecules react and combine with each other to form larger hydrocarbon molecules. Such process can be used to react butenes (olefin molecules with four carbon atoms) with iso-butane (branched paraffin molecules, or isoparaffins, with four carbon atoms) to obtain a high octane olefinic petrol blending component called polymer gasoline.

Hydrotreating and sulphur plants

A number of contaminants are found in crude oil. As the fractions travel through the refinery processing units, these impurities can damage the equipment, the catalysts and the quality of the products. There are also legal limits on the contents of some impurities, like sulphur, in products.

Hydrotreating is one way of removing many of the contaminants from many of the intermediate or final products. In the hydrotreating process, the entering feedstock is mixed with hydrogen and heated to 300 - $380oC$. The oil combined with the hydrogen then enters a reactor loaded with a catalyst which promotes several reactions:

• hydrogen combines with sulphur to form hydrogen sulphide ($H$2S)

• nitrogen compounds are converted to ammonia

• any metals contained in the oil are deposited on the catalyst

• some of the olefins, aromatics or naphthenes become saturated with hydrogen to become paraffins and some cracking takes place, causing the creation of some methane, ethane, propane and butanes.

Sulphur recovery plants

The hydrogen sulphide created from hydrotreating is a toxic gas that needs further treatment. The usual process involves two steps:

• the removal of the hydrogen sulphide gas from the hydrocarbon stream

• the conversion of hydrogen sulphide to elemental sulphur, a non-toxic and useful chemical.

Solvent extraction, using a solution of diethanolamine (DEA) dissolved in water, is applied to separate the hydrogen sulphide gas from the process stream. The hydrocarbon gas stream containing the hydrogen sulphide is bubbled through a solution of diethanolamine solution (DEA) under high pressure, such that the hydrogen sulphide gas dissolves in the DEA. The DEA and hydrogen mixture is the heated at a low pressure and the dissolved hydrogen sulphide is released as a concentrated gas stream which is sent to another plant for conversion into sulphur.

Conversion of the concentrated hydrogen sulphide gas into sulphur occurs in two stages.

1. Combustion of part of the $H$2S stream in a furnace, producing sulphur dioxide ($SO$2) water ($H$2O) and sulphur (S).
  2H2S + 2O2 -> SO2 + S + 2H2O
2. Reaction of the remainder of the $H$2S with the combustion products in the presence of a catalyst. The $H$2S reacts with the $SO$2 to form sulphur.
  2H2S + 2O2 -> 3S + 2H2O

As the reaction products are cooled the sulphur drops out of the reaction vessel in a molten state. Sulphur can be stored and shipped in either a molten or solid state.

Refineries and the environment

Air, water and land can all be affected by refinery operations. Refineries are well aware of their responsibility to the community and employ a variety of processes to safeguard the environment.

The processes described below are those used by the Shell refinery at Geelong in Victoria, but all refineries employ similar techniques in managing the environmental aspects of refining.

Air

Preserving air quality around a refinery involves controlling the following emissions:

• sulphur oxides
• hydrocarbon vapours
• smoke
• smells

Sulphur enters the refinery in crude oil feed. Gippsland and most other Australian crude oils have a low sulphur content but other crude's may contain up to 5 per cent sulphur. To deal with this refineries incorporate a sulphur recovery unit which operates on the principles described above.

Many of the products used in a refinery produce hydrocarbon vapours. The escape of vapours to atmosphere are prevented by various means. Floating roofs are installed in tanks to prevent evaporation and so that there is no space for vapour to gather in the tanks. Where floating roofs cannot be used, the vapours from the tanks are collected in a vapour recovery system and absorbed back into the product stream. In addition, pumps and valves are routinely checked for vapour emissions and repaired if a leakage is found.

Smoke is formed when the burning mixture contains insufficient oxygen or is not sufficiently mixed. Modern furnace control systems prevent this from happening during normal operation.

Smells are the most difficult emission to control and the easiest to detect. Refinery smells are generally associated with compounds containing sulphur, where even tiny losses are sufficient to cause a noticeable odour.

Water

Aqueous effluent's consist of cooling water, surface water and process water.

The majority of the water discharged from the refinery has been used for cooling the various process streams. The cooling water does not actually come into contact with the process material and so has very little contamination. The cooling water passes through large "interceptors" which separate any oil from minute leaks etc., prior to discharge. The cooling water system at Geelong Refinery is a once-through system with no recirculation.

Rainwater falling on the refinery site must be treated before discharge to ensure no oily material washed off process equipment leaves the refinery. This is done first by passing the water through smaller "plant oil catchers", which each treat rainwater from separate areas on the site, and then all the streams pass to large "interceptors" similar to those used for cooling water. The rainwater from the production areas is further treated in a Dissolved Air Flotation (DAF) unit. This unit cleans the water by using a flocculation agent to collect any remaining particles or oil droplets and floating the resulting flock to the surface with millions of tiny air bubbles. At the surface the flock is skimmed off and the clean water discharged.

Process water has actually come into contact with the process streams and so can contain significant contamination. This water is treated in the "sour water treater" where the contaminants (mostly ammonia and hydrogen sulphide) are removed and then recovered or destroyed in a downstream plant. The process water, when treated in this way, can be reused in parts of the refinery and discharged through the process area rainwater treatment system and the DAF unit.

Any treated process water that is not reused is discharged as Trade Waste to the sewerage system. This trade waste also includes the effluent from the refinery sewage treatment plant and a portion of treated water from the DAF unit.

As most refineries import and export many feed materials and products by ship, the refinery and harbour authorities are prepared for spillage from the ship or pier. In the event of such a spill, equipment is always on standby at the refinery and it is supported by the facilities of the Australian Marine Oil Spill Centre at Geelong, Victoria.

Land

The refinery safeguards the land environment by ensuring the appropriate disposal of all wastes.

Within the refinery, all hydrocarbon wastes are recycled through the refinery slops system. This system consists of a network of collection pipes and a series of dewatering tanks. The recovered hydrocarbon is reprocessed through the distillation units.

Wastes that cannot be reprocessed are either recycled to manufacturers (e.g. some spent catalysts can be reprocessed), disposed of in EPA-approved facilities off-site, or chemically treated on-site to form inert materials which can be disposed to land-fill within the refinery.

Waste movements within the refinery require a "Process liquid, Sludge and Solid waste disposal permit". Wastes that go off-site must have an EPA "Waste Transport Permit".