Petroleum naphtha is an intermediate hydrocarbon liquid stream derived from the refining of crude oil.[1][2][3] It is most usually desulfurized and then catalytically reformed, which re-arranges or re-structures the hydrocarbon molecules in the naphtha as well as breaking some of the molecules into smaller molecules to produce a high-octane component of gasoline (or petrol).
There are hundreds of different petroleum crude oil sources worldwide and each crude oil has its own unique composition or assay. There are also hundreds of petroleum refineries worldwide and each of them is designed to process either a specific crude oil or specific types of crude oils. That means that it is virtually impossible to provide a definitive, single definition of the word naphtha since each refinery produces its own naphthas with their own unique initial and final boiling points and other physical and compositional characteristics. In other words, naphtha is a generic term rather than a specific term.
In addition, naphthas may also be produced from coal tar, shale deposits, tar sands such as in Canada, the destructive distillation of wood and coal gasification or biomass gasification to produce a syngas[4][5] followed by the Fischer-Tropsch process to convert the syngas into liquid hydrocarbon products. For that reason, this article is entitled Petroleum naphtha and deals only with naphthas produced by the processing of crude oil in petroleum refineries.
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The first unit process in a petroleum refinery is the crude oil distillation unit. The overhead liquid distillate from that unit is called virgin or straight-run naphtha and that distillate is the largest source of naphtha in most petroleum refineries. The naphtha is a mixture of very many different hydrocarbon compounds. It has an initial boiling point (IFP) of about 35 °C and a final boiling point (FBP) of about 200 °C, and it contains paraffin, naphthene (cyclic paraffins) and aromatic hydrocarbons ranging from those containing 4 carbon atoms to those containing about 10 or 11 carbon atoms.
The virgin naphtha is often further distilled into two streams:[6]
It is the virgin heavy naphtha that is usually processed in a catalytic reformer because the light naphtha has molecules with 6 or less carbon atoms which, when reformed, tend to crack into butane and lower molecular weight hydrocarbons which are not useful as high-octane gasoline blending components. Also, the molecules with 6 carbon atoms tend to form aromatics which is undesirable because governmental environmental regulations in a number of countries limit the amount of aromatics (most particularly benzene) that gasoline may contain.[7][8][9]
The table below lists some typical virgin heavy naphthas, available for catalytic reforming, derived from various crude oils. It can be seen that they differ significantly in their content of paraffins, naphthenes and aromatics:
Crude oil name Location |
Barrow Island Australia[10] |
Mutineer-Exeter Australia[11] |
CPC Blend Kazakhstan[12] |
Draugen North Sea[13] |
---|---|---|---|---|
Initial boiling point, °C | 149 | 140 | 149 | 150 |
Final boiling point, °C | 204 | 190 | 204 | 180 |
Paraffins, liquid volume % | 46 | 62 | 57 | 38 |
Naphthenes, liquid volume % | 42 | 32 | 27 | 45 |
Aromatics, liquid volume % | 12 | 6 | 16 | 17 |
Some refinery naphthas also contain some olefinic hydrocarbons, such as naphthas derived from the fluid catalytic cracking, visbreakers and coking processes used in many refineries. Those olefin-containing naphthas are often referred to as cracked naphthas.
In some (but not all) petroleum refineries, the cracked naphthas are desulfurized and catalytically reformed (as are the virgin naphthas) to produce additional high-octane gasoline components.
Most uses of petroleum refinery naphtha require the removal of sulfur compounds down to very low levels (a few parts per million or less). That is usually accomplished in a catalytic chemical process called hydrodesulfurization which converts the sulfur compounds into hydrogen sulfide gas that is removed from the naphtha by distillation.
The hydrogen sulfide gas is then captured in amine gas treating units and subsequently converted into byproduct elemental sulfur. In fact, the vast majority of the 64,000,000 metric tons of sulfur produced worldwide in 2005 was byproduct sulfur from petroleum refining and natural gas processing plants (which also use amine gas treating units to remove hydrogen sulfide from the raw natural gas).[14][15]
In lieu of hydrodesulfurization, light naphthas may be treated in a Merox unit to remove any hydrogen sulfide and, more particularly, to remove mercaptans.
Some petroleum refineries also produce small amounts of specialty naphthas for use as solvents, cleaning fluids, paint and varnish diluents, asphalt diluents, rubber industry solvents, dry-cleaning, cigarette lighters, and portable camping stove and lantern fuels. Those specialty naphthas are subjected to various purification processes.
Sometimes the specialty naphthas are called petroleum ether, petroleum spirits, mineral spirits, paraffin, benzine, hexanes, ligroin, white oil or white gas, painters naphtha, refined solvent naphtha and Varnish makers' & painters' naphtha (VM&P) . The best way to determine the boiling range and other compositional characteristics of any of the specialty naphthas is to read the Material Safety Data Sheet (MSDS) for the specific naphtha of interest.
On a much larger scale, petroleum naphtha is also used in the petrochemicals industry as feedstock to steam reformers and steam crackers for the production of hydrogen (which may be and is converted into ammonia for fertilizers), ethylene and other olefins. Natural gas is also used as feedstock to steam reformers and steam crackers.