Chapter 2

CRUDE OILS - CHEMISTRY AND COMPOSITION

1/16/2012

Crude Oil-Chemistry and Composition

CRUDE OIL SAMPLER

1/16/2012

Crude Oil-Chemistry and Composition

1/16/2012

Crude Oil-Chemistry and Composition

INTRODUCTION
Petroleum, literally, means rock oil. It is natural organic material composed principally of hydrocarbons which occur in the gaseous or liquid state in geological traps. The liquid part obtained after the removal of dissolved gas is commonly referred to as crude petroleum or crude oil or simply crude.

Crude oil occurs in many different parts of the world, and its structure and composition varies according to its source to such an extent that each producing area, and field, and reservoir bears its own profile just as individually as finger prints identify man.

1/16/2012

Crude Oil-Chemistry and Composition

1/16/2012

Crude Oil-Chemistry and Composition

CHARACTERISTICS OF CRUDE OILS

Crude oil has been defined as a naturally occurring mixture, consisting predominantly of hydrocarbons and/or sulphur, nitrogen and/or oxygen derivatives of hydrocarbons, which can be removed from the earth. Crude oil is commonly accompanied by varying quantities of extraneous substances such as water, inorganic matter and gas.

Crude oils range widely in their physical and chemical properties. Typical properties of several crudes are given in Table 2.1. Crude oils are brownish (light oils having large amounts of distillates) to brownish black (heavy oils) in colour. Heavy oils have an unpleasant odour (garlic like) due to the sulphur compounds, while the light crudes have pleasant aromatic like smell.

1/16/2012

Crude Oil-Chemistry and Composition

 Specific gravities of crude oils vary from 0.73 to 1.02 out of which most of the crudes have there specific gravities lying in between 0.80 and 0.95. The kinematic viscosities vary from 0.7 to 1300 cSt at 37.8C; the bulk of the values being in the range of 2.323 cSt . In terms of elements, crude oils are composed principally of carbon and hydrogen. Of the other elements present, sulphur, nitrogen and oxygen appear as heteroatoms in hydrocarbon derivatives, some of which occur as complexes involving traces of metals (mainly vanadium and nickel). The carbon hydrogen ratio is usually between 6 and 8.

1/16/2012

Crude Oil-Chemistry and Composition

CONSTITUENTS OF CRUDE OILS

The main constituents of crude oils are hydro - carbons . The proportions of the different types of hydrocarbons vary from one crude oil to another . Naphthenic acids , complex nitrogen compounds , and mercaptans account for some of the oxygen , nitrogen and sulphur present in crude oils . The resinous and asphaltic substances present in some of the crudes contain oxygen and sulphur . Inorganic sulphur can be present as hydrogen sulphide (H2S) dissolved in the oil . Crude oil also contains traces of metals mostly dissolved in water as impurities or existing as complexes in the hydrocarbon phase .
1/16/2012 Crude Oil-Chemistry and Composition 8

 Chlorophyll porphyrins have been found in small amounts in many crude oils . These compounds indicate a contribution from plant sources , animal type porphyrins have also been detected in traces.

Isoprenoid hydrocarbons have been recognized; these compounds have structures typical of substances formed biologically .
1/16/2012 Crude Oil-Chemistry and Composition 9

PROPERTIES OF CRUDE OILS

Properties Ankaleshwar North/ Gujarat Bombay High Basrah UMM Shaiff Kirkuk

1. Sp. gr. at 15C 2. API

3. Colour 4. Total sulphur, wt.% 5. RSH,ppm 6. H2S, ppm 7. RVP at 37.8C , kPa 8. Pour point, C 9. Wax content, wt.% 10. Flash point, C 11. Kinematic viscosity at 37.8 C , cSt

0.7887 48.0 Brownish black

0.05 vol.% 66.86 18 9.3 <27 2.02 Nil 0.05 3-5 12.0

0.8868 28.0
Black 0.07 vol.% 15.23 27 10.8 19.68 @50C 1.5 1.0 30-35 11.8

0.8366 38.0 Brownish black

0.13 21.37 30 12.5 < 27 3.816 0.04 0.05 8.0 0.0047 11.7

0.852 34.5
Black 1.9 Nil 54.45 -15 6 15 5.9 Nil 0.15 7.0 0.006 .

0.839 37.0
Brown 1.38 20 42.73 -15 7 3.8 0.1 0.2 1.5 0.004 -

0.840 35.5
1.9 200 55-65.5 0.2 0.2 5.0 10

12. Water content, vol.% 13. BS&W, vol.% 14. Salt content, wt.% 15. Ash content, wt. % 16. Kuop
1/16/2012

Crude Oil-Chemistry and Composition

ELEMENTAL COMPOSITION OF CRUDE OILS Element C H S N 0 Metals Amount, wt. % 83.9-86.8 11.0-14.0 0.06-8.00 0.02-1.70 0.08-1.82 0.00.14

1/16/2012

Crude Oil-Chemistry and Composition

11

HYDROCARBONS

Hydrocarbons are compounds composed solely of hydrogen and carbon . The main types of hydrocarbons present in crude oils are alkanes, cycloalkanes, arenes and hybrids involving combination of these types .They range widely in boiling point , and many cannot be distilled under atmospheric pressure without breakdown .

1/16/2012

Crude Oil-Chemistry and Composition

12

Alkanes
These are open chained saturated hydrocarbons . They are also known as paraffins . They can be divided into two types : Straight chain alkanes - normal . Branched chain alkanes - iso or neo .

Alkanes have a general formula CNH2N+2 , where N is the number of carbon atoms .The names of alkanes end in - ane . The first four alkanes are methane ,ethane , propane , butane . All higher alkanes starting from butane are isomeric .

1/16/2012

Crude Oil-Chemistry and Composition

13

Cycloalkanes

1/16/2012

Crude Oil-Chemistry and Composition

14

 The heavier fractions of crude oil contain the fused polycyclic type napthenes , i.e. bicyclic C10 compounds and tetracyclic C27 compounds .

substituted cyclopentane, cyclohexane, bicyclic species

1/16/2012

Crude Oil-Chemistry and Composition

15

ARENES OR AROMATICS

substituted aromatics - xylene, naphthalene, perylene

1/16/2012

Crude Oil-Chemistry and Composition

16

Crude oil also contains polynuclear aromatic hydrocarbons anthracene, phenanthrene etc .

such

as biphenyl , naphthalene,

The most common aromatics found in crude oils are toluene and m-xylene . The polynuclear species, if present contain at least eight condensed rings . Many polycyclic aromatic hydrocarbons present in petroleum are carcinogens .

1/16/2012

Crude Oil-Chemistry and Composition

17

ALKENES

1/16/2012

Crude Oil-Chemistry and Composition

18

 Alkenes apart from structural isomerism also show geometrical isomerism ,due to the double bond .

The geometrical isomers are classified by the Latin prefixes cis (same side) and trans (across) indicating the relative locations of the two end methyl groups . Alkenes incorporating two or more C=C bonds are known as dienes ,trienes and so on, and collectively as polyenes .

1/16/2012

Crude Oil-Chemistry and Composition

19

ALKYNES
Alkynes are open-chain hydrocarbons containing one carbon-carbon triple bond . The first member of this series is acetylene , C2H2, which is a linear molecule . The IUPAC system of nomenclature applies throughout the series as with the alkenes ,but the system treats the lighter members as derivatives of acetylene . The boiling points and relative densities of the alkynes are slightly higher than those of the corresponding alkanes .
1/16/2012 Crude Oil-Chemistry and Composition 20

CYCLOALKANOARENES

1/16/2012

Crude Oil-Chemistry and Composition

21

NON-HYDROCARBONS
Crude oils contain appreciable amounts of organic compounds with one or more atoms of sulphur ,nitrogen or oxygen in addition to carbon and hydrogen and some of these are associated with metals such as vanadium and nickel ,i.e. they are organometallic in nature .

1/16/2012

Crude Oil-Chemistry and Composition

22

SULPHUR COMPOUNDS
Sulphur is the most abundant atomic constituent of crude oils , other than carbon and hydrogen . The origins of sulphur compounds in crude oil are :The natural sulphur content of the tissues of the plant and animal remains deposited in ancient geological beds . The biogenic reduction of sulphate . Crude oils vary considerably in there sulphur content ,ranging from traces to as much as 8 % of sulphur . The sulphur content of 13.95% found in Rozal point ( USA) is the highest recorded sulphur content for crude oil.

1/16/2012

Crude Oil-Chemistry and Composition

23

 Sulphur compounds present in crude oils can be divided into thiols , mono- and disulphides and thiophenes . Thiols are the main sulphur compounds of lower boiling petroleum fractions(below 200C) .
EXAMPLES OF THIOLS.

1/16/2012

Crude Oil-Chemistry and Composition

24

 Thiol presence in the petroleum fractions causes corrosion problems ,catalyst poisoning and unpleasant laboratory and plant odours. Thiols are often used as odourants in LPG .The lower thiols are most malodourous (offensive smell). One part in 50 million of ethane thiol can be detected in air by the human nose. The odour is strong at 0.6 ppm and distinct at 0.3-0.07 ppm. At higher concentrations the odour is something like that of chloroform. Thiols are stronger acids than alcohols , and use is made of this to remove low molecular weight thiols from light gasolines with caustic soda solution.
1/16/2012 Crude Oil-Chemistry and Composition 25

MONOSULPHIDES
Monosulphides (thialkanes and thiacycloalkanes) are compounds formally derived by replacement of both hydrogen of HSH by hydrocarbon groups . These appear in traces in crude oils .

As in case of thiols the sulphides are generally very malodourous.

1/16/2012 Crude Oil-Chemistry and Composition 26

DISULPHIDES AND THIOPHENES

These occur in very small quantities in crude oil. The occurrence of disulphides in crude oils may be owing to the secondary reaction of thiols with an oxidant such as air or free sulphur .

1/16/2012

Crude Oil-Chemistry and Composition

27

NITROGEN COMPOUNDS
Nitrogen occurs in crude oils to a lesser extent than sulphur , frequently amounting to only one tenth of the sulphur present. The nitrogen compounds present are divided into : Basic nitrogen compounds . Non basic nitrogen compounds .

1/16/2012

Crude Oil-Chemistry and Composition

28

 The non-basic nitrogen compounds are most abundant and are found in higher boiling fractions of crude oil.

Anilines ,phenazines and nitriles have also been found in petroleum fractions after catalytic cracking . Porphyrins may also be present either in free state or as complexes containing nitrogen compounds and organic derivatives of vanadium and nickel. Unlike sulphur compounds ,the nitrogen compounds are relatively stable towards heat and do not decompose under refining conditions .

1/16/2012

Crude Oil-Chemistry and Composition

29

OXYGEN COMPOUNDS
The total amount of oxygen in crude oils is relatively low , varying from traces to a maximum of 2%. The oxygen concentration increases from lighter fractions to heavier ones. In the low and medium-boiling range distillate fractions, oxygen is mainly present in the form of carboxylic acids and to a limited extent, phenols.

1/16/2012

Crude Oil-Chemistry and Composition

30

METALLIC COMPOUNDS
Large number of metallic compounds including iron, vanadium, nickel, aluminum, sodium, calcium, copper, magnesium, manganese, barium, silicon, chromium, strontium, lead, molybdenum, cobalt, gold, silver, titanium have been found . The most abundant is vanadium (0.1% by weight) nickel and iron follow in next at comparative concentrations .Other metals occur in traces . They are undesirable in refining operations due to the fact that they produce undesirable reactions .
1/16/2012 Crude Oil-Chemistry and Composition 31

ASPHALTENES AND RESINS

Asphaltenes are black amorphous solids. These are generally considered as highly aromatic materials of fairly high molecular weight. Different methods of determining molecular weights have led to values ranging widely from 600 to 30000. Resins are dark-coloured, solids or semi-solids. These possess lower molecular weights (800-2000) than asphaltenes and are generally less aromatic in nature and comprise fewer condensed rings. These are present in the asphaltic residuum which remains after removal of distillable material from crude oil. Asphaltenes and resins contain in addition to carbon and hydrogen, some nitrogen, sulphur and oxygen and some trace metals .

1/16/2012

Crude Oil-Chemistry and Composition

32