Composition, Classification, & Physical Properties of Crude Oils

Composition & Classification of Crude Oils

Main groups of compounds in crude oils Saturated Hydrocarbons: Usually the major group, except in degraded heavy oils; Contain normal plus isoalkanes (paraffins) & <1% S [methane, ethane, propane & n-butane are gases at STP; first liquid at STP is n-pentane (C5H12); first solid is n-hexadecane (C16H34)]; cycloalkanes (naphthenes) [cyclopropane (C3H6), and cyclobutane (C4H8) are gases at STP. First liquid is cyclopentane (C5H10); cyclopentane and cyclohexane predominate in most oils] and paraffinic-naphthenic oils Aromatic-naphthenic oils

Aromatic-Intermediate oils: contain <50% saturated HC & usually >1% S

Aromatic (Aromatic-Asphaltic) Hydrocarbons: Comprised of pure aromatics, naphthenoauromatics (condensed aromatic and saturated cycles) and benzothiophene derivatives (containing heterocycles with sulfur) Resins and Asphaltenes: These are high molecular weight polycyclic molecules containing N, S, and O atoms. There is strong positive correlation between the concentrations of aromatics, resins plus asphaltenes and the sulfur content

Paraffin-base crudes constitute only a tiny fraction of modern world crude supplies (~2%) The standard is Pensylvania crude; this and most other North American crudes are Paleozoic in age (from Michigan, Ohio, Oklahama) Nearly most of the paraffinic crudes from other continents are much younger: Mesozoic in southern Chile, Brasil, Southern Russia; even Tertiary in some African Basins, Caucasus, Borneo, Chinese basins Crudes dominated by the naphthenic components are called Asphalt-base oils, as asphalts are closely associated with the naphthenes and not with the paraffins. ~15% of world crude supplies are truly naphthene based; These are the black-oils of Venezuela, Mexico, parts of California, Gulf coast, and many Russian crudes The great majority of crude oils are of mixed base (naphthene paraffin); they include nearly all Middle East, Mid-continent, and North Sea oils Most crude oils contain minor quantities of HC (pristane and phytane) belonging to neither the paraffins nor the naphthene series; occurrences of these in crude oil and ancient sediments are believed to be derivatives of chlorophyll, and they constitute useful indicators of an oils origin The ratio between pristane and phytane content of a crude oil or rock extract indicates the type of organic matter from which the oil originated and/or the level of thermal maturation of the source. The ratio is therefore a vital fingerprint for any crude oil containing both molecules

Evolution & alteration change the composition of crude oils

Process
Thermal evolution Alteration (Degradation)

Initial crude
Paraffinicnaphthenic oil Paraffinic & Paraffinicnaphthenic oil Aromaticintermediate oils

Product
Paraffinic oil Aromatic- naphthenic (<1% S) Aromatic- asphaltic oils (>1% S)

Natural Gas
Natural gas consists of HC not condensable at 20C (68F) and atmospheric pressure These are the first four members of the paraffin series (methane through nbutane) Gas composed almost entirely of methane is dry gas; if the proportion of ethane (C2H6) and heavier molecules exceeds some arbitrary value (conventionally 0.3 US gallons of vapour / cubic feet of gas, or between 4 and 5%, in North America), the gas is called wet gas

Natural gases consisting largely or wholly of methane may have any one of three distinct origins Petroleum gas: formed as a byproduct of the generation of petroleum
Associated gas: accompanies oil Non-associated gas: no longer accompanies oil; formed by the thermocatalytic modification of petroleum

Coal gas: formed by the modification of coal, thermocatalytically or otherwise Bacterial gas: formed by the low-temperature alteration of organic matter at or near the earths surface The amount of gas in solution increases with increasing reservoir pressure, and exerts great effect upon the oils physical properties. This is also responsible for many oil wells to flow their oil to the surface without artificial assistance If the gas content is sufficient to saturate the oil under the existing conditions, the amount unable to go into solution forms a free gas cap above the oil

Non-HC constituents of oil & natural gases

Common non-HC constituents: Heterocompounds (S-N-O compounds) and Organocompounds containing certain heavy metals (principally V, Ni) in crude oil Natural gas may also contain N, H, He, Ar

S and its compounds

(most important heterocompound) Few are wholly without it Few contain >3% by weight S content is higher in heavy oils (higher MW, BP with more polar fractions i.e., resins and asphaltenes) than in light oils Small proportion of S in crude oil is in the form of elemental form in solution or of H2S; the greater part is bonded with C in organic combination Crude oils containing detectable amount of H2S Sour Crudes S content as low as 0.1 0.2% Sweet Crudes (Algeria, Angola, Nigeria) Low sulfur crude < 0.6 % S Intermediate crude: 0.6 1.7 % S High sulfur crude > 1.7 % S

High S content are found in reservoirs of dolomite anhydrate facies Middle EastArabian heavy fields, Iran, Suez graben 2.8 4.9 % S Athabasca tar sand in Alberta (very heavy degraded oil) 5.5 % S Boscan in Venezuela 5.4 % S In most of the major exporting countries (Middle East, Mexico, Venezuela) High S crudes are 5 10 times of sweet crude

H2 S
Gases high in H2S occur typically in carbonate-sulfate reservoirs and also contain higher than normal concentrations of N & CO2 H2S Concentrations exceeding 100 ppm in gas/oil Dangerous as it is highly corrosive to drilling equipment, particularly in deep well with high temperature North American Basins (the Permian Alberta, Tampico, and Reforma Campeche basin and Texas Panhandle); Permian of Ural Volga region; Jura Cretaceous of Aquitaine Basin in France 15 16 % H2S Deep Smackover in Southeastern USA (Jurassic) 30 % routine, 80-90% Deep carbonate reservoirs of Rocky Mt. Foothills 60-65% below 4000 m

Nitrogen
Nitrogen in crude oil is primarily related to the asphalt content 0.2 % N considered high (as in Los Angeles, Maracaibo (Venezuela), Tampico (Illinois) basins) High N gases occur especially in Paleozoic strata Up to 80 % San Juan Basin of New Mexico (He 3.0 7.5 % in addition) Up to 90 % Eastern part of Rotliegendes (Western Poland) Basin Pennsylvanian gases 19 % South Alberta gases 8 85 % Pakistani gas field 28 % N + high CO2 Orenburg (USSR) Sour gas in the Permian Reservoir (5.8 % N + 28 ppm Ar + 4.5 % H2S)

Oxygen Compounds
Oxygen compounds of definite structure in crude oils are acids (in many fields in southern USSR) and phenols Natural gases may contain considerable quantities of CO2 Paradox Basin in Utah (Carboniferous to Triassic reservoirs) Up to 90% Wyoming (Ordovician & Mississippian carbonates) 80 % Northern Mexico, Pakistan (some fields) ~ 50 %

Other elements in oil & gas

Natural gas may also contain H, He, or Ar Hydrogen in no case exceeds 0.5 %; usually < 0.1 % Helium Occurs in some dry gases particularly in those with high N content Fields producing both oil & gas more commonly contain 1 % or more He than dry gas fields In North America, most of the He-bearing reservoirs are over large basement uplifts Argon rarely exceed 0.1 % in natural gases Ar in gases is enriched in 40Ar to the extent of 6 10 % (derived from the decay of 40K) Radon occur in many crude oils

Organometallic compounds
Porphyrins are HC ring complexes containing N & a metallic (V, Ni) nucleus Porphyrin (traces 400 ppm in crude oils) C numbers range from 25 36, mostly 30 32 V 30 300 ppm (high S); Venezuela 1100 ppm Ni 20 85 ppm (low S) V : Ni ratio is highest in Paleozoic oils (> 1) Mesozoic & Cenozoic oils (< 1) There is good correlation between metals, sulfur, & asphaltene content Degraded oils, enriched in asphaltenes, contain also more metals than the nondegraded oils of similar origin Other metals, may be present are: Fe, Zn, Cu, Pb, As, Md, Co, Mn, Cr, etc.

Correlation Index
Useful means of classifying oils on a qualitative basis. CI is a number whose magnitude indicates certain characteristics of a crude oil distillation Paraffins: CI 0 (zero) Benzene: CI 100 Lower the CI greater the concentration of paraffins Higher the CI greater the concentration of naphthenic and aromatic HC

Physical properties of Oils

Chemical compositions of crude oils are the principal determinants of their physical properties

Specific Gravity of oil

Range 0.73 slightly above 1.0 Paraffin-base oils light Asphalt-base oils invariably heavy Earlier, gravity was expressed in degrees of the European Beaum scale, read directly on a hydrometer at 15.6C (60F); degree goes up as the density decreases; i.e., A high gravity oil is not a heavy oil but a light oil B = (140 / r) 130 Later, B has been replaced by API scale API value = (141.5 / r) 131.5 So that water under STP conditions becomes 10 API Relation between API & B API value = (1.01071 x B) 0.10714 Presently, the measured quantity is Density Relative to Water Kgdm-3

Relation between API gravity & relative density

API gravity Density

30 0.876

33 0.860

36 0.845

LPG 0.570

By general convention Oils with API gravities > 30 light 30 - 22 medium < 22 heavy < 10 extra-heavy Worldwide average value is ~33.3 API Most favoured grade of crude oil is ~37 API Oils heavier than 12 API difficult to be distinguished on the basis of gravity; viscosity provides a more useful discriminant Oils lighter than ~50 API not really oils but rather condensates / distillates

Tansleep sand (Elk Basin, Pennsylvania) gas 460-490 cf gas per barrel of oil 0.867/ 31.8 API 134 cf gas per barrel of oil 0.892/ 27.1 API

Rangley field, Colarado

Hawkins pool, (NE Texas)

0.849/ 35.2 API

0.870/ 31 API

0.869/ 31.3 API

0.960/ 16 API

~37 API Middle East, Mid-continent, Appalachian provinces (USA), Alberta, Libya, North Sea, etc. crudes
>40 API large quantities in Algeria, south-eastern Australia, Indonesia, Andes, etc. crudes

Very heavy crudes California, Mexico, Venezuela, Sicily, etc.

<6 API + ~8 % S some crudes from fractured Miocene reservoir rocks in California (Santa Maria Basin)

Viscosity of oil
Viscosity is the internal friction of a fluid, causing its resistance to change of form. It is the ratio of stress to shear per unit time; shear in liquid is not constant, but is proportional to time Viscosity = Force x Distance / Area x Velocity MLT-2L / L2 LT-1 = ML-1T-1 CGS Unit Poise Conventional Unit centipoise [1 cP = 10-2 Poise, viscosity of water at 20C (68F)] SI Unit mPas [1 cP 1 mPas] Saybolt Universal Second (SUS) number of seconds needed for a steel ball to roll through a standard volume of the fluid SUS = viscosity in cP x 4.635 / relative density Typical oil viscosities measured in SUS at STP are from ~1000 to 50 Viscosities of light oils: < 30 mPas Typical values (mPas): between 5.0 & 0.6 (gasoline) mPas Heavy asphaltic oils: 50,000 mPas (Miocene oil in Bolivar coastal field (W. Venezuela) Very heavy oil ~1,00,000 mPas (Cold Lake, Alberta); >106 mPas (Athabasca) HC having viscosities > 10,000 mPas are known as natural tars

Viscosity vary directly with densities Hence, viscosities of oil are a function of the number of C atoms and of the amount of gas dissolved in the oil

Figure: Effect of dissolved gas on viscosity & gravity of crude oil

Pour Point
A useful indicator of viscosity of crude oils; the lowest temperature at which the crude flows under prescribed, controlled conditions Pour points > 40C (more than 100F) are relatively common among crudes having high contents of paraffin wax (Middle eastern and African crudes flow at ~ - 36C) Oils with high pour points because of high wax contents have a shiny appearance & are associated with formation waters with low salinity When oils with high pour point rise in the traps, their temperatures are lowered and the waxes crystalise out, forming a residue of high molecular weight paraffins & oil becomes lighter Prolific basins in which the original oils were paraffinic and derived oils, in younger strata are asphaltic include the Carpathian Basin (Romania), & Niger delta basin (off Africa)

Both paraffinic & asphaltic crudes may undergo prolific volatilization through surface or near surface alteration that they become totally dried-up, so viscous that they effectively solids. The drying-up process is INSPISSATION

Very waxy crudes Uinta Basin (Western USA), Anaco trend (Eastern Venezuela) Reconcavo Basin (Brasil), Mendoza Basin (Argentina), Beatrice field (off Eastern Scottland), Mangyshlak field (east of the Caspian Sea), several fields in the Sirte Basin (Libya & Sudan); Remarkable proportion of the fields in young sandstone reservoirs in Eastern Asia & Australia, (many oils from West India & Upper Assam Basin of North Eastern India contain 10 15 % wax), most crudes from China, Sumatra, and the Gippsland off-shore basin in Australia.

Colours & RI of oils

Paraffinic oils are commonly light in colour yellow to brown by transmitted light, & green (of automobile engine oil) by reflected light Asphalt-base oils are commonly brown to black; RI of oils vary with the relative density, between 1.42 and 1.48 for most of the oils Lighter oils Lower indices At lower temperature Lower indices Within any one molecular weight range RI increase from paraffins through naphthenes, to aromatics

Volume
Oil in reservoir contains dissolved gas, and the volume of the solution depends upon the formation gas-oil ratio reservoir pressure

The gas that may be dissolved in oil under increasing pressure increases the volume of the solution until the saturation pressure (bubble point) is reached after which the volume decreases with increased pressure
0.5 0.8 barrel of gas-free oil on the ground (stock tank oil) may represent 1 barrel of oil in the reservoir at the saturation pressure The volume of liquid petroleum at constant pressure increases with increasing temperature, but at a much lower rate than gases The solubility of gas in oil increases linearly with pressure in accordance with Henrys law. Heavy crudes have much less capacity to hold gas

Fluorescence
Fluorescence is observed under UV radiation (2537 3650 ) All oils exhibit more or less fluorescence (bloom) Aromatic oils most fluorescent Fluorescent colours of crudes range continuously from yellow through green to blue Fluorescence is used in the logging of wells to locate oil showings in the cores, cuttings, and drilling mud Fluorescence rapidly reduces by aging; this helps in differentiating fresh oil from oil previously caught in the drilling mud

Optical Activity
Most crudes have optical activity (the power to rotate the plane of polarization of polarized light) Optical activity pertains to the presence of cholesterin (cholesterol), an alcohol (C26H45OH) Measured by a polariscope in degrees/mm Average range 0 1.2 degrees Plane rotated to the right dextrorotary left levorotary

Odor
Paraffins, naphthenes, aromatics, S, H2S, N-compounds have characteristics odor

Calorific value
Calorific value of the crude oil decreases as the specific gravity increases

Flash & Burning Point

These are the measurements of the hazard involved in handling and storing petroleum and petroleum products Flash point Temperature at which the vapours rising off the surface of the heated oil ignites with a flash Burning point At higher temperature ignition and burning with a steady flame at the surface

Coefficient of expansion
For an increase in temperature of 1F for crude oils, the coefficient of expansion varies between 0.00036 0.00096 For most crude oils 0.00040 to 0.00065 Average coefficient of expansion Pennsylvania crude oils 0.000840 Baku crude oils 0.000817

Heavier crude oils (lower API) lower coefficient & vice-versa