ENERGY ENGINEERING

4th Term, B.Sc. Chemical Engineering Session 2009 Delivered by:

Mr. Usman Ali
Department of Chemical Engineering University of Engineering & Technology, Lahore

Division Of Petroleum & Related Materials Into Various Classes

Petroleum Properties
Hydrocarbon properties vary regularly with increasing molecular weight As molecular weight increases, the melting point, boiling point, and density of the compound increase
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CLASSIFICATION OF PETROLEUM
Natural materials
Petroleum

Manufactured materials
Wax

Derived materials
Oils

Mineral wax
Asphalt or bitumen Asphaltite Asphaltoid

Asphalt
Tar Pitch Synthetic crude oil

Resins
Asphaltenes Carbenes Carboids

Bituminous rock

CLASSIFICATION OF PETROLEUM
By Compound type:
Paraffin Base: This classification was based on the fact that some petroleum oils separated paraffin wax on cooling leading to the conclusion, that these consisted mainly of paraffin's (e.g. methane, ethane, propane etc. with generic formula CnH2n+2). Asphaltic Base: These were the petroleum oils which gave no separation of paraffin wax on cooling again leading to the conclusion that these predominantly contained cyclic (or napthenic) hydrocarbons. Mix Base: These petroleum oils leave a mixture of paraffin wax & asphaltic bitumen when subjected to nondestructive distillation & hence the name. Hybrid Base: These are basically asphaltic oils that contain a small amount of wax.

By Density :
Density (specific gravity) since the early times of petroleum processing has been the principal method of classification. It is still used as an index for finding out the proportion of gasoline & particularly, kerosene present. However, density measurement remained an important criteria for classification till other properties of crudes were discovered & came into use. Nowadays, it is only one of the various properties for petroleum classification & no classification is solely based on density.
The use of density values has been advocated for quantitative application using a scheme based on the American Petroleum Institute (API) gravity of fractions.

Light (b. p. 250-270 C) fraction

Heavy (b. p. 275-300 C) fraction

Class
Paraffin ParaffinIntermediate Intermediate-

API* 60/60 F
> 40.0 > 40.0

Sp. Gr.
< 0.8251 < 0.8251

Type
Paraffinic Paraffinic
Intermediate Intermediate Intermediate

API 60 F
> 30.0 20.1 -29.9

Sp. Gr. 60/60 F

< 0.8762 0.9334 0.8767

33.1 - 39.9

0.8597 0.8256

> 30.0

< 0.8762

Paraffin
Intermediate Intermediate Napthene
33.1 - 39.9 0.8597 0.8256 20.1 -29.9 0.9334 0.8767

33.1 - 39.9

0.8597 0.8256

< 20.0

> 0.9340

Napthene
Intermediate

< 33.0

> 0.8602

Napthenic Napthenic Paraffinic Napthenic

20.1 -29.9

0.9334 0.8767

Napthene Paraffin napthene Napthene Paraffin

< 33.0 > 40.0

> 0.8602 < 0.8251

< 20.0 < 20.0

> 0.9340 > 0.9340

33.0

> 0.8602

> 30.0

< 0.8762

By Carbon Distribution:
The distribution according to volatility of the various fractions of petroleum is considered the main property for classification. Any fractionating column with sufficient number of theoretical trays may be used for generating a curve in which the boiling point of each fraction is plotted against percentage by weight.
A method known as the n-d-M method (n: refractive index, d: density, M: molecular weight) Is used for characterization of various fractions of petroleum. This method enables determination of carbon distribution &, thus, indicates the percentage of carbon in aromatic structure (%CA), the percentage of carbon in napthenic structure (%CN), & the percentage of carbon in paraffinic structure (%CP).

Fractions
Natural gas, often associated with petroleum, contains one to four carbon toms (C1 to C4) The compounds from C6 to C10 makes up the gasoline fraction Kerosene is composed of C10 to C16 compounds. C17 to C22 compounds make up lubricating oils and petroleum jelly Those C22 and C29 are often called tar or asphalt

Viscosity-Gravity Constant:
The viscosity- gravity constant was one of the early indexes proposed to characterize (or classify) oil types & is an indication of the paraffinicity of crude oil.
vgc = {10d 1.0752log (v-38)} / {10 log (v 38)}

where d is the sp. gravity 60 / 60 F & v is the saybolt viscosity ay 38 C The lower the index number, the more paraffinic the stock

Correlation Index:
This index, developed by the U. S. Bureau of Mines, is based on the plot of specific gravity at 60/60 F versus the reciprocal of the boiling point in degrees Kelvin for pure hydrocarbons on which the line described by the constants of the individual members of the normal paraffin series is given a value of CI = 0, & a parallel line passing through the point for the values of benzene is given as CI = 100. From this plot, the following empirical equation is derived: CI = 473.7d 456.8 + (48640/K) Where K is the average boiling point, determined by the US Bureau of Mines standard distillation method & d is the specific gravity.

Contd.
The values of the index between 0 & 15 indicate a predominance of paraffinic hydrocarbons in the fraction. Values from 15 to 50 indicate a predominance either of napthenes or of mixtures of paraffins, napthenes, & aromatics. Values above 50 indicate the predominant aromatic character.

Contd.
The horizontal axis represents a progression from paraffinic oils to aromatic oils with 0 representing n-paraffins & 100 representing benzene. The position of a crude on this scale is determined by the avg. correlation index for its fractions boiling between 200 C at atmospheric pressure & 275 C at 40 mm Hg, & the paraffinic, or cyclic nature of the fractions, & thereby, the nature of the bulk of the crude, are expressed directly. The height of the vertical bar above the horizontal indicates the wax content of the heavy gas oil & light lubricating fractions of that crude &, hence, the crystalline wax content of the crude can be assessed. The length of the vertical bar below the horizontal is a measure of the carbon residue (Conradson) of the undistilled residuum &, thereby the content of each crude. By combining these indicative properties with results of distillation, the petroleum can be classified in terms of composition & application.

The Universal Oil Products (UOP) Characterization factor:

This factor is perhaps one of the more widely used of the derived characterization or classification factors & is defined by the formula: K = ( TB )1/3 / d
where TB is the average boiling point in degrees Rankine & d is the specific gravity 60 / 60 F. This factor has been shown to be additive on a weight basis. It was originally devised to show the thermal cracking characteristics of heavy oils; thus, highly paraffinic oils have K~ 12.5 to 13.0 while cyclic (napthenic) oils have K~ 10.5 to 12.5.