Monday, August 6, 2012

Refinery Feedstocks

The basic raw material for refineries is petroleum or crude oil, even though in some areas synthetic crude oils from other sources (Gilsonite, tar sands, etc.) and natural gas liquids are included in the refinery feedstocks. The chemical compositions of crude oils are surprisingly uniform even though their physical characteristics vary widely. The elementary composition of crude oil usually falls within the following ranges.

In the United States, crude oils are classified as paraffin base, naphthene base, asphalt base, or mixed base. There are some crude oils in the Far East which have up to 80% aromatic content, and these are known as aromatic-base oils. The U.S. Bureau of Mines has developed a system which classifies the crude according to two key fractions obtained in distillation: No. 1 from 482  to 527°F (250 to 275°C) at atmospheric pressure and No. 2 from 527 to 572°F (275 to 300°C) at 40 mmHg pressure. The gravity of these two fractions is used to classify crude oils into types as shown below.

The paraffinic and asphailic classifications in common use are based on the properties of the residuum left from nondestructive distillation and are more descriptive to the refiner because they convey the nature of the products to be expected and the processing necessary.

Crude petroleum is very complex and, except for the low-boiling components, no attempt is made by the refiner to analyze for the pure components contained in the crude oil. Relatively simple analytical tests are run on the crude and the results of these are used with empirical correlations to evaluate the crude oils as feedstocks for the particular refinery. Each crude is compared with the other feedstocks available and, based upon the operating cost and product realization, is assigned a value. The more useful properties are discussed.

API Gravity
The density of petroleum oils is expressed in the United States in terms of API gravity rather than specific gravity; it is related to specific gravity in such a fashion that an increase in API gravity corresponds to a decrease in specific gravity. The units of API gravity are °API and can be calculated from specific gravity by the following:

In equation (1), specific gravity and API gravity refer to the weight per unit volume at 60°F as compared to water at 60°F. Crude oil gravity may range from less than 10°API to over 50°API but most crudes fall in the 20 to 45°API range. API gravity always refers to the liquid sample at 60°F (15.6°C). API gravities are not linear and, therefore, cannot be averaged. For example, a gallon of 30°API gravity hydrocarbons when mixed with a gallon of 40°API hydrocarbons will not yield two gallons of 35°API hydrocarbons, but will give two gallons of hydrocarbons with an API gravity different from 35°API. Specific gravities can be averaged.

Sulfur Content, wt%
Sulfur content and API gravity are two properties which have had the greatest influence on the value of crude oil, although nitrogen and metals contents are increasing in importance. The sulfur content is expressed as percent sulfur by weight and varies from less than 0.1% to greater than 5%. Crudes with greater than 0.5% sulfur generally require more extensive processing than those with lower sulfur content. Although the term ‘‘sour’’ crude initially had reference to those crudes containing dissolved hydrogen sulfide independent of total sulfur content, it has come to mean any crude oil with a sulfur content high enough to require special processing. There is no sharp dividing line between sour and sweet crudes, but 0.5% sulfur content is frequently used as the criterion.

Pour Point, °F (°C)
The pour point of the crude oil, in °F or °C, is a rough indicator of the relative paraffinicity and aromaticity of the crude. The lower the pour point, the lower the paraffin content and the greater the content of aromatics.

Carbon Residue, wt%
Carbon residue is determined by distillation to a coke residue in the absence of air. The carbon residue is roughly related to the asphalt content of the crude and to the quantity of the lubricating oil fraction that can be recovered. In most cases =the lower the carbon residue, the more valuable the crude. This is expressed in terms of the weight percent carbon residue by either the Ramsbottom (RCR) or Conradson (CCR) ASTM test procedures (D-524 and D-189).

Salt Content, lb/1000 bbl
If the salt content of the crude, when expressed as NaCl, is greater than 10 lb/1000 bbl, it is generally necessary to desalt the crude before processing. If the salt is not removed, severe corrosion problems may be encountered. If residua are processed catalytically, desalting is desirable at even lower salt contents of the crude. Although it is not possible to have an accurate conversion unit between lb/1000 bbl and ppm by weight because of the different densities of crude oils,1 lb/1000 bbl is approximately 3 ppm.

Characterization Factors
There are several correlations between yield and the aromaticity and paraffinicity of crude oils, but the two most widely used are the UOP or Watson ‘‘characterization factor’’ (KW) and the U.S. Bureau of Mines ‘‘correlation index’’ (CI).
TB _ mean average boiling point, °R
G _ specific gravity at 60°F.
The Watson characterization factor ranges from less than 10 for highly aromatic materials to almost 15 for highly paraffinic compounds. Crude oils show a narrower range of KW and vary from 10.5 for a highly naphthenic crude to 12.9 for a paraffinic base crude.

The correlation index is useful in evaluating individual fractions from crude  oils. The CI scale is based upon straight-chain paraffins having a CI value of 0 and benzene having a CI value of 100. The CI values are not quantitative, but the lower the CI value, the greater the concentrations of paraffin hydrocarbons in the fraction; and the higher the CI value, the greater the concentrations of naphthenes and aromatics.

Nitrogen Content, wt%
A high nitrogen content is undesirable in crude oils because organic nitrogen compounds cause severe poisoning of catalysts used in processing and cause corrosion problems such as hydrogen blistering. Crudes containing nitrogen in amounts above 0.25% by weight require special processing to remove the nitrogen.

Distillation Range

The boiling range of the crude gives an indication of the quantities of the various products present. The most useful type of distillation is known as a true boiling point (TBP) distillation and generally refers to a distillation performed in equipment that accomplishes a reasonable degree of fractionation. There is no specific test procedure called a TBP distillation, but the U.S. Bureau of Mines Hempel and ASTM D-285 distillations are the tests most commonly used. Neither of these specify either the number of theoretical plates or the reflux ratio used and, as a result, there is a trend toward using the results of a 15:5 distillation (D-2892) rather than the TBP. The 15:5 distillation is carried out using 15 theoretical plates at a reflux ratio of 5:1. The crude distillation range also has to be correlated with ASTM distillations because product specifications are generally based on the simple ASTM distillation tests D-86 and D-1160. The TBP cut point for various fractions can be approximated by use of Figure bellow. A more detailed procedure for correlation of ASTM and TBP distillations is given in the API Technical Data Book—Petroleum Refining published by the American Petroleum Institute, Washington, DC.

Metals Content, ppm
The metals content of crude oils can vary from a few parts per million to more than 1000 ppm and, in spite of their relatively low concentrations, are of considerable importance. Minute quantities of some of these metals (nickel, vanadium, and copper) can severely affect the activities of catalysts and result in a lowervalue product distribution. Vanadium concentrations above 2 ppm in fuel oils can lead to severe corrosion to turbine blades and deterioration of refractory furnace linings and stacks.

Distillation concentrates the metallic constituents of crude in the residues, but some of the organometallic compounds are actually volatilized at refinery distillation temperatures and appear in the higher-boiling distillates.

The metallic content may be reduced by solvent extraction with propane or similar solvents as the organometallic compounds are precipitated with the asphaltenes and resins.

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