Petroleum Refinery Basics

Crude Oil components Refinery Flowchart Other refinery units Unit Opns & Unit Proces in refining

Physical and process Hazards

Thanks to
John Kulluk Ph.D.
Torrance Fire Department & Robert Distaso PE 714/573-6253 Orange County Fire Authority

Petroleum is extracted from underground reserves;

then it is cracked or refined into end products for various uses. The petroleum industry thus has two parts: an oil exploration and production industry upstream and a refinery industry downstream. Most oil producers also own refineries. But the reverse is not true; a high proportion of oil is sold

to refinery companies that do not produce crude

oil.

Refining Means. . .
1. To reduce to a pure state, to remove impurities
2. To improve or perfect

Salable products are made from crude.

What is Crude Oil?

Mixture of organic

carbon chain molecules Impurities include sulfur and nitrogen compounds Some metals and salts too

Components such as . . .
Straight-Chain

Hydrocarbons Olefins Cyclic H/C Aromatics (Benzene, toluene, xylenes)

Mercaptans Hydrogen Sulfide

(H2S) Greases Propane LPG

Other Hazardous Materials

Sulfur Hydrofluoric Acid (HF) Sulfuric Acid (H2SO4) Ammonia (NH3) Sodium Hypochlorite Radioactive Materials Chlorine Amines

MEK Sulfur Dioxide (SO2) Heavy Metal Catalysts Sour Water Caustic (fresh/spent) Alcohol Asbestos

Heat & Mass Transfer Opns

Heat & Mass Transfer Opns

The reactor effluent is then cooled via heat exchange with unit feedstocks, fractionated into the desired product streams via distillation, which are then further cooled via heat exchange with unit feedstocks. Individual refinery processes are described subsequently, simplified process flow diagrams will be provided to illustrate the specific process flow sequence for the applicable process.

In fractionation or distillation the feedstock is distilled into various cuts of target boiling ranges or even separated into individual hydrocarbon compounds. Distillation is accomplished by

imposing a temperature profile across the tower

enabling differences in the equilibrium compositions of the vapor and liquid phases to change the compositions throughout the distillation tower.

Heat is added to the hydrocarbons at the bottom of the tower through heat exchange in a reboiler

which vaporizes a portion of the tower bottoms

liquid for recirculation to the bottom of the tower. Heat is removed from the top of the tower through heat exchange in an overhead condenser and then returning a portion of the condensed hydrocarbons back to the tower as .reflux..

This heat addition at the bottom and heat removal from the top of the tower establishes the temperature profile across the tower. In some applications, additional heat is removed by heat exchange with circulating liquid pump-around streams which are withdrawn and returned at intermediate levels of the tower. Perforated tray decks or packed bed sections allow intimate contacting of the liquid and vapor phases followed by separation.

Composition of crude oil

Petroleum crude oils are : numerous hydrocarbons.

Hydrocarbons are chemical compounds made up of

predominantly carbon and hydrogen. Hydrocarbons found in crude oils generally also

contain the elements sulfur and nitrogen. Many crude

oils also contain absorbed levels of the toxic gas hydrogen sulfide (H2S).

Components_ To be removed
Crude oils may contain trace amounts of metals

such as nickel and vanadium, as well as salts.

Most of the nonhydrogen, non-carbon elements found in crude oils are undesirable and are removed from the hydrocarbons in total or in part during refinery processing.

Refinery Process Flow Chart

Sulfur Gas Plant Isom Splitter Reformer Hydrotreating Jet Fuel Distillate Fuel Alky Gasoline Fuel Gas

Leffler, 1985

Distilling

Hydrotreating

CCU
Flasher Visbreaker

Residual Fuel

The principal products, with their

approximate boiling points, are petroleum

gas (20C), naphtha (40C), petrol (70C),

kerosene and jet fuel (120C), diesel (200C),

lubricant (300C), and furnace oil (370C);

solid petroleum coke collects at the bottom

after the liquid fractions are removed.

FLUID CATALYTIC CRACKING

HYDRO TREATING

Many fuels products are treated as a finishing step prior to being shipped as .finished. products. Treating removes impurities which cause objectionable odors, unwanted colors or corrosion of the product. Hydrogen sulfide (H2S) and other sulfur compounds such as mercaptans

are examples of such impurities.

Amine contacting using aqueous amine solutions such as

monoethanolamine (MEA), diethanolamine (DEA), or methyldiethanol amine (MDEA) are commonly used to remove H2S from light ends streams prior to disposition as fuel gas or propane (i.e., Liquefied Petroleum Gas or .LPG.) product. The amine solution is then regenerated in a still in which the application of heat drives off the H2S. The H2S-rich stream produced

from the still (called acid gas.) is then routed to the Sulfur
Conversion process.

Other Refinery Units

Steam Generation Wastewater Treatment Hydrogen Generation Power Generation (e.g., cogen) Air Separation Plant Loading/Unloading - Railcar, Trucks, etc. Storage (high pressure hydrocarbon, crude oil, intermediates) Floating-Roof Tanks - 150 diameter is common Spherical Tanks - 50 are common Horton Spheroid (refrigerated) Steam-Heated Tanks for Heavier Products Self-Contained Firewater Supply Firewater Pumps

Whats All this Stuff?

What Goes on at a Refinery. . .?

Separation of components by distillation, e.g.:

Atmospheric Vacuum Hydrotreating (uses excess hydrogen)

Breaking apart molecules to make smaller ones, e.g.:

catalytic cracking hydrocracking

Reforming - alkylation that lengthens the hydrocarbon chain Reforming - cyclic that generates hydrogen

Joining molecules to make bigger ones, e.g.:

Physical Hazards

High Pressure/Temperature Steam Oil/Gas-Fired Furnaces Acoustic High Voltage (4160V, 480V, 13.2 kV) Falling Hazards Confined Space Hazards Cranes/Lifting Hazards Hot Work Hazards Acid Exposure Toxic Vapors Radiation Flammability Hazards

Common PPE Requirements

Hardhat Hardsoled / Hardtoe Shoes Safety Glasses with Side

Protection Safety Goggles or Faceshield Fire-Resistant Clothing

Process Hazards

Emergency Flare Atmospheric Pressure Relief High Temperature (up to 2000oF) Low Temperature (e.g., Brittle Fracture) High Pressure (up to 3000 psig) Low Pressure (e.g., vacuum)

Some petrochemicals are produced in large enough bulk to

take a significant proportion of refinery products: the world consumed 345 million tons of hydrocarbons in 2004

to make 310 million tons of petrochemicals.

Most of the hydrocarbons are first turned into one of three intermediates - ethylene, propylene and aromatics before being converted to other products. Of the latter, plastics accounted for 225 million tons, and fibres for 38 million tons; solvents, detergents and synthetic rubber accounted for most of the rest.