Distillation columns in an oil refinery Photo courtesy Phillips Petroleum

Fractional Distillation
The various components of crude oil have different sizes, weights and boiling temperatures; so, the first step is to separate these components. Because they have different boiling temperatures, they can be separated easily by a process called fractional distillation. The steps of fractional distillation are as follows: 1. You heat the mixture of two or more substances (liquids) with different boiling points to a high temperature. Heating is usually done with high pressure steam to temperatures of about 1112 degrees Fahrenheit / 600 degrees Celsius. 2. The mixture boils, forming vapor (gases); most substances go into the vapor phase. 3. The vapor enters the bottom of a long column (fractional distillation column) that is filled with trays or plates. The trays have many holes or bubble caps (like a loosened cap on a soda bottle) in them to allow the vapor to pass through. They increase the contact time between the vapor and the liquids in the column and help to collect liquids that form at various heights in the column. There is a temperature difference across the column (hot at the bottom, cool at the top). 4. The vapor rises in the column. 5. As the vapor rises through the trays in the column, it cools. 6. When a substance in the vapor reaches a height where the temperature of the column is equal to that substance's boiling point, it will condense to form a liquid. (The substance with the lowest boiling point will condense at the highest point in the column; substances with higher boiling points will condense lower in the column.). 7. The trays collect the various liquid fractions. 8. The collected liquid fractions may pass to condensers, which cool them further, and then go to storage tanks, or they may go to other areas for further chemical processing Fractional distillation is useful for separating a mixture of substances with narrow differences in boiling points, and is the most important step in the refining process. The oil refining process starts with a fractional distillation column. On the right, you can see several chemical processors that are described in the next section. Very few of the components come out of the fractional distillation column ready for market. Many of them must be chemically processed to make other fractions. For example, only 40% of distilled crude oil is gasoline; however, gasoline is one of the major products made by oil companies. Rather than continually distilling large quantities of crude oil, oil companies chemically process some other fractions from the distillation column to make gasoline; this processing increases the yield of gasoline from each barrel of crude oil.

In the next section, we'll look at how we chemically process one fraction into another.

From Crude Oil
The oil refining process starts with a fractional distillation column. The problem with crude oil is that it contains hundreds of different types of hydrocarbons all mixed together. You have to separate the different types of hydrocarbons to have anything useful. Fortunately there is an easy way to separate things, and this is what oil refining is all about. Different hydrocarbon chain lengths all have progressively higher boiling points, so they can all be separated by distillation. This is what happens in an oil refinery - in one part of the process, crude oil is heated and the different chains are pulled out by their vaporization temperatures. Each different chain length has a different property that makes it useful in a different way. To understand the diversity contained in crude oil, and to understand why refining crude oil is so important in our society, look through the following list of products that come from crude oil: Petroleum gas - used for heating, cooking, making plastics
   

small alkanes (1 to 4 carbon atoms) commonly known by the names methane, ethane, propane, butane boiling range = less than 104 degrees Fahrenheit / 40 degrees Celsius often liquified under pressure to create LPG (liquified petroleum gas)

Naphtha or Ligroin - intermediate that will be further processed to make gasoline
 

mix of 5 to 9 carbon atom alkanes boiling range = 140 to 212 degrees Fahrenheit / 60 to 100 degrees Celsius

Gasoline - motor fuel
  

liquid mix of alkanes and cycloalkanes (5 to 12 carbon atoms) boiling range = 104 to 401 degrees Fahrenheit / 40 to 205 degrees Celsius

Kerosene - fuel for jet engines and tractors; starting material for making other products
  

liquid mix of alkanes (10 to 18 carbons) and aromatics boiling range = 350 to 617 degrees Fahrenheit / 175 to 325 degrees Celsius

Gas oil or Diesel distillate - used for diesel fuel and heating oil; starting material for making other products

  

liquid alkanes containing 12 or more carbon atoms boiling range = 482 to 662 degrees Fahrenheit / 250 to 350 degrees Celsius

Lubricating oil - used for motor oil, grease, other lubricants
  

liquid long chain (20 to 50 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 572 to 700 degrees Fahrenheit / 300 to 370 degrees Celsius

Heavy gas or Fuel oil - used for industrial fuel; starting material for making other products
  

liquid long chain (20 to 70 carbon atoms) alkanes, cycloalkanes, aromatics boiling range = 700 to 1112 degrees Fahrenheit / 370 to 600 degrees Celsius

Residuals - coke, asphalt, tar, waxes; starting material for making other products
  

solid multiple-ringed compounds with 70 or more carbon atoms boiling range = greater than 1112 degrees Fahrenheit / 600 degrees Celsius

You may have noticed that all of these products have different sizes and boiling ranges. Chemists take advantage of these properties when refining oil. Look at the next section to find out the details of this fascinating process. HALOGENATION Halogenation is almost always chlorination, for the difference in cost between chlorine and the other halogens, particularly on a molar basis, is quite substantial. In some cases, the presence of bromine (Br), iodine (I), or fluorine (F) confers additional properties to warrant manufacture.

Chlorination proceeds (1) by addition to an unsaturated bond, (2) by substitution for hydrogen, or (3) by replacement of another group such as hydroxyl (–OH) or sulfonic (–SO3H). Light catalyzes some chlorination reactions, temperature has a profound effect, and polychlorination almost always occurs to some degree. All halogenation reactions are strongly exothermic. In the chlorination process (Fig.1), chlorine and methane (fresh and recycled) are charged in the ratio 0.6/1.0 to a reactor in which the temperature is maintained at 340 to 370oC. The reaction product contains chlorinated hydrocarbons with unreacted methane, hydrogen chloride, chlorine, and heavier chlorinated products. Secondary chlorination reactions take place at ambient temperature in a light-catalyzed reactor that converts methylene chloride to chloroform, and in a reactor that converts chloroform to carbon tetrachloride.

By changing reagent ratios, temperatures, and recycling ratio, it is possible to vary the product mix somewhat to satisfy market demands. Ignition is avoided by using narrow channels and high velocities in the reactor. The chlorine conversion is total, and the methane conversion around 65 percent. Equipment for the commercial chlorination reactions is more difficult to select, since the combination of halogen, oxygen, halogen acid, water, and heat is particularly corrosive. Alloys such as Hastelloy and Durichlor resist well and are often used, and glass, glass-enameled steel, and tantalum are totally resistant but not always available. Anhydrous conditions permit operation with steel or nickel alloys. With nonaqueous media, apparatus constructed of iron and lined with plastics and/or lead and glazed tile is the most suitable, though chemical stoneware, fused quartz, glass, or glass-lined equipment can be used for either the whole plant or specific apparatus.

Label: Chemical Process

Pressure Chemical has been performing alkylation chemistry for a wide range of industries for over 40-years. Alkylation processes involve the use of reactive and hazardous raw materials. In addition, alkylations require stringent process control in order to produce desirable product in high yield. Temperature management, exclusion of oxygen and moisture, and engineering

controls to avoid personnel exposure are integral parts of a successfully executed alkylation project.

Safe Handling of Materials PCC has the expertise to manage the chemicals and processes required for alkylation chemistry. We routinely handle materials such as boron trifluoride, ammonia, and alkali metals, and have procedures and practices in place to ensure sound EHS stewardship. Our project leaders and process personnel have substantive experience in the effective management of such materials. Process Control All projects are individually assessed for their process control requirements. Often, custom control systems are implemented to maintain optimal reaction conditions. This capability ensures a safe alkylation process. Please see our Chemical Production Equipment List. Post Reaction Workup Product isolation from alkylation reactions can be challenging. After your process chemistry is complete, we maintain a wide variety of ancillary equipment to facilitate isolation of your product (high-rectification distillation, precipitation followed by filtration or centrifugation, and rotary vacuum or tray drying). Process Waste Safe handling and disposal of alkylation process waste is assured by detailed waste characterization and profiling. Wastes are closely monitored on a projectspecific basis and streams that require special handling can be segregated and managed.

Each project is a collaborative endeavor. Our customers' familiarity with their process, along with our broad insights and experiences, will maximize your alkylation projects probability for success.

Acrolein is a federal hazardous air pollutant and was identified as a toxic air contaminant in April 1993 under AB 2728. CAS Registry Number: 107-02-8 Molecular Formula: C3H4O

Acrolein is a colorless or yellowish, flammable liquid with an unpleasant, extremely pungent odor. It is soluble in petroleum ether, water, and alcohol and miscible with hydrocarbons, acetone, and benzene (Sax, 1989). Acrolein polymerizes (especially in the presence of light, alkali, or strong acid) forming disacryl, a plastic solid (Merck, 1989).

Physical Properties of Acrolein
Molecular Weight Boiling Point 56.06 52.5 oC

Melting Point Flash Point Vapor Density Vapor Pressure Density/Specific Gravity Log Octanol/Water Partition Coefficient Water Solubility Henry's Law Constant Conversion Factor

-88.0 oC -18 oC (< 0 oF) (open cup) 1.94 (air = 1) 210 mm Hg at 20 oC 0.8389 at 20/4 oC -0.09 208,000 mg/L at 20 oC 4.4 x 10-6 atm-m3/mole 1 ppm = 2.29 mg/m3

(Howard, 1990; HSDB, 1991; Merck, 1989; U.S. EPA, 1994a)

A. Sources

Acrolein is emitted from sources where it is manufactured and used as an intermediate for glycerine, methionine, glutaraldehyde, and other organic chemicals. It is also found in tobacco smoke, forest fire emissions, and gasoline and diesel exhaust. Acrolein is also a photooxidation product of various hydrocarbons including 1,3-butadiene (Howard, 1990). The primary stationary sources that have reported emissions of acrolein in California are paper mills, and abrasive, asbestos, miscellaneous non-metallic mineral, and wood products (ARB, 1997b). Acrolein has been detected but not quantified in motor vehicle exhaust by the Air Resources Board (ARB) (ARB, 1995e). Acrolein is a registered pesticide in California. It is registered as an antimicrobial and is used to control fungi and bacteria in secondary oil recovery injection systems. Acrolein is also registered as an algicide and herbicide for control of algae and water borne weeds in lakes, ponds, reservoirs, and other aquatic areas. The licensing and regulation of pesticides for sale and use in California are the responsibility of the Department of Pesticide Regulation (DPR). Information presented in this fact sheet regarding the permitted pesticidal uses of acrolein has been collected from pesticide labels registered for use in California and from DPR's pesticide databases. This information reflects pesticide use and permitted uses in California as of October 15, 1996. For further information regarding the pesticidal uses of this compound, please contact the Pesticide Registration Branch of DPR (DPR, 1996).

B. Emissions

The total emissions of acrolein from stationary sources in California are estimated to be at least 40,000 pounds per year, based on data reported under the Air Toxics "Hot Spots" Program (AB 2588) (ARB, 1997b).
C. Natural Occurrence

Acrolein and aldehydes are reported to be common products of a variety of microbial and vegetative processes. Acrolein is also found as a volatile component of essential oil extracted from the wood of oak trees (Howard, 1990).

No ARB data exist for ambient concentrations of acrolein. However, the United States Environmental Protection Agency (U.S. EPA) has compiled information from 1961 to 1980 for two urban locations that reported a mean concentration of 14.3 micrograms per cubic meter (µg/m3) or 6.2 parts per billion (ppb) with a range of concentrations from 8.2 to 24.6 µg/m3 or 3.6 to 10.7 ppb (U.S. EPA, 1993a).

The major sources of acrolein in the indoor environment are cigarettes and wood smoke (Hodgson and Wooley, 1991). Acrolein was measured in 59 of 128 homes studied in Woodland, California. The average indoor concentration of acrolein was reported as 7.1 µg/m3 with a standard error of 1.7 µg/m3. No outdoor concentrations of acrolein were reported in this study (Sheldon et al, 1992).

Acrolein exists in the atmosphere in the gas phase. The dominant atmospheric loss process for acrolein is by reaction with the hydroxyl radical. Based on this reaction, the atmospheric half-life and lifetime of acrolein is estimated to be 12 hours and 17 hours, respectively. The reaction products include formaldehyde, glyoxal, and the peroxyacyl nitrate (Atkinson, 1995). Because acrolein has been detected in rainwater, wet deposition may also contribute to its removal from the atmosphere (Howard, 1990).

The Office of Environmental Health Hazard Assessment reviews risk assessments submitted under the Air Toxics "Hot Spots" Program (AB 2588). Of the risk assessments reviewed as of 1996, for non-cancer effects, acrolein contributed to the total hazard index in 14 of the approximately 89 risk assessments reporting a total chronic hazard index greater than 1 and presented an individual hazard index greater than 1 in 9 of these risk assessments. Acrolein also contributed to the total hazard index in 17 of the approximately 107 risk assessments reporting a

total acute hazard index greater than 1, and presented an individual hazard index greater than 1 in 2 of these risk assessments (OEHHA, 1996b).

Probable routes of human exposure to acrolein are inhalation and ingestion (HSDB, 1991). Non-Cancer: Inhalation exposure to acrolein causes irritation of the eyes, nose, throat, and respiratory tract. In severe cases, pulmonary edema may occur (HSDB, 1991; U.S. EPA, 1994a). An acute Reference Exposure Level (REL) of 2.5 µg/m3 and a chronic REL of 0.02 µg/m3 is listed for acrolein in the California Air Pollution Control Officers Association Air Toxics "Hot Spots" Program, Revised 1992 Risk Assessment Guidelines. The toxicological endpoint considered for acute and chronic toxicity is the respiratory system (CAPCOA, 1993). The U.S. EPA has established a Reference Concentration (RfC) of 0.02 µg/m3 for acrolein. The U.S. EPA estimates that inhalation of this concentration or less, over a lifetime, would not likely result in the occurrence of chronic, non-cancer effects. The U.S. EPA has not established an oral Reference Dose (RfD) for acrolein. However, they have calculated a provisional RfD of 0.02 milligrams per kilogram per day. The U.S. EPA estimates that consumption of this dose or less, over a lifetime, would not likely result in the occurrence of chronic, non-cancer effects (U.S. EPA, 1994a). Birth defects have only been observed in animal studies where acrolein was injected directly into the embryonic tissue (U.S. EPA, 1994a). Cancer: No information is available on the carcinogenic effects of acrolein in humans. An increased incidence of adrenocortical tumors in female rats exposed to acrolein in drinking water was reported in one study. The U.S. EPA has placed acrolein in Group C: Possible human carcinogen (U.S. EPA, 1994a). The International Agency for Research on Cancer has placed acrolein in Group 3: Not classifiable (IARC, 1987a).

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