The Petrochemicals Industry

Petrochemicals from C4-based Processes

ChE 313 Industrial Chemistry Lecture Engr. May V. Tampus

Butadiene
Chemical formula: C4H6 Molar mass: 54.092 Isomers: CH2 =CHCH=CH2 1,3-Butadiene (economically the most important unsaturated C4-hydrocarbon) CH2 =C=CHCH3 1,2-Butadiene (thermodynamically less stable thus has no technical importance) 1,3 Butadiene a commodity product of the petrochemical industry with a 1989 U.S. production of 3.1 billion pounds

Physical Properties of Butadiene

Noncorrosive, colorless, flammable gas at room temperature and atmospheric pressure. Has a mildly aromatic odor Sparingly soluble in water, slightly soluble in methanol and ethanol, and soluble in organic solvents like diethyl ether, benzene, and carbon tetrachloride. Boiling point : 4.411 C Melting point: 108.902 C Vapor pressure: 8690 torr at 25C Density of liquid : 0.6274 g/cm3(15 C), 0.6211 g/cm3 (20o C), and 0.6194 g/cm3 (25o C) Enthalpy of vaporization at 25 C: 20.88 kJ/mol Enthalpy of formation, gaseous, at 298 K, 0.1013 MPa:110.16 kJ/mol Entropy of formation, gaseous, at 298 K, 0.1013 MPa: 278.74 J mol1 K1

Chemical Properties of Butadiene

the simplest conjugated diene has two conjugated double bonds and, therefore, can take part in numerous reactions, which include 1,2- and 1,4-additions with itself (polymerization) and with other reagents, linear dimerization and trimerization, and ring formation the conjugation of the double bonds makes it 15 kJ/mole (3.6 kcal/mol) more thermodynamically stable than a molecule with two isolated single bonds The s-trans isomer, often called the trans form, is more stable than the s-cis form at room temperature. Although there is a 20 kJ/mole (4.8 kcal/mol) rotational barrier, rapid equilibrium allows reactions to take place with either the s-cis or s-trans form.

Commercial Uses of Butadiene

Production Butadiene
1. 2. 3. 4. Production from Acetylene Production from Ethanol Dehydrogenation of Butane and Butene Isolation of Butadiene from C4 Steam Cracker Fractions

Dehydrogenation of Butane and Butenes

Reactions are endothermic Dehydrogenation reactions at 430oC Butane 1-Butene + H2 Butane cis-2-Butene + H2

cis-2-Butene Butadiene + H2

H = 131 kJ/mol H = 118 kJ/mol H = 126 kJ/mol

Yield is limited by thermodynamics. Yield is increased by: decreasing the partial pressure of the reaction products raising the reaction temperature Undesirable reactions: Cracking, Isomerization, Polymerization

Dehydrogenation of Butane: Houdry Catadiene Process

Best known one-step dehydrogenation adiabatic process Makes use of several packed bed reactors, arranged parallel to each other, and operated alternatingly Catalyst: Aluminum oxide mixed with approximately 20 % chromium oxide Cycle life of the catalyst is about 10 minutes because of coke buildup Usually carried out 600 700 C and 10 25 kPa Thermodynamics limits the conversion to about 30-40% and the ultimate yield is 60-65 wt %

Oxydehydrogenation of n-Butenes
Conversion is no longer limited by thermodynamics because of the oxidation of hydrogen to water Reaction temperature is below about 600C to minimize over oxidation. Pressure is about 34-103 kPa (5-15 psi). Highly selective Exothermic oxidation of hydrogen partially covers the heat requirements of the endothermic dehydrogenation reaction and, in addition, the oxygen, together with steam added during the reaction, reduces the coke deposits on the catalyst. Catalyst: bed of tin, bismuth, and boron C4H8 + 1/2 O2 C4H6 + H2O Production methods: Oxo-D process and O-X-D process

Isolation of Butadiene from C4 Steam Cracker Fractions

Butadiene cannot be separated from this C4 hydrocarbon mixture by means of simple distillation, because 1,3-butadiene and butane form an azeotrope.

Methods: Liquid-liquid Extraction (CAA-cuprous ammonium acetate- Method) Extractive Distillation

BUTENES
unsaturated olefinic hydrocarbons, C4H8, Mr 56.1080 Four isomers:
"Butylenes", the older name for "butenes", is still used today; 4 is frequently referred to as "isobutylene". The designation "nbutenes" refers to mixtures of 1, 2, and 3.

These isomers are usually coproduced as a mixture and are commonly referred to as the C4 fraction. The C4 fractions are usually obtained as by-products from petroleum refinery and petrochemical complexes that crack petroleum fractions and natural gas liquids.

BUTENES
colorless, flammable gases at room temperature and atmospheric pressure. completely miscible with alcohols, ethers, and hydrocarbons only slightly water soluble and water is only slightly butene soluble main reactions are acid-catalyzed addition reactions, isomerization, and polymerization

Isobutylene
IUPAC name: 2-methylpropene Other names: Isobutene, -Butylene, 2Methylpropylene At STP, a colorless flammable gas

Properties of Isobutylene
Molecular formula Molar mass Appearance Density Melting point C4H8 56.11 g mol1 Colorless gas 0.5879 g/cm3, liquid 140.3 C

Boiling point
Solubility in water

-6.9 C, 266 K, 20 F
Insoluble

Industrial Production of Isobutylene:

1. 2. 3. 4. Catalytic or Thermal cracking Steam cracking Catalytic Dehydrogenation of Isobutane Catalytic dehydrogenation of n-butane

Group Assignment
INSTRUCTIONS: Write assignment on a short bondpaper. Submit it not later than August 8, MON, 5:00 PM. 1. Identify the raw materials in each of the production methods of isobutylene. 2. Write down the chemical reactions (if applicable) in each of the production methods of isobutylene. 3. Identify the process conditions in each of the production methods of isobutylene. 4. Identify the catalyst used (if applicable) in each of the production methods of isobutylene.