Petrochemical Engineering ChE 364.

3
J. Soltan, Ph.D., P.Eng. Associate Professor of Chemical Engineering Department of Chemical and Biological Engineering University of Saskatchewan Term 1 2012-2013

Outline
Introduction Process considerations Petrochemical Feedstock C2 processes C3+ processes Aromatics Polymers Synthetic fuels Fertilizers Environmental concerns Trends in petrochemical industry

Aromatics
Aromatics
Benzene
Ethylbenzene Styrene Cumene Phenol Cyclohexane

Toluene
Benzoic acid Benzyl aldehyde

Xylenes

Benzene, Toluene & Xylenes (BTXs)

Benzene

Benzene
Structure of Benzene
All carbons are sp2 hybridized Clouds of electrons are -bonded

-bonds make them react by substitution by a different mechanism than paraffins but at mildest conditions
Benzene + nitric acid nitrobenzene + H2O
Electrophilic substitution at normal conditions

Will react by addition only under severe conditions

Benzene + hydrogen cyclohexane
Hydrogen addition requires a catalyst and high pressures

Toluene
C7H8 Methyl group(s) activate ring for electrophilic attack, Methyl group Hs are more susceptible to attack because the phenyl group draws electrons in Easy oxidation or chlorination

Xylene
C8H10

(1,3 dimethylbenzene)

(1,4 dimethyl benzene)

(1,2 dimethyl benzene)

Benzene, Toluene, Xylenes

BTXs are refinery streams, particularly catalytic reformate and cracking streams along with steam cracking pyrolysis gasoline and coal liquids Recovered from these streams by extensive separation processes

Products from BTX

Benzene
Most important aromatic hydrocarbon
Does not polymerize stabilized ring

Production of Benzene
1. Catalytic Reforming (30% of Benzene)
Aromatics produced by dehydrogenation of cycloparaffins , dehydroisomerization of alkyl cyclopentanes, and cyclization dehydrogenation of paraffins

2. Toluene hydrodealkylation 3. Transalkylation (or disproportionation)

2 toluenes are converted to 1 benzene and 1 molecule of mixed xylene isomers

4. Pyrolysis Gasoline
Steam cracking of heavy naptha

Electrophilic Aromatic Substitution

Benzene undergoes substitution addition and cleavage reactions, substitution being the most important A substituent that increases electrophilic substitution relative to benzene is an activating group
an unshared electron group on the atom next to the ring contributes to the electron density of the aromatic ring (stabilization) Common activating groups (in order of decreasing effectiveness: -NR2, -NHR, NH2, -OH, -OR, -NO, -NHCOR, alkyls, -F, -Cl, -Br, -I, aryls, -CH2COOH,

Electrophilic Aromatic Substitution

Deactivating groups decrease reactivity.
No free electrons next to ring Often attached to an electronegative atom by double or triple bonds Common deactivators (in order of decreasing effectiveness):
-N+R3 -NO2, -CN2, -SO3H, -CHO, -COOR, -COOH, -CONH2, -CCl3

Alkylation of Benzene
C6H6 can be alkylated using a Lewis or Bronsted-Lowry acid catalyst Ethylene, propylene and C12 C14 -olefins are important reactants to produce ethylbenzene, propyl benzene and surfactants respectively
C6H6 + C2H4 C2H5-CH2CH3 (ethylbenzene)

Alkylation of Benzene
Rate Mechanism:
Step 1: Generate Carbocation RHC=CH2 H+ [RC+HCH3]
Friedel-Crafts alkylation catalysts can be used with an alkyl hadile as the reagent

RCl + AlCl3 [R+AlCl4-] Step 2: Attack by the carbocation on the benzene ring Step 3: Elimination of a Proton

Ethylbenzene
Used to produce styrene
Ethylbenzene from benzene:
C6H6 + C2H4

Reaction often catalyzed with AlCl3 HCl Typical reaction conditions:

AlCl3 Catalyst 40-100oC 2-8 atm Side products: diethyl benzene, higher alkylated forms

Ethylbenzene
Typical vapor-phase reaction (Badger Process):
Zeolite heterogeneous catalyst in a fixed bed 420oC 13-21 atm 98% yield @ 90% conversion of benzene Side products & unreacted benzene are recycled to reactor

Styrene
Aka vinylbenzene Easily polymerizes when initiated by a free radical or when exposed to light

Produced by dehydrogenation of ethylbenzene over a metal oxide catalyst

Oxides of Fe, Cr, Si, Co, Zn, etc.

Styrene
Typical reaction conditions for vapor phase reaction:
600-700oC Atmospheric pressure 90% styrene yield @ 30 - 40% conversion
Monsanto/Lummus Crest plant

Endothermic rxn
Heat provided by superheated steam (also a diluent)

Equilibrium-limited reaction
Effects of process variables P, T, Steam/EB

Styrene
Dow chemicals produced styrene from butadiene
Step 1: liquid phase catalytic reaction to produce vinylcyclohexane (VCH)
100oC, 18 atm

Step 2: catalytic oxidation of VCH in the presence of steam X > 90%, selectivity of 92%

Styrofoam

Extruded or expanded polystyrene foam

>95% air
Insulating properties

Trademarked by Dow, developed in 1941

Cumene
Aka isopropyl benzene B.P. = 152.7oC Produced by alkylation of benzene with propylene Liquid or gas-phase reaction

Cumene
Liquid process
50oC, 5 atm H2SO4 or H3PO4 catalyst H = -113 kJ/mol

Cumene
Vapor phase process:
250oC, 40 atm Supported phosphoric acid is a common catalyst Propane used to dilute propene to limit polyalkylation High benzene: propylene ratio to suppress polyalkylation Selectivity of 97% (benzene based)

Phenol
Cumene is mainly used to produce phenol
Figure 10-6 in handouts

Step 1: Oxidize cumene with air to cumene hydroperoxide

100-130oC 2-3 atm Metal salt catalyst Liquid phase

H = -116 kJ/mol

Phenol
Step 2: Decomposition of hydro peroxide in an acidic environment
80oC, < 1 atm

Hydrogenation of Benzene

H = -266 kJ/mol Catalyzed by Ni/Alumina or Ni/Pd) 160-220oC 25 30 atm Gas phase reaction
Large change in volume (gas phase) Highly exothermic reaction
See fig 10-12 for effect of process conds on conversion

Older, liquid phase reaction in Fig. 10-11

Toluene
Methyl Benzene
More active than benzene because of activating CH3 (methyl) group (electron-donating) Less useful than benzene because of its propensity to produce polysubstituted products Primary reactions in industry are:
1.Dealkylation to benzene 2.Oxidation of the methyl group 3.Hydrogenation of the phenyl group

Dealkylation of Toluene
Occurs over a nickel catalyst A cracking reaction favored at high temperatures and pressures (~700oC, 40 atm) Benzene yield is ~96% or more

Dealkylation of Toluene
Can also be achieved using steam with a variety of catalysts
NiCr2O3 or NiAl2O3 320-630oC Yields of ~90% Produces H2 instead of consuming it

Oxidation of Toluene
Benzoic Acid
Liquid-phase reaction over a cobalt acetate catalyst 165oC, 10 atm Yield >90% Used to fix dyes in printing, season tobacco, preserve foods, kill fungus, etc. Precursor to many substances such as phenol
+ 1 O2 + H2O

Phenol from Benzoic Acid

A reaction with a copper salt catalyst Overall reaction:
+ O2 + CO2

Lummus process (Fig. 10-15) is a vapor phase process

250oC, yield of 90% Multi-step mechanism

Benzyl Aldehyde
Solvent, artificial almond flavor and scent Step 1: Oxidation of Toluene to Benzyl Alcohol

+ O2

Benzyl Aldehyde
Step 2: Reaction of Benzyl Alcohol to Benzyl Aldehyde
+ O2 + H2O

Benzyl Aldehyde
Step 3: (Side Product)
+ O2

Each step occurs more readily than the proceeding one

Since introducing O, makes Hs more acidic, facilitating reaction

Benzyl Aldehyde
To minimize Step 3, a selective catalyst is used
UO2 (93%) + MnO2 (7%) at 500oC Gives 30-50% yield at conversions of 10-20% Also FeBr-CoBr2 with methanol at 100-140oC

Also, short residence times are needed

Xylenes (Dimethylbenzene)
Para-xylene is the most important isomer Meta is present in highest quantities at equilibrium compositions from catalytic reforming M-xylene is isomerized to p-xylene 65% of xylenes are used to make chemicals The rest are used as solvents or blended with gasoline
Used to make terephthalic acid (HOOCC6H4COOH)

Teraphthalic Acid
Formed from catalytic oxidation of p-xylene Cobalt acetate promoted with NaBr or HBr is the catalyst in an acetic acid medium (liquidphase) ~200oC, ~15 atm Yield is ~95%

Teraphthalic Acid

3/2 O2

+ H2O

P-toluic acid (side product)

dont want the reaction to stop here

Teraphthalic Acid
Preferred esterification reaction:
3 O2 + 2CH3OH + 4H2O

The resultant dimethyl terephthalate (DMT) may be hydrolyzed to terephthalic acid

The DMT process encompasses four major processing steps:

Oxidation, esterification, distillation, crystallization