PETROCHEMISTRY BSK3513 Dr. Mohd Hasbi Ab.

Rahim

Reactions and Chemicals of Benzene Oxidation, , Hydrogenation, Alkylation, Chlorination, Nitration

Reactions and Chemicals of Toluene Oxidation, Chlorination, Nitration, Carbonylation, Dealkylation, Dispropornation Chemicals from Xylene Terepthalic acid, Phthalic Anhydride, Isophthalic Acid

AROMATIC HYDROCARBONS
Benzene, toluene, xylenes (BTX), and ethylbenzene are the aromatic hydrocarbons with a widespread use as petrochemicals. They are important precursors for many commercial chemicals and polymers such as phenol, trinitrotoluene (TNT), nylons, and plastics. Aromatic compounds are characterized by having a stable ring structure due to the overlap of the -orbitals (resonance). Accordingly, they do not easily add to reagents such as halogens and acids as do alkenes. Aromatic hydrocarbons are susceptible, however, to electrophilic substitution reactions in presence of a catalyst.

Aromatic hydrocarbons are generally nonpolar. They are not soluble in water, but they dissolve in organic solvents such as hexane, diethyl ether, and carbon tetrachloride.

Catalytic reforming for aromatics production

The reactions are:
60-90C cut for benzene 90-110C cut for toluene 110-140C for xylenes

Desired reactions in Catalytic reforming

 Benzene (C6H6) is the most important aromatic hydrocarbon. Almost all compounds derived from benzene are converted to other chemicals and polymers. Benzene is not easy to polymerize due to the resonance stabilization of benzene ring.

Uses of benzene

Oxidation of Benzene
Oxidation of benzene to maleic anhydride, 380 oC, atm. Pressure with V2O5/MO3 cat. 90% Conversion with 50 60% selectivity.

+ 9/2 O2

+ 2 CO2 + 2 H2O

The main route is oxidation of n-butane

Hydrogenation of Benzene (production of cyclohexane)

Hydrogenation which involved an addition of H2 into benzene ring to produce cyclohexane. Ni/Al, Ni/Pd cat. , 160 220 oC, 25 30 atm. The pressure of H2 play an important role in controlling the catalytic activity and selectivity.
Cyclohexane is oxidized in a liquid-phase process to a mixture of cyclohexanol and Cyclohexanone. (Cobalt acetate & orthoboric acid as cat., 95 120 oC, 10 atm). With similar catalyst at lower temperature and longer residence time produces adipic acid.
OH H2 O2 O

+
-H2 HNO3

Cyclohexane 2.5 O2 Adipic acid

N2O

COOH COOH

Enviro-friendly routes for adipic acid

(current route) COOH COOH adipic acid (Noyori's route)
R. Noyori, Science 281 (1998) 1646

(Biocatalysis; Frost's route) COOH COOH muconic acid O OH

OH OH OH OH D-glucose

K.M. Draths & J.W. Frost, JACS 120 (1998)10545

J. M. Thomas & R. Raja, Chem. Commun. Feature Article, 675 ( 2001)

O2

COOH O2 COOH

Alkylation
Alkylation is the introduction of an alkyl group into a molecule It may involve a new C-C, O-C, N-C bond formation Alkylation is catalyzed by acidic or basic catalysts Acid catalysts are used mainly in aromatics alkylation at ring-C Basic catalysts are used in alkylation at side-chain-C

CH3 CH3 + MeOH Basic Catalyst (p-Xylene) Acid Catalyst CH3 CH2CH3 (Ethylbenzene)

Some important industrial alkylation reactions

Reactants Product Catalyst Process licensors
Mobil-Badger /NCL etc

Benzene + ethylene /EtOH

Benzene + propylene

EB
Cumene

ZSM-5
H-Y; H-M; H-

DOW, UOP etc

Benzene + C11 C13 olefins LAB

Solid acid/ RE-Y UOP / NCL

Alkylation of Benzene
1. Production of ethyl benzene (EB), C6H5CH2CH3 Colorless liquid with boiling point of 136 oC. C6H6 + CH2=CH2 C6H5CH2CH3 (AlCl3-HCl, 40-100 oC, 2 8 atm)

(Diethylbenzene and higher alkylated also form which later recycled and dealkylated to EB) Main use of EB: Manufacture of styrene (C6H5CH=CH2) Dehydrogenation of EB produce styrene C6H5CH2CH3 C6H5CH=CH2 + H2

kg

Mobil-Badger process
Mobil-Badger process is based on ethylene and uses ZSM-5; Other licensors are UOP, CDTECH etc; use other zeolites CDTECH process uses reactive distillation
CH2 CH3 + CH3 CH2 OH + H2O

Reactors Temp. (C) WHSV (h-1) Pressure Benzene / alc. (mole) Alcohol sel. (%) EB + DEB (%) EB (%) Cycle length (days) No. of cycles

3 beds in series 380 420 C 5 10 (6) 1-4 4 15 (5) 98 95 85 45 >25

Catalyst is Encilite pentasil (ZSM-5) type

Mobil-Badger process
Uses ethylene as the alkylating agent T = 370 - 420C; P = 7 27 bars;

2. Production of Cumene or isopropylbenzene, C6H5CH(CH3)2

Benzene + propylene Cumene

Main use of cumene: in the production of phenol

Kg

> 40 SPA units have been licensed (UOP

[Degnan et al. Appl. Catal. A 221 (2001) 283]

CUMENE

Benzene + propylene Cumene

Process licensors: UOP, CDTECH, Enichem, Mobil-Badger, DOW Zeolite processes involve a transalkylation (with benzene) step to convert >10 % di i-pr-Bz into cumene
Comparison of NCL (H-beta) and SPA catalysts CATALYST Mole Ratio (benz./C3) Temperature (C) Pressure (bar) WHSV (h-1) Products (wt. %) Aliphatics Toluene + Ethylbenzene Cumene Di-isopropylbenzene Conversion of propylene 0.003 0.01 22.03 1.70 99.99 0.67 0.01 17.18 1.11 99.90 N.C.L. 6.0 150 30 3.5 S.P.A. 8.0 210 30 2.5

Yield of cumene in zeolite processes is more as transalkylation is not possible with SPA catalysts
NCL processes for alkylation and transalkylation are available

CDcumene process (CDTECH)

Features Reaction is done in catalytic distillation reactor The catalyst is held in distillation trays A transalkylation reactor converts the di-iprBz.

Phenol production
OOH O H3PO4/zeolite (Benzene) (Cumene) (Cumene hydroperoxide)

N2O FeZSM-5 H2O2/ TS1

OH

(phenol)

Phenol is a white crystalline material with a distinctive odor, highly soluble in water and Soluble in weakly acidic solution. Important monomer for phenolic resins, reaction with acetone produce bis-phenol A which Is important monomer for epoxy resin and polycatbonates., Aspirin, salicyclic acid

3. Production of linear alkylbenzene (LAB), C6H5CH(CH3) R

C6H6 + RCH=CH2

C6H5CH(CH3) R

The alkylating agents are either linear C12 C14 mono olefins or monochloroalkanes. Alkylating with olefin is industrially preferred
Normally to produce biodegradable anionic detergents.

Evolution of LAB processes;

Becoming GREENER

Catalyst
AlCl3 AlCl3 HF Solid acid

Green

Benefits in product quality use of solid acid UOP

Production of LAB Alkylation of benzene with C11 C13 olefins

Linear alkyl benzene (LAB) using a solid-acid catalyst Detal process for Linear Alkyl Benzene production
Fresh n-paraffin
H2 recycle Make up H2
Dehydrogenation

H2 rich off gas

Fresh benzene

Pt/Al2O3

Selective Hydrogenation

PACOL
N-paraffin recycle

DEFINE

Alkylation Solid-acid CATALYST

Benzene recycle

LAB

Distillation

Paraffin Recovery

Benzene Recovery

Heavy alkylates

Industrial alkylation Processes

Chlorination of Benzene
Electrophilic substitution reaction in which Cl serve as electrophile. Lewis acid i.e. FeCl3 as catalyst, 80 100 oC, atm. Pressure. The products are a mixture of mono- and dichlorobenzenes. The ortho- and the paraDichlorobenzene are more common than meta-

Nitration of Benzene
Electrophilic substitution reaction in which (nitronium ion) NO2 serve as electrophile.

Concentrated nitric and sulfuric acids as catalysts at 50 oC.

HNO3 + 2H2SO4 C6H6 + NO2+ 2HSO4- + H3O+ + NO2+ C6H5NO2 + H+

Nitrobenzene use to produced aniline, C6H5NH2 (hydrogenation of nitrobenzene), quinoline, benzidine and as a solvent for cellulose ethers.

Reactions and Chemicals of Toluene

Toluene (methylbenzene) is similar to benzene as mononuclear aromatic, but it is more active due to the presence of the electron-donating methyl group. Could produced more polysubstituted products compared to benzene.

DeAlkylation of Toluene (produce benzene)

DeAlkylation of toluene produce benzene C6H5CH3 + H2 C6H6 + CH4

(La, Ce, Pr, Nd, Sm, Th or Ni-Cr2O3 as catalyst, 600 800 oC or Ni-Al2O3 catalyst at 320-630 oC)

Disproportionation of Toluene (produce benzene & xylene mixture)

Disproportionation of toluene produce benzene and xylene mixture 2C6H5CH3 + H2 C6H6 + C6H5(CH3)2

(450 530 oC, 20 atm, CoO-MoO3 on aluminosilicates/alumina catalyst, ZSM5)

Alkylation of Toluene

Some important industrial alkylation reactions

Reactants Toluene + methanol Naphthalene + propylene Naphthalene + methanol Biphenyl + propylene Product P-Xylene 2,6-DIPN 2,6-DMN Catalyst Process licensors

Modified ZSM-5 Mobil H-mordenite Zeolite Chiyoda Rtgerswerke DOW

4,4-DIPB H-mordenite

Oxidation of Toluene (produce benzyl alcohol, benzaldehyde, benzoic acid)

1. Production of benzoic acid C6H5CH3 + 1.5O2 C6H5COOH + H2O

(cobalt acetate, 165 oC, 10 atm)

Benzoic acid is a white crystalline solid, soluble in water and most common organic solvents. Use to season tobacco, preserve food, make dentifrices, precursor for caprolactam, phenol, Terepthalic acid Phenol from benzoic acid: C6H5COOH + 1/2O2 C6H5OH + CO2

2. Production of benzaldehyde and benzyl alcohol C6H5CH3 + 1.5O2 C6H5COH + 1.5O2 + C6H5CHO + H2O 1.5O2

C6H5COOH
Esterification
O O

Benzyl benzoate

How to limit over oxidation? Selective catalyst, short residence time, high toluene-to-oxygen ratio, low reaction temperature Benzaldehyde use as a solvent for oils, resin, cellulose esters, ethers, As flavoring compound and synthetic perfumes.

Chlorination of Toluene
Free radical reaction with Cl resulting benzyl chloride, benzal chloride, benzotrichloride Benzyl chloride can produce benzyl alcohol by hydrolysis: C6H5CH2Cl + H2O C6H5CH2OH + HCl

Benzyl alcohol use as precursor for butylbenzyl phtalate, a vinyl chloride plasticizer, Precursor for phenylatic acid which later produced phenobarbital (sedative)

Carbonylation of Toluene (produced p-Tolualdehyde)

Carbonylation with CO in the presence of HF/BF3 catalyst C6H5CH3 + CO C6H4(CH3)CHO ? C6H4(COOH)2 P-Tolualdehyde use as intermediate in perfume synthesis, dye and in pharmaceutical.

Chemicals from toluene

Production of xylenes
Raffinate Disproportionation Pt/Mordenite Benzene

Reforming Naphtha (Pt-Re-Sn/ (bp, 110 - 140C) Alumina)

Arom. Extraction

Fractionation
C9+Arom.

Toluene
Xylenes + EB

Transalkylation Pt/Mordenite

Xylene isomerizatrion m- + EB Mol. Sieve Separation (Pt-ZSM-5; (PAREX) Pt-Mord.; Pt-MAPO)

Fractionation

o-Xylene
p-Xylene

Xylene isomerization

Catalysts are usually bifunctional types Typical examples: Pt-ZSM-5, Pt-mordenite & Pt-(silica)-alumina

Xylene isomerization
CH3 Zeolite CH3 CH3 CH3 + + CH3 CH3 CH3 CH3

Catalyst: ZSM-5, Mordenite; MAPO; SiO2-Al2O3 loaded with Pt

Mechanism

XYLOFINING developed by NCL-ACC-IPCL in 1986

Production of Terephthalic Acid (HOOCC6H4COOH)

Oxidation of p-Xylene with cobalt acetate/NaBr or HBr as catalyst in an acetic acid medium, 200 oC, 15 atm pressure.

p-Xylene + 3/2O2

HOOCC6H4CH3 (p-Toluic acid) + H2O

HOOCC6H4COOH

Has an annual capacity of approximately 610,000 tonnes and employs over 170 full-time employees. PTA is the key raw material for the manufacture of polyester for fabric, as well as audio and videotapes, and in making plastic drink bottles. *With 1 tonne of PTA , can make approximately 3,500 car tyres

Production of Phtalic anhydride (

Oxidation of o-Xylene with metal oxides catalyst i.e. V2O5 + TiO2/Sb2O3

Vapor phase, 375 435 oC, 0.7 atm, yield about 85% Liquid phase, 150 oC, Cobalt or manganese acetate in acetic acid medium as catalyst.

C6H4(CH3)2 + 3O2

+ 3H2O

Use for producing plasticizer.

Production of Isopthalic Acid (HOOCC6H4COOH)

Liquid phase Oxidation of m-Xylene with ammonium sulfite

m-Xylene + 2(NH4)2SO3
Main use for producing polyesters

HOOCC6H4COOH + 2H2S + 4NH3 + 2H2O

END