Lecture 3

Catalysis in Petrochemical production

CONTENTS
1. 2. 3. 4. 5. 6. 7. 8. 9. Petroleum feedstocks Petrochemicals from different hydrocarbons Alkylation reactions Shape-selectivity Isomerization reactions Disproportionation Catalytic reforming Selective oxidation reactions Green polycarbonate synthesis

INTRODUCTION
Feed stocks for petrochemicals are gas and light to middle petroleum liquids Nearly all the petrochemicals are produced over catalysts Both homogeneous and heterogeneous catalysts are involved

Chemicals from methane

 Ethane, propane, butane, isobutane, naphtha and kerosene are also feed stocks for many chemicals C2H6 - C3H8 C4H10 - naphtha C2H4; C3H6; C4H8 (steam cracking) + Pyrolysis gasoline

Pyrolysis gasoline BTX

Naphtha BTX (Catalytic reforming)

Kerosene n-paraffins n-olefins LAB (separation and alkylation)

AROMATIC COMPOUNDS

Uses of benzene Nitrobenzene Cyclohexane

Cumene

Ethylbenzene

Chemicals from toluene

Xylenes are also important petrochemical products / feed stocks

Petrochemicals some more examples

MeOH acetic acid Vinyl acetate

Ethylene ethylene oxide ethylene glycol Ethylene acetic acid Ethylene ethyl alcohol Ethylene vinyl chloride

OLEFINS ARE NOT PRESENT IN PETROLEUM

Propylene propylene oxide Propylene glycol Propylene acrylic acid ; acrylonitrile Propylene allyl chloride epichlorohydrin propylene oxide Butenes Maleic anhydride

Cyclohexane cyclohexanol + cyclohexanone Cyclohexanone Cyclohexanoneoxime Caprolactam Nylon-6 Cyclohexanol adipic acid Nylon-6,6 Cumene Phenol + acetone Ethylbenzene styrene
Benzene Maleic anhydride Benzene Chlorination; nitration etc. p-Xylene Terephthalic acid o-Xylene Phthalic acid Many polymers are derived from the above petrochemicals Hundreds of other chemicals are derived from olefins, BTX, phenol, acetic acid, methanol etc.

Major reactions in petrochemical production

1. Alkylation 2. Isomerization 3. Disproportionation 4. Selective oxidation 5. Dehydrogenation

Greening of petrochemical production Petrochemical production has been a major polluting industry Recently, there is an increasing effort to make petrochemical production greener

Examples: 1. Replace mineral acids by solid acids 2. Green selective oxidation reactions a) Adipic acid b) Propylene oxide c) Oxidation of alkanes d) Phenol e) Alkane oxidations with air 3. Caprolactam production

Alkylation of Aromatics

Some important industrial alkylation reactions over acidic zeolites

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

Toluene + methanol

P-Xylene

Modified ZSM-5 Mobil

Solid acid/ RE-Y UOP / NCL Modified ZSM-5 NCL / IPCL H-mordenite Zeolite Chiyoda Rtgerswerke

Benzene + C11 C13 olefins LAB EB + EtOH Naphthalene + propylene Naphthalene + methanol P-DEB 2,6-DIPN 2,6-DMN

Biphenyl + propylene

4,4-DIPB H-mordenite

DOW

Industrial alkylation Processes

INTRODUCTION 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)

Example of an alkylation mechanisms Cumene production:

Mechanism 1; Sec-C+ is formed

Because the Sec-C+ is more stable, mostly cumene is (> 99.9 %) is produced and not n-propyl benzene (requires the Prim-C+)

The most important solid acid catalysts in industrial use are ZEOLITES

What are ZEOLITES ? - Aluminosilicates - Crystalline - Framework of AlO4 and SiO4 Td-units - Possess ordered pore systems - Acidity arises from Al-ions

Example of building zeolite structures

4 & 6 membered rings

Sodalite
(SOD) Pores ~3

[SiO4 ]4[AlO4]5-

Zeolite - A
LTA -cages FAU

(LTA) pores ~ 4

Zeolite - X, Y
A large cage (~ 12) formed in A and X,Y

(FAU) pores ~ 7.4

ETHYL BENZENE
Main use of EB: Manufacture of styrene

kg

Data as of year 2000

NCL

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

Albene process (NCL)

15,000 tpa plant was in commercial operation for some years

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

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.

Comparison of two different zeolites in the alkylation of benzene by propene _____________________________________________________________________ Parameters Catalyst Catalyst MCM-22 MCM-56 _____________________________________________________________________ Temperature, oC 112 113 Propene flow, WHSV, h-1 1.3 10.0 Propene conversion, % 98.0 95.4 Selectivity, % - Cumene 84.35 84.98 - Diisopropyl benzene 11.30 13.20 - Triisopropyl benzene 2.06 1.28 - C3 Oligomers 1.8 0.52 - n-Propyl benzene, ppm 70 90 _____________________________________________________________________
(J.C. Chang et al., US Patent. 5,453,554 (1995))

Diisopropyl benzene transalkylation

i-Pr

CH3

+
i-Pr

i-Pr

Catalyst

Influence of zeolite-type on m/p ratio of DIPrB

LINEAR ALKYL BENZENE

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

NCL alkylation process for LAB using solid acid catalyst

Feed: mixed olefins (C10 - C13) Temp. (C) = 130 - 180 Press. = 5 - 10 bars WHSV (h-1) = 2 - 3 - Conversion > 99.99%; product BI < 50 ppm - The catalyst life was >50 days in a single cycle - Catalyst could be regenerated many times Operated in RIL in a semicommercial scale (~ 800 tpa)

Shape-selective alkylation reactions

1. p-Ethyl toluene

2. P-Diethyl benzene
3. 2,6-Dialkyl naphthalene 4. 4,4-Dialkyl biphenyl

Product shape selectivity most useful in aromatic aklkylation

Alkylation of toluene with ethylene (Mobil)

Catalyst: (%) Toluene conv. Ethyltoluene Ethyltoluene: Para Meta Ortho 34.0 55.1 10.9 26.8 60.6 12.6 96.7 3.3 0 AlCl3 HCl 51.7 35.9 ZSM-5 25.6 22.0 3.0 Modified ZSM-5 13.8 12.3 1.5

Other aromatics 15.8

P-Diethylbenzene

CH2 CH3 + CH3 CH2 OH Zeolite

CH2 CH3

CH2 CH3

Catalyst

Product shape-selectivity in a zeolite

Pore-size engineered zeolite Temp. () 340 410 EB / Alc. (mole) 4 10 WHSV (h-1) 14 Pressure (bar) 2 5 Conversion per pass (%) 10 16 p-DEB sel. (%) >97

NCL Process operated in a commercial scale (500 tpa)

Alkylation of naphthalene
2,6-dicarboxy naphthalene is a valuable monomer for the synthesis of PEN polymers This can be produced from the oxidation of alkyl naphthalenes Direct alkyklation yields ten isomers that are difficult to separate

1,4-DIPN 2-IPN 1-IPN 1,2-DIPN

1,5-DIPN

1,8-DIPN

1,3-DIPN

1,6-DIPN

1,7-DIPN

2,3-DIPN

2,6-DIPN

2,7-DIPN

Scheme Indirect1. The two mono and tentherefore, been adoptedduring the isopropylation routes have, isomeric diisopropyl naphthalenes formed for their synthesis of naphtalene

BP-Amoco route for synthesis of 2,6-dimethylnaphthalene

CH3 CH3 + CH2=CH-CH=CH2 CH3 Zeolite Catalyst Cyclisation 1,5-DMT CH3 Alkali Metal Catalyst NaK Alkenylation CH3 CH2-CH2-CH=CH-CH3 OPT

Pt / Al2O3 Dehydrogenation 1,5-DMN

Zeolite Beta Isomerization

2,6-DMN

[Lillwitz, Appl. Catal. A 231 (2001) 337]

Chevron-Texaco route for synthesis of 2,6-dimethylnaphthalene

CH3 + Zeolite Y C5H10 Alkylation C5H11 Pt / Re / Al2O3 / Cl Reforming C5H11 Pd / Beta Hydroisomerization DMTs TPs CH3

CH3

DMNs

Pd / Beta Hydroisomerization 2,6-DMT

Pt / Na-ZSM-5 Dehydrogenation 2,6-DMN

[Lillwitz, Appl. Catal. A 231 (2001) 337]

The 2,6-dialkyl isomer is narrower than the other isomers Can the product shape selectivity of zeolites be applied for the selective alkylation of naphthalene to the 2,6-isomer ? Framework structures and pore characteristics of some conventional zeolites
BEA FAU MOR

6.4 x 7.6 / 3D

7.4 / 3D
Cages, 13.2

6.5 x 7 / 1D

A comparison of the activity and selectivity of conventional Zeolites in the isopropylation of naphthalene
Table 3 Isopropylation of naphthalene over conventionalconventional zeolites Isopropylation of naphthalene over zeolites (from Ref. 22) _______________________________________________________________________ Catalyst SiO2 /Al2 O3 Conversion Product Distribution of di-isopropyl naphthalene,% Ratio % 1,3- 1,4- 1,5- 1,6- 1,7- 2,6- 2,7_______________________________________________________________________ HZSM-5 HY HL HM 70 7.3 6.1 25.3 1.0 96.1 95.1 68.3 23.7 39.9 5.3 6.8 15.3 7.1 4.9 16.3 6.1 -32.6 6.7 50.8 31.2 7.2 24.9

0.6 7.9 3.8

0.2 6.7 1.9

* HY and HL zeolites are extremely active, but not selective to 2,6 DIPN * HL has a wider product distribution, rather a poor selectivity to 2,6 and 2,7 DIPN * HM is the most selective (for both 2,6 and 2,7 DIPN), but less active under identical Conditions of reaction
[Y. Sugi et al., Recent Res.Dev.Mat.Sci.Engg., 1 (2002) 395]

Isopropylation of Biphenyl
Three monoalkyl and six dialkyl biphenyls are possible

+ 2,4'-IBP 2-IBP 2,2'-IBP

+ 3-IBP 3,2'-IBP 3,3'-IBP

4-IBP

4,4'-IBP

3,4'-IBP

Selectivity for 4,4-DIPB over various zeolites in the isopropylation of biphenyl

100
ZS M-12 SS Z-24 HM SAPO -5 SS Z-31

80
Selectivity of 4,4'-DIP N (% )

60

40
ZS M-22 U T D-1 H

CIT -5

20
HY HL

Reaction conditions: Temp.= 250oC; C3= pressure = 0.8 Mpa (Y. Sugi et al., Catal. Surveys Japan, 5 (2001) 43)

CIT -1

ISOMERIZATION REACTIONS

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

Restricted transition state shape-selectivity

In the isomerization of m-xylene, bimolecular disproportionation into benzene and TMB also take place Use of zeolites with the right poresize or cavities to prevent the bimolecular transition state formation increases isomerization selectivity

RTS selectivity is also responsible for: - Resistance of medium pore zeolites to coking

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)

Fraction- o-Xylene ation

p-Xylene

Disproportionation and transalkylation reactions

CH3

Catalyst

CH3 CH3

Toluene disproportionation

CH3 CH3

+
CH3 CH3

Catalyst

C9+ aromatics transalkylation

CH3 CH3

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

Selective oxidation reactions

Adipic acid Current method is the oxidation of cyclohexanol with HNO3 producing N2O

Noyoris method is oxidation of cyclohexene in biphasic medium (commercially attractive)

Frosts method uses an enzyme and a renewable raw material glucose Oxidation of n-hexane or cyclohexane over MAPOs

Current process for adipic acid

OH H2 O2

+
-H2 HNO3

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

Oxidation of alkanes

- Avoiding multi-step processes - Alterante cheaper raw materials The present route for acetic acid and vinyl acetate manufacture is:
CH4 H2 + CO CH3OH (+CO) CH3COOH -- (1)
C2H6 C2H4 ------ (2) C2H4 + CH3COOH CH2CHOCOCH3 (VA) ----- (3)

Direct vapour-phase catalytic oxidation of ethane to HOAc and ethylene and vinyl acetate:
SABIC C2H6 CH3COOH + C2H4 CH2CHOCOCH3

Use of alternate raw materials selective oxidation reactions that need to be commercialized

1. Propane to acrolein and acroleic acid (presently use propylene) 2. Butane to methacrylic acid (presently butene is used) 3. Propane to acrylonitrile (propylene used at present) 4. Ethane to vinyl chloride (ethylene is used at present) 5. Methane to methanol to HCHO and HCOOH (Syn gas used at present) 6. n-Hexane to adipic acid (Cyclohexanol and nitric acid used)

Phenol production

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

N2O FeZSM-5 H2O2/ TS1

OH

(phenol)

Production of Caprolactam w.o. (NH4)2SO4 co-production

- Less polluting - Less number of steps - Benign reagents

TS-1

MFI

Sumitomo

Environmentally safe route to polycarbonate

Route 1
NEt3
Na O O Na + COCl2 O

)n

Bisphenol-A (BPA) (Na salt)

Bisphenol-A Polycarbonate (BPC)

Route 2
2 CH3OH + CO + 1/2 O2
H3C O

O C O

CH3 + H2O

DMC DMC + 2 OH Transesterification DPC + CH3OH

HO BPA

OH +

473 - 593 K
O

Catalyst

BPC + 2

OH

DPC

Conventional routes to polycarbonate

The green Asahi-Kasei Polycarbonate process

CH 2

CH 2

1/2 O

CH 2 O CH 2

CH 2 (EO)

CH 2

CH 2

CO 2

CH 2
O

O C
O

(EC) + HOCH 2 CH 2 OH (MEG) MeOCOMe O (DMC) 4 3

CH 2 O C O

CH 2 O (EC)

2 MeOH

MeOCOMe O (DMC) PhOCOPh O (DPC) CH 3 +

2 MeOCOPh O (MPC)

PhOCOPh O (DPC)

HO

C CH 3

OH

CH 3 H O C CH 3 OC O n OPh + PhOH 5

PC prepolymer (n=10~20)