Petrochemical Processes Aromatics

M. GUISNET

University of Poitiers Instituto Superior Tcnico (F. Gulbenkian)

Lisbon December 2005

Petrochemicals : a) Benzene, Paraxylene

Naphtha reforming Steam cracking Aromatization

BTX (+ EB) Excess of toluene, meta and ortho xylenes Selective Toluene disproportionation (modified MFI)
2 +

Isomerization (I) of the C8 aromatic cut and p xylene separation (S)

pX

S ((K, Ba)X)
Aromatic loop EB, X I (PtHMOR)

EB mX oX
nC6 + 4 H2

Aromatization of light naphtha (Pt(K, Ba) LTL)

Petrochemicals : b) Alkylaromatics
Ethylbenzene
+ C C

Styrene
MFI (gaz phase) MCM22, BEA (Liq phase)

Cumene
+ C C C

Phenol
MCM22, BEA

Linear Alkylbenzene (LAB)

Biodegradable detergents
MOR MCM22

Selective toluene disproportionation (STDP)

How to obtain selectively paraxylene (p : 5.5 / o : 5.8 )

1) Choice of MFI (ZSM5) 10 5.1 x 5.5 10 5.3 x 5.6

2) Large Crystal size - Chemical treatment (B, P, Mg) - Coking at high temperature

Pore structure of MFI

5.1 x 5.7

8.5

5.3 x 5.6

[ 10 5.1 x 5.5 10 5.3 x 5.6]***

Beneficial coke
Increase of the shape selective properties :

e.g 2

High selectivity to paraxylene with ZSM5 zeolite coked at high temperature

Coke on surface Internal pore volume View of surface on molecular scale

Sieving effect

Elimination of non selective outer sites

Para xylene Manufacturing

Demand : 70% of xylenes films, fibers, resins Production 25% (Reforming Steam cracking)

Xylene isomerization Th Eq 75% (ortho + meta) + 25% (para)

Separation + Recycle Ethylbenzene produced with xylenes. (17% reforming, 50% steam cracking)

Too high cost of separation

Isomerization

Dealkylation

Bifunctional Zeolite Catalysts

PtHMOR (Na), Others (IFP, UOP)

Xylene isomerization with ethylbenzene isomerization

Xylene isomerization Ethylbenzene isomerization
EB +2 H2 Pt H+ Pt

Acid mechanism Bifunctional mechanism

X
-2 H2

ECHE

DMCHE

Pt/Al2O3 HMOR mixtures under H2 pressure

Secondary reactions :
Disproportionation and transalkylation Dealkylation Hydrocracking e.g. EB
H2

e.g. 2X

T + TMB

B + C2

Ethylbenzene isomerization
Influence of the balance between hydrogenating and acid functions on selectivity at 35% conversion

60

100
50

Selectivity (%)

80
Selectivity (%)
40 30 20 10 Cracking 0 0.00 0.50 Disproportionation Dealkylation

60 40 20 0 0 2 4 6 8 nPt/nH+ 10 12

1.00

1.50

2.00

nPt/nH+

Isomerization

Disproportionatio n Dealkylation Cracking

Ethylbenzene isomerization
Influence of the Na exchange of the HMOR component on selectivity at 35% conversion

100 80
Slectivity %

Isomerization
NaHMOR

60 40 20 0 0,0 0,5 1,0

HMOR

1,5

2,0 nPt/nH+

2,5

3,0

3,5

Isomerization of the C8 aromatic cut Recent advances

New processes based on zeolites more efficient than mordenite UOP (I 210), IFP (Oparis) p Xylene yield of 93% instead of 88-89%

Most likely pore mouth catalysis

Separation of C8 aromatics
Crystallization (Chevron-Amoco) high cost of equipment, high energy consumption

p-xylene
Adsorption : Parex (UOP), Aromax (Toray), Eluxyl (IFP)

m-xylene

Complexation with HF/BF3 Mitsubishi

o-xylene

Fractional distillation

Separation of p-xylene by selective adsorption

* adsorbent : X (K,Ba) * 120 - 180C ; 20 bar * Desorbent : toluene or p-diethylbenzene (low adsorption capacity) p-xylene (99.5%)

p-xylene

a : p-xylene; b : other C8; c desorbent

L N Aromatization

RC Pt

DH Pt

Confinement model (Derouane)

LTL (Linde Type L): [001] 12 7.1x7.1*

Aromax Catalyst Performance

Relative Feed Aromatization Rate n-hexane 1.00 n-heptane 0.80 n-octane 0.70 n-nonane 0.70 2-methylhexane methylcyclopentane 0.75 2-methylpentane 0.60 3-methylpentane 0.60 Selectivity (%) 90 90-94 86-94 90-94 97 89 83 83

Petrochemicals : b) Alkylaromatics
Ethylbenzene
+ C C

Styrene
MFI (gaz phase) MCM22, BEA (Liq phase)

Cumene
+ C C C

Phenol
MCM22, BEA

Linear Alkylbenzene (LAB)

Biodegradable detergents
MOR MCM22

Old catalyst (1950) AlCl3+HCl

AlCl3 corrosivity and problems associated with safe handling and disposal
For 1 tonne of EB, use of 2-4 kg catalyst, 1kg of HCl, 5 kg of caustic solution, production of salts Zeolite catalysts - 1980 Mobil Badger vapour phase process MFI (ZSM5) 370-420C, 7-27 bar, B/C2= 5-20, WHSV 300-400 h-1, recycling of DEB, yield > 99.5%, life time : 1 year - 1995 EB Max liquid phase process MWW (MCM22) 200C , B/C2= 3.5, Yield > 99.9%, life time > 3 years, more energy efficient

Pore structure of MCM-22 (MWW)

(B) (A)

Channel (4.0 x 5.5 ) Supercages (7.1 x 18.4 )

External Cups (7.1 x 7.0 )

(C)

Sinusoidal Channels (4.0 x 5.0 )

Sinusoidal channels openings

Alkylation over MCM-22. Location

Effect of collidine (
N

A) Eb synthesis (B/C2= = 3.5, 220C) C2= conversion Undoped sample 95.6 %

Collidine doped sample

1.4 %

B) No effect on ethylbenzene adsorption (no pore mouth blocking) Benzene alkylation occurs in the external cups
H. Du and D.H. Olson, J. Phys. Chem. B 2002

Initial significant coke deposition within the supercages

Method for determining the catalytic role of the three MCM-22 pore systems
Conversion (%)

Deactivation by coke
Activity (A) of supercages and product distribution Trap cages: large (7.1 x 18.2 h) with small apertures (4.0 x 5.5 )

15 10 5 0 0

D = 10 %

D = 0.3 %
5 10 15 TOS (h) 20 25

Poisoning of the large external cups (7.1 x 7.0 ) with a bulky

basic molecule:
N

(2,4-DMQ)

A of external cups and product distribution

A of sinusoidal channels = A Total A supercages A cups

Product distributions are those expected from the size and shape of pores and apertures.
S. Laforge et al, Micropor. Mesopor. Mater. 2004

Method for determining the acid site distribution in the three MCM-22 pore systems
4 3 2 1 Q Fresh Coked 24 h

0.1

DX (%)

CSinusoidal channel sites

=
Ctotal Csupercages - Ccups
0 200 400 2,4-DMQ (mol.g-1) 1550 1500 1450 Wavenumber (cm-1)

CCup sites

DCPyH+ = CSupercage sites

Comparison of MCM-22 samples with different crystallite sizes

A : m-Xylene conversion B : Brnsted sites 60 % % 40 20 0 A B Sext = 38 m.g-1 25 % 10 % 60 40 Supercages Sinusoidal channels Cups

48 %

20
0 A B Sext = 114 m.g-1

18 %

How to increase the external surface ?

Corma et al, (1999)

MCM-22

MCM-36

Swollen MCM-22

ITQ-2

Synthesis of cumene over HBEA zeolites Eniricerche process

C C
+

C C C

Comparison of HBEA with the usual catalysts PA (H3PO4/kieselguhr)

T C3= conversion Oligomers (wt %) Cumene (wt %) n propylbenzene (ppm) DIPB (wt%) Selectivity C 9/C6 (%) IPBS /C3 HBEA 150C 90 % 0.3 94.3 175 PA 200C 90 % 1.1 95.1 400

4.5 95.7 98.3

3.2 97 96.4
Bellussi 1995

HBEA a very particular zeolite

Tridimensional channel system 12 6.6 x 6.7** 12 5.6 x 5.6* Intergrowth hybrid of two distinct structures (polymorphs A and B) many internal local defects (T atoms not fully coordinated to the framework Lewis acid sites) Generally synthesized under the form of small crystallites ( 20-50 nm large external suface diffusion limitations)

Acid treatment of BEA (12)

% dealumination (total, framework). Acidity (H+, Lewis)

EFAL species : monomeric (360), polymeric (290) mol.g-1 Structure defects (120) Bridging OH (470)

CONCLUSIONS
Shape selectivity Adaptability Remarkable Acid Properties

Efficient adsorbents and catalysts

GREEN CHEMISTRY Refining Petrochemicals

Depollution Fine Chemicals

CONCLUSIONS
Recent advances
Isodewaxing
Methanol to olefins

New industrial processes

SAPO11, TON
SAPO 34

Ethylbenzene and cumene synthesis MWW, BEA etc.

Isomerisation of the C8 arom cut

Aromatization

IFP OPARIS process

KL, Ga/MFI

NEW CONCEPTS

New Concepts
Shape Selectivity of the external surface
External cups (MCM 22) Pore mouth (SAPO 11, TON, FER ) and key lock catalysis

Synthesis of zeolites with large external surface (nanocrystalline, delaminated zeolites)

Synthesis of zeolites with cups on the outer surface Coke molecules as active species