Petrochemical Processes

Aromatics

M. GUISNET

University of Poitiers

Instituto Superior Técnico

(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)
EB
Aromatic loop mX
EB, X oX
I (PtHMOR)

 Aromatization of light naphtha (Pt(K, Ba) LTL) nC6 + 4 H2

 Petrochemicals : b) Alkylaromatics

Ethylbenzene Styrene

MFI (gaz phase)

+ C C
MCM22, BEA (Liq phase)

Cumene Phenol

+ C C C MCM22, BEA

Linear Alkylbenzene (LAB) Biodegradable detergents

MOR
+ MCM22
 Selective toluene disproportionation (STDP)

2 +

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

1) Choice of MFI (ZSM5)

10 5.1 x 5.5 10 5.3 x 5.6 Å
2) Large Crystal size
- Chemical treatment (B, P, Mg…)
- Coking at high temperature
 Pore structure of MFI

5 .1 x 5 .7 Å

8 .5 Å

5 .3 x 5 .6 Å

[ 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 Acid mechanism
Ethylbenzene isomerization Bifunctional mechanism
EB X
+2 H2 Pt Pt -2 H2
H+
ECHE DMCHE

Pt/Al2O3 – HMOR mixtures under H2 pressure

Secondary reactions :
 Disproportionation and transalkylation e.g. 2X T + TMB
H2
 Dealkylation e.g. EB B + C2
 Hydrocracking
 Ethylbenzene isomerization
Influence of the balance between hydrogenating and acid functions
on selectivity at 35% conversion

60
100
50
80
Selectivity (%)

Selectivity (%)
40
60
30
40
20 Disproportionation

20
10 Dealkylation

0 Cracking
0
0 2 4 6 8 10 12 0.00 0.50 1.00 1.50 2.00
nPt/nH+ nPt/nH+

Isomerization Disproportionatio
n Dealkylation
Cracking
 Ethylbenzene isomerization
Influence of the Na exchange of the HMOR component on selectivity
at 35% conversion

Isomerization
100
NaHMOR
80

HMOR
Sélectivity %

60

40

20

0
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5
nPt/nH+
 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 - 180°C ; 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 DH
Pt Pt

Confinement model (Derouane)

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

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

Ethylbenzene Styrene

MFI (gaz phase)

+ C C
MCM22, BEA (Liq phase)

Cumene Phenol

+ C C C MCM22, BEA

Linear Alkylbenzene (LAB) Biodegradable detergents

MOR
+ MCM22
 + C C

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)
370-420°C, 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)
200°C , 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 Å) External Cups Sinusoidal Channels
(7.1  x 7.0 Å) (4.0 x 5.0 Å)
(C)
Supercages
(7.1  x 18.4 Å)
Sinusoidal channels
openings
 Alkylation over MCM-22. Location

 Effect of collidine ( N
)

A) Eb synthesis (B/C2= = 3.5, 220°C)

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
15
 Deactivation by « coke »

Conversion (%)
D = 10 %
10
 Activity (A) of supercages and product distribution 5 D = 0.3 %
Trap cages: large (7.1  x 18.2 Å h) 0
with small apertures (4.0 x 5.5 Å) 0 5 10 15 20 25
TOS (h)

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

basic molecule: (2,4-DMQ)
N

 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 Fresh
Q
Coked 24 h 0.1

3
DX (%)

2 CSinusoidal channel sites

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

CCup sites DCPyH+ = CSupercage sites

 Comparison of MCM-22 samples with
different crystallite sizes

Supercages
A : m-Xylene conversion
Sinusoidal channels
B : Brönsted sites
Cups

60 60 48 %

40 25 % 40
%

%
18 %
20 10 % 20

0 0
A B A B

Sext = 38 m².g-1 Sext = 114 m².g-1

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 C

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

HBEA PA
T 150°C 200°C
C3= conversion 90 % 90 %
Oligomers (wt %) 0.3 1.1
Cumene (wt %) 94.3 95.1
n propylbenzene 175 400
(ppm)
DIPB (wt%) 4.5 3.2
Selectivity C 9/C6 (%) 95.7 97
IPBS /C3 98.3 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)
µmol.g-1 Structure defects (120)
Bridging OH (470)
 CONCLUSIONS

Remarkable Acid
Shape selectivity
Properties

Adaptability

Efficient adsorbents and catalysts

GREEN CHEMISTRY

Refining Depollution
Petrochemicals Fine Chemicals
 CONCLUSIONS

Recent advances New industrial processes

Isodewaxing SAPO11, TON

Methanol to olefins SAPO 34
Ethylbenzene and cumene synthesis MWW, BEA etc.
Isomerisation of the C8 arom cut IFP OPARIS process
Aromatization 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