Professional Documents
Culture Documents
11 - Chapter 6 PDF
11 - Chapter 6 PDF
CHAPTER 6
6.1 INTRODUCTION
stocks (Biswas and Maxwell 1990). ZSM-5 and other pentasil-ring zeolites
are added as additives to the cracking units in order to enhance the yield of
light olefins. Recently, applications of unidimensional 10-membered ring pore
zeolite and zeotype structures such as ZSM-22, ZSM-48, ZSM-23 and
SAPO-11, 17, 34 and uni dimensional 12-membered ring pore ZSM-12 were
reported. Low concentration of strongly acidic sites results in high cracking
activity to ethylene and propylene and suppression of hydrogen transfer
reactions (hydrogen transfer index-HTI) leading to paraffins, cyclolefins,
aromatics and coke like polyaromatic molecules. The HTI can reflect the
difference in hydrogen transfer activities on zeolites with different structures.
The hydrogen transfer reactions, which involve the formation of bulky
bimolecular reaction intermediates, are mainly controlled by steric constrains
due to space available inside the micropore of zeolites (Zhu et al 2005).
Of course they can also occur on the outer surface of the particles.
The smaller the pore size of zeolite, the greater the extent of suppression of
the hydrogen transfer reactions of alkenes. In other words the HTI decreases
with the pore size of the zeolite. For example, the decrease of order is
Y > beta > MCM-22 > ZSM-5 > other zeolites (Zhu et al 2005).
+
OH -
+ Si Al +
H4C + + CH4
+
OH - +
Si Al + H2C CH2 HC CH2 + H2C CH2 + H 2C CH2
+
H
O
H+ H
- +
+ Si Al + +
O -
Si Al
+
OH -
Si Al +
+
OH -
+
+ Si Al
+ +
O -
Si Al
H
H+
O
Si
-
Al + H2C CH2 + +
H+ +
O -
+ Si Al + +
O -
Si Al
Cyclisation
+
High HTI OH -
+ Si Al
H+ +
O -
+ Si Al CH4
Cyclisation
+
High HTI OH -
+ Si Al
Catalyst
Gas fraction Commercial HZSM-5 HZSM-5 HZSM-5
HZSM-5(25) (25) (50) (75)
CO 0.9 0.4 0.4 0.5
CH4 9.6 6.6 8.1 6.8
CO2 0.4 0.2 0.0 0.2
C2= (Ethylene) 19.6 18.4 21.6 19.0
C2 (Ethane) 8.5 5.6 7.4 6.0
C3= (Propylene) 15.7 18.8 17.7 19.4
C3 (Propane) 7.2 4.0 5.3 4.0
C4 (Butane) 7.0 8.3 7.4 8.7
C5 (Pentane) 5.9 5.3 2.7 5.2
Unknown 0.7 1.8 0.9 2.0
C2= + C3= 35.3 37.2 39.3 38.4
C2=/C3= 1.3 1.0 1.2 1.0
Gas yield 75.3 69.4 71.7 71.9
The data in Table 6.1 indicate higher yield of olefins for the
synthesised samples than for the commercial sample. As the synthesised
samples without phosphoric acid possess low bulk density than the reference
100
samples, 0.3 g of them was used for catalytic studies compared to the
reference sample of about 0.5 g. But the low density of synthesised samples in
fluoride medium without phosphoric acid is not a problem, as our latter
experiments with phosphoric acid gave solids of high density. It is known that
zeolite crystals of large dimensions yield less olefins than those of small
dimensions due to promoted hydrogen transfer reactions that facilitate
formation of aromatics and oligomeric products. Though the synthesised
samples possess larger crystal dimension than that of commercial one, they
produced high olefin yield. Based on the products yield and composition, it
could be suggested that there may be minimum bimolecular hydrogen transfer
reactions occurred in all the synthesised samples. There may be possibly
minimum or no external acid sites, and very scattered distribution of acid sites
inside the channel instead of assembled them closer. Such close acid sites can
be suggested to be the main cause for the enhanced consumption of olefins to
yield aromatics and oligomers (Wang et al 1994). Hence, fluoride with its
high mineralising and complexing properties is indirectly proved to exhibit
the property of planting acid sites internally and also keeping them well
scattered inside the channel. Although these properties were not verified
experimentally at this stage, they are to be established in the future work.
HZSM-5(50) showed higher yield of olefins than HZSM-5(25). The acid sites
are certainly better isolated in the former than the latter as the Si/Al is high.
Hence, it could be expected that by avoiding close acid sites hydrogen
transfer activity could be largely suppressed and this is in accordance with the
previous report (Wang et al 1994). Moreover, the acid sites of the present
catalysts are weak and medium type and so hydrogen transfer reactions of
naphtha cracking are still minimised. Therefore, the olefins can freely diffuse
through the pores of such catalysts without being rapidly converted to side
products.
cracking activity. Generally ZSM-5 with high density of acid sites could
exhibit high naphtha cracking activity as well as high hydrogen transfer
activity and hence those with low density of acid sites (optimum) could be
adequate.
6.3 CONCLUSION
out above 650 °C in steam. Though this study was not undertaken right now,
it becomes a main part of our study in the future. Phosphoric acid
modification of ZSM-5 has been very elaborately examined for hydrothermal
stability and hence this will also become part of our future investigation.
The influence of rare earths has also been investigated on the hydrothermal
stability of ZSM-5 for naphtha cracking. This will also form yet another study
in the future.