95

CHAPTER 6 CRACKING OF NAPHTHA TO LIGHT OLEFINS

6.1

INTRODUCTION Light olefins have five or lower number of carbons. Ethylene and

propylene are the monomers for polyethylene and polypropylene respectively. Butene and pentene are the feed stocks for high octane gasoline components. They are also important feedstocks for the production of oxygenates used as octane boosting additives. Currently they are manufactured mainly form naphtha by thermal cracking also called steam cracking. The current steam cracking process uses as much as 40% of the energy consumed by the entire petrochemical industry. Therefore global environmental issues have stimulated the development of process that maximise energy, resource savings and minimise CO2 emissions. Besides, it is difficult to control the composition of olefins formed. Hence, there is an increase in demand for processes capable of controlling the composition of olefins. Naphtha catalytic cracking has been started to achieve better olefin yield and lower energy consumption. In addition use of alternative feedstocks such as methane, LPG, gas oil, crude oil and ethanol have also been presumed. However, the conventional naphtha is the most attractive feedstocks for this process as it can take advantage of the existing facilities that are used for steam cracking. Zeolites are the mostly employed catalysts for cracking of heavy oil. The fluidised bed catalytic cracking units in petroleum refineries are the major source of light olefins which are the important petrochemical feed

96

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). Cracking of naphtha to light olefins is also an additional process in refineries that is carried out mainly over ZSM-5. The advantage of using ZSM-5 zeolite is its medium pore which can discourage coke formation due to absence of large cavities in the pore structure and low concentration of acid sites. Based on the products of naphtha cracking two mechanisms have been proposed. Haag and co-workers have proposed that the acid catalysed cracking of simple paraffins occurs by both unimolecular and bimolecular mechanisms (Haag et al 1981, Haag et al 1991). In the unimolecular mechanism feed olefins are chemisorbed on the Brnsted acid sites to form carbenium ions which then cracked by beta scission to yield olefins. In the cracking of paraffins, protons of ZSM-5 are transferred to them to form a

97

penta-coordinated carbonium ions as transition state as shown in Scheme 6.1. The carbonium ion expels methane to form a carbenium ion. The latter undergoes beta scission to form olefins.
OH
+

+
+

Si

Al

+ H4C

CH4

OH Si

Al

H2C

CH2

+ HC

CH2 H

H2C

CH2

H 2C

CH2

Scheme 6.1 Cracking of paraffins Similarly n-olefins are protonated by zeolite to form secondary carbonium ion which is then cracked by beta scission to form ethylene and propylene as shown in Scheme 6.2.
H+
Al
-

O Si

+
O Si Al
-

H +

Si

+ OH Al

OH Si

Al

+
O Si

+
Al
-

O Si

H+
Al
-

H2C

CH2

Scheme 6.2 Cracking of n-olefins The bimolecular mechanism is composed of the following steps: ethylene or propylene is chemisorbed on the Brnsted acid sites to form the respective carbenium ion. Such a carbenium ion converts the feed alkane into

98

a carbenium ion by a hydride ion abstraction. The resulting carbenium ion cyclises to form naphthene which is converted to an aromatic by a sequence of hydrogen transfer reactions (Scheme 6.3).

O Si

H+
Al
-

+
O Si

+
Al
-

Cyclisation High HTI

OH Si
+

Al

Scheme 6.3 Bimolecular mechanism for cracking Sequential hydrogen abstraction from naphthenes by this

mechanism results aromatics as shown in Scheme 6.4. It depends on HTI which inturn depends on the strength and density of acid sites. Zeolites with high HTI promote formation of naphthenes and aromatics. As the pore size of ZSM-5 is about 5.5 , large space demanding bimolecular cracking

mechanism is largely suppressed and the interaction between the channel surface and the reactants is enhanced. The latter factor is important as it could result in high conversion.

O Si

H+
Al
-

+ CH4 Cyclisation High HTI

OH Si
+

Al

Scheme 6.4 Formation of naphthenes and aromatics

99

6.2

CRACKING ACTIVITY OF THE CATALYST HZSM-5(Si/Al = 25, 50 and 75) synthesised in fluoride medium

containing phosphoric acid were tested for cracking of naphtha to light olefins. The cracking of naphtha was carried at 675 C in 6 ml/min He flow, 3 ml/min N2 flow, 0.58 g/h water flow and naphtha at a flow rate of 1.15 g/h. The results of naphtha cracking activity are presented in Table 6.1. The data obtained for commercial HZSM-5(25) are also presented in the same table for comparative purpose. The data obtained at 625 and 650 C were not given as the conversion and yield of olefins were very much low. Table 6.1 Naphtha cracking activity over HZSM-5 zeolites Catalyst HZSM-5 HZSM-5 (25) (50) 0.4 0.4 6.6 8.1 0.2 0.0 18.4 21.6 5.6 7.4 18.8 17.7 4.0 5.3 8.3 7.4 5.3 2.7 1.8 0.9 37.2 39.3 1.0 1.2 69.4 71.7

Gas fraction CO CH4 CO2 C2= (Ethylene) C2 (Ethane) C3= (Propylene) C3 (Propane) C4 (Butane) C5 (Pentane) Unknown C2= + C3= C2=/C3= Gas yield

Commercial HZSM-5(25) 0.9 9.6 0.4 19.6 8.5 15.7 7.2 7.0 5.9 0.7 35.3 1.3 75.3

HZSM-5 (75) 0.5 6.8 0.2 19.0 6.0 19.4 4.0 8.7 5.2 2.0 38.4 1.0 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. Since all the catalysts showed same yield of olefins irrespective of Si/Al ratios, high density of acid sites is not a prerequisite for high naphtha

101

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. Generally cracking of naphtha to light olefins resulted total gas yield higher than the liquid yield. In this study the gas yield was about 3 times higher than the liquid yield. The liquid product was mainly composed of aromatics, namely, benzene, toluene and xylene. This result, therefore, suggested existence of still hydrogen transfer reactions, though the catalysts carry mainly weak and medium acid sites. So hydrogen transfer reactions may not be exclusively controlled by strong acid sites. Even weak acid sites at high temperature may be capable of effecting such reactions. Further, HZSM-5 synthesised in fluoride medium gave less yield of olefins than the commercial catalyst. Another important observation is the ratio of ethylene to propylene, which is close to one in all cases. This ratio is important because of high propylene demand. Commercial as well as ZSM-5 catalysts synthesised in alkaline medium generally showed high ratio of ethylene to propylene. But the present HZSM-5 catalysts synthesised in fluoride medium gave ethylene to propylene ratio close to one. This is an additional advantage of HZSM-5 for cracking of naphtha to light olefins. 6.3 CONCLUSION The study concluded that fluoride mediated synthesis of HZSM-5 is advantageous for application in the catalytic cracking of naphtha. Though the medium planted only weak and medium acid sites in the catalysts, the yield of olefins is same as that of a commercial catalyst with strong acid sites. Hence, presence of strong acid sites is not a necessity for naphtha cracking. The hydrothermal stability of ZSM-5 is mandatory as the cracking is carried

102

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.