Peter Wiseman University of Manchester Institute of Science and Technology P.O.

Box 88 Manchester M ~ IOD, O United Kingdom

Ethylene by Naphtha Cracking

Free radicals in action
Table 1.
Raw Materialsfor Ethylene
1970
50.9
Propane

Many university chemistry teachers consider industrial chemistry to be uninteresting and often inexplicable. In most university courses this aspect of the subject receives little attention, which is a pity since chemistry owes much .of its status as an academic subject to its industrial importance and ignoring its applications presents a distorted view of the subject. In reality, shying away from applied chemistry because of a supposed lack of intellectual coherence and appeal is not justified; it can be discussed rationally a t a level appropriate to university courses (1). This artide sets out to illustrate this by discussing an important topic in industrial organic chemistry.
Ethylene Manufaciure The manufacture of ethylene by thermal cracking of hydrocarbon feedstocks is one of the cornerstones of the petrochemical industry (2). I t is carried out on an enormous scale-the current rates of ethylene production in both the 1 million tons per USA and Western Europe are about 1 annum-and is the basis for the manufacture of a very wide range of organic chemicals. Thermal cracking involves passing a mixture of feed, which may be ethane, propane, butane, or a liquid petroleum fraction, and steam, through a tube heated in a furnace, where its temperature is raised to a level in the region of 750-900C. After a reaction period of 0.14.5 s the products are rapidly cwled to 300-400C to quench the reaction. The products are separated by distillation. In Europe and Japan the feed most often used for ethylene manufacture is naphtha, one of the products obtained in refineries by fractionally distilling crude oil. In the USA, ethane and propane have been the major feeds, though for a number of reasons, including diminishing availability of these materials, there is now a marked trend towards the use of naphtha Products typically and other liquid feedstocks (see Tahle 1). obtained in naphtha cracking are shbwn in Tahle 2. At first sight, this process has all the characteristics calculated to discourage the chemistry teacher. I t uses an ill-defined raw material, puts it through a brutal reaction system, and gives an extremely complicated set of products. What can one possibly say about such a process? One can, in fact, say quite a lot. Mechanism ot Ethylene Formailon Naphtha is the name given to any fraction in the approximate boiling range 25-185T obtained by the distillation of crude oil. A "full range naphtha" covering the whole of this range contains mainly compounds having four to twelve carbon atoms. The compounds, which will be numbered in the hundreds, will be the C4 to C12 alkanes, cycloalkanes,' and aromatics which were present in the original crude oil. Although naphthas contain alarge number of components, the individual compounds have relatively simple structures, and the reactions involved in cracking can be considered in terms of model alkanes, cycloalkanes, and aromatics. Consider n-nonane as a model straight-chain alkane. At the cracking temperature thermal cleavage of carbon-carbon bonds occurs readily; e.g.

Manufacture, USA (31

1980 (en.)
40.0-35.0 11.5 4.5 44.0-49.0

1975 lest.)
54.0-49.0

33.9

:y'd;Oh,

3.4

and other liquid feedstocks

11.8

21.5 3.5 21.0-26.0

%total ethylene.

Table 2. Typical Product Distribution in Na~htha Crackins 14)

Products

wt %

This provides the initiation step for a free radical chain reaction. The radicals thus formed can undergo a series of @-scission reactions, each giving rise to a molecule of ethylene

CHFH2CH2.

CHc

CH2=CH2

and
CH8CH,CH,c~,.
--t

CH&H,.

+ CH,=CH,

Hydrogen atom abstraction from a substrate molecule by a methyl or ethyl radical (or a hydrogen atom-see below) continues the reaction chain

Most molecules of substrate enter the reaction through hydrogen-atom abstraction rather tban carbon-carbon cleavage. For both energetic and statistical reasons the radicals thus formed will be predominantly secondary radicals, and when these undergo @-scission, alkenes other tban ethylene will be produced; e.g.

CH,CH,CH,CH,CH.CH.~HCH,CH~
+

CH3CH&H,CH2CH2. + CH2=CHCH&H,

The primary radical then produced can undergo further @scissions producing ethylene
CH,CH&H,CH&H<
+

CH,.

2CH,=CH,

I t has been indicated above that ethyl radicals carry out. hydrogen atom abstractions: they can also undergo carbonhydrogen @-scission CH3CH,. CH,=CH, H.

'The cycloalkanesin crude oil contain five- and six-memberedrings only.

Maxlrnlzlng Ethylene Yield In naphtha cracking i t is normally desirable to produce the highest possible yield of ethylene. This is achieved by adprocess conditions to favor the ethylene-producing iustine .. the . reactions described a h v e over the many other reactions which can occur in the system. From the reaction scheme discussed it can he seen that high ethylene yields will be favored by ensuring that primarv alkyl radicals, once formed, undergo 8scission reactions . . . . . - - - - to the maximum extent. Thus.it is desirable to avoid termination and chain transfer reactions.
~ ~~~~ ~

Table 3.

Effect of Pressure on Cracking of

Products
1

n-Hexadecane 15)
reacfedn

Mole/100 mole hexsdecene

2
17.4
23.3

CH.

16.5

50.9

C,H6

1 . 7
20.1

Termination + .CH-CHtCHr--CH,. Chain Transfer + CBHm ---CH3 C,H,*. (secondary) -CH%. Since these are himolecular, their rates may he reduced reactions by compared to those of the unimolecular @-scission operating a t low partial pressure. This also has a favorable effect on the positions of the equilibria of the alkene-forming reactions. Table 3 illustrates the effect of pressure on product distribution in cracking. In cracking processes low partial nressures are achieved hv usine steam dilution. a weieht to weight steam to feed ratioin therange 0 . 4 4 8 being ty$ally used in nanhtha crackine.2 The effect of steam ratio on ethylene yield is illustratedh Tahle 4. The other main fador hv which control is achieved over the product distribution is by the reaction temperature. The initiation. B-scission,and termination reactions have activation energies of app;oximately 350.45, and 0 kJ mole-' respectively (7).Thus, increasing the temperature increases the rite constants of the initiatioAactions and to a lesser extent the &scission reactions, hut has no effect on that of the termination reactions. This has a two-fold effect on the nroduction of ethylene. Firstly, a t higher temperatures a higher proportion of the substrate molecules enter the reaction via cleavage to two primary radicals, rather than by hydrogen atom abstraction to give a secondary radical, which can only give an alkene other than ethylene as the product of its first @-scission.Secondly, the ethylene-producing &scission reactions are favored over the termination reactions. Durine the past 25 vears developments in furnace desim and t u h ~ m e ~ l l u r have g y allowed>racking temperaturesio he raised from about 750 to over 900C, and maximum ohtainable ethylene yields have increased from about 20 to over 30%.

C,H,

0.9 19.1

C2'm
CsHt~

CP,,

C. and above

92.9

3.3 14.8 1.0

13.8 14.3 8.1 111.9

dconditions for column 1: Temperature SOO'C: merrure I atm; con~e~sio 42.4%. n FOT column 2: 5 0 0 ' ~ ;21 atm. 47.5%.

Table 4.

Steam Dilution and Ethylene Yield in Nallhtha Cracking (61 0.6 31.0
1.2 34.5

Yield C,H,

H,O/naphtha ratio (wt %)

outlet temperature 8

4 0 ~ residence ~ ; time

0.35 r.

secondary reactions

~~~~

~~~

~~~~~

Effeci of Feedstock CornDosltlon Naphtha does not of course consist solely of normal alkanes, hut contains in addition branched-chain alkanes, cycloalkanes, and aromatic hydrocarbons. It can readily he seen from the mechanism discussed above that these will give lower yields of ethylene than normal alkanes. For example, consider a tvpical reaction path in the cracking of a model branched. chain alkane, 2-methyloctane

-Severity

Variation 01 prduct dishibution with MCking severity in naphma cracking. The shaded region represents high severihl cracking,operated to obtain maximum elhyiene yield.

20peratingst reduced absolute pressure would involve engineering difficulties and is potentially hazardous-air could be drawn into the system through leaks. Also, the steam help reduce carbon deposition in the furnace tubes: C + HzO + CO + Hz.

One molecule of ethvlene is formed compared with two from an analogous sequence of reactions involving n-nonane. Similar ronsiderations a o d v to cvcloalkanes. In this case. conjugated dienes c& i t can also be seen that the &htio;of he expected
V o l m 54. Number 3, March 1977 1 155

and
H.

CH,CH=CH, CH,CH,CH,.

CH,CH,CH,. CH,. + CH,=CH,

Naphthas containing a high proportion of cycloalkanes give hieher vields of butadiene than predominantly paraffinic . . naphthas. Aromatic hydrocarbons undergo cracking essentially only in side chains, the aromatic ring being relatively stable under cracking conditions. It canbe seen from the above discussion that for maximum ethylene yield the most desirable naphtha feed is one containing a high proportion of normal alkanes.
Secondary Reactions

Other secondary reactions result in the consumption of ethylene and other alkenes and the formation of dienes, aromatic hydrocarbons, and high-molecular-weight carbonaceous materials known as coke. Consequently, as the severity of cracking, that is the extent to which the overall reaction is allowed to proceed, is increased, the product distribution changes as indicated in the figure. The variation in ethy1ene:propyIene ratio with cracking severity allows considerable flexibility in cracker operations in response to market demands. When,maximum ethylene yield is required, cracking is operated a t 'high severity,' i.e. in the shaded region in the figure. At higher levels than this, coke formation in the furnace tubes becomes a problem, and in any case there is little further to he gained in ethylene yield.
(1) See, for example: (a) Reuben, B. G.. and Bumtall. M. L., "The Chemical Ee,m~my: Langmsn Group Ltd., London, 1973: lbl Todder, J. M., Nechustal, A,. and dubb,A. H., "BasieOrganicChemistry, Part5 Induateal P n d u ~ . " h h n Wileyand &,ns Ltd.. Landan. 1975; lcl Wiseman. P.. "An lntruduction to Industrial O~aniechemistry: Applied Seienee Publishers Ltd., London, 1972. (21 Bsba,T. B.,and Kennedy, J. R.,Chrm. Ewf.,83, (11,116 (19761. , (121.61 lL9lZi. (3) Taylor,E.D.,Chem. E n ~ . P r o p r 68, (41 Zdonik. S. B., Bassler, E. J., and Hallce, L. P.. Hydroeorbon Proees&#. 53. (2). 13
, . " g , ,

The products formed in the reactions discussed above can undergo further 'secondary reactions' which are complex and less well characterized than the primary cracking reactions. Some of these, e.g. the cracking of propene and higher alkenes, can give rise to further production of ethylene. Among suggested routes from propene to ethylene are
CH&H=CH, CHP=CH.
--c

CH,.
+

RH

.CH=CH, CH2=CH, R.

\.m,.,.

151 Voho,H.H.,and Gmd,G. M., J Amar Chsm.Soe., 71,593 (19491. (61 Europeon Chomieal Neus, 27, (6841.39 (25th. April 1975). (71 ReE (lb), p.41.

156 I Jwmal of Chemical Education