20th European Symposium on Computer Aided Process Engineering ESCAPE20 S. Pierucci and G.

. Buzzi Ferraris (Editors) 2010 Elsevier B.V. All rights reserved.

Pyrolysis of Naphtha Feedstocks: Automatic Generation of Detailed Kinetics and Lumping Procedures
Mario Dentea, Eliseo Ranzia*, Giulia Bozzanoa, Sauro Pieruccia Florian I. Kleinendorstb, Marco W.M. van Goethemb
a

Politecnico di Milano, CMIC Department Piazza Leonardo da Vinci, 32, 20131 Milano, Italy

PYROTEC - TECHNIP Zoetermeer (The Netherlands)

* Corresponding author: Eliseo.Ranzi@polimi.it

Abstract
This paper analyses and revises the critical steps in the computer generation of complex reaction schemes for pyrolysis reactions of naphtha feeds. Moving from the pioneering experience of the well known SPYRO kinetic model, the critical steps in the simplification and lumping procedures are explained, critically discussed and partially removed. The availability of parallel processors and always more efficient computer facilities allows enlarging the description details of the overall reacting system. With reference to typical naphtha feedstocks, different description levels of feed characterization and different simplifications of the reaction network can be used. Namely, a large number of branched paraffin isomers are used to characterize the feed and the effect of possible refinery treatments of the naphtha feed are discussed. Moreover, the complex reaction scheme of hydrocarbon pyrolysis needs to be simplified both in terms of decomposition and recombination reactions, in order to avoid an excessive increase of the overall dimension of the mechanism, without significant improvements in the obtained results. As a result of this kinetic study, the SPYRO kinetic scheme is further extended to cover new possible feeds and more complex situations. Several examples illustrate the advantages and the limits of the proposed approach Keywords: Pyrolysis, detailed kinetics, ethylene, steam cracking

1. Introduction
Feedstocks ranging from light gases up to naphthas and gas oils are converted into valuable products at high temperatures in tubular coils in steam cracking furnaces (Dente et al. 1970; Froment, 1992). The complexity of this system is due both to the large number of elementary reactions and to the difficulty of properly characterizing the reacting mixture. The main focus of this paper is to critically review and discuss the main simplifications applied during the development and validation of these detailed kinetic schemes (Dente et al. 1992; Dente et al. 2007). Apart from the analysis of the chemistry involved in the process, it is also critical to characterize the internal composition of the naphtha feed.

M. Dente et al. 2. Kinetic Mechanism Free radical reactions dominate the thermal degradation of hydrocarbons. Only radical kinetic schemes can provide reliable descriptions of the pyrolysis process (Benson 1976; Dente et al., 2007). Radical chain propagation process is simply summarized with the following reaction classes: 2.1. - Initiation and termination reactions CH3-CH2-CH3 CH3 + C2H5 Unimolecular initiation reaction involves the breaking of a covalent C-C bond with the formation of two radicals. This initiation process is sensitive to the stability of the formed radicals. Total radical concentration in the reacting system is controlled by radical initiation and recombination reactions. 2.2. - Propagation reactions 2.2.a - H-abstraction reactions R + CH3-CH2-CH3 RH + C3H7 Once initiation reactions generate the propagating radicals, the primary and main decomposition products are well explained by the H abstraction reactions and the subsequent, fast decomposition of primary radicals. Kinetic parameters of these reactions are mainly function of the H abstracting radical and of the site from which Hatom is removed. 2.2.b- -decomposition and dehydrogenation reactions and reverse radical addition reactions. CH2CH2-CH3 CH2=CH2 + CH3 CH3-CH-CH3 H + CH2=CH-CH3 At high temperature, -decomposition reactions constitute the prevailing fate of alkyl radicals. At high pressure and high concentration of unsaturated species, reverse radical addition reactions also become significant. 2.2.c- Alkyl radical isomerization reactions CH2CH2- CH2-CH2-CH3 CH3-CH2-CH2-CH-CH3 CH2(CH2)3 -CH2-CH3 CH3(CH2)3-CH-CH3 CH2(CH2)4 -CH2-CH3 CH3(CH2)4-CH-CH3 At low temperature, large radicals can isomerize through 5, 6 and 7-membered ring intermediates, before decomposition. 2.3. Concerted path molecular reactions CyC6H12 CH2=CH-CH2-CH2-CH2-CH3 CH3CH=CH-CH3 CH2=CH-CH2-CH3 CH2=CH-CH2-CH3 CH2=CH-CH=CH2 + H2 CH2=CH-CH2-CH2-CH3 CH3-CH=CH2 + CH2=CH2 Concerted path molecular reactions, via four and six centers, can also play a significant role. Diels-Alder, cyclo-alkane and olefin isomerization as well as dehydrogenation and ene decompositions are typical examples of this reaction class. 2.4. Successive condensation reactions Once significant amounts of ethylene and propylene are formed, vinyl, allyl and benzyl radicals are present in the reacting system. Successive addition and condensation reactions of unsaturated species explain the formation of benzene and heavier species. These reactions decrease the overall ethylene selectivity. The interactions of unsaturated species are the first hierarchical step and the core of the pyrolysis mechanism. In fact,

Automatic Generation of Detailed Kinetics and Lumping Procedures high temperature pyrolysis of large hydrocarbons rapidly gives rise to small radicals and species, and their interactions are common ground shared by all pyrolysis systems. Figure 1 shows the primary propagation reactions of n-decane and itself confirms the complexity of the pyrolysis mechanism. All the different H-abstracting radicals produce five isomers of n-decyl radical (nC10H21). These radicals can then isomerize and/or decompose. In the temperature range of major interest for steam cracking process, decomposition prevails at high temperatures, while isomerizations dominate at low temperatures.

3. Automatic generation of kinetic schemes and lumping procedures

The manual compilation of the whole set of reactions becomes unmanageable, particularly when the hydrocarbon molecular weight is increased. Therefore, it is convenient to classify the reactions and to apply an automatic generation of the reaction scheme on the basis of a small set of reference kinetic parameters. As an example, the resulting mechanism of n-decane pyrolysis includes 5 initiation reactions, 5 generic Habstraction reactions and 35 primary propagation reactions of the 5 n-decyl radicals. Figure 2 shows the successive isomerization and decomposition reactions of lower alkyl radicals formed via -decompositions. The number of elementary reactions, and reacting species, rapidly increases with the number of C-atoms, mainly in the case of cycloalkane and alkene components.
RH + C2H4 +

+ RH + + C2H5

R +

RH + +

RH + +

RH +

Figure 1. H abstraction reactions of n-decane.

3.1

Lumping of reactions (single event micro kinetics)

Due to the huge number of possible reactions and intermediates products, it is a need to simplify the pyrolysis mechanism. Fortunately, the monomolecular reactions of large alkyl radicals are much faster than the bimolecular ones. Thus, the -radical hypothesis allows assuming the pseudo steady state assumption (PSSA) for large radicals, so that the overall reaction scheme is drastically reduced (Dente and Ranzi, 1983; Van Geem et al., 2008). Alkyl radicals containing more than 4-5 C atoms are supposed to be

+ + CH3

M. Dente et al. instantaneously transformed (via isomerisation and decomposition reactions) into their final products, without loss of model accuracy. Isomerisation and decomposition reactions largely prevail on possible H-abstraction, recombination and addition reactions. Thus large sections of the decomposition scheme are reduced to simpler equivalent or lumped reactions.

C2H4 +

+
+ + C2H5 + CH3 + C2H5

+ C2H4 +

+ CH3 + C2H5 +

C3H6 + C2H4 + C2H4 + + C2H5 + CH3 + C2H5

Figure 2. Successive isomerization and decomposition reactions of alkyl radicals. The kinetic generator, MAMA program, manages these calculations and produces equivalent stoichiometries that compress and lump several reactions into a single equivalent reaction whose apparent stoichiometry is only a relatively weak function of cracking temperature. The elementary H abstraction reactions of n-decane shown in Figure 1 and 2 are thus lumped into a single equivalent reaction whose stoichiometry, evaluated at 1040 K, simply becomes: R+nC10H22 RH +.0205 H +.0803 CH3 +.2593 C2H5 +.406 nC3H7 +.234 1C4H9 + .3785 C2H4 + .3127 C3H6 + .2114 1- C4H8 + .1870 1-C5H10 + .1815 1-C6H12 + .1461 1-C7H14 +.1284 1-C8H16 + .0540 1-C9H18 + .0025 1-C10H20 + .0006 2-C5H10 + .0012 C6H12s + .0013 C7H14s + .0005 C8H16s + .0100 C10H20s MAMA program is more than a simple mechanism generator. It may lump isomerization and decomposition reactions of large radicals, by solving the overall system and evaluating primary distribution products according to PSSA of intermediate

Automatic Generation of Detailed Kinetics and Lumping Procedures radicals. The net result is the generation of equivalent or lumped reactions that drastically simplify the reacting system, in terms of both species and reactions.

3.2 Naphtha Characterization and Lumping of Species

Light and heavy naphthas are mostly aliphatic but they also contain significant amounts of cyclo-alkanes and aromatics. Detailed description of naphtha feed involves several isomers, mainly in branched and cyclo-alkane fractions. There are significant differences in the potential pyrolysis yields of major olefins from structural isomers. Table 1 shows the variability of these yields from the pyrolysis of different isomers of branched alkanes C8, at the same typical operating conditions of steam cracking process. Ethylene yields can span from less than 15% from trimethylpentane to more than 30% from the three mono-methylheptanes.. Table 1: Yields predictions from pyrolysis of different branched C8 isomers. (Lumping Temperature 1000 K).
(wt. %) H2 CH4 C2H4 C3H6 13C4H6 1C4H8 2C4H8 iC4H8 C52methyl C7 0.79 12.73 30.84 21.44 4.54 2.38 0.76 5.56 84.75 3methyl C7 0.75 14.45 30.44 18.88 5.58 2.81 1.45 2.20 82.46 4methyl C7 0.81 13.00 32.16 21.61 5.28 2.01 0.57 1.88 83.97 23dimethyl C6 0.78 16.45 22.28 21.22 6.69 2.18 2.41 2.04 79.09 234trimethylC5 0.82 18.48 14.95 20.98 7.12 2.15 3.83 3.63 76.00 3ethylC6 0.86 14.83 31.71 14.94 7.16 2.92 0.88 1.31 81.69

The number of species in naphtha feeds is large and the number of elementary steps in pyrolysis mechanism amounts to more than 105 (Van Geem et al., 2008). In spite of the different origin of the naphtha feeds, there are evident regularities with regard to their composition. The distribution of structural isomers is largely independent of the origin of the feedstock and it is possible to describe the naphtha feed with only a limited number of pseudo-components. Mono methyl-alkanes prevail on di-methyl- and ethylalkanes. Tri-methyl-alkanes are less abundant and quaternary C atoms are of very limited importance. On this basis, it is possible to empirically derive lumped components with statistically defined internal isomer distribution. Thus, structural isomers of large hydrocarbons are conveniently grouped into equivalent components. One lumped component is assumed for each number of C-atoms and per class of components (branched alkanes, cyclo-alkanes and alkyl-aromatics) in the naphtha fraction. Lumped species react in a similar way and their internal distribution remains almost unchanged along the reaction process. Each pseudo-component consists of structural isomers and only one continuity equation needs to be considered. The equivalent reactions of the different pseudo-components are obtained by averaging the equivalent reactions of the different isomers, taking all the elementary reactions of these isomers into account. As a result of the combination of PSSA of intermediate

M. Dente et al. radicals and the lumping of different isomers into the lumped pseudocomponent {isoC8}, the resulting lumped H abstraction reaction for the standard {isoC8} pseudocomponent simply becomes:
R + {isoC8} = RH + .0167 H + .1842 CH3 + .218 C2H5 + .1835 nC3H7+ .1296 iC3H7 + .0671 i-C4H9 + .1415 1C4H9 + .0592 2C4H9 + .1628 C2H4 + .2499 C3H6 + .107 1C4H8 + .0414 2C4H8 + .1417 iC4H8 + .0704 1C5H10 + .0326 2C5H10 + .0510 2me-1C4H8 + .0599 3me-1C4H8 + .0103 2me-2C4H8 + .009 1C6H12 + .0214 2C6H12 + .0047 3C6H12 + .1012 me-C5H10s + .0155 1C7H14 + .1402 C7H14s + .0137 C8H16s

4. Adaptive kinetic schemes and flexible lumping.

The simplifications applied to the lumping of species and to reaction products, partially restrict the validity range of the overall kinetic model. It is viable to remove the above simplifications, without increasing the dimension of the overall model. Although the stoichiometries of lumped components are temperature-dependent, they are tailored to actual cracking temperatures through proper reaction tables. Thus the kinetic model easily derives a temperature dependent stoichiometry based on three or more reference temperatures. Furthermore, the fixed weight factors of isomers in lumped component definition makes impossible to describe the decomposition of structural isomers or particular mixtures. The correct approach is to determine the internal weight factors from the analytical composition of naphtha. In this way, new pseudo-components are defined for each feedstock. This approach has been applied and lumped components are modified according to naphtha composition, when available. The adaptive kinetic scheme becomes more flexible to particular feedstocks and to different operating conditions. Several examples of industrial interest already shown limits and advantages of these extensions of the overall pyrolysis model.

5. Acknowledgements
Authors acknowledge the unforgettable enthusiasm and activity of Peter Valkenburg.

References
Benson, S.W. (1976) "Thermochemical Kinetics (2nd ed)." John Wiley and Sons, New York Dente, M., Ranzi, E., Antolini, G., Losco F. (1970) 97th EFCE Symposium, Florence Dente, M., Ranzi, E. (1983) Chapter 7 in Pyrolysis: Theory and Industrial Practice (L.F.Albright, B.L.Crines, W.H.Corcoran Eds), Academic Press: San Diego Dente, M., S. Pierucci, E. Ranzi, G. Bussani (1992) Chem. Eng. Sci. 47, 2629 M. Dente, G. Bozzano, T. Faravelli, A. Marongiu, S. Pierucci, E. Ranzi Advances in Chemical Engineering (G. Marin Ed.) vol. 32: 52-166, Elsevier Inc. Froment G.F. (1992), Chem. Eng. Sci. 47, 2163. Van Geem, K.M., M.F. Reyniers, G.B. Marin (2008) Oil & Gas Science Technology IFP, 63 (1).