You are on page 1of 11
hen, Pgs ears, 98, Vo). p, MALN46]_ © 99KOPA Ovens bn Ameo Rept ale city fm he pbs Fioccoyine eile nly FORMATION OF SOOT PARTICLES AS A PROCESS INVOLVING CHEMICAL CONDENSATION OF POLYINES A.V. KRESTININ Institute of Problems in Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region, Russia [A dale kinetic mode of s001 particle formation i hydrocarbon pyrolysis is ‘escrbed, The model sesseatlly based on an idea of radcal-branched poly- merization of polyine C,H, (n = 2, 3,..) molecules asa result of which sot particles are inially formed as polymeric globules. Soot nuclei arse ia the ‘model naturally a radial centers plyine polymerization, New aot particles form solely whenever the nice can iveversibly grow due o fast polymeriza tion of plyine molecules on ther surface, This crea condition is writen in the form of an inequity between the concentrations of polynes and other hydrocarbons in the ambient slmospbere. The model allows calculation of the basic quantitative characteristics of the sot formation process: the induction perind, nicleation rate, numberof incipient sot particles formed, soot viel nd effective rate constant for soot grow. The above quantities are calculated ‘numerically for pyrolysis of methane, ethane, ethylene, and acetylene (1300— 1900 K, 2" 102+ 10" C.atomslem. The detiled kinetic reaction mecha- hsm includes steps taking place in the gas phe and on the suace of soot pamicls, The calvlation results ft quite well the avaiable experimental dts (Reveived October 28, 1996) INTRODUCTION ‘By the present time the sot formation mechanism in flames and in thermal hydrocarbon decomposition have been studied in numerous works. In site of significant progress in understanding some details ofthe mechanism, soot formation sill remains among the least explored problems in combustion. Reviews in this field [1-4] outline only a general schematic ofthe process including as the basic stages decomposition of the initial hydrocarbon ‘molecule, formation of polycyclic aromatic hydrocarbons (PAH) from the decomposition products, and coagulation of large PAH molecules, which yields in the final run, as supposed in the existing theories, soot particles. Maat 1442 A.V. KRESTININ ‘This approach is a basis of many attempts to construct a detailed ‘mathematical model of soot formation [4,5]. However the available computer codes are incapable of calculating the basic characteristics of the soot formation process — the induction period, nucleation rate, and soot particle yield — even in the simple case of hydrocarbon pyrolysis. The theory of coagulation of heavy polyaromatic molecules even fails to explain such well recognized experimental facts asthe soot formation threshold (in terms ofthe C/O ratio inthe intial fuel) (2), explosion-ike behavior of the ‘nucleation and soot growth processes, the high EPR signal recorded when ‘new soot particles are formed [6], and the high rate of surface soot particle ‘growth which is two or three orders of magnitude higher than the pyr0- ‘carbon growth rate [7]. That polycyclic aromatic molecules are capable of ‘coagulating 0 produce aerosol particles is hardly consistent with some ‘experimental findings. For example, the authors of [8] inferred from their laser spectroscopic studies of smoking flames that “soot precursors (incipient solid phase) are not aggregates of large polycyclic aromatic ‘molecules and consist mostly of fragments incorporating two or three aromatic rings connected by aliphatic or perhaps oxygen bridges". The authors of (9] conducted a laser desorption and mass-spectrometric study of ‘condensate sampled at the early soot formation stage in an ethylene flame 'As follows from their data, carbonaceous particles consist of C-fragments ‘whose size is smaller (C\,— Cy) than that of the carbon backbone of polyaromatic molecules which dominate upstream in the lame (C., — C,) In [10}, it has been revealed that in pyrolysis of an acetylene/benzene mixture with a benzene concentration ranging from 0 to 30 vol. % and at a ‘constant acetylene concentration of & vol.% the amount of soot particles formed in the process remains at a constant level rather than increases with the benzene concentration, as would be expected because of the more favorable conditions for formation of polycyclic aromatic molecules. ‘The results of early experimental studies served a basis for putting forward a hypothesis of the decisive role played by polyine molecules in formation of soot particles [11, 12] which, was not seriously developed further on. However an attempt to use this idea for developing & mathema- tical soot formation model yielded unexpectedly good results in calelations of the basic characteristics of acetylene and methane pyrolysis reactions [13-15]. Further investigations have shown that of the two types of ‘molecules — polycyclic aromatics and polyines, the only compounds omaining stable ata high temperature — molecules with conjugated triple ‘bonds are remarkably superior because of their high reactivity in copoly- ‘merization processes which quickly rises with increasing number of conjugated triple bonds [16,17]. In this work, an attempt is made to ‘consider & mechanism of soot particle formation as chemical condensation ‘of “vapor” of polyine molecules (C,H, = 2, 3.) formed in thermal FORMATION OF SOOT PARTICLES as decomposition of the initial hydrocarbon fuel. This approach serves as a natural physical basis forthe mathematical model developed previously and tion. The process of soot formation from some simple hydrocarbons is also ealoulated and the results are ‘compared with available experimental data, ‘THE GENERAL SCHEME OF SOOT FORMATION ADOPTED IN THE MODEL, “The diagram of the process, as adopted inthis wotk, is shown in Figs.1, and 2. The basic idea of the approach to describing the process consists in ‘an assumption that soot particles arise primarily as polymeric globules, as sult of fast polyine polymerization. New polymeric globules can form ‘only whenever soot particle nce’ which arise continuously in the system has an opportunity of growing irreversibly. The critical condition for this to occur in the form of fast polyine polymerization onthe nucle (polymeri= zation centers) i formulated as inequality W,, > Wg, where Mi, isthe rate of radical center multiplication onthe surface of a polymeric globule due to polyine polymerization and W,,. isthe rate of decay ofthese centers in their reactions with chemically ative species inthe gas atmosphere. The polymer ‘growth on the globule surface is schematically shown in Fig.2. First, an intermediate stricture is formed after (wo or mote polyine molecules are ‘Added tothe free valence of a C atom. It is meeting of the critical condition for fast polymerization which makes it possible to form these complexes from several polyine molecules. The ahove structure, as a fragment of ‘condensed phise, possesses a high excess tree Gibbs energy and will ‘undergo rearrangement with partial aromatization and gradual carbonization. ‘This structure rearrangement is a requisite pat of the polyine condensation process. It is cyclization processes which increase the number of radical centers on the surface ofa polymeric globule due to opening of triple bonds in polyine molecules and create thereby conditions for a fast growth of aerosol particles. The aforesaid also suggests that within the model conside~ red a soot nucleus has a meaning of a minimum-size particle (radical) capable of initiating fast polyine polymerization. ‘The polyine concentration in the gas gradually rises inthe course of the induction period. Soot nuclei (polymerization centers) are also formed ‘during this period, but, having no opportunity of ther irreversible growth, are converted into molecules with aromatic fragments of various structure Which enter further on into both the growth and decay reactions. As soon 15 the polyine concentration attains & necessary value, an intense polymeri- zation process starts. At tis stage, the major contribution to the growth of soot nuclei comes from polyines which thereby provides the radical nature waa A.V. KRESTININ of the entire surface of growing polymeric globules. Aerosol particles at this stage coagulate with an efficiency close to unity owing to which the process proceeds in the form of coalescence. Wy < Wane Wy > Wan Wy < Wane induction period | fast polymerization | carbonization, a ‘of polyines | formation of fractals = / p epyon Pesan e - 0 Graphite) Time > FIGURE 1. Diagram ofthe pyrolysis process. Foe Gibbs energy AG yy/C-atom (Keat/mot for reactions nCigraphite) + mH; = CHa is ploted onthe y-axis and Indicated in parentheses. All estimates are made by the Benson method with up parameters borrowed ffom [26]; P stands for pelyines and PAH, for polycyclic aromatic hydrocarbon. ‘The formed soot particles start influencing the chemical process in the gs phase only after a sufficiently large aerosol surface area per gas volume Unit is produced. As a result, the low of polyines tothe surface of aerosol particles starts exceeding the rate of their formation in the gas-phase pyrolysis of intial hydrocarbon and therefore their concentration gradually ‘decreases. After the polyine concentration finally drops below its eritical value the fast polymerization process stops, the particle surface drastically loses its reactivity, and, as result, the particle growth rate becomes several orders lower. The fast build-up of the soot aerosol mass virtually ceases at FORMATION OF SOOT PARTICLES 14s this instant. Formation of a large non-reactive soot surface gives rise 10 effective heterogeneous destruction of the gas-phase radicals suppressing thereby chain gas-phase processes, Thus, the chemical reaction changes over to a slow stage. Chemical rearrangement ofthe initial polymeric stracture ‘of soot particles leading to their gradual carbonization keeps going and the particles coagulate to form mostly fractal clusters ee Be Be — * a CAH, + CH a > FIGURE 2, (e) Schematic of poyine polymerization on the surface of «growing polymeric globule, (b) possible pathways of sot nucleation 1446 A.V. KRESTININ THE SET OF EQUATIONS OF THE MODEL AND SOME ‘COMPUTING DETAILS ‘Soot formation from hydrocarbons is govemed by several chemical and physical factors: (D gas-phase chemical reactions, (i) soot nucleation from ‘gaseous molecules, i) heterogeneous reactions on the surface of condensed particles, (iv) coagulation of aerosol particles. As result, the general set of equations describing the process as a whole under spatially homogencous ‘conditions reads as follows 2X, _ (contributionof “ae gas-phase reactions ba (aucleaton «(surface growth) + (coagulation), ic where X, 1 = I,.., isthe concentration of chemical components in the ‘gas phase and Z(2) is the size distribution function of aerosol particles, 4314.) ‘The size distribution function Z(d) was approximated in the numerical ‘model by a piecewise constant function (sectional representation) with & finite number of sections within the particle size interval [dda], where d., is quite large. The appropriate equations are similar to those used in [18] ‘The numerical approximation of heterogeneous particle growth preserved the number of aerosol particles. In calculations we used, as « rule, 10 sections per digital order for approximating the size distribution function of Particles. This ensures sufficient accuracy of numerical computations [18] To estimate quantitatively the effect of the picoewise approximation on the concentration of soot particles formed, we conducted calculations with a doubled number of sections of the size interval. The difference between the ‘numbers of particles at the end of the process did not exceed 5 or 7%. It should be emphasized that the finite number of soot particles is « complex function of the contributions from all the above-mentioned processes. However the main factors governing the process are reactions in the gas phase, nucleation, and heterogeneous reactions on aerosol particles. CHEMICAL GAS-PHASE REACTIONS Since polyines HH, n = 2—6, play a key roe inthe model of nucleation and growth of soot particles, description of the gas-phase chemical process ‘must include all reactions contributing to formation and consumption of

You might also like