‘Chem Pos Reports lun 11,1994. 191-210 tops ron ot ns Soe (4 THE MECHANISM OF SOOT FORKATION FROM ACETYLENE Av, RRESTININ fesdeny of Sciences, Chernogoloves (hecetved July 18, 1993) Scetylene decomposition and Based onthe hypotheels for coat fnuclous formation fron polyine molecules (Can n= 2 = 1) 4a snproved. The schene for reactions In the gas pase, Ip tvallable In the Literature. For a quantitative verif teat ion or Ute model, mncrical calculations. are perferned in the Tange. of tenporature. {row 1420 to” 2200 K (P= 1 ~ 10 atm 1254 Cally In an Anert gas) and concentrations from 2 to 30% Cally (P= ata; T= IST KD. The data obtained agree well A large body of Literature ix devoted to soot formation tron hydrocarbons. The critical reviews concerning the current. status of the problem (including various theoretical interpretations) are Im the modern Literature, it 18 generatly accepted that th mechanism proposed by Fronklach et al. (4, 5] correctly steutate snted in [1 ~ 3]. Unfortunately, the process of formation of doa of thts hypothesis is that polyaromatic hydrocarbons similar to pyrene, coronene, etc. ere formed im Ube course of pyrolysis of tue Initial fuel, and chomleal coagulation of auch suftictently large-sized molecules (more than 1000 ams (61) yields a soot particle. Unfortunately, quantitative calculations within the framovork of this model and a comparison of thelr results with experiments have not yot been adequately perfermed. This deprives concerning the erucial role of polyine molecule Canlly (n= 2, 3...) An nucleation hae repeatedly been advanced in the Iiterature (7 ~ 9]. Based on the experimental data, Bonne, Nomnn, and Wagner (71 considered the possibility of forming a bulk soot nucleus ty aggregation of suffielentiy long polyline chains. Sobsequontly, this Idea renained undeveloped. for soot formation In thermal decomposition of acetylene 101, The model vas alse based on a hypothesis for the format on of a soot micleus {row polyine molecules. Numerical calculations porformed according Lo this model shoved good ngreonent with the obtain the tomporature dependences of the specific soot surface, Induction period, and nucleation rate (10 ~ 121. This demonstrated 4 tasto possiblity of experimental verifteation of the hypothests ‘by numerical simulation of thermal decomposition and soot Formation. A a result, it was found that the experimental and calculated dependences of the specific oot surface on the acetylene concentration differed markedly. According to the data ‘obtained by Tesner and Shorupov [13], the specific soot surface S (0a) rowains constant over acetylene concentration (fron 2 to 908) In course of the pyrolysis we whole range of verying the of the acetylene-hellun alxturee, Previously, this fact wae noted for stock tuber [14]. At the same Une, the model developed in M101 gives S = const=[C,lhJ°-75, Te discrepancy observed wasOs oe ae Table 1. Te Mechanism of Soot Formation from Acetylene The present work 18 devoted to a further verification of the = —— validity of the aypothosis concerning the formation of soot nuclet tis, Reactlon Z 1 References fron polyine chains by a comparison betveon the nunortcal ble experimental data. For thts Psa eneriitieaeenae oon ease anes nce pacity ogra yf cnetaumee peepee gs ee orci eee peeved afore fs esi ee ae ee tee eee reactions ot the formation and graith or polyings tn the ge pinee 3 Cyhjecanaeytyit 410% 65 te accurately and cmpletely ae possible. The ne data reported 4 hve ieee wee fecently In {181 on the mechanton ef therm! decomesttion of 5 Cyl fee iota ene tceale seins Sues tae ]ca Cats et as aceon eee ee aural die cae este orig tatae Geecription of the mcieation remslng thus far entrencly 7 CHWGiplytGdy 430 08 feeerliend and hence very slaplifled because af he abe of 8 GUS iCaly 110 1S = the meceerary exertaenal date eieahmecgie too! 25.1 = Comtex of 10 oF soot 1 cacti 810 0 Cala > Cala ig MET metas 12 cytes = a.eeiolt ete A series of numerical calculations was performed in order that the > "2N*Ha~Calkt nae ek -_ result of a comparison between the quantitative data obtained and 4 Cal*CallartleCaly ere a Tae enone: fexperinental ones could either further strengthen the hypothesis | CeltCalltCee ae a fo seme underlying the model or refute it. In conclusion, the 1 “t*Caanleray Lcaestiitater oe as a thermodynamic possibility of the scot micleation from several 17 ClaetCaH feet a Eo oo polyine molecules 1s discussod, Caer te 210 0 0.2 -20.8 eae ook ss 20 cuca, cee 2b Cylealocg wo = 2.1, Chenteat Reactions in the Gas Phas 22 Cqleglll 0 02 29. Gall oon Table 1 presents the scheme assumed In this work for chemleal op cya pee reactions In the gas phase. The thernodynamic data used in. the a 25. GyllgHCyly o 02 calculations of the equilibrium constants for the chenicat conponents are collected in Table 2. The reactions presented in 26 CaletollsCaM 2.60107 13,9 = = 27 Getic 410 98.2 28 Croll 2.510" Table 1 snvolves the elenentary stages which determine the tineTable 1 (Continuation 1) Table 1 (Continuation 29 te, teacton opti ae ESSER a rarences 2 Gahecgnegicg, 10 0 55 eythane ao 0 - 30 CalerCanlireal 107.3 = 56 tates ao 0 31 calstetecataem 110! 29 2» St calrcgheGatya 00 32 Gyiyetonygh,—.O aTe 98 Cyl ylt a 2 Gg, 10 0 59 CyglimyaCyatya 2408 00.2 20.8 ate 28 caigsCaledly TI 9k =e 6 Caley, 25108 20 = = 35 Gaither 0 6h GalhacatyaCgh A100 36 CCCI 210 0 = 62 Galea 1109 == ie coarsest tree eee ere ee Formation of Cyd 28 cahcgtcgecgh ato 9 te 39 cataract, 240 200 = ae 69 Cualleatbcatam, 210 0 = 40 caecalaecdl, 240 20 61 GallCagsCyge 0 = An caecgiscgincgl, 26102 200 65 CyllCdacyet 210 0 = se catlscacainc OLeeeeHeeeeeaeeeeeeaageeeee 6 ClhCaeCulo 210% 0 = 49 calscaocatirca Ceuiaeeatseieicseetiteee OF Cy sCaoCayal tO - Formation of Cielas Cy 68 Cicgiscyih —1tate 84 GalxCacoe 210% 90.215 Fotimation Formation of soot 45 GlscaiecgeH 410 0 6 Cleats? aio 0 atination 46 CatisCgacyaiH 210 _ ip remecadecenaia ttl atleast Hoeee ee eeeeeeeee loterogencous reactions on soot parLicles"*"* Galeeieues aa oH 10 Deghszety 2108 ona 119,201 © Gulipeiyl 210 9 a2 -0.8 nh zocgicet ato 0 == Bet ination 50 CyaatCalerC HC, 210 20 Te IWC wor ae = St CilergtGaH 10% 0a 1 neice ao 0 - 52 cghcsocgirc tot 9 14 ZHCggtely a - Formation of Cyl. Cl peas gee 50 CygtCaHeC oH 210 00.2 AS Eettmation Deemer Be Hae Se GolCeC att G10 0k AS. eer eee