pee memrapouaeor—— S| MU!atioN OF Propane Venyarogenation Leila Vafajoo! ‘Mohammad Kazemeini? to Propylene in a Radial-Flow Reactor over Mosiem Fattahi* Pt-Sn/Al,0; as the Catalyst Tnprewng samickend Calapan dehydrogenation for manufacturing olefins it consered tobe Univers Sou Tern cone ofthe most sgnieant production routes inthe petrochemical insti. A ‘Branch Teva, tan, reactor kinetic model for the dehydrogenation of propane to propylene in a rcial-flow reactor over PL-Sn/Al5Os a8 the catalyst was investigated. here. The ceeeetntctengench model showed thatthe catalyst activity was highly time dependent. In addition, ‘Somie Azad Unvesty Tehran, the component concentrations and the temperature varied along the reactor radi- van, us owing to the occurring endothermic reaction. Moreover, a similar trend was noticed for the propane conversion as for the propylene selectivity, with both of “Deparment ofchemisl ard ther decreasing over the time period studied. Furthermore, a reveril of this Young Researchers and Ete Perse thang Sut etl ng tre posed hen teed tenpetae sence or when on bent eet edn he ed a in “oeparmantsfChenal___ Kayes Ca Propane dhygeaton Mops, fd ec Saton fa yo Exe Aan FU fay 205 6 25 cp Sete 205 Darden Umestyo! DO TE2een2015082 Tectnology Abana, 1 Introduction Catalytic deyrogenation of prin to olefins hasbeen per. formed commer since the late 18306 Daring World War 1, catalytic dehydrogenation of butane over CrAl,0, a5 the aust as ubkzed forthe production of butene to eance the octane numberof icra fel [1,2 In general, der fencton ractone are cai out through amt mechs isn. Meannfule, other reactons including coking astally ccured, ending to catalyst desctvasion, thereby lowering the reaction ate over a pei of ine [In adtion, coke for- maton and the dehydrogenation reecion unaided tach other. Thus semi-eperimentl models were wtlzed for camaystdeacvaon descriptions. These were based on into dhacing a deacivation function in terms of measurable variables i, ‘Olefin ave en considered as he fd of many indusies inching perochemical plans (6) Om the other hand, ight sfkane deiydrogenation is usualy considered san indus ined manufactarng method of cis (7) Te oght tobe men- tioned that. due wo the hart operating conditions resized for the reaction, catalyst dectinaton normally occured. very quid; hence coatiauoussegeacrave techniques forthe et flys sere needed. In tis vente, moving reactors th continous egenernine stems vee employ i some ess Comepondene Dr. Mohan Karena (seminsehaiics, chen ad etc Enpeing Shan Unie ‘of Tecnology PO. Box 11365365 Tear. wonacetjoumalcom ©2015 WILEY Vian Gb & Co KSA Were (sl Im another sty the catalyst regeneration vas catied ot eniodally in fied bed reactors. Her, the bod temperature ‘yas increased to bura out the enke, thus renewing the catst {er the endothermic propane deydrogeation (PDH) [810 ‘Yet another research article (11) presented the combiaation of exothermic and endothermic recone of this Kin Other ‘seuchers compared simultaneous end sequential methods to ‘combine non-oadtive PDE andthe methane-propane bart Jngreaction on «Pt catalyst in ced be reactors (12,13). ‘Propylene has alvays been mentioned as one ofthe most sexportan gh oleneacorcng tot wage in perchensel plants and ts valuable role dovmstrcam chemical procs “The spsaes posttes higher added vase than other pete cherncal raw materials ike natural gas and naphtha. Besides, ‘oth the economic tems of supply and demand being onthe postive side provided an add advantage fo this material 7) in addition, the increasing demand fr ight olefins (lik this) due to ther enszonmena impacts drew even more attention to this chemical [8]. Meanie, propylene has ben produced ‘Hyoagh maay diferent wuts. All ofthese methods were en ployed to il up the gp between its demand and sop [3 Some of these commercial routs ae seam cracking. caaytic ‘racking in fudize bed dep catalytic racking, metathesis, propyl ala debydation end propane catalyic deiydogen tin Inthe st dnd second mathods,propyiene i prodiced ‘of perafin dehydrogenation canbe divided into two major ea cgories ordinary paraffin dchyrogenation and oxidative par {Eh dcpcogeiion Whie cna Scpdrogeaton an tothe acon and amped by ver rducon, (he Eg Tcno 2005 35, No. 12, 2198-2208fondinary dehydrogenation isan endothermic reaction 14-16), Asa consquence of many side reactions acing the appropriate yd and esas act, extensive remarch ‘ns been caved out in ecent yrs onthe appropriate atayat selection, the optimum operation conditions, and on suitable resco [17-21]. Oa the ocher hand, ada low reactors have ‘ben widely use in processes such as parafin and etl ben ene dchydeogeaation Furthermore, thes lowes pressure drops {nd smaler reactor volumes might be counted a ther advan- tages in comparion with convetional tubular tears 1,22). In this regard, PDH reactors are commoniy operated at 525-625°C and around simospherc pressure, assisted by plat- ‘mum or chroma aaa supports [323]. there ae some research suds on the Kites of PDH indifferent rectors, investigations on the impact of Pressure, temperature, and ine gases on the PDH reaction tna radial fw reactor have nt been published yet. in the petent sy,che simulation of PDH amin tarde prop fene production in 2 ral reactor over PESWIALO, as the catalyt war investigated For thie purpose, 2 bine model was proposed to predict the propane conversion and the propylene Selectivity 2 fancion of the inlet fed tem (puciae Moover, the extdyst dascuranoa and proces 2 Reactor Modeling and Simulation 2.1. POH and Side Reactions Propylene prodiction reaction in th presence of «pln ‘atalst base on alimina have been investigated exerimen™ tally [5 The following reactions were suggested. The main reaction of PDH to propylene sas follows (3,3): HSH +H, o While the above rection isan equim rea tion, other reactions lke cracking and ethyiene hydrogenation effecting the main product form ton afe tn the center ofthe modeling approaches “Sr and simulations cared outin this study [3.5 Cracking rscton Poweriow Ci $C CH, ® xylene hydrogenation: Gis HOC, © aan 2.2 Proposed Mechanism and Kinetics ‘of the POH Reaction ft preset sy ine it ma sen debs ie considved experimental data, Moreover, was assumed that ‘repane absorption was negigle, as confined in previons sestuchss [3.5 Tn addon, the proposed rate expressions for the reectons cof ciaciag and ethylene hydrogentlon ae shown i Tab. 2 B53. 23. Radial-Flow Reactor Model tn the present sud the PDI reaction in radio ied ‘ed reactor (REBR) was considered. Accordingly [24] de reac ‘or mode fran REBR i provided in By 8) Ae Treas OEM) @ ‘where indatesthe 2h chemical component. Eq, (4) wa plied for ylindrical fund bed veator at fed length as fellows ou_2 tad © 24 Material and Energy Balances for Components “With respect tothe intial concentration ofthe participating ‘components and the inert material in the RFBR, the materal balances for ms, Jet Jas Fee AN ay are ten as Iilow Phan BiB in Pay rn oo Fe Te a Ob ta, tba ey = Ss a a o “Table 1, Proposed mods forthe PH reaction. Table 2 Reaction ate expressions forthe aching and ethylene hyekopenation “Thre diferent mods have ben proposed forthe smain PDH reacion rate [5] and are provided in “Cag eation Fe abst. Out ofthese the LangmulHinsebood- rogension mike Fa, Hougen-Watson 2 (LHHVE2) model wae chosenzs ea HIE eye % gn yea ey 0) eo) ‘Moreover, the material balances for other components [24] eau + (2 Ye) 5] a [venues + (1~ yer)r2yemy's] 2) ee PN ears + (-ree)8] 8) Furthermore, the energy balance for the reactor regarding the thee consdeed eactons was detennined as flaws: ot_ ania "inte ((Akiar) +(ARie) +(ARG)] 0) ‘where AH, AH, and AH, ae the reaction enthalpies of the conesponding reactions (1), (2) and (3). respectively. 25 Coke Formation and Deactivation Model Several authors have developed ferent mae fr the coke fonmuten ofthe PDH reacon. A rather poplar uchanistic ‘oda scaled the monoliyermtdayercoke growth model (MIMCGAN 25). Tas was generalized and modied [6 his been employed by many authors (3, 5, 27-2], and was also lid inthe preseat stad. Tab. 3 indicates hoe cata ‘ty mol fo the PDE reaction thst have been invested eeu) “Te D3 model was chosen for dhe cat activity [3-5] ia ‘he present model owing w the lower errs resigns inpemesaon = 16a) +160e0(- 2) ow» Table 3. Cats octvty mrs Noll __hay Br atta ba AG +7 C a +6) bs AGH Gy enfGICI memcetiouralcom (©2015 LEV! Verag GmbH Co. KGaA, Wel Research Article chen ngineing Tediolgh a6, an os) os) 26 Reaction Kinetic Constants and AH Correlations According to the Artenias oqution chemical Knees and resus avaoble inthe btertue, the rection and equlibour ‘constants an be writen a in Eas. (20)(23) 13, 5,24. A = haexn EH 20) Kon, a kysor[iss e In accordance with dasa thermovdynamic the final rea: tion het involve at temperature T can be writen a Eg 23) bol Agr = ABs + a(t 298) +98 (298) +8 29) » sovhich Mig = 8A 2 a= Sha & B=, ro) y= Don en Values of the thermodynamic parameters and components ‘ofthe model ae presented in Tabs. and 3. Solution Method and Procedure “The developed model was sslved. izing the th-onder -Runge-Karatechaigue inthe radial econ eth appropriate Ghee, eco 205,38 No. 12218-2208Campane @ Beal reavl om 8 SAR om 1 nme 6015 % 3209 om - oon ue 08, 2168 or a we on om hast pms ssa Table 5. Model values used in the present simulation arto" ego) rasa ey malg'e"P exc Dgathza1 Fe en aka awn Fea as Hog, Dee] assur AF, Dear] 124260 2, sat) 20 a8, Dar] ses oy orsas fate") ws rm exes Poa w esta condinces it ought wo be aoted that the texspeatare {ind th component concentstons xe wel =a other variable Chom Eng. echo 2075.28. No 12298-2205 parameters involved needed updating ovr the reactor rads increments for cach tration ode Aikticoally at the end of cach iteration cyl, the step sie was halved ul the conrer- feicecnteno ner sesched. The cleltion ow char ae ell the appropriate nal and boundary conditions for heey tenn ued inthis esearch ate provided in Tab, Sand Pg. 4 Results and Discussion Ava ky epi any simulation work, afer developing» mate- ‘matical mode it has tobe vere. This was dane fo the pres ‘ent work through «comparison ofthe resus generated by the ‘model with those avaiable in the open iteratre (29, 32.33]. ‘Theesu ate shown in the party plot of ig 2- It an be co ‘ind that thie model was vorfled lining independently ‘btanod experimental data wth 2 maximum eror of 38.1035 ‘worth meting tha the preparation parameters ofthe cat Iysts in references (29,32.88) are not the same, which may have led to diferent particle ses and catalytic performance, ‘To clan the aforementioned ft, the uslzed mode in this study predicted the expenmentl rests for she diferent cate yet stracates wth good accuracy rather than reconfining the robustnes ofthe preset model, Tig. luster she cetaytactnty a function ofthe wesc tor radios and ime. Ie reveals that the catalyst activity imi “shod overtime dus tothe coke formation progressing froma oughly 1 19 030 (ie, 100% down to 3086) in about 2h. Moreover a a rent of the occurring endothermic reaction ‘and the temperature drop in the radial direction during this petod af time. the rate ofthe eacionskape decreasing. None theless a ight ancrese in actvgy towards the end of the exc tor was observed atthe end ofthe time prio. "As mentioned above, the PDH reaction wes endothermic die to which the teats were conver in the radial die ‘ons wie the temperature fl. ig soos the temperate profile in the redial direction of she reactor, fling gradually fom $29 to 730K. It wae « predicable conclusion (Goma both gp 3 and 4) that the maximum reacion rate would be ‘observed in the reactor rads range of O7-Lm, ohare the ‘marina temperature drop occured. ‘ig 5 reveal the unsteady state pros ofthe propane on ‘sersion andthe proplene elect, respective It shown ‘2 ig 52 that the propane convention grew sdesdy Fem 598 to about 108 over Hine, 2 + presnue of 100KPs and = temperature of 813 ‘Ga te onz hand the behevice evel ia Fig Se was con sequence ofthe comslauve conversion ofall solved specs ‘mentioned ear in hi paper. addon, the slope of the raph inthis igce decline’! over ine, emphasing the cat lyst deactivation and showing that other undesitedresctons became more pronounced compared tothe main one. On the er hand, athe reactant were convened along the rads, the bed temperature decened det the endothermic maine ofthe reaction, resting in 2 reduction of the rate conan snd ts loverog the reaction rte sn ten eacon Pome cemued. esa, rg sb demonstatas that th propiene electing deceased Gramm apprenimatly 77% 0 70% over time Ae the rationale for this behavior i can once aga be (© 01S WLEVYCH VergGmbH&.Co GOA Weinheim waeztouralcomTapa a Bows Centos 1. 80.0) Seep Seu Retr Ras v ‘Calais Al|Vnables Depending on ICC v Saks Cauaoas se v Up al wie, Pande ¥ Ren Ose Reo Sep Sets Si ‘Sete St of Equations y Uae avalon TP as suk OWEReak New Reval New Rea F v e-atoltent OH Rest New) Figure 1, Scheme ofthe process eaeulaton forthe model developed in this stay, pointed oot thst his wes doe to the side (ie. undesied) eae- on aking lace more pronouncedycompate with the main one inthis stm. Besides the propeneyld almost di not Change wath the reaction ine ae ote fact hatte propylene eld is the product ofthe propane conversion and the Prop nucetouralcom EnorToee Pro Rale Pkt (©2015 WLEV.VOHVerag Gb & Co HGaR Wenheim Research Article cheisnanetng eben 3 Conclusions A thematic model for PDH twas propyiene reduction in ¢eaiao reactor oer commer ‘a Pe Sn/ AIO» a8 the catalyst as developed. The sul demonstuted tht parameters such es the sccm ofthe ata, the esto empertue 2d ‘he feed compostion vere pronsuscedly depan- ‘dent on the ie and on te dial epatal ection. ‘a addon, was aowevorhy thar Hee vrales {aflunced eachother eather dramatically. Fue ‘more, the developed model showed tha the pot [pane conversion dectesed ove time wie ie ‘ened when the fond temperate wae enbanced. (On the ether hand, the propylene sdacty eves the reverse Behavior a cent of the progresing ie tnd undesired cectons. In ther words te model rested ecru ofthe seca turds propiene ae a fancuon of ‘he feed tempera wth progresing ime In sddton,edding cert fu tt the fend caused an echuncement ofthe pro horn Techno 2015.38, No 12. 2156-2205© weasus “a goo 7 yo 5 . gn . io tf he oe Fi fio cae Ga 08 os moda verte Joo co Sele mode verso ,° ium oF sage Comer hte) Peopae Comes iii “AT Th Ho i Lae ai HE LIT i tn the studied syst. sd he aco radu on he cata cv nthe cof tha tne andthe oe Figure 3 no used ms Symbols the propiene eden. ate cmv we ening he een ty. ht sey a on pudnm 4 ‘aula i ta might mig units Se } onolaer cae accra) of aonceacveeance P< eens Rah bee pee an cose Feces come ee ae Deal meet t OE ee ae ier ga aaion he . no conft of st ‘exes eg conan aa xe sexton L ‘ow aFigure 4, unsteady varasons of the tomporatur along the act radius forthe suid stom ays pan Tf aE i feo ale : igure 5. unstcadystata pola ofthe propane conversion and b)tha propylene select 3.cteateeinn Rescach tie 8 Propane Conversion 2) a & a 2 presse R eactoc adie ikem sensi yt seanoe rial darance rok compere Vue Im) seacoe volume yo component mle acon Subacripts bed ce ca equim F Srecon = moclayer Mo mulerer References G Ziheds Haga AL Be Stara, ppl Cont 2008, 358 (). 3-8 (MEN. Bhai HL McCain 8. Vora. T mai. PR Pua (pl Catal 4 200 21 (2). 397=408. 2 Samrat A Fatah E rateh Ko [Cho Beg 2013.20 (0) 55-62 B Birghl MU Femahh F Khoraheh, React Kinet, Mack Cas 202, 1070), 1-155. MEP Lobe C. Tales, Heide, ML. Menéader Al (Cen, 3008 56922), 156-160 Date, S AL Fabel Ghat Pt Sl Tcl 2013.35 (9386-602, 10, om wl eo a ts 6 wn ns, 8 Powe 6 ney te ane conversion pros and ce aPToOlns nt pats ‘00 brgon. obtained By the Seve ped mode 2 Novas F Bao | ha FW [Ded Bap Cho 2005, 190254. 2a) sei HL Zale, T Tarek Chom dnp Femur 1987, 55 6), MLS. Kalba, MB Ducakovie AICKE J 1996 42 (0) 97-2910 vam Sin Analg. Rupr, WBC wan Ses, (Cent Toga 2001, 66 2-0,.27-026. Sivae Sit maland[30 Rupr, WBC wan Ses, (Chem Bog Se 201, 36(6 157=4 AU Forati ML Roseman F Xhorsbeh A Rashi fad (Ee. Chae 2014, 29 4) 2236-2087, SivEsraty D0 Kosamesn, E Keon A Darel AML ‘Rashid Cham np. Tecl 2013, 36 (10 1681-1700 X Us, WE Lang LA Lang. Col Hu, L-F Chu, V5 (Guo, Cho gf 2004. 247 183-192. 2 Novae E Wek {Ind bey Chom, 201,17 2389-295, 2 Navas FW { Ind Sep Chom 2010, 15(5), 77478, 2 Novae ¥ Chuo lang X tang Wang FW Ind (Ee. Chae es 2010, 4910), 514-4612 She Chas © Janey, Nate DS Sha FS. Moore Ya BS Date 1G Pendens CAE 2015, 61 3) MCB Taber Telex). Hergid Y Schowrman, M. Mee endex Chem Eng } 201.1713). 1317-1528 D Sor A Banos Sehneaer DWT Rapan EE ‘Newaon, Chem Bey Se 1990, 48 (8), 2168 2076. 1 Gases © Ten | Henge, M Bndnden, Chom. Bag {7 20,1369, 91-86.X Dheng Xow W Youn, CIESC J 008, 60 (10, 244 T'S Na JR Kita nd eg Chee Pre Des De 3904,25(2,257-20. Ta Fea 3 Monséa 1 Simms 16. Bene, Appt By Ba Research Article chemi tngacsing cimiosy 1. Smith B.C. Yas Nem MLM. Abt noun (Chemis Exgmering Thomodjnamion Me rd Merwe at New e308, [BE Paing |B Freie). Coon, The Popes fxs a Lips te. MG New Too 2001 G2 Sui X chow Chen App Cat 4 2011 358 ta8-26 F Takes Zing, § Mobvaams, &. Shei, Fl ‘Prcas Teen HLS 102,516 8