http: /comut.ibic..>r/comut/do/atendimento. .. Pec 38 ¥ ene Pa FOMULAMODE ENCAMMOUMENTO-PERIEDICO sewmcackoo0 rem100 ~ CS crtiieiaceeas ommmasooen (hO-CES Se me gnc 4 ATES -UA be ORM. E4UA = imunghoworecico: | |Atenaia | Rapa | Cutan cau Do poe CNAL TOTAL OF Aa. cOMRIEUACRO SSERVACAO, | at urges sc-eimuoneca comer unsvo: comune NE GABRIEL ORL MIFELEAES SUCITINTE: C0O1GO m CFF Gear nesses urormer. aBLoTECA ree nyse wenmea¢000Pt000 Et: tongs gman EAA comune Moar Es:0i¢o CHEMICAL ENOMIEERENG SCIENCE 168 ‘vouume: 47 raselowomes: sa YOR DOARTOO HACIEL UM. ROOMNGUES, A. ‘Lo Bag 1H ATTUBULAR REACTOR FOR GRTENTION OF ACETAL DEMYOC BY CXIDATON F Cy ‘ora oe Pcs a noms uA BE ENOL EAR, rk 0 HEA sora oe pha cauneuaghon Tawar [EREGO:© IOV OLMECME, SPY CABA POSTAL 18000 tsb ‘oDAnE UF. cuRrmaAoR 31-08-2010 15:4Engineering Science, Vol. 47, No, 11, pp. 25712576, 1992. 0009-2509°92 $5.00+0.00 ed in Great Briain. © 1992 Pergamon Press Lid A MULTITUBULAR REACTOR FOR OBTENTION OF ACETALDEHYDE. BY OXIDATION OF ETHYL ALCOHOL : R. Maciel Filho” and A. Domingues”* “= UNIVERSIDADE ESTADUAL DE CANPINAS, Faculdade de Engenharia Quimica, OPQ, Cx Postal 6056, ax _ SEP 13081, Canpinas, SP, Brasil ~ BHODIA S.A.AGEEG/CCEIA, (Groupe RhSne-Poulenc), Av. Haria Cablhe Agutor 215, BL.B-3and: 05804-J1.5.Luiz, S80 Paulo, SP, Brast] 7 ° . ABSTRACT Ih this work an alternative process for the obtention of acetaldehyde is presented. It is based on the oxidation of ethyl alcohol over comercial Fe-Mo catalyst. Experimental kinetic data, obtained in an integral reactor, were interpreted by a Tenkin's type mechanism, although it 1s possible to treat the data by known mechanism similar to the oxidation of methanol to formaldehyde. A new multitubular reactor is then proposed with the obtained rate equation . It is baffled but windowless, so that better temperature control is achieved when compared with conventional reactors. The process considered here exhibits better performance than the best known processes in terms of higher conversions, stability and yield in acetaldehyde. KEYWORDS: acetaldehyde production, ethy! alcohol oxidation mechanism, Fe-Ho catalyst, packed-bed multitubular reactor INTRODUCTION Acetaldehyde is an important component in many chemical processes so that there is incentive for its ‘ion. Conventionally it comes from petrochenical via, but relatively low conversions (less than 728) yields (less than 95%) are normally found. Silver is usually employed as catalyst besides being a very sive metal. The current commercial processes present difficulties because they require an efficient stream separat ion. Alternative procedures for the obtention of acetaldehyde have been propased in the literature and those ‘ethyl alcohol as feedstock may be an interesting alternative, especially when it is available at price. Sone studies on this via have been carried out (e.g. Day, 1931) and recent studies (Houra, 1984: jel Filho, 1985) have denonstrated the potential of this route. However, it is essential to explore the tires of selectivity, conversion and stability in relation to a convenient reactor design, to quarantee desired performance, In this work is proposed an alternative procedure for the obtention of acetaldehyde through the dation of ethyl alcohol, by air. over comercial Fe-Mo catalyst in the range of 180-240% at atmospheric sure. Making use of the rate equation derived from kinetic data, a reactor simiation is carried out for trial conditions in order to evaluate its performance for a range of conditions. As the reaction is ily exothermic a new multitubular reactor 1s proposed. The simulation results are based on detailed 1s describing the packed bed as well as the coolant environment accounting for the effect of some nial detatTs on the coolant Flow. ACETALDEHYDE OBTENTION BY ETHYL ALCOHOL OXIDATION Experimental studies of the oxidation of ethyl alcohol to produce acetaldehyde over comercial Fe-Ho lyst have been carried out in a laboratory scale reactor. The rig is designed to allow on-line kinetic f4 aquisiction at isothermal and controlled conditions, in an integral reactor, placed inside a well itated thermostatic bath with thermal fluid. The isothermicity of the catalyst bed could be checked whith 25712572 R. Mactet Fino and A. Dosineues at least five bed temperature measurenents, Construction, catalyst data and operational details can found elsewhere (Naciel Fitho, 1965). Extensive studies reveal the convenient operating conditfons for obtention of acetaldehyde by on dati of ethanol as being in the tenperature range of 180-240% (namely 160, 200, 225 and 240°C) and f concentrations, at atnospheric pressure. At these conditions anly acetaldehyde was detected by cromatogeaphy. Teaperatures below 180°C lead to very low conversions, and above 263°C undesired reactl accur, anong them the format ion of formaldehyde, carbon dioxide and other subproducts. Thus the viabil of the process depends. on the good reactor temperature control. Other important operating conti involve the residence time choice to be between 120 and 660 kicat-S/NI react. and air/ethanal molar between 3 and 22. Figure 1 shows the experinental data of conversion wersus residence tine at vark concentrations for tenperature of 240%, It can be seen that conversion as high as 98 % in acetald can be achieved with 100% of selectivity. These results are very encouraging when compared with conventional processes, including an alternative process based on the oxidation of ethanol over investigated by Moura (1984). r e- : 7 Reaction Rate Two mechanisms are used to interpret the experimental data, namely one similar to the oxidation methanol to formaldenyde due to Dente et al. (1964), and other based an Temkin mechanism (Texkin, 1979 In the former the reaction rate takes the form: Poe "Pet Ne + where ky = ayPexp(by/RT) (R= 8.31438 J/mole/K) w Paoli + Pev/kg where "n" and "n" are parameters with values of either 0.5 or 1.0 in accordance with Dente et al.(196i where the mechanism details are presented. Table 1 shows the kinetic parameters in such situati corresponding to the global reaction stoichiometry (m-1/2, nel). If a Temkin type mechanism is consi for the global reaction: CHCHyOH + 1/20) => CH3CHO + HO The following routes are possible: Nis CH3CHGOH + 1/20, ---» CHACHO + Hod 2: CH3CHQOH + 1/202 ~=-> CHACHO + Hod -> Cigbtig0H + 1/20 with the react ion steps mom 1s CHyCHgOH + 209 SLs cugeno + go + 20 14 2:0) +22» 20, wee 2's 200 -—-> 11,109 wo 33 CH3CHO + 7 t2 ‘cHgcho moi 4 + ZOHgCHO + Hy0 “E-> cHyCHigoH + 20 - 4 In this proposed mechanism it is considered that steps 1,2 and 4 are slow and irreversible, step 2! very fast, being 3 an equilibrium step. It is supposed adsorption of molecular oxygen without. di ssociat ‘in only one active site. Also it is admitted that the ethanol molecules in vapour phase colide ‘adsorbed oxygen leading to acetaldehyde, water and adsorbed oxygen. Using such hypothesis the folll rate equation is obtained: 2kykePoePer tw where ky = ay*exp(by /T) @) aPer + 2kePog + KakaPacPizo + RakiPerPac The paraneter values are 8 S= E [(WE) - W/Fleyp]? 3) i raluated by minimization of the objective funct ian (3)Multitubular reactor for obtention of acetaldehyde 2573 here Mis the nunber of experimental data. Details of mechanisms, derivation of rate equation and 1985). unerical procedure are given elsewhere (Maciel Filhs ay by (d/note)| ay by (J/mole) ky (MP /(sekgcaesPayh | 5.7992E-2 -58.02119 | ky Atm? /(sekgege-Pa)) | 247988560 -7260,7632 hy (Wr? /(sskgeae-Pal/2)}} 12.7400 -66.27375 ky {Ni /(S-kGcge Pa)? | 178.48331 -96787 .2852 ky Panty 6.01961E-10 422332832 ky (Nm? /(S-kgcae-Pa)) | 295435.68 — -108486..9283 Table 1 - Reaction rate constants for Dente's Table 2 Reaction rate constants for Tenkin's mechanism mechanism Figure 2a and 2b show the Arrhenius plots (In kj XT!) for the two mechanisms. A very good correlation He otaned only for the Teain mecanisn, espaclly whe high conereios aro considered. the. Sid Hines in figure 1 are obtained by equation (2) using the Kinetic values presented in table 2. As this feuation represents better all data, it is used to propose an industrial reactor to this process AM ULAR REA TALDEHYDE PRODUCTION The objective is to find out an industrial reactor design able to be operated safely and at high Performance teking into account the process restrictions. These are especially related to a very close temerature control along the reactor length. This is because if temperature higher than 243°C is achieved in the reactor, the selectivity lowers, but to obtain good conversions relatively high feed temperature has to be used. The problem fs to Tenove the heat conveniently. To achieve this and a Feasonable production, multitubular reactors (MTR) appear to be convenient. The heat managenent in this systen is such that the reaction «.. ic controlled conveniently (keeping high reaction rate even with a Gecrese in alcohol concentration) . In order to take decisions based on simulation, detailed models have to be used, This for the case of MR requires to account for to different domains: the tube side, where the chemical reaction in a fatalytic packed bed is occurring, and the shell side, where the interactions between tubes and the coolant flow pattern take place. These two’ domains are inherently .related since the coolant environment becones a boundary condi tion on the tube side. Failure in doing so implies describing the MIR behaviour ith single-tube models considered as representative of the whole bundle (HcGreavy and Maciel (1989a). Conventional MIR with baffles to pranote cross flow, and therefore increase the heat transfer Geefficient, presents operational problems in tubes located in the window zone (Maciel Filho, 1989). This fs because there is a change in the cross flow at the baffle ends, causing a mixed type of Flow which ults in @ parallel component in velocity. To overcome these operational problems, and hence allow the ctor to be operated at high performance, a new MIR design (shown in figure 3) is proposed in this work. It is baffled but windowless, so that there are na window regions where the coolant flows in parallel to he tubes. The coolant my be fed in different conditions in each chanber, so that there is more Flexibility to find out satisfactorily operation in all tubes along the reactor length, To describe the phenomena occurring in the packed-bed of Fe-Mo catalyst pellet, a modified steady- te two dimensicnal pseude-homogeneous model with radial dispersion based on Froment and Bischoff (1990) formulation is used and the equations are as follows (Maciel Filho & Domingues, 1991; Domingues, 1992) ass balance Bey ac ac. “s- gz 7 Yer‘ (are * yar) ~ PBtw «) teray balance for the gas aT aT ar Ms" Og -CPa' az = ree (#2 +, 2) + Oy CDH) ny 3) Energy balance for the coolant QQ, a Ge 7 UnD; (ly - Te) @