Industrial & Engineering Chemistry Research Volume 43 Issue 15 2004 [Doi 10.1021_ie049846s] Honkela,...

8/10/2019 Industrial & Engineering Chemistry Research Volume 43 Issue 15 2004 [Doi 10.1021_ie049846s] Honkela, Maija L.;

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KINE TIC S, CATALYSIS , AND RE ACTION E NG INE ERI NG

Thermodynamics and Kinetics of the Dehydration oft er t-Butyl

Alcohol

Maija L. Honkela,* Tuomas Ouni, and A. Outi I. Krause

H elsin ki U ni versit y of Technology, Departm ent of Chemi cal T echnology, P.O. Box 6100,

E s poo F I N - 02 0 15 H U T , F i n l a n d

The dehydr a tion of tert-butyl a lcohol to wa ter a nd isobutene wa s stud ied using an ion-excha ngere sin cata lyst at te m p era tu re s b e twe e n 60 a n d 90 C . A t e m pe ratu re -d e pe n d en t e qu il ib riu mconsta nt for the dehydrat ion reaction wa s obta ined that gave a reaction entha lpy of 26 kJ mol-1,in good a greement w ith va lues in the litera ture. Measured da ta w ere used for kinetic modelingo f th e re actio n . T h e b e st m o d e l with p h ysical ly m e an in g fu l p aram e te rs was o f L an g m u ir -Hinshelwood type where isobutene does not adsorb on the catalyst. The activation energy forth e re action in t h is case w as 18 k J m ol-1.

Introduction

B o t h t h e de h y dra t ion of tert-butyl alcohol (TBA) toisobutene and the reverse react ion have been studiedwidely. TBA production is of interest because of the useof TB A as a ga soline component [RON (resear ch octa nenumber) ) 109, MON (motor octane number) ) 91].1

TB A formed as a side product in 1,2-epoxypropanesynt hesis is used not only as a ga soline component 2 bu talso in t he production of isobutene for methy l tert-butylether (MTBE) and other high-octane gasoline compo-nents.3,4 Also, direct routes fr om TB A to ethers (wit houtisobutene formation in between) exist. 5-7

G a t e s e t a l .8 studied TBA dehydration on Amberlyst15 ion -e xch a n g e re s in ca t a ly s t a n d p rop os e d a ca r-bonium ion mechanism at low TBA concentrations. Inthis mechanism TBA an d th e proton of the cat alyst forma tert-butyl cation. This cation can either react back toTB A or form isobutene a t the sa me t ime a s t he protonis regenerated. At higher concentra t ions, the react ionwa s re a s on e d t o p roce ed a c cordin g t o a con ce rt edmechanism involving the par ticipat ion of several a ctivesites. In later studies, Gates and Rodriguez 9 proposeda r at e equa tion that ta kes into account t he act ive sitesthat result from alcohol adsorption. In the presence ofwa t e r , t h e re a c t ion wa s o f f i rs t o rder wit h re sp ect t othe TBA concentrat ion, and with low water contents,the rates were represented by Langmuir-Hinshelwood-type kinetics. Abella et a l.10 a lso studied the kinetics of

the dehydra t ion of TB A in the liquid phase. However,they used a n a tmospheric-pressure system, an d becausethe isobutene that was produced evaporated from themixture, the reaction was considered irreversible.

The hy dra tion of isobutene on ion-excha nge r esins isdifferent from th e dehydra t ion of TB A because a largeamount of water is present on the catalyst . Gupta andDouglas,11 f or e xa mp le, ca rr ie d ou t e xp erimen t s inwh ic h wa t e r wa s p re s e n t in la rg e e x c e s s s o t h a t t h e

resin was fully swollen. They obtained first-order ir-reversible kinetics for the hydration reaction.

Delion et al.12 applied va rious solvents in t he hydra -t ion of isobutene with the a im of keeping the m ixturein a single liquid phase. They tested p-dioxan e, a cetone,nitr ometha ne, buty lcellosolve (2-butoxyetha nol), isopro-pyl alcohol, cyclohexanol, tetrahydrofurfurylic alcohol,and acetic acid and calculated solvent-dependent equi-librium consta nts for t he reaction. Velo et a l.13 obtainedboth equilibrium consta nts a nd kinetics for the hydra -tion of isobutene. The kinetic equations were based ona carbonium ion mechanism in which isobutene formsa tert-butyl cation with the proton of the catalyst. Theya ls o c on clu ded t h a t TB A in h ibi t s t h e h y dra t io n o f

is o bu t e n e mo re t h a n wa t e r . I n a n o t h e r s t u dy ,14 theyfound tha t int rapa rt icle diffusivity increased with tem-pera ture a nd decreased w ith TB A concentra t ion.

Diffusion has also been studied in other publications.TB A de h y dra t io n s t u die s in dica t e t h a t , wh e n ma c ro-porous ion-excha nge resins are used a s cata lysts, ma ss-transport l imitat ions do not exist . 8,15 M a s s t ra n s p o rtseems to affect the rates of isobutene hydrat ion, how-ever.16 Studies in a trickle-bed reactor with an aqueousp h a s e a n d is o bu t e n e a s t h e g a s in dic a t e d t h a t in t ra -part icle diffusion has a greater effect on the rate thandoes liquid-to-part icle m ass tra nsfer.17 In trickle-bedreactors, both the w ett ing efficiency a nd ma ss tra nsferinfluence the total rate.18

On a n acidic ion-exchange resin cata lyst , isobutenere a ct s t o f orm di is obu t en e s a n d h ig h er o lig ome rs.M ore ov er , wh e n di is obu t en e s n e ed t o be p rodu ce dselectively, polar components such as TBA, water, orm et h a n ol a r e a d d ed t o t h e d im er i za t i on .19-21 Thismeans that the dehydrat ion of TBA (or the hydrat ionof isobutene) might also occur in the dimerizat ion ofisobutene.

Although TBA dehydration and isobutene hydrationon ion -e xch a n g e re sin ca t a ly s t s h a v e bee n s t u diedwidely, few studies have been carried out under isobutenedimerizat ion condit ions, i .e. , in the liquid phase with

* To whom correspondence should be addressed. E-mail :[email protected]. Fa x: +358-9-451 2622.

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low init ial water content . The purpose of the presentwork w as to study the equilibrium of TB A dehydra t ionunder t hese conditions and to constr uct a kinetic modelfor the reaction. Experimental data were used to obtainequilibrium constants and react ion enthalpies and tode t ermin e p a ra me t e rs f or k in e t ic e q u a t ion s de riv edfrom various mechanist ic a ssumptions.

Experimental SectionReactor System. Experiments were carried out in

a stainless steel batch reactor (80 cm 3) in t h e l iq u idphase. The catalyst (1 g) was placed in the reactor in ametal gauze basket . The reactor included a magnetics t irre r a n d a mix in g ba f f le . I t wa s p re s s u rize d wit hnitrogen to about 1.3 MPa to keep the reaction mixturein t h e l iq u id p h a s e, a n d i t wa s h e ld in a t h e rmos t a t e dwa ter bat h with w hich various tempera tures (60-90 C )could be maintained. The mixing speed in the batchreactor wa s 1000 rpm so that no externa l mass-tran sferlimitat ions would occur. Sa mples w ere taken ma nuallyfrom the reactor via a sample valve.

Analytical Methods. The samples taken from there a ct o r w e re a n a ly zed wit h a H e wlet t -P a ck a rd 5890Series II ga s chroma tograph (GC) equipped with a DB -1

capillary column of length 60 m, film thickness 1.00m,and diameter 0.250 mm. A flame ionization detector wasu s ed. Th e p ro du ct s we re q u a n t i f ie d by t re a t in g t h es olve n t a s a n in t ern a l s t a n da rd.

Water in the product could not be analyzed by GC,and the molar ba lance for isobutene wa s poor becauseof i t s h i gh v ol a t i li t y. Th e a n a l y s is of TB A ca n b econsidered reliable, however, and the amounts of waterand isobutene were accordingly calculated from the TBAmolar balance.

Chemicals and Catalyst. TB A (Merck S chuchardtO H G , >99%) wa s the r eactant an d isopenta ne (FlukaCh e mik a AG , G99%) the solvent . Isooctane (FlukaCh e mik a AG , G99. 5%) w a s a dde d t o t h e re a ct ionmixture to study the reliability of the sampling. The

am ount of wa ter in th e TBA wa s less than 0.1 wt %.The catalyst was a commercial acidic ion-exchange

resin consisting of a styrene-divinylbenzene-ba sed sup-port to which sulfonic acid groups had been added asact ive sites. The surface area of the dried cata lyst w asmea sured t o be 37 m2/g (B ET a na lysis), the a cid ca pacity5.1 mmol/g (by t itr a tion 22), and the particle size between0. 42 a n d 1. 0 mm. B e f o re u s e , t h e c a t a ly s t wa s drie dovernight in a n oven a t a bout 100 C . The wa ter contentof the dried cata lyst w as m easured to be 1.7 ( 0.5 w t %(AMB 310 moisture analyzer).

Intraparticle Resistances. The dried catalyst wassieved to different part icle sizes a nd t ested at 80 C ina con t in u ou s f low s y s t em t o s t u dy wh e t h e r in t e rn a ldiffusion limitations existed. The reactor system usedhas been described in detail in our previous publica-tion.21 The tota l flow of isopenta ne a nd 2 mol %of TB Awa s about 36 g h-1. The conversion of TB A at t he st ead ys t a t e w a s t h e s a me (43-44%) in the experiments w ithca t a ly s t p a rt icle s ize s of 0 .42-0.59, 0.59-0.71, an d0.71-1.0 mm. Unfortunately, the experimental setupdid not allow for the test ing of smaller part icle sizes.The results suggest t ha t internal diffusion limita t ionswere not present . The unsieved catalyst was used infurther experiments.

Experiments. In t his w ork, the dehydra t ion of TBAwas studied in the absence of isobutene with TBA ast h e s ole re a c t in g comp on e n t in t h e in it ia l re a ct ionmixture. Experiments were carried out with TBA con-

tents of 2-18 mol %, w ith a n isoocta ne content 1 mol%, a nd with isopenta ne a s t he solvent . The tempera-tures studied w ere 60-90 C, an d the pressure wa s keptat about 1.3 MPa . Several sa mples were ta ken from thereactor during each experiment.

The react ion was carried out for about 6 h, duringwhich t ime the system reached equilibrium. Two ormore points were used in every experiment to determinewh e t h e r e q u il ibr iu m wa s re a c h e d, a n d in u n c e rt a in

situat ions, the experiment was repeated. An exampleof mo la r f ra c t ion s a s a f u n ct ion of t ime in a t y p ica lexperiment is presented in Figure 1. Under the condi-t ions applied, isobutene did not dimerize appreciably(diisobutene content < 0. 06 mol % a t 90 C). Th eis obu t en e dimeriza t ion ra t e clea rly de cre a s es wit hincreasing TBA content.21 This explains the negligiblediisobutene forma tion in these experiments with rela-t iv ely h ig h TB A con t e n t s . B e ca u s e of t h e low TB Aconversions, the isobutene a nd w at er content s w ere lowand only one liquid phase wa s observed.

Thermodynamics. Equilibrium constants Ka can becalculated with equation

wh e re ai i s t h e a c t ivi t y of comp on e n t i, xi i s t h ecorresponding mole fraction at equilibrium, and iis theactivity coefficient. Activity coefficients were calculatedby the D ortmund modified UNI FAC m ethod.23

Eq uilibrium consta nts can a lso be expressed in termsof the G ibbs free energy change for th e react ion (rG)

wh e re rH is the enthalpy chan ge and rS the entropyc h a n g e f o r t h e re a c t io n a n d R i s t h e u n i v e r s a l g a scon s t a n t . I f t h e t e mp er a t u r e r a n g e i n ves t ig a t e d i sn a rro w, rH a nd rScan be a ssumed to be independentof tempera ture.

Kinetic Modeling. The parameters of the kineticmodels were determined using Kinfit software24 wit hthe Levenberg-Marquardt optimizat ion algorithm. Inthe optimiza tion, var ious kinetic models w ere combinedwit h a n idea l ba t c h re a c t or mode l, a n d t h e c a lcu la t e dcomposit ions were compared with the measured ones.

The temperature dependence of the rate constantswa s described by t he Arrhenius equat ion

Figure 1. Mole fract ions as a function of t ime in a n experimenta t 6 0 C .

Ka )

aIB aH 2O

aTBA)

xIB xH 2O

xTBA

IB H 2O

TBA(1)

Ka ) exp(-rG

R T) ) exp(- rH

R T +

rS

R) (2)

k) F exp(- ER T) (3)

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where Fis t he preexponentia l factor, E is the activatione n erg y , a n d R i s t h e u n iv er s a l g a s con s t a n t . Th isequation was reparametrized to the form

wh e re Tre f is the r eference tempera ture a nd Fre f a nd E

are t he para meters to be optimized. Tre f was chosen tobe 343 K (70 C ). The a dsorption equilibrium pa ra m-eters were a ssumed to be independent of t empera ture.

In the tested models, the react ion on the surface oft h e c a t a ly s t wa s c o n s ide re d a s t h e ra t e - de t e rmin in gstep, an d the a ct ive sites of the cata lyst w ere assumedto be equivalent . Pa ram eters for a model tha t t ook intoaccount the different active sites that result from alcoholadsorption 9 we re de t e rmin e d, bu t t h e y did n ot g ivesat isfactory results.

Furthermore, adsorbed components were assumed tooccupy one surface site, a nd t he react ion w as assumedto proceed through carbonium ions. B ecause very lowadsorption equilibrium consta nts (


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calculated for experiments with init ial TBA contentsunder 4 mol %were a ccordingly assumed t o be mislead-ing and were omitted in calculat ing the average equi-librium consta nts.

The average equilibrium constants were calculatedusing th e results from four or more experiments a t ea cht e mpe ra t u re . Th e se con s t a n t s a s a f u n ct ion of t h einverse temperature ar e presented in Figure 3, whichs h ows t h a t t h e e q u il ibr ium con s t a n t in cre a s es wit h

tempera ture. This indicat es tha t t he react ion entha lpyi s p os it i ve a n d t h a t t h e d e h y dr a t i on of TB A i s a nendothermic react ion. To obta in rH a nd rS, t h elog a ri t h m of Ka i s p re se nt e d a s a f un ct i on of t h etemperature according to eq 2. With regression analysis,we obtain

The correlation consta nt R2 for the regression is 0.972.From these results, we obtain a reaction enthalpy of 26( 9 kJ mol-1 and a reaction entropy of 60 ( 30 J mol-1

K-1.Figure 3 compares the obtained equilibrium consta nts

with those determined by Delion et al.12 using differents ol ve nt s a n d b y I b or r a e t a l .28 (both originally forisobutene hydrat ion). Our equilibrium constants arealmost the same as those determined by Delion et al .with nitromethane solvent , whereas the constants ob-ta ined by Delion et a l. with p-dioxane as the solvent andthose obtained by Iborra et al . are about 50%smaller.In a ddition, Table 2 presents the r eaction entha lpies forthe dehydra t ion of TB A determined in t his w ork alongwith those obtained by Delion et al. ,12 Velo et al.,13 a n dIborra et al .28 Iborra et a l . obtained a react ion entha lpyof 3 9 k J m ol-1 in t h e ir s t u dy of t h e s imult a n e ou ssynt heses of MTB E a nd TB A. The other enth a lpy valuesvary between 26 and 34 kJ mol-1, and thus, our value

is of the sa me order of magnit ude as t he values reportedin these previous publications.

Th e w a t e r con t en t s of t h e s a m pl es cou ld n ot b emeasured, and the calculat ions described above werecarried out by a ssuming tha t t he amounts of isobuteneand wa ter formed were equal. The effect of extra w at erin th e feed (the wa ter content in TB A is 0.98). The othercorrelat ions are weak (


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data. This is evident from Figure 4, which shows thecalculated amounts of TBA as a function of the mea-sured amounts for the three models. The closer thepoints in the figure are to the diagonal, the better thefit is. The models show similar trends, which means thatthey present the data equally well.

U sing m odel 1, th e a dsorption equ ilibrium coefficientf o r is o bu t e n e wa s de t e rmin e d t o be la rg e r t h a n t h ecoefficients for TBA an d wa ter. This does not seemre a s o n a ble g iv e n t h a t bo t h T B A a n d wa t e r , a s p o la rcomponents, should adsorb on the act ive sites morereadily than isobutene does.25 B e ca u s e t h e p a ra me t erest imation does not give physically meaningful para m-eters, the f irst model was discar ded.

Because of its high activity coefficient, the activity ofwater is higher than that of TBA and isobutene. Theadsorption of water on the catalyst is also stronger thanthat of the other components.25 As a re su lt , t h e t e rmKH 2OaH 2O d o m i n a t e s i n t h e d e n o m i n a t o r o f t h e r a t eequations. This means that the rat io of the preexpo-nential factor (Fre f) to t he a dsorption equilibrium con-s t a n t f o r wa t e r (KH 2O),Fre f/KH 2O, can be considered as acombin e d p a ra me t er a n d t h e p a ra me t ers ca n n o t bedetermined separately. The high correlat ion betweenthe preexponential factors a nd adsorption equilibriumconstants observed in the models follows.

T h e R SS v a lu e s f o r mo de ls 2 a n d 3 a re a lmo s t t h esam e. Because the para meters were better identified formodel 2, however, this model can be considered morereliable. According to model 2, th e dehydr a tion of TB Ahas an act ivat ion energy of 18 ( 6 k J mol-1, a n d t h eadsorption equilibrium constant of water is 1.5 t imesthat of TBA.

Conclusions

The thermodynamics of the dehydration of TBA wasstudied, and the temperature-dependent equilibriumconsta nt tha t w as obtained gave a react ion entha lpy of26 kJ mol-1. The thermodyna mic values agr ee well withthose reported in ea rlier studies on similar systems.

The kinetics of the dehydration of TBA was studiedas well, and parameters for three different models weree st i m a t ed on t h e b a s i s of t h e m e a s u r ed d a t a . Th eLangmuir-Hinsh elwood-type model w ith a dsorption ofisobutene included did not give physically meaning-ful para meters because it gave higher a dsorption equi-l ibr iu m c o n s t a n t s f o r is o bu t e n e t h a n f o r wa t e r a n dTB A. The other tw o models gave physically meaning-f ul p a r a m e t er s a s w e ll a s s im i la r f it s t o e a c h o t h er .The para meters w ere well identified for a Lan gmuir-

Hinsh elwood-type m odel in wh ich isobutene ad sorptionwa s omitted. The act ivat ion energy in t his case wa s 18kJ mol-1.

Acknowledgment

F u n din g f ro m F o rt u m O il a n d G a s O y is g ra t e f u l lyacknowledged.

Notation

i) activity coefficient of component iai) activity of component iE) activa tion energy of the Arrhenius equa tion, kJ m ol-1

F ) preexponential factor of the Arrhenius equation (eq3), mol s-1 kg ca t-1

Fre f ) preexponential factor of reparametrized Arrhenius

equa tion (eq 4), mol s-1 kg ca t-1

rG) Gibbs free energy change for reaction, kJ mol-1

rH ) ent ha lpy cha nge for rea ct ion, kJ mol-1

k )rea ct ion ra t e const a n t , mol s-1 kg ca t-1

Ka ) reaction equilibrium constant based on activitiesKi ) adsorption equilibrium consta nt of component iR ) universal gas constant, 8.314 J mol-1 K-1

ri ) reaction ra te of component i, mol s-1 kg ca t-1

rS) entropy change for reaction, J mol-1 K-1

T )t empera t ure, KTre f ) reference temperat ure of repar am etrized Arrhenius

equa tion (eq 4), Kxi )molar fraction of component i

Abbreviat ions

D I B ) diisobutenes, 2,4,4-trimethyl pentenesH+ ) prot on of t he ca t a lys tI B ) isobutene, 2-methyl propenei-oct )isooctan e, 2,2,4-trimet hyl pentan eI P ) isopentane, 2-methyl butaneL H ) L a ngmuir-HinshelwoodMTB E ) met hyl tert-butyl ether, 2-methoxy-2-methy l

propaneR S S ) res idua l s um of s qua resTB A ) tert-buty l a lcohol, 2-meth yl-2-propan ol

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Figure 4. Calculated amount of TBA (moles) as a function ofmeasured amount (moles).

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(27) Petr us, L. ; De Roo, R. W.; Sta mhuis, E. J . ; J oosten, G . E.H. Kinetics and Equilibria of the Hydration of Linear Butenes overa Strong Acid Ion-Exchange Resin as Catalyst . Chem. E ng. Sci.1986, 41, 217.

(28) Iborra , M.; Tejero, J .; E l-Fa ssi, M. B .; Cun ill, F.; Izquierdo,J . F. ; Fit e, C . Experimental Study of the Liquid-Ph ase S imulta-neous Syntheses of Methyl tert-Butyl Ether (MTBE ) and tert-ButylAlcohol (TB A). I n d. E n g. Chem. R es. 2002, 41, 5359.

Receiv ed for review February 25, 2004Revised man uscript received April 28, 2004

Accepted May 4, 2004

IE049846S

Ind. Eng . C hem. R es. , Vol. 43, No. 15, 2004 4065

Industrial & Engineering Chemistry Research Volume 43 Issue 15 2004 [Doi 10.1021_ie049846s] Honkela,...

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