Kinetics of Catalytic Dehydrogenation of Ethanol over Copper-Chromia Catalyst CHInG-YeH SHrau' AND TsuNG-WEN CHEN? Department of Chemical Engineering, National Taiwan Institute of Technology, pei, Taiwan 10772, R.O.C. Ethanol, Acetaldehyde, Dehydrogenation, Copper-Zine Catalyst, Copper Chromia Catalyst Key Words: Abstract—The catalytic dehydrogenation of ethanol into acetaldehyde over copper- chromia catalyst in a fixed bed reactor in the temperature range 210-290°C at atmospheric pressure and time factor values ranging from 0.5 to 8.0g-cat-hr/mole Is investigated. By the differentiating method it is found that the dehydrogena- — tion appears to take place at a single site on the catalyst surface in which product hydrogen gets adsorbed and where the adsorption of ethanol is controlling the rate of reaction. Based on this mechanism, a rate equation is derived which is able to predict the experimental date quite well. INTRODUCTION Acetaldehyde is widely used as an inter- mediate for the production of acetic acid, ethyl acetate, vinyl acetate and anti-oxidant etc. One of the major industrial routes to produce acetaldehyde is the dehydrogenation of ethanol over metal catalyst. Several copper based catalysts have been found to be suitable for this, reaction. ‘As early as 1951, Church and Joshi"? selected Cu-Co-Cr as catalyst and found that copper accompany with 5% cobalt and 2% cromium supported on pumice or asbestos has a good activity for ethanol dehydrogenation. Later on, Franckaerts and Froment” used Church’s catalyst to determine the rate equation of ethanol dehydrogenation and found that the reaction is controlled by the surface reaction of ethanol. In 1975, Takezawa ef al.’ studied the reaction mechanism of ethanol dehydrogenation over MgO catalyst and discovered that ethanol first formed ethoxide and acetate on the catalyst, the former then decomposed to acetaldehyde under an ethanol vapor environment. Tn 1985, Prasad et al. investigated the deactivation of copper catalysts by using XRD and SEM and found that the deactivation was mainly due to copper sintering and coking of catalyst surface. They also found that adding chromia would increase the stability and the activity of catalyst. Recently, Doca and Segal’~° used Cr, Mn, Fe and Ni promoted copper catalysts to investigate the kinetics of low aliphatic alcoholic (C,-C.) dehydrogenation in the temperature range of GR, * PB To whom correspondence should be addressed. 200°-280°C by a chromatographic pulse technique. From their results, it was found that the fresh copper catalyst is very active, but its activity decreases rapidly with pulse number. If promoters Cr and Mn are added, the activity of catalysts can remain fairly constant due to the formation of Cu-oxide junction. The kinetics of low aliphatic alcohols dehydrogenation can be described by a first order rate equation. In this paper, copper based catalysts are prepared and tested for the dehydrogenation of ethanol. The kinetics of the reaction is investigated and a possible mechanism for the reaction system is postulated, EXPERIMENTAL 1. Catalyst preparation All catalysts were supported on SiO,. The supporter used in this study was nonporous SiO, with particle size of 0.012 4m and surface area 200m'/g, purchased from Confong Co. Catalysts were prepared by impregnating SiO, with chro- mium nitrate and copper nitrate solution. After 30minutes mixing, the precursor of catalyst was dried at 110°C for 16 hours. ‘The dried powder was then calcined at 450°C for 3hours. Due to the agglomeration of SiO, particles, the prepared catalyst has a size distribution ranging from 100 to 300 Tyler mesh with average about 200 mesh. 2. Apparatus and analysis The kinetics studies were carried out in a continuous flow apparatus with a fixed catalystue Journal of The Chia, |. Ch. E., Vol. 22, No. 3, 1991 bed at atmospheric pressure. The reactor was made of Pyrex tube with 136mm inner diameter, equipped with a thermocule well along the central axis, The experiments were performed in the range of 210° and 290°C, with partial pressure of ethanol from 0.25 to 0.7 atm. Most of runs were carried out at a low conversion in order faciliate kinetic analysis. To prevent possible condensation, all connecting gas lines and valves were wrapped with heating tapes. The compositions of inlet and outlet streams were determined chromatographically using a 6-ft column loaded with Porapak Q° RESULTS. Catalyst activity Copper-chromia catalysts, prepared at dif ferent pH values were tested. In order to prevent the copper catalyst from sintering, all the testing were conducted below 300°C. Among the catalysts, the one containing 10% copper and 3% chromia prepared at pH=10 had the best result, with a higher activity and a better stability. In addition, almost no side rezctions were observed, and the selectivity of acetadehyde was greater than 99%. From these results, the catalyst with 10% copper and 3% chromia prepared at pH=10 was selected for the kinetic study. 2, Equilibrium constant Since the dehydrogenation of ethanol does not go to completion in the temperature range of 210-290°C, it is necessary to determine the value of the equilibrium constant for the kinetic, analysis. In this study, the equilibrium constants at different temperatures were obtained using the thermodynamic principle. The values of 4H", S* and heat capacity of ethanol, acetaldehyde, and hydrogen used for the calculation were obtained from Danil ef al. (1969) and Doca and Segal (1985). Knowing the equilibrium constant, the eq brium conversions X, at different temperatures and different initial ethanol partial pressures can be evaluated by the following equation: OF K PE The calculated results are tabulated in Table 1. ‘Table 1. PDvrium constant and conversion for the dehydrogenation ofethanol T Temperature | ae tont | Py (atm) | ‘conversion Coy K (atm) Xs (%) ¢ 0.25, | 58.1 | ov | wo \) 0.7 82 | 0.85 40.7 02 | ep 0.37 68 20 | 0.399 || 0.80 99.3 | 0.70 | ‘54.7 } Yous | a ral 0.25 | 8.6 {| or na 250, 0.6042 | i 0.50 70.0 | ee | \) 0.85 63.3 | (| 02} 56 | or aa mmo | 10 || 05 | m8 | 07 52 4) os | a2 (| 02 | ws i] os | os oo | ater | oso | ase | ]| om | wz 0.85, | B11 3. Dehydrogenation reaction ‘The main variables influencing the reaction rates are temperature, time factor and initial pressure of ethanol. Table 2 lists the experi- mental results at different operating conditions. It can be seen from this table that at constant time factor and initial partial pressure of ethanol, the conversion increases with tempera- ture, and the rate of increase becomes faster at a higher temperature. Table 2 also shows that when keeping other variables unchanged, the conversion increases steadily with the initial partial pressure of ethanol. Also, when keeping the temperature and the initial partial pressure of ethanol constant, the conversion increases with time factor then gradually levels off. 4, Influence of addition of products Hydrogen, in a molal ratio of 1 to 1 to ethanol, was passed along with the feed stream at various operating conditions. The results are shown in Table 3. A comparison of Tables 2Yeh Shisw and Tsung-Wen Chen: inetice of Catalytic Dehydrogenation of Ethanol over Copper-Chromie Catalyst 143 Table 2. Effects of process variables on reaction ‘Table 4. Effects of acetaldehyde addition on conversion reaction conversion Ph | Time factor | ___Conversion (%) PL | Time factor co atm |(-eat-r/emol)io:cJaaarc|asorc|amorc| mur (atm) | ethremote) “penec_| 20°C 2.0 4.0| 7.3| 12.3| 21.2 | 30.2 ] 20 e7 | 15 | 20.5 40 77) 14.3 | 24.1 | aa | 52.2 1 40 | as | as | sz2 5.0 93 16.1 | 30.2 45.5 | 58.2 5.0 15.2 | 25.5 43.9 | 18 4.2| 7.8) 12.7| 21.0 | 31.2 1s 69 | 8 | 20.5 2.5 5.9| 11.7 /18.5| 33.1 43.6 | 2s 109 | 18.1 | 316 3.0 7.9 | 19.0 | 26.4 | 42,0 | 81.1 3.0 9 | 24 | 37.0 1.0 3.6) 7.1| 11.2) 19.6 | 30. 1.0 7 | 9.8 | 18.0 os | rs |esfwsfins|m2 joe | | as | a) ms | 28) | 7.8] 15.a] 25.2] a7! 72 | as ws | 23 i 0.5 2.4] 4.7) 7.5] 14.4 | 19.9 (| 0.5 | 38 5 66 | 12.0 1.5 6.9| 12.9) 21.3 | 33.1 46.3 : 1.5 9.9 | 36.1 | 28.1 20 | oa |6.2|25.8| 98.9 36.4 no | wa | m2 | m2 Table 3. Effects of hydrogen addition on reac- Table 4 shows the addition of acetaldehyde tion conversion resulting in a more noticeable drop in the conversion. PL | Time factor | Conversion (#) (atm | e-eatchr/emole) |"oa9ec | aso | 270°C 5. Diffusional resistance ae ea eee eace ‘The role of external diffusion can be deter- 02s | 3.0 w.5 | 180 | 30.6 mined by conducting experiments at constant 4.0 we | 28 | 92 temperature, feed composition and time factor 5.0 | 166 | 275 | 46.0 (W/F), but varying the total feed rate (F) and 18 so | 128 | 217 catalyst weight (W), Experimental runs clearly | 20 } os | w2 | 2s show that when the total flow rate was greater oar} oe ue | a0 | see than 100cc/min, there was no further increase ’ in the conversion. This indicates that the i a aan eee 58-7 external diffusion effect can be neglected. ) 6.9 | 1.0 | 19.0 ‘Therefore, in order to avoid the effect of | 20 20 | 20 | 28 runs for the kinetic study were carried out at | 2.5 Wa 22.9 38.1 a flow rate over 120cc/min. On the other hand, os neces since the support wed in this study is non- porous particle and the catalyst particle size 07 | te lave lass | owes used is small (<0.15 mm), the internal diffusion . - effect is negligible. and 3, shows that the addition of hydrogen results in only a slight drop in the conversion, This is probably due to the activating influence of hydrogen on catalyst. Acetaldehyde was also added into the feed (acetaldehyde/ethanol=0.1) to see its effect on the conversion at various operating conditions. REACTION MECHANISM 1. Elucidation of the rate-controlling step ‘The kinetic mechanism for the dehydrogena- tion of ethanol over copper-chromia catalyst was selected according to the Hougen-Watson me- chanisms'’. In these mechanisms the surface4 Journal of The Chia. |. Ch. E.y Vol. 22, No. 3, 1991 steps involved in the reaction are the adsorption of alcohol, surface reaction and desorption of product on either single or dual site, occurring in series. Based on the different controlling me- chanisms, six rate expressions can be formulated for a pure feed stream. To elucidate correct rate-controlling step, the differential method was employed. In this method, the effect of the initial partial pressure on the initial reaction rate was examined and the shape of the curves of rvs. Pi was used to find the rate controlling step. In order to eliminate bias in the numerical differentation of the conversion-time-factor curves for rf, the initial rate data were calculated by the following equation, which was derived based on the conversion vs. time-factor data and the equilibrium conversion information’”. Figure 1 is the plot of the data obtained from the differential method, As can be seen from Fig. 1, a linear relationship between ri and P% was obtained. According the Hougen~ Waston mechanism, this relationship reveals that the kinetic mechanism for the dehydrogenation of ethanol is either the adsorption of ethanol controlling on single site with one of the two products adsorbed or the adsorption of ethanol controlling on dual site. The rate expressions corresponding to these three reaction mechanisms jal Reaction Rate (gmole/g—cat/hr) 0.0 0.2 0.4 0.8 0.8 Initial Partial pressure (atm) Effect of initial partial pressure of ethanol on initial reaction rate. Fig. 1 Mechanism 1: Adsorption of Ethanol Controlling Single Site (A adsorbed), (a mre= Mechanism 2: Adsorption of Ethanol Controlling Single Site (H adsorbed), ~1e= TE KPa co Mechanism 3: Adsorption of Ethanol Controlling Dual Site, ee ac) ee OF KPa t KaP ut KePa) . 2, Evaluation of the rate and adsorption co- efficients To determine the correct mechanism among Eqs. (3) to (5), Kittrell” has proposed a criterion that all the coefficients for the mechanism must be positive at all temperatures, as only positive rate constants have physical meaning. Hence, the rate and the adsorption constants are first evaluated by the method of least squares. For this purpose, Eqs. (3) to (5) are recast as: Mechanisms 1 or 2: Single site (A or H adsorbed) yeatfe' (6) ‘Mechanism 3: Dual site yratbx tex, (7) where y={Pp—(PaPp)/KVM—re) 1=Pm t= Pay 1k, B= Kylk, c=Kalk, f is either 6 or c, and x’ is either x, or x. If the partial pressure and the equilibrium constant are known, and the reaction rate can be calculated by Eq. (2), the values of a, b, and c in Eqs. (6) and (7) may be determined by a regression method. The results are shown in Table 5. The result of Table 5 shows that the dual-site mechanism was incorrect. ‘To distinguish between hydrogen and acetal- dehyde adsorbed, the experimental data from the runs with product addition in the feed were used to determine the coefficients. The results are shown in Table 6. Based on Kittrell’s criterion, we conclude that it is the product hydrogen which gets adsorbed. This is consistent with Permutter and Ford'? and Perona and Thodos'”,Ching-Yeh Shiau and Tsung-Wen Chen: Table 5. Coefficients of simplified mechanism | a 6.70 6.40 Fa | 8 | 8.8 ~{ije| 4 © | _ 0.3L afi jas] a eo | = 5.404 © _ -1.14 Table 6, Coefficients of simplified mechanism eavation Thai eC) Coefficients ee) 1 2 |e 8.81 . = bot | 6 =1.69 35.93 wo | @ | as bear | nr nm { ca ; 9 ‘Therefore, the dehydrogenation of ethanol takes place at a single site where product hydrogen gets adsorbed on the catalyst surface, and the adsorption of ethanol is the controlling step of the reaction. ‘The reaction rate constant & and the adsorp- tion equilibrium constant of acetaldehyde Ky were calculated from the coefficients of the fitted equation. The temperature dependence of & and that of K, were further examined by the Arrhenius plot. ‘The results are presented in Fig. 2. The obtained reaction rate # shows a linear relation- ship with 1/7 with a negative slope, while the adsorption equilibrium constant K, shows a linear relationship with 1/T with a positive slope. These results satisfy the criterion given by Kittrell. ‘The overall expressed as: rate equation can then be ies of Catalytic Dehydroge ion of Ethonol over Copper-Chromia Catalyst 145 {8)— 7 _—— Ka Unk of Lak 4 75 785 185 205 1/T91000 (1/k) Fig. 2. Archerius plot of rate constants. 1.0 Conv. of C,H,0 (calculated) ° & where a=1o-1a-exn( K=3085 107-39 3, Reliability of reaction mechanism equation To verify if the derived mechanism is adequate for the description of the experimental data, ethanol conversion was calculated at various operating conditions, and compared with the experimental results shown in Fig.3. This figure shows that the mechanism suggested representsue Journal of The Chin. |. Ch, Es, Vol. 22, No, 8, 1991 the experimental values quite satisfactorily. The standard deviation is 9.57%, CONCLUSION Copper-chromia catalyst is found to be a suitable catalyst for the dehydrogenation of ethanol. The performance of the catalyst with 10% copper and 3% chromia prepared at pH=10 is the best. A single-site mechanism is proposed based on the experimental results. The overall rate of reaction is postulated to be controlled by the adsorption of ethanol. It is assumed that product hydrogen gets adsorbed on the catalyst surface. The governing equation based on this mechanism gives a fairly good prediction for the experimental data. ACKNOWLEDGEMENT ‘The authors wish to thank the financial support of the National Science Council of R.0.C. NOMENCLATURE 4,6, coefficient of simplified mechanism equation F total feed rate, (g-mole/hr) Fy feed rate of ethanol, (g-mole/ir) k reaction rate constant, (gmole/g-cat-hr-atm) K, adsorption constant for acetaldehyde, (atm) Ky adsorption constant for hydrogen, (atm) K, equilibrium constat of dehydrogenation of ethanol, (atm) Pz partial pressure of ethanol, (atm) P% initial partial pressure of ethanol, (atm) P, parttal pressure of acetaldehyde, (atm) Py partial pressure of hydrogen, (atm) -rz Reaction rate of ethanol, (gmole/g-cat-hr) =r} Initial reaction rate of ethanol, (gmole/ g-cathr) R gas constant T Reaction temperature, (°K) W weight of catalyst, (g) X, equilibrium conversion of dehydrogenation of ethanol Greek Symbols @ parameter of curve fitting function + W/Fe=time factor based on ethanol feed rate, (g-cat+hr/gmole) 10 u. 2. 1 . (Manuscript Received October |. Doca, N. and E. Segal, “Dehydrogen - Doca, N. and E. Segal, "Dehydrogen: - Doca, N. = Franckaerts, J . Yang, KH. 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Kobayashi, “The Mechanism of Dehydrogenation Ethanol on Magnesium Oxide", Journal of Catalysis, 38, 101 ag7s). and 0.A. Hougen “Determination of Mechanism of Catalyzed Gaseous Reactions”, Chemical Engineering Progress, 46(3), 146 (1950). 16, 1990, Accepted March 1, 1991)‘Ching-Yeh Shiau and Tsung-Wen Chen: Kinetics of Catalytic Dehydrogenation of Ethanol over Copper-Chromie Catalyst 147 CESARE LR REAM eR OB BRM LRP IR co] = RICE BBR ZEW R-AZ ZBI © FEZ i ST HS 210-290°C fi)» BEE FAM 05-80 g-catohr/g mole ZW © APIA TU TE PO BL EMG » ZAG MME 2 RSS HE DM RRL ARHEEL GAA » TMI TARR R ©