Chemical Engineering and Processing 40 (2001) 33 40 www.elsevier.

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Kinetics of the synthesis of higher aliphatic alcohols from syngas over a modied methanol synthesis catalyst
Maria Kulawska *, Jerzy Skrzypek
Institute of Chemical Engineering, Polish Academy of Sciences, 44 -100 Gliwice, Ba*tycka 5, Poland l Received 2 February 2000; received in revised form 17 April 2000; accepted 17 April 2000

Abstract Kinetic investigation on the synthesis of a mixture of methanol and higher aliphatic alcohols from the synthesis gas has been conducted over a Cs-doped Cu Zn composite catalyst in an experimental gradientless reactor. The kinetic equation was described in a simple power law form. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Kinetics; Higher aliphatic alcohols; Methanol; Syngas

1. Introduction The synthesis of a mixture of methanol and higher aliphatic alcohols is one of the most interesting processes in C1 chemistry. Recently, the works in this area are focused on the effective production of an octane booster for clean gasoline. The reaction requires special composite catalysts working in severe conditions. The catalysts can be divided into the two main classes: modied catalysts for methanol synthesis and those often referred to as modied catalysts of Fischer Tropsch synthesis. In the rst class, by analogy to methanol synthesis high and low temperature catalysts are distinguished. A promoter containing alkali or alkali earths species should be used in all cases. The products include primary and secondary alcohols of both normal and branched carbon chains. The stoichiometry of higher alcohol synthesis from synthesis gas is based on the following reactions: CO+2H2 l CH3OH 2CO+4H2 l C2H5OH + H2O 3CO+6H2 l C3H7OH + 2H2O (1) (2) (3)

The water-gas shift reaction is always present and assumed as attaining chemical equilibrium under the process conditions [1]: CO+ H2O l CO2 + H2 (4)

Undesired side reactions of hydrocarbon formation may occur, especially that of methane: CO+ 3H2 l CH4 + H2O (5)

Other oxygenates: ketones, aldehydes and esters are also formed.

* Corresponding author. Tel./fax: +48-32-2310318.

From the thermodynamic point of view, lower temperatures and higher pressures are protable for the formation of alcohols, because these reactions are exothermic and proceed with volume contraction. From the kinetic point of view, higher temperatures, about 600 K, should be employed to yield a sufcient reaction rate. The values of the yield can differ distinctly in spite of the same composition of catalysts. Table 1 provides some data concerning low-temperature modied methanol synthesis (copper-based) catalysts. The reaction mechanisms suggested in the literature include a slow step for the formation of C2 species from C1 species [810]. The rate of ethanol formation appears to limit the overall rate of chain growth. According to Nunan [11], ethanol is produced due to the reaction between the adsorbed formaldehyde and the formyl group created by hydrogenation of the adsorbed CO.

0255-2701/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 2 5 5 - 2 7 0 1 ( 0 0 ) 0 0 1 0 7 - 0

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Table 1 Literature data concerning copper-based catalysts Nunan et al., 1989 [2] Cu/Zn=30/70 +0.34 wt.% Cs 583 7.6 3260 0.45 0.16 0.16 0.08 c(kg/lcat/h) 0.3 c(kg/lcat/h) 0.5 0.45 1.5 1.12 *(l/lcat/h) 0.38*(l/lcat/h) 560 6.2 *9000 [1/h] 598 7.6 *860 Cu/Th/Zr/K = 63/18/9/9 Cu/Zn=30/70 +0.4 wt.% Cs US patent 4 943 551, 1990 [3] Herman, 1991 [4] Stiles et al., 1991 [5] Beretta et al., 1996 [6] (double bed) Cu/ZnO/Cr2O3 +3mol.% CsZn/Cr2O3+4 wt.% Cs 598/678 7.5 18 375 0.75 0.18 0.30 Burcham et al., 1998 [7] (double bed) Cu/ZnO/Cr2O3 = 30/45/25+3mol.% Cs 598/613 7.5 18 375 0.75 0.57 0.36

Number

Reference

Catalyst composition (mol.%)

2 3 4

Cu/Mn/Zn/Co=4/3/1/0.025 +10wt.% Cr2O3+4 wt.% K2CO3 673 17 *40 000

M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

Temperature (K) Pressure (MPa) GHSV (l/kgcat/h) *(1/h) Gas composition H2/CO (mol ratio) Methanol yield (kg/kgcat/h) Higher alcohol yield (kg/kgcat/h) 23.8 wt.% of liquid product 57.3 wt.% of liquid product

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The growth schemes of the alcohol molecules and the prediction of the product mixture distribution for assigned values of the operating conditions have been given by some authors [12,13] for modied methanol catalysts. Few works have been made at modelling the kinetics of the overall rate of the synthesis. The paper of Calverley and Smith [1] concerned the alcohol synthesis over the low-temperature modied methanol catalysts. Recently, Burcham et al. [7] presented a kinetic reaction network to predict product yields over a double bed Cs Cu/ZnO/Cr2O3 catalyst. The kinetic model originally developed by Smith et al. [14,15] was based on the mechanism of alcohol formation over caesiumpromoted copper-based catalysts proposed by Nunan et al. [2,11]. The earlier report about double bed reactor working over high-temperature and low-temperature catalysts has been given by Beretta et al. [6]. Tronconi et al. [16] and recently Beretta et al. [17] conducted their kinetic investigations over the high-temperature modied methanol synthesis catalyst. Both the experiments of Calverley and Smith [1] and Tronconi et al. [16] have been conducted at xed temperature and xed pressure, so the dependence of reaction rate on these parameters is not known. Our work is an attempt of modelling the kinetics of the synthesis of higher alcohols globally applicable over ranges of operating conditions.

2. Experimental The catalyst containing mainly CuO and ZnO with additions of Zr, Fe, Mo, Th and Cs oxides has been prepared in our laboratory. It is a kind of low-temperature modied methanol synthesis catalyst. Three different methods of catalyst preparation were used; the best results were obtained with the thermal decomposition of organic complexes containing metallic components of catalyst. The catalyst was calcined in the temperature range 370 650 K, then reduced in a 3% H2/N2 mixture by a heating rate 5 K/min to the maximum temperature 450 K at xed gas ow 60 ml/min. Prior to the reaction, the catalyst was activated (525 650 K, 4 MPa, 1850 per h). The optimal composition of the catalyst was CuO (50 60), ZnO (25 30), ZrO2 (7 14), Fe2O3 (14), MoO3 (715), ThO2 (1 3), Cs2O (0.5 1.5), wt.%. The yield obtained was 130 170 g/kgcat/h of liquid product that contained methanol (35 53), wt.%, higher aliphatic alcohols C2 + (20 35), wt.%, and water. The catalyst exhibits a remarkable stability during one-year experiments and high selectivity towards alcohols. Hydrocarbons were practically absent, but traces of methane were detected. So, a risk of uncontrolled heat production due to the methanation [5] is ruled out over this catalyst. Higher aliphatic alcohols C2 + contained

ethanol (5164), wt.%, n-propyl alcohol (1927), wt.%, and C4 C7 linear aliphatic alcohols. Branched aliphatic alcohols C3 C5 constituted 5.58.5 wt.%. Only traces of other oxygenates were formed. The surface area of the catalyst was measured by the BET method using argon. The surface area of the oxidized catalyst was 20.3 m2/g and increased to 30.4 m2/g after reduction by hydrogen. The mean pore radius was 16 10 9 m. The Cu metal surface area of the reduced catalyst was measured using the pulse N2O decomposition technique. Assuming a Cu atom density of 1.46 1019 atoms/m2, the Cu surface area was 6.2 m2/g. Kinetic experiments were carried out in a high-pressure continuous gradientless stirred tank reactor. This type of reactor allows a direct determination of the reaction rate. The gaseous feed was supplied from a battery of gas cylinders through owmeters and a gas mixer placed inside an electric oven maintaining a suitable temperature. The reactor (Robinson Mahoney 300cc) consisted of stainless steel tube 46 mm in a diameter with a magnetic stirrer. Grains of the catalyst (0.40.63 mm in a size, about 30 g in a weight) were placed into a wire basket (40 mm outer and 32 mm inner diameter, respectively) inside the reactor tube. Temperature was controlled by a thermocouple. The efuent stream, after cooling and after pressure was reduced to 0.1 MPa, was a liquid mixture of methanol, higher aliphatic alcohols and water. Liquid products were analysed chromatographically (Varian, Star 340 with FID and TCD detectors) in a DBWAX column 0.53 mm in a diameter and 30 m long. Inlet and outlet gases were analysed in a Carbosieve II packed column 4 mm in diameter and 2 m long. The range of experimental parameters used was P= 4.010.0 MPa, T =593623 K, H2/CO= 0.853.16, GHSV= 7000 per hour to make sure only low conversions would been attained. The reaction was far from chemical equilibrium and the reverse reactions were negligible. The process proceeded in the intrinsic kinetic regime. The kinetic results are collected in Table 2.

3. Results and discussion The mechanism of alcohol synthesis is catalyst specic and cannot be generalized from one system to another. We have considered which mechanism of reaction can be taken into account in this case. It seemed that a reaction between substrates was the rate-controlling step (LangmuirHinshelwood mechanism). The increase in the reaction rate followed the increase in pressure of hydrogen. No maximum was observed in the rate with an increase in the pressure of hydrogen (see Figs. 1 and 2). Also, there was not a distinct dependence of the reaction rate on the CO pressure.

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Table 2 Results of the kinetic experiments XH 2 3 0.709 0.709 0.709 0.709 0.709 0.709 0.709 0.709 0.709 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.60 0.512 0.512 0.512 0.512 0.512 0.512 0.512 0.512 0.427 0.427 0.427 0.427 0.427 0.427 0.427 0.427 0.427 0.224 0.224 0.224 0.224 0.224 0.224 0.224 0.224 0.224 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.32 0.392 0.392 0.392 0.392 0.392 0.392 0.392 0.392 0.501 0.501 0.501 0.501 0.501 0.501 0.501 0.501 0.501 55.3 56.3 53.1 50.7 50.6 47.9 44.8 41.4 36.4 47.3 47.5 46.5 44.8 47.5 46.8 41.2 37.8 38.3 48.1 47.5 46.0 41.6 42.6 39.7 37.4 35.7 45.9 46.6 42.6 43.4 41.5 40.8 34.8 33.6 33.4 14.6 14.6 14.6 14.4 15.2 14.6 14.2 13.7 12.5 13.2 14.6 13.4 12.8 15.3 15.4 13.9 13.0 13.6 18.1 18.5 18.3 19.4 18.4 18.0 17.0 16.3 17.6 16.6 16.2 16.4 17.8 18.7 17.7 17.1 16.1 6.0 6.0 6.2 5.7 6.4 6.1 5.9 5.7 5.5 5.6 5.3 5.7 5.2 5.5 5.6 5.1 4.7 5.0 7.9 8.8 8.4 9.6 9.6 9.2 9.2 9.2 7.5 6.5 6.9 6.8 9.3 9.3 10.2 10.1 10.2 22.8 22.7 23.0 22.0 23.7 22.7 22.1 21.5 20.2 22.3 23.3 23.2 21.6 24.1 24.5 22.2 20.7 21.8 29.6 31.6 30.7 33.9 32.2 31.8 31.9 32.5 31.3 29.8 29.9 30.2 32.7 34.5 34.5 34.3 33.4 1.563 2.531 2.875 1.031 1.563 2.094 0.50 0.375 0.563 1.375 1.719 2.344 0.813 1.47 1.44 0.219 0.25 0.719 0.75 1.31 0.594 0.75 1.16 0.094 0.188 0.344 0.625 1.41 1.56 1.53 0.41 0.688 0.125 0.125 0.188 0.284 0.456 0.549 0.208 0.328 0.446 0.109 0.086 0.132 0.268 0.387 0.472 0.165 0.328 0.377 0.054 0.063 0.182 0.195 0.354 0.170 0.241 0.345 0.028 0.059 0.109 0.170 0.351 0.411 0.400 0.128 0.216 0.040 0.049 0.069 0.089 0.144 0.179 0.063 0.106 0.143 0.035 0.027 0.044 0.087 0.108 0.154 0.051 0.090 0.105 0.015 0.017 0.051 0.065 0.129 0.060 0.092 0.135 0.011 0.025 0.047 0.056 0.105 0.134 0.127 0.051 0.082 0.018 0.022 0.034 4 5 6 7 8 9 10 11 XCO MeOH (wt.%) EtOH (wt.%) PrOH (wt.%) HA (wt.%)
3 r. MeOH 10 (mol/gcat/h) 3 r. EtOH 10 (mol/gcat/h) 3 r. PrOH 10 (mol/gcat/h)

Number

T (K)

P (Mpa)

r . HA103 (g/gcat/h) 12 M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340 20.4 32.6 39.8 14.6 23.5 31.9 7.8 6.2 9.8 20.8 28.4 37.6 12.8 23.8 27.6 4.0 4.6 13.4 14.7 27.8 13.1 19.4 27.8 2.3 5.1 10.0 14.0 29.0 34.9 33.9 10.8 18.3 3.6 4.5 6.6

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35

593 608 623 593 608 623 593 608 623 593 608 623 593 608 623 593 608 623 593 608 593 608 623 593 608 623 593 608 623 623 593 608 593 608 623

10.0 10.0 10.0 7.0 7.0 7.0 4.0 4.0 4.0 10.0 10.0 10.0 7.0 7.0 7.0 4.0 4.0 4.0 10.0 10.0 7.0 7.0 7.0 4.0 4.0 4.0 10.0 10.0 10.0 10.0 7.0 7.0 4.0 4.0 4.0

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37

Thus, the effect of CO appeared to be negligible. The classical Langmuir Hinshelwood expression with terms in the denominator gave no sufcient results by tting. We used simple pseudohomogeneous rate equation [18]. The following expression ts the experimental data quite well by the mean error 9.7% at condence level of 0.95.

r = k0 exp(E/RT)p n 2 H

(6)

Fig. 3. Exactness of t for the rate of ethanol formation. Open symbols refer to-T= 593 K; solid symbols T= 608 K; slashed symbols T= 623 K. -P=10 MPa, -P=7 MPa, D-P= 4 MPa.

Fig. 1. Effect of hydrogen pressure on the rate of the formation of ethanol. Stars refer to T= 593 (K); rhombuses T= 608 (K); circles T = 623 (K).

where n= 2 for methanol synthesis; n =1.5 for higher alcohol synthesis. The values of activation energy are 72190, 81450, 78100 J/mol for MeOH, EtOH, PrOH, respectively, at k0 = 59.4, 268, 48.3 mol/gcat/h/MPan, respectively. The values of activation energy are typical for catalytic reactions. Kinetic conclusions can be drawn from Eq. (6) on the nature of the catalyst used. Since the methanol formation rate can be described by: rMeOH = k pCO p2 1+ KCOpCO H2 (7)

Fig. 2. Effect of hydrogen pressure on the rate of the formation of higher alcohols. Stars refer to T= 593 (K); rhombuses T= 608 (K); circles T = 623 (K).

the correlation (Eq. (6)) would be a good approximation for the case of KCO pCO1 and n=2. Eq. (7) corresponds to the well-known situation when a reaction of chemisorbed CO with gaseous H2 is the ratecontrolling step. It may suggest that the LangmuirRideal mechanism can exist [19]. Similar conclusions can be given for the description of the reaction rate of higher alcohol formation. The adequacy of the model is shown in Figs. 3 and 4. In the paper of Calverley and Smith [1], the expression describing the overall rate of higher alcohol formation was based on LangmuirHinshelwood kinetics. The assumption was made that the formation of carboncarbon bonds occurs between any two formyl intermediates, produced from carbon monoxide, carbon dioxide and methanol on different type of active sites:

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Table 3 Effect of carbon dioxide presence in the gas on a productivity of higher alcohols Catalyst system Temperature (K) Pressure (MPa) GHSV (h1) Feed gas ratio H2/(CO+CO2) (mol.%) 6 1/1 2/1 7 0.42 40 Reaction conditions C2+ OH yield without CO2 in the gas C2+ OH yield at CO2 presence CO2 conc. (mol.%)

Number

Reference

1 673 673 8.5 8000 8.5 8000

9 6.0 3.0

Tronconi et al., 1987 [16] Forzatti et al., 1988 [20] 558 562 6.5 10.0 20 000 1/2 1/2

0.15 [mol.% in outlet gas] 8 [g/lcat/h]

3 4

0.02 1.47

0.06 [g/gcat/h] 0.47 [mmol/gcat/h]

4.0 9.0

ZnO/Cr2O3 1/1 metal ratio+3 wt.% K2O K/Zn/Mn/Cr 2.06/1/1.1/1.03 metal ratio Elliot, 1988 [21] CuO/ZnO= 30/70 Calverley and CuO/ZnO/ Cr2O3+4 Smith, 1991 [22] wt.% K2CO3 (30/60/10 metal ratio)+0.5 wt.% K2CO3 592 4.0 3000 10.0 20 000 1/2 2/1 K3O/CuO/ZnO/Al2O3 563 0.5/60/30/10 wt.%

2.74 1.25 1.25 1.25

2.12 [mmol/gcat/h] 2.4 [mol/l/h] 0.25 0.0

9.0 2.0 6.0 10.0

M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

Boz et al., 1994 [23]

rHA =

M. Kulawska, J. Skrzypek / Chemical Engineering and Processing 40 (2001) 3340

1/2

39

pCO(pH2) +C pMeOH(pH2) 3/2 A+B pMeOH pCO2(pH2)1/2 D + E pCO2/pco

(8)

where a =1.0010 5, b =0.126, c =6.82 10 4, d= 3.03; A= 7782, B=1853, C =0.331, D = 34.15, E= 18640; MeOHmethanol; HA mixture of higher alcohols without methanol. The direct comparison between this study and our work cannot be conducted. The experiments of Calverley and Smith [1] were conducted at xed temperature 558 K and xed total pressure 10 MPa. The third term in Eq. (8) indicates the enhancing inuence of carbon dioxide. The role of CO2 is one of controversies about the kinetics of higher alcohol formation. The suppression of the higher alcohol formation is reported in most cases see Table 3. Stiles et al. [5] have also found a decrease in the alcohol formation over composite copper systems at 24 mo1% CO2 concentration in the feed gas; similarly, Skrzypek et al. [24] observed the same for Cu/Zn/Zr/Fe/Mo/Th systems doped with both Cs and K, with traces of CO2 in the feed gas. In contrast to such ndings, Elliott [21] observed an enhancing effect of CO2, although for the undoped Cu Zn catalyst only. In our earlier investigations concerning the methanol synthesis over copper zinc catalyst the Langmuir Hinshelwood mechanism has been found. The detailed characteristic of this copper zinc catalyst was given [25]. A similar catalyst but modied to higher alcohol synthesis, prepared by us as described above, has a different characteristic.

The mechanism of higher alcohol synthesis is different for different catalytic systems, depending on the metal, the support, the promoter and the reaction conditions. Probably it is not possibly to determine one universal mechanism of this process. Different intermediates and therefore different products can be formed. In our work, the good selectivity towards alcohols and only traces of by-products allow the simple correlation suitable for reactor modelling.

Appendix A. Nomenclature

E GHSV HA KCO k k0 p r T x Subscripts CO CO2 EtOH H2 HA MeOH PrOH

activation energy (J/mol) gas hourly space velocity (per hour) higher aliphatic alcohols adsorption equilibrum constant (per MPa) rate constant (mol/gcat/h/MPan) pre-exponential factor (mol/gcat/h/ MPan) partial pressure (MPa) reaction rate (mol/gcat/h) temperature (K) mole fraction carbon oxide carbon dioxide ethanol hydrogen higher aliphatic alcohols methanol propanol

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Fig. 4. Exactness of t for the rate of total higher alcohol formation. Open symbols refer to T =593 K; solid symbols T= 608 K; slashed symbols-T=623 K. -P= 10 Mpa; -P= 7 Mpa; D-P= 4 MPa.

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