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University of Groningen Mass Transfer Effects in the H2SO4 University of Groningen Mass transfer effects in the H2SO4 catalyzed pivalic acid synthesis Brilman, D.W.F.; Meesters, N.G.; Swaaij, W.P.M. van; Versteeg, Geert Published in: Catalysis Today DOI: 10.1016/S0920-5861(00)00618-0 IMPORTANT NOTE: You are advised to consult the publisher's version (publisher's PDF) if you wish to cite from it. Please check the document version below. Document Version Publisher's PDF, also known as Version of record Publication date: 2001 Link to publication in University of Groningen/UMCG research database Citation for published version (APA): Brilman, D. W. F., Meesters, N. G., Swaaij, W. P. M. V., & Versteeg, G. F. (2001). Mass transfer effects in the H2SO4 catalyzed pivalic acid synthesis. Catalysis Today, 66(2), 317-324. DOI: 10.1016/S0920- 5861(00)00618-0 Copyright Other than for strictly personal use, it is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license (like Creative Commons). Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Download date: 11-02-2018 Catalysis Today 66 (2001) 317–324 Mass transfer effects in the H2SO4 catalyzed pivalic acid synthesis D.W.F. Brilman∗, N.G. Meesters, W.P.M. van Swaaij, G.F. Versteeg Department of Chemical Engineering, University of Twente, PO Box 217, 7500 AE Enschede, Netherlands Abstract The synthesis of carboxylic acids from alkenes, carbon monoxide and water according to the Koch process is usually carried out in a stirred gas–liquid–liquid multiphase reactor. Due to the complex reaction system with fast, equilibrium reactions and fast, irreversible reactions the yield and product distribution depend on a number of process parameters. The effect of some of these parameters was studied for the production of pivalic acid, using sulfuric acid as a catalyst. For the 96 wt.% sulfuric acid catalyst solution used the main reactions are relatively fast with respect to mass transfer and mixing. Therefore, aspects like the position of the injection point, inlet concentration, agitation intensity and injection rate all influence the yield obtained. The presence of an inert organic liquid phase was found to be beneficial, due to a combined effect of enhanced gas–liquid mass transfer and a ‘local supply’ effect for carbon monoxide near the hydrocarbon reactant inlet. © 2001 Elsevier Science B.V. All rights reserved. Keywords: H2SO4; Pivalic acid; Alkenes; Mass transfer; Mixing; Multiphase; Gas–liquid–liquid 1. Introduction to the desired reaction steps also oligomerization, isomerization and disproportionation reactions may The production of sterically hindered carboxylic occur. In the present contribution, the effect of some acids through the Koch synthesis is an example of of the process parameters on the acid yield and prod- a complex reaction system with challenging chemi- uct composition was studied for the production of the cal reaction engineering aspects. The production of smallest Koch acid, pivalic acid, using sulfuric acid these Koch acids is generally characterized by the as catalyst solution. presence of two liquid phases and one gas phase, a In the industrially applied fully backmixed stirred parallel/consecutive reaction scheme with fast, equi- tank reactors the hydrocarbon reactants and the acids librium reactions and fast (irreversible) undesired side produced constitute a dispersed organic liquid phase. reactions. The acid yield and the product distribution Previous work has shown that the presence of the obtained for this process depend on a number of pro- reaction product in the catalyst phase significantly cess parameters, e.g. temperature, carbon monoxide affects the reaction kinetics [1]. The relatively small partial pressure, agitation intensity (liquid mixing), reactants used in this study, isobutene and tert-butanol, and composition of the catalyst solution. In addition form a gas–liquid two-phase system with the sulfuric acid catalyst phase under the conditions studied. By ∗ Corresponding author. Tel.: +31-53-489-4479; using heptane as an immiscible liquid phase the ef- fax: +31-53-489-4774. fects of this immiscible liquid phase on mass transfer E-mail address: [email protected] (D.W.F. Brilman). and product yield can be separated from the effects of 0920-5861/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved. PII: S0920-5861(00)00618-0 318 D.W.F. Brilman et al. / Catalysis Today 66 (2001) 317–324 the presence of the reaction products on the reaction • isobutene (293 K), [3] kinetics. log10(k1,app) =−1.35Ho − 3.3(2>Ho>− 9) • text-butanol (293 K) [1] log10(k1,app) = 1.45Ho − 14.0 (− 6.5>Ho>− 8.5) 2. Reaction mechanism and reaction kinetics In these correlations k1,app is the apparent first order (in the alkene concentration) reaction rate The generally accepted mechanism for the Koch constant and Ho is the Hammett acidity function. reaction includes four reversible main reaction steps: Details of hydrocarbon solubility in strong sulfuric (I) formation of a carbocation from an alkene or al- acid solutions and the correlation used for Ho vs. cohol, (II) addition of carbon monoxide (CO), (III) H2SO4 concentration can be found elsewhere [4]. addition of water and finally (IV) deprotonation of The protonation/dehydration kinetics for tert-butanol, the carboxylic acid formed [2]. The reaction kinetics as presented above, are determined by measuring under Koch reaction conditions ( >75 wt.% H2SO4) the CO consumption rate. When comparing these are not well known. Recent work [1] for the kinetics k1,app values with dehydration rates for other com- of the pivalic acid formation starting with isobutanol ponents, it is found that the apparent protonation (and in a few experiments tert-butanol) as reactant rate for tert-butanol is much lower than may be has shown for these reactants that in absence of mass expected from dehydration kinetics found in litera- transfer limitations the carbocation formation is rate ture for tert-pentylalcohol and 2-phenyl-2-propanol determining. [1]. Considering the log–linear relationship with the In this work the more reactive isobutene and catalyst solution acidity and the reported carbonyla- tert-butanol have been applied as reactant at high acid tion rates in other media [5], it is most likely that concentrations. The rate of protonation under these the equilibrium position for the dehydration reaction conditions can be estimated using (extrapolations of) causes the apparently relatively low CO consumption the following correlations: rate. Fig. 1. (Simplified) Scheme of competing reactions in the Koch synthesis of pivalic acid. D.W.F. Brilman et al. / Catalysis Today 66 (2001) 317–324 319 Using the log–linear relationship found for k1,app and the gas–liquid volumetric mass transfer coefficient vs. Ho the protonation rate constants k1,app at 96 wt.% kLa have been described elsewhere [1]. The experi- −1 H2SO4 can be estimated to be 3 (s ) for tert-butanol mental setup is shown schematically in Fig. 2. When and approximately 1010 (s−1) (thus a more or less the injection vessel is used for feeding the hydrocar- instantaneous reaction) for isobutene. Under these bon reactant, it was filled with the liquid phase re- conditions the protonation reaction rate is not likely to actant, in most experiments a mixture of tert-butanol be rate determining. The reaction rate for the carbony- containing 8 wt.% of heptane to keep the tert-butanol lation step may be estimated from experimental data in the liquid phase at 293 K. for the carbonylation reaction of the tert-butyl cation After saturating the catalyst solution with CO, stir- 3 in superacidic media (kcarbonylation ≈ 1.0(m/mol s), ring was stopped and the reactor pressure was reduced see [5]). by 1.5 bar by opening the valve to the (initially 30 bar An overview of the most important competing reac- CO containing) dump vessel. In this way a pressure tions is presented in Fig. 1. Most byproducts are due to drop over the injection vessel is created. Then the oligomerization and consecutive reactions including gas-inducing stirrer is started again. Both valves of the isomerization, disproportionation and carbonylation injection vessel are opened and the CO flow is used (leading to higher acids). At acid concentrations ex- to inject the reactant. The relevant pressures and tem- ceeding 90 wt.% stable polyalkyl-cyclopentyl (PACP) peratures (indicated in Fig. 2) are recorded. The CO cations may be formed irreversibly [6]. Unfortunately, pressure in the reactor is kept constant by the pressure the kinetics for these side reactions are not known. reducer or a pressure regulating system (±0.01 bar), From Fig. 1 it can be concluded that at high dehy- consisting of a PC + PID controller. Data acquisition dration rates of tert-butanol (or high protonation rates is stopped when no longer CO is consumed, mini- of isobutene) transport of CO to the reaction zone and mally after 45 min. In the experiments with the reac- 2− mixing to avoid locally high alkene (C4 ) concentra- tant injector, the reactor is kept at 40 bar CO partial tions are essential. Attention will therefore be focused pressure and the injection time could be varied sep- on these topics, together with the effect of adding an arately. The minimum injection time for a 13 ml of immiscible, inert, liquid to the reaction system. tert-butanol/heptane solution (containing ca.
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