Chemical Engineering and Processing 44 (2005) 687694

Distillation of formaldehyde containing mixtures: laboratory experiments, equilibrium stage modeling and simulation
Michael Otta , Hartmut Schoenmakersb , Hans Hassea,
a

Institute of Thermodynamics and Thermal Process Engineering, University of Stuttgart, D-70550 Stuttgart, Germany b BASF AG, Global Process Engineering, Ludwigshafen, Germany Received 28 March 2003; received in revised form 3 September 2003; accepted 3 September 2003 Available online 11 November 2004

Abstract Formaldehyde is one of the most important chemical intermediates. In technical processes, it is used in aqueous solutions, which also contain methanol. These solutions are complex reacting mixtures, in which formaldehyde is bound in a variety of oligomerization products. Distillation experiments with mixtures of formaldehyde, water and methanol were carried out in a 50 mm diameter column with 3.5 m of structured packing. Two types of separations were studied: (a) removal of methanol, for which the bottom product is formaldehydewater, and (b) removal of formaldehyde, for which the bottom product is pure water. Reux ratio, pressure, and the feed composition were systematically varied. A physico-chemical model of vaporliquid equilibria of formaldehyde containing mixtures was used as a basis for a process simulation with an equilibrium stage model. It is assumed that chemical equilibrium is established on each stage. Predictions with that simple model together with stage efciencies from the internals supplier show good agreement only in some cases and indicate that the inuence of reaction kinetics has to be taken explicitly into account. Reactive distillation line diagrams for the ternary system formaldehydewatermethanol are presented for the rst time. 2004 Elsevier B.V. All rights reserved.
Keywords: Distillation; Formaldehyde; Water; Methanol; Reactive distillation

1. Introduction Formaldehyde (CH2 O, FA) is one of the most important chemical intermediates. It is processed to a variety of products including technical polymers, resins and foams [1]. Due to its high reactivity, it is commonly used in aqueous solutions. These solutions also contain methanol, which stems from the formaldehyde production process and it is used as stabilizer to avoid solid precipitation. Typical technical formaldehyde solutions contain 0.350.45 g g1 formaldehyde and less than 0.02 g g1 methanol. In these solutions, formaldehyde is almost entirely chemically bound to the solvents in methylene glycol (HOCH2 OH, MG), poly(oxymethylene) glycols (H(OCH2 )n OH, MGn , n > 1), hemiformal (HOCH2 OCH3 , HF), and poly(oxymethylene)

hemiformals (H(OCH2 )n OCH3 , HFn , n > 1), which are formed in the following reactions: CH2 O + H2 O HO(CH2 O)H (I) HO(CH2 O)n H + H2 O (II) CH3 O(CH2 O)H (III)

HO(CH2 O)n1 H + HO(CH2 O)H (n 2) CH2 O + CH3 OH

CH3 O(CH2 O)n1 H + CH3 O(CH2 O)H CH3 O(CH2 O)n H + CH3 OH (n 2) (IV)

Corresponding author. Tel.: +49 711 685 6105; fax: +49 711 685 6140. E-mail address: hasse@itt.uni-stuttgart.de (H. Hasse).

These reactions always occur in aqueous and methanolic formaldehyde solutions and are explicitly taken into account in the model used in the present work. Under certain con-

0255-2701/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.cep.2003.09.011

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ditions additional reactions may occur, like the Cannizzaro reaction yielding formic acid or the formation of acetals like methylal. The formation of formic acid or acetals occurs only at high temperatures in alkaline or acidic solutions, respectively. For more information, see [2]. In formaldehyde distillations, these conditions are usually not given. The model presented here can be extended straightforwardly to include such reactions also. Whereas the formation of new species by reactions (I)(IV) is explicitly taken into account in the process model, in the presentation of its results the overall composition is used in this work. This allows a direct comparison with results from standard analysis (titration for formaldehyde and water, gas chromatography for methanol). The formation of the oligomers can only be monitored by NMR-spectroscopy [36]. The most important operation for separating formaldehyde containing mixtures is distillation. Due to the reactions (I)(IV), formaldehyde distillations are always reactive distillations. It should be kept in mind that distilling an aqueous methanolic formaldehyde solution is in fact a separation of a reactive system with about 20 reacting components present in appreciable amounts. Despite its technical importance, there are only very few reports in the literature on distillation of formaldehyde containing mixtures, most of which are over 20 years old [711]. Both experimental data and reports on modeling and simulation are scarce. The previously published experimental work only covers distillation in tray columns. The process models from the literature are meanwhile outdated as they do not properly take into account the reactions (I)(IV). A very recent work [12] is a modeling study, which does not include comparisons with experimental data. The present work closes the gap by presenting results from extensive experimental work on distillation of formaldehyde containing mixtures and a study on their modeling and simulation with a state-of-the-art equilibrium stage model. The equilibrium model is based on extensive vaporliquid and chemical equilibrium data. It takes the chemical reactions (I)(IV) explicitly into account in the liquid phase. In the gas phase, it is sufcient to consider only reactions (I) and (III)

as the vapor pressures of the higher oligomers are low. The gas phase is treated as a mixture of ideal gases, whereas in the liquid phase non-idealities are taken into account using the UNIFAC method. For more details, see [13,16,18]. Distillation process models rely on the accurate description of the thermophysical properties of the mixtures which are separated. Modern thermophysical models of formaldehyde containing mixtures explicitly take into account both the reactions (I)(IV) as well as non-idealities in the liquid phase [1319]. In the present work, the latest model developed in the group Maurer [18] is used, which is based on experience and extensive experimental data from 15 years of research. The quality of the representation of vaporliquid equilibria with that model is good and compares favorably to that typically obtained for well-studied non-reacting systems. The process model used in the present work is an equilibrium stage model. It is based on the assumption that both chemical and physical equilibrium are reached on each stage. As values for NTSM are taken from the internals suppliers data sheets, the process model is completely predictive. It is known that the kinetics of reactions (I)(IV) may inuence distillation processes [20]. It is, however, not in the scope of the present work to include reaction kinetic in the process model. The equilibrium model presented here is a prerequisite to such an extension. For that extension a thermodynamically consistent reaction kinetic model is needed, which has become available only very recently but is not yet tested for the ternary mixtures formaldehydewatermethanol [21]. This will be the aim of future work. It should be noted that previously published process models for formaldehyde distillation [811] either neglect all oligomerization reactions (II) and (IV) or consider only short-chain oligomers, so that an extension to include reaction kinetic effects is not possible in a meaningful way. To be able to test the model, laboratory experiments were carried out in a 50 mm diameter column equipped with 3.5 m Montz A3-500 structured packing. Two types of separations were studied: (a) removal of methanol, for which the bottom product is formaldehydewater, and (b) removal of formaldehyde, for which the bottom product is pure water (cf. Fig. 1).

Fig. 1. Two types of technically important formaldehyde distillations.

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of dew and bubble lines, especially with the prediction of azeotropic points [22]. Instead of touching at the azeotropic point, the dew and bubble line show unphysical behavior with two points of intersection. For a more detailed discussion and an example, see [22]. The model used here is free from such aws. 3. Reactive distillation lines Distillation lines are important tools for conceptual process design and were up to now not available for formaldehyde containing systems. Therefore, based on the physico-chemical vaporliquid equilibrium model described in the previous section distillation lines for the system formaldehydewatermethanol were calculated in the present work. The result for 1 bar in overall concentrations is shown in Fig. 3, which also contains information on the boiling temperatures. Fig. 3 can be considered as a reactive distillation diagram for a complex system with more than 20 components represented in overall concentrations. In calculating that diagram the assumption of chemical equilibrium is used. There is a low-boiling azeotrope in the binary system formaldehydewater and a distillation boundary running from that azeotrope to the pure methanol node, which separates the diagram into two distillation elds. The experiments from the present work were carried out in both distillation elds. The separations of the type methanol removal were carried out in the upper distillation eld, those of the type formaldehyde removal in the lower distillation eld (cf. Fig. 1). At high formaldehyde concentrations, solid precipitate occurs which has to be avoided. The solidliquid equilibrium line in Fig. 3 is only qualitative. 4. Experiments The set-up used for the reactive distillation experiments which were carried out at BASF, Ludwigshafen, is shown in Fig. 4. A 50 mm diameter laboratory column equipped with 3.5 m structured packing (Montz A3-500, specic surface area 500 m2 m3 ) was used. The internals were divided in seven packing sections with sampling valves and temperature measurements below all sections. Concentrations and temperatures were also measured in the feed, bottom product and distillate. For all experiments, the feed location was above the fourth packing segment. The column was equipped with a total condenser, an electrically heated thermosyphon reboiler and a protection heating to ensure adiabatic operation. The distillate ow rate and the reboiler heat duty were set. A stable steady-state was typically observed after 2 h. Measurements were made after at least 2 h of steady-state operation. The sodium sulte method [2] was applied for the determination of the overall formaldehyde content in the samples. The KarlFischer titration [23] was used for analysing the overall water content. For that titration, the solution was

Fig. 2. Vaporliquid equilibrium in the system formaldehydewater methanol.

Reux ratio, pressure, and the feed composition were systematically varied.

2. Thermophysical properties The uid property model for formaldehyde containing mixtures on which the simulations of the present work are based was developed by Albert et al. [18]. The model of Albert et al. [18] takes into account chemical reactions in both phases and physical interactions between all species in the liquid phase. The vapor phase is described as an ideal mixture of formaldehyde, water, methanol, methylene glycol and hemiformal. The vapor pressures of higher oligomers are assumed to be negligible. Fig. 2 depicts that model. The vaporliquid equilibrium is calculated using the extended form of Raoults law, with activity coefcients from the UNIFAC group contribution method. More details and model parameters are given in [18]. Case studies carried out in the frame of the present work showed that it is sufcient to consider only poly(oxymethylene) glycols and -hemiformals with up to 10 formaldehyde segments if the overall formaldehyde concentration does not exceed 0.45 g g1 (the amount of the oligomers with higher chain length is small under that condition). Hence, for all simulations 10 reactions leading to MGMG10 as well as 10 reactions leading to HFHF10 were considered. Besides the very good prediction of experimental vaporliquid equilibria, an additional advantage of the model used here is the thermodynamic consistency of the description of chemical and physical equilibria. In all previously published models on distillation of formaldehyde containing mixtures pseudo chemical equilibrium constants, which are formulated with mole fractions and not with activities, were used. This procedure results in an inconsistent description of chemical and vaporliquid equilibria. With such inconsistent models, problems can arise with the calculation

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Fig. 3. Distillation lines in the system formaldehydewatermethanol at p = 1 bar.

thermostated to 50 C as elevated temperatures favor the decomposition of the poly(oxymethylene) glycols, which release water. For the determination of the overall methanol concentration gas chromatography was used with a SPB1 capillary column from Supelco. The relative error for each of the three methods is typically below 2%. The sum of the overall mass fractions of formaldehyde, water and methanol as determined by those methods was in most cases between 0.98 and 1.02 g g1 . Twenty-one distillation experiments were carried outgrouped into two series: experiments of the type methanol removal in the upper distillation eld and experiments of the type formaldehyde removal in the lower distillation eld (cf. also Figs. 1 and 3). In both series, the experimental work program was structured around a base case. Only one parameter compared to that base case was varied. The varied parameters were reux, overall ow rate, the pressure and the feed composition. The feed compositions cover a wide range in each distillation eld. An overview is given in Tables 1 and 2.

Table 1 Overview of the distillation experiments of the type methanol removal Number 1 2 3 4 5 6 7 8 9 10 Varied parameter Base case Feed ow rate Feed ow rate Reux Reux Pressure Pressure Feed concentration methanol Feed concentration methanol Feed concentration methanol Change compared to base case Decrease Increase Decrease Increase Decrease Further decrease Increase Further increase Further increase

Table 2 Overview of the distillation experiments of the type formaldehyde removal Number 11 12 13 14 15 16 17 18 19 20 21 Varied parameter Base case Feed ow rate Feed ow rate Reux Reux Pressure Pressure Feed concentration methanol Feed concentration methanol Feed concentration methanol Feed concentration methanol Change compared to base case Decrease Increase Decrease Increase Decrease Further decrease Increase Further increase Further increase Further increase

5. Comparison model-experiment Only some typical results from the experimental study are presented here together with their prediction by the equilibrium stage process model described above. In the simulations, the feed ow rate and the column pressure as well as the reux and distillate ow rate were specied according to the experimental numbers. The values for NTSM were taken from the internals supplier Montz. The F-factors in the experiments

are in the range in which a NTSM value of 6 m1 can be assumed. It should be noted that the results for the concentration and temperature proles from these simulations are entirely predictive.

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Fig. 4. Laboratory distillation column.

5.1. Methanol removal Fig. 5 shows the results for the base case experiment 1. The predicted proles of experiment 1 are in qualitative agreement with the experimental data. Quantitative agreement is fair at a rst glance. Deviations, however, occur in the predictions of the small number for the methanol concentration in the bottom product, for which the simulation gives results which are too low. The relative error is about 60%. Furthermore, the experimental value for the formaldehyde concentration in the top product is larger than the predicted value. These ndings are typical for all simulations carried out for the separations of the type methanol removal. The deviations can be interpreted as a result of the neglection of reaction kinetic effects. Due to the comparatively slow oligomeriza-

tion reactions, methanol bound in the poly(oxymethylene) hemiformals is not readily released in the stripping section. This explains why the experimental methanol concentration in the bottom product is higher than the predicted one. Also the difculty of removing formaldehyde in the rectifying section can be understood as resulting from a chemically limited process, in this case an absorption. The reactions in the liquid phase are too slow for binding formaldehyde from the gas phase in the oligomers up to the equilibrium concentration. Therefore, formaldehyde is only poorly absorbed and the measured formaldehyde concentration in the rectifying section is larger than that predicted by the equilibrium model. Fig. 6 shows the predicted proles for experiment 10 together with the experimental data. In this experiment, the methanol concentration in the feed was very large. The feed

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Fig. 5. Experimental and predicted concentration proles of experiment 1 (base case and methanol removal). Symbols: experimental data (open: column, lled: feed), lines: prediction.

location was not optimal, as can be seen from Fig. 6. The agreement of the prediction with the experimental data is very good for that experiment. This is probably due to the fact that the separation capacity installed in the column was very large compared to the fairly simple separation task in that experiment (cf. proles in Fig. 6). 5.2. Formaldehyde removal Fig. 7 shows results for the base case experiment of the series in which separations of the type formaldehyde removal were studied (experiment 11). It can be seen that only the

concentration prole for methanol and the composition of the top product are correctly predicted. The concentrations of formaldehyde observed in the experiments are higher than the predictions. Accordingly, the predicted water concentrations are too high. The results for the other experiments of the type formaldehyde removal are similar. Also these deviations can be understood as a consequence of reaction kinetic effects. The slow oligomerization reactions keep formaldehyde bound in heavy boiling products in reality, whereas the equilibrium model predicts an easy release. The variation of the reux has an important inuence on the column performance. By decreasing the reux ratio, the

Fig. 6. Experimental and predicted concentration proles of experiment 10 (methanol removal). Symbols: experimental data (open: column, lled: feed), lines: prediction.

Fig. 7. Experimental and predicted concentration proles of experiment 11 (base case and formaldehyde removal). Symbols: experimental data (open: column, lled: feed), lines: prediction.

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ferent NTSM values are observed for aqueous and organic systems, respectively. The result of this t is a NTSM value in the rectifying section of 3.33 m1 and in the stripping section of only 1 m1 , which is much lower than the suppliers value of 6 m1 . This shows that tting NTSM values is not the method of choice to obtain reliable process simulations for formaldehyde distillations. It is only an empirical means to compensate reaction kinetic effects, which, however, should be taken into account explicitly. The aws of this empirical procedure become evident when it is applied to the simulations of the type methanol removal, where even tting NTSM values does not give satisfactory results.

6. Conclusion Laboratory-scale formaldehyde distillations were carried out in a 50 mm column equipped with 3.5 m of Montz A3500. The inuence of different operating parameters (feed concentration, pressure, overall ow rates and reux) were studied. The results are compared to predictions based on an equilibrium stage model. For describing the properties of the complex reacting multicomponent mixtures studied in the present work, a thermodynamically consistent physicochemical model is used, which was taken from the literature. With NTSM values taken from the internals supplier, the distillation process model is entirely predictive. The comparison with the new experimental data shows that such equilibrium stage models work only in some cases for formaldehyde distillations. Deviations result from reaction kinetic effects. Adjusting NTSM values is no way to cope with that problem. Reaction kinetics have to be explicitly taken into account in the process simulation. This is the aim of current work of the authors.

Fig. 8. Experimental and predicted concentration proles of experiment 14 (formaldehyde removal). Symbols: experimental data (open: column, lled: feed), lines: prediction.

Fig. 9. Experimental concentration proles of experiment 14 (formaldehyde removal) compared to a simulation with tted NTSM numbers. Symbols: experimental data (open: column, lled: feed), lines: prediction.

Acknowledgements The authors would like to thank Harald B ader and J urgen Brauch from BASF and David Oberle from University of Stuttgart for their contributions.

internal ows in the column are reduced, the residence time on the stages increases, so that reaction kinetic effects in the column become less important. Fig. 8 shows results of experiment 14, which was carried out with a decreased reux ratio. The predicted column prole is in better agreement with the experimental data than in the base case experiment 11. Of course, the simulation results can be improved by adjusting the NTSM value. The drawback of this procedure is that the simulations are no longer predictive. Fig. 9 shows the simulated and measured concentration proles for experiment 14 which result when the NTSM value is tted to the experimental data. Different numbers of NTSM for the rectifying and stripping section were used. As the mixture in stripping section is predominantly aqueous, whereas in the rectifying section it contains large amounts of methanol, this could be justied by the experience that in many cases dif-

Appendix A. Nomenclature

formaldehyde hemiformal poly(oxymethylene) hemiformals with n formaldehyde segments ME index for methanol MEOH methanol MG methylene glycol MGn poly(oxymethylene) glycol with n formaldehyde segments NTSM number of theoretical stages per meter

FA HF HFn

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W x i

water overall mass fraction of component i

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