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Chemical Engineering and Processing 44 (2005) 687–694 Distillation of formaldehyde containing mixtures: laboratory
Chemical Engineering and Processing 44 (2005) 687–694 Distillation of formaldehyde containing mixtures: laboratory

Chemical Engineering and Processing 44 (2005) 687–694

Chemical Engineering and Processing 44 (2005) 687–694 Distillation of formaldehyde containing mixtures: laboratory

Distillation of formaldehyde containing mixtures: laboratory experiments, equilibrium stage modeling and simulation

Michael Ott a , Hartmut Schoenmakers b , Hans Hasse a,

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 formaldehyde–water, and (b) removal of formaldehyde, for which the bottom product is pure water. Reflux ratio, pressure, and the feed composition were systematically varied. A physico-chemical model of vapor–liquid 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 efficiencies from the internals supplier show good agreement only in some cases and indicate that the influence of reaction kinetics has to be taken explicitly into account. Reactive distillation line diagrams for the ternary system formaldehyde–water–methanol are presented for the first time. © 2004 Elsevier B.V. All rights reserved.

Keywords: Distillation; Formaldehyde; Water; Methanol; Reactive distillation

1. Introduction

Formaldehyde (CH 2 O, FA) is one of the most impor- tant 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 aque- ous 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 0.35–0.45 g g 1 formaldehyde and less than 0.02 g g 1 methanol. In these so- lutions, formaldehyde is almost entirely chemically bound to the solvents in methylene glycol (HOCH 2 OH, MG), poly(oxymethylene) glycols (H(OCH 2 ) n OH, MG n , n > 1), hemiformal (HOCH 2 OCH 3 , HF), and poly(oxymethylene)

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

0255-2701/$ – see front matter © 2004 Elsevier B.V. All rights reserved.

doi:10.1016/j.cep.2003.09.011

hemiformals (H(OCH 2 ) n OCH 3 , HF n , n > 1), which are formed in the following reactions:

(I)

CH 2 O + H 2 O HO(CH 2 O)H

HO(CH 2 O) n1 H + HO(CH 2 O)H HO(CH 2 O) n H + H 2 O

(n 2)

(II)

CH 2 O + CH 3 OH CH 3 O(CH 2 O)H

(III)

CH 3 O(CH 2 O) n1 H + CH 3 O(CH 2 O)H

CH 3 O(CH 2 O) n H + CH 3 OH

(n 2)

(IV)

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-

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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, respec- tively. For more information, see [2]. In formaldehyde dis- tillations, 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 re- sults from standard analysis (titration for formaldehyde and water, gas chromatography for methanol). The formation of the oligomers can only be monitored by NMR-spectroscopy

[3–6].

The most important operation for separating formalde- hyde containing mixtures is distillation. Due to the reactions (I)–(IV), formaldehyde distillations are always reactive dis- tillations. 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 [7–11]. Both experimental data and reports on mod- eling and simulation are scarce. The previously published experimental work only covers distillation in tray columns. The process models from the literature are meanwhile out- dated 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 ex- tensive experimental work on distillation of formaldehyde containing mixtures and a study on their modeling and sim- ulation with a state-of-the-art equilibrium stage model. The equilibrium model is based on extensive vapor–liquid and chemical equilibrium data. It takes the chemical reactions (I)–(IV) explicitly into account in the liquid phase. In the gas phase, it is sufficient 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 descrip- tion of the thermophysical properties of the mixtures which are separated. Modern thermophysical models of formalde- hyde containing mixtures explicitly take into account both the reactions (I)–(IV) as well as non-idealities in the liquid phase [13–19]. In the present work, the latest model devel- oped 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 vapor–liquid 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 equi- librium 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 supplier’s data sheets, the process model is completely predictive. It is known that the kinetics of reactions (I)–(IV) may influence 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 prereq- uisite to such an extension. For that extension a thermody- namically consistent reaction kinetic model is needed, which has become available only very recently but is not yet tested for the ternary mixtures formaldehyde–water–methanol [21]. This will be the aim of future work. It should be noted that previously published process models for formaldehyde dis- tillation [8–11] 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 formaldehyde–water, and (b) removal of formalde- hyde, for which the bottom product is pure water (cf. Fig. 1).

for which the bottom product is pure water (cf. Fig. 1 ). Fig. 1. Two types

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

M. Ott et al. / Chemical Engineering and Processing 44 (2005) 687–694

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Chemical Engineering and Processing 44 (2005) 687–694 689 Fig. 2. Vapor–liquid equilibrium in the system

Fig. 2. Vapor–liquid equilibrium in the system formaldehyde–water– methanol.

Reflux ratio, pressure, and the feed composition were sys- tematically varied.

2. Thermophysical properties

The fluid 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 vapor–liquid equilibrium is calculated using the extended form of Raoult’s law, with activity coefficients from the UNI- FAC group contribution method. More details and model pa- rameters are given in [18]. Case studies carried out in the frame of the present work showed that it is sufficient to consider only poly(oxymethylene) glycols and -hemiformals with up to 10 formaldehyde segments if the overall formalde- hyde concentration does not exceed 0.45 g g 1 (the amount of the oligomers with higher chain length is small under that condition). Hence, for all simulations 10 reactions leading to MG–MG 10 as well as 10 reactions leading to HF–HF 10 were considered. Besides the very good prediction of experimental vapor–liquid equilibria, an additional advantage of the model used here is the thermodynamic consistency of the descrip- tion of chemical and physical equilibria. In all previously published models on distillation of formaldehyde contain- ing mixtures pseudo chemical equilibrium constants, which are formulated with mole fractions and not with activities, were used. This procedure results in an inconsistent descrip- tion of chemical and vapor–liquid equilibria. With such in- consistent models, problems can arise with the calculation

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 flaws.

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 vapor–liquid equilibrium model de- scribed in the previous section distillation lines for the sys- tem formaldehyde–water–methanol 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 calcu- lating that diagram the assumption of chemical equilibrium is used. There is a low-boiling azeotrope in the binary sys- tem formaldehyde–water and a distillation boundary running from that azeotrope to the pure methanol node, which sepa- rates the diagram into two distillation fields. The experiments from the present work were carried out in both distillation fields. The separations of the type ‘methanol removal’ were carried out in the upper distillation field, those of the type ‘formaldehyde removal’ in the lower distillation field (cf. Fig. 1). At high formaldehyde concentrations, solid precipitate occurs which has to be avoided. The solid–liquid 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, specific sur- face area 500 m 2 m 3 ) was used. The internals were divided in seven packing sections with sampling valves and temper- ature measurements below all sections. Concentrations and temperatures were also measured in the feed, bottom prod- uct 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 opera- tion. The distillate flow 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 sulfite method [2] was applied for the de- termination of the overall formaldehyde content in the sam- ples. The Karl–Fischer titration [23] was used for analysing the overall water content. For that titration, the solution was

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M. Ott et al. / Chemical Engineering and Processing 44 (2005) 687–694

/ Chemical Engineering and Processing 44 (2005) 687–694 Fig. 3. Distillation lines in the system

Fig. 3. Distillation lines in the system formaldehyde–water–methanol at p = 1 bar.

thermostated to 50 C as elevated temperatures favor the de- composition of the poly(oxymethylene) glycols, which re- lease 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 g 1 . Twenty-one distillation experiments were carried out- grouped into two series: experiments of the type ‘methanol removal’ in the upper distillation field and experiments of the type ‘formaldehyde removal’ in the lower distillation field (cf. also Figs. 1 and 3). In both series, the experimental work pro- gram was structured around a base case. Only one parameter compared to that base case was varied. The varied parame- ters were reflux, overall flow rate, the pressure and the feed composition. The feed compositions cover a wide range in each distillation field. An overview is given in Tables 1 and 2.

5. Comparison model-experiment

Only some typical results from the experimental study are presented here together with their prediction by the equilib- rium stage process model described above. In the simulations, the feed flow rate and the column pressure as well as the reflux and distillate flow rate were specified according to the exper- imental numbers. The values for NTSM were taken from the internals supplier Montz. The F-factors in the experiments

Table 1 Overview of the distillation experiments of the type ‘methanol removal’

Number

Varied parameter

Change compared to base case

1

Base case

2

Feed flow rate

Decrease

3

Feed flow rate

Increase

4

Reflux

Decrease

5

Reflux

Increase

6

Pressure

Decrease

7

Pressure

Further decrease

8

Feed concentration methanol

Increase

9

Feed concentration methanol

Further increase

10

Feed concentration methanol

Further increase

Table 2 Overview of the distillation experiments of the type ‘formaldehyde removal’

Number

Varied parameter

Change compared to base case

11

Base case

12

Feed flow rate

Decrease

13

Feed flow rate

Increase

14

Reflux

Decrease

15

Reflux

Increase

16

Pressure

Decrease

17

Pressure

Further decrease

18

Feed concentration methanol

Increase

19

Feed concentration methanol

Further increase

20

Feed concentration methanol

Further increase

21

Feed concentration methanol

Further increase

are in the range in which a NTSM value of 6 m 1 can be assumed. It should be noted that the results for the concen- tration and temperature profiles from these simulations are entirely predictive.

M. Ott et al. / Chemical Engineering and Processing 44 (2005) 687–694

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Chemical Engineering and Processing 44 (2005) 687–694 691 Fig. 4. Laboratory distillation column. 5.1. Methanol

Fig. 4. Laboratory distillation column.

5.1. Methanol removal

Fig. 5 shows the results for the base case experiment 1. The predicted profiles of experiment 1 are in qualitative agree- ment with the experimental data. Quantitative agreement is fair at a first glance. Deviations, however, occur in the pre- dictions 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%. Further- more, the experimental value for the formaldehyde concen- tration in the top product is larger than the predicted value. These findings are typical for all simulations carried out for the separations of the type ‘methanol removal’. The devia- tions 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 difficulty of removing formaldehyde in the rectifying sec- tion can be understood as resulting from a chemically limited process, in this case an absorption. The reactions in the liq- uid phase are too slow for binding formaldehyde from the gas phase in the oligomers up to the equilibrium concentra- tion. 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 profiles for experiment 10 to- gether with the experimental data. In this experiment, the methanol concentration in the feed was very large. The feed

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/ Chemical Engineering and Processing 44 (2005) 687–694 Fig. 5. Experimental and predicted concentration profiles

Fig. 5. Experimental and predicted concentration profiles of experiment 1 (base case and methanol removal). Symbols: experimental data (open: column, filled:

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. profiles in Fig. 6).

5.2. Formaldehyde removal

Fig. 7 shows results for the base case experiment of the se- ries in which separations of the type ‘formaldehyde removal’ were studied (experiment 11). It can be seen that only the

were studied (experiment 11). It can be seen that only the Fig. 6. Experimental and predicted

Fig. 6. Experimental and predicted concentration profiles of experiment 10 (methanol removal). Symbols: experimental data (open: column, filled:

feed), lines: prediction.

concentration profile 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 concentra- tions are too high. The results for the other experiments of the type ‘formaldehyde removal’ are similar. Also these devia- tions can be understood as a consequence of reaction kinetic effects. The slow oligomerization reactions keep formalde- hyde bound in heavy boiling products in reality, whereas the equilibrium model predicts an easy release. The variation of the reflux has an important influence on the column performance. By decreasing the reflux ratio, the

the column performance. By decreasing the reflux ratio, the Fig. 7. Experimental and predicted concentration profiles

Fig. 7. Experimental and predicted concentration profiles of experiment 11 (base case and formaldehyde removal). Symbols: experimental data (open:

column, filled: feed), lines: prediction.

M. Ott et al. / Chemical Engineering and Processing 44 (2005) 687–694

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Chemical Engineering and Processing 44 (2005) 687–694 693 Fig. 8. Experimental and predicted concentration profiles

Fig. 8. Experimental and predicted concentration profiles of experiment 14 (formaldehyde removal). Symbols: experimental data (open: column, filled:

feed), lines: prediction.

data (open: column, filled: feed), lines: prediction. Fig. 9. Experimental concentration profiles of experiment

Fig. 9. Experimental concentration profiles of experiment 14 (formaldehyde removal) compared to a simulation with fitted NTSM numbers. Symbols:

experimental data (open: column, filled: feed), lines: prediction.

internal flows 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 reflux ratio. The predicted column profile is in better agreement with the experimental data than in the base case experiment 11. Of course, the simulation results can be improved by ad- justing the NTSM value. The drawback of this procedure is that the simulations are no longer predictive. Fig. 9 shows the simulated and measured concentration profiles for exper- iment 14 which result when the NTSM value is fitted to the experimental data. Different numbers of NTSM for the rec- tifying 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 justified by the experience that in many cases dif-

ferent NTSM values are observed for aqueous and organic systems, respectively. The result of this fit is a NTSM value in the rectifying section of 3.33 m 1 and in the stripping sec- tion of only 1 m 1 , which is much lower than the supplier’s value of 6 m 1 . This shows that fitting 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 flaws of this empirical procedure become evident when it is applied to the simu- lations of the type ‘methanol removal’, where even fitting 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 A3- 500. The influence of different operating parameters (feed concentration, pressure, overall flow rates and reflux) 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 physico- chemical model is used, which was taken from the literature. With NTSM values taken from the internals supplier, the dis- tillation 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 dis- tillations. Deviations result from reaction kinetic effects. Ad- justing 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.

Acknowledgements

The authors would like to thank Harald Bader¨ and Jurgen¨ Brauch from BASF and David Oberle from University of Stuttgart for their contributions.

Appendix A. Nomenclature

FA formaldehyde HF hemiformal

HF n poly(oxymethylene) hemiformals with n formalde- hyde segments ME index for methanol MEOH methanol

MG

MG n poly(oxymethylene) glycol with n formaldehyde segments NTSM number of theoretical stages per meter

methylene glycol

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M. Ott et al. / Chemical Engineering and Processing 44 (2005) 687–694

W

water

x˜ i

overall mass fraction of component i

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