You are on page 1of 25

Distillation of Formaldehyde Containing Mixtures: Laboratory Experiments, Equilibrium Stage Modeling and Simulation

Michael Ott1, Hartmut Schoenmakers2, Hans Hasse1*

University of Stuttgart, Institute of Thermodynamics and Thermal Process Engineering, BASF AG, Global Process Engineering, Ludwigshafen, Germany

Stuttgart, Germany
2

* Corresponding author Prof. Dr. H. Hasse, University of Stuttgart, Institute of Thermodynamics and Thermal Process Engineering, D-70550 Stuttgart, Germany, Phone: ##49/711/685-6105, Fax: ##49/711/685-6140, E-mail: hasse@itt.uni-stuttgart.de

Ott et al.: Formaldehyde Distillation

Page 2

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. Distillations 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.

Ott et al.: Formaldehyde Distillation

Page 3

1. Introduction

Formaldehyde (CH2O, 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 g-1 formaldehyde and less than 0.02 g g-1 methanol. In these solutions, formaldehyde is almost entirely chemically bound to the solvents in methylene glycol (HOCH2OH, MG), poly(oxymethylene) glycols (H(OCH2)nOH, MGn, n > 1), hemiformal (HOCH2OCH3, HF), and poly(oxymethylene) hemiformals (H(OCH2)nOCH3, HFn, n > 1), which are formed in the following reactions:

CH 2 O + H 2 O

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

(I) (II)
(III) CH 3O(CH 2 O) n H + CH 3OH (n 2) (IV)

HO(CH 2 O)n-1H + HO(CH 2 O)H


CH 2 O + CH 3OH

CH 3O(CH 2 O)H

CH 3O(CH 2O) n-1H + CH 3O(CH 2O)H

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 conditions 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, respectively, occurs only at high temperatures in alkaline or, respectively, acidic solutions. For more information, see [2]. In formaldehyde distillations these conditions are usually not given. The model presented here can be extended straightforwardly to include also such reactions.

Ott et al.: Formaldehyde Distillation

Page 4

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 NMRspectroscopy [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 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 only consider 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].

Ott et al.: Formaldehyde Distillation

Page 5

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 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 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 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 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 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 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 formaldehyde water, and b) removal of formaldehyde, for which the bottom product is pure water (cf. Figure 1). Reflux ratio, pressure, and the feed composition were systematically varied.

Ott et al.: Formaldehyde Distillation

Page 6

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. Figure 2 depicts that model. The vapor liquid equilibrium is calculated using the extended form of Raoults Law, with activity coefficients 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 sufficient 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 g-1 (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 vapor-liquid 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 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.

Ott et al.: Formaldehyde Distillation

Page 7

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 described in the previous section distillation lines for the system formaldehyde water methanol were calculated in the present work. The result for 1 bar in overall concentrations is shown in Figure 3, which also contains information on the boiling temperatures. Figure 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 formaldehyde water and a distillation boundary running from that azeotrope to the pure methanol node, which separates 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. Figure 1). At high formaldehyde concentrations, solid precipitate occurs which has to be avoided. The solid liquid equilibrium line in Figure 3 is only qualitative.

Ott et al.: Formaldehyde Distillation

Page 8

4. Experiments

The set-up used for the reactive distillation experiments which were carried out at BASF, Ludwigshafen, is shown in Figure 4. A 50 mm diameter laboratory column equipped with 3.5 m structured packing (Montz A3-500, specific surface area 500 m/m) was used. The internals were divided in 7 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 4th 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 flow rate and the reboiler heat duty were set. A stable steady state was typically observed after 2 hours. Measurements were made after at least 2 hours of steady state operation.

The sodium sulfite method [2] was applied for the determination of the overall formaldehyde content in the samples. The Karl Fischer Titration [23] was used for analyzing the overall water content. For that titration, the solution was thermostated to 50C 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 g-1.

21 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 Figures 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

Ott et al.: Formaldehyde Distillation

Page 9

varied. The varied parameters 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 equilibrium 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 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 m-1 can be assumed. It should be noted that the results for the concentration and temperature profiles from these simulations are entirely predictive.

a) Methanol Removal Figure 5 shows the results for the base case experiment 1.The predicted profiles of experiment 1 are in qualitative agreement with the experimental data. Quantitative agreement is fair at a first 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 findings 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 oligomerization reactions,

Ott et al.: Formaldehyde Distillation

Page 10

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 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.

Figure 6 shows the predicted profiles for experiment 10 together with the experimental data. In this experiment the methanol concentration in the feed was very large. The feed location was not optimal, as can be seen from Figure 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 Figure 6).

b) Formaldehyde Removal Figure 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 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 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.

Ott et al.: Formaldehyde Distillation

Page 11

The variation of the reflux has an important influence on the column performance. By decreasing the reflux ratio the 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. Figure 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 adjusting the NTSM value. The drawback of this procedure is that the simulations are no longer predictive. Figure 9 shows the simulated and measured concentration profiles for experiment 14 which result when the NTSM value is fitted 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 justified by the experience, that in many cases different 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 section 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 simulations of the type methanol removal, where even fitting NTSM values does not give satisfactory results.

Ott et al.: Formaldehyde Distillation

Page 12

6. Conclusion

Laboratory scale formaldehyde distillations were carried out in a 50 mm column equipped with 3.5 meters of Montz A3-500. The influence of different operating parameters (feed concentration, pressure, overall flow rates, reflux) was 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 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.

Ackowledgement

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

Appendix A: Nomenclature

FA HF

formaldehyde hemiformal

Ott et al.: Formaldehyde Distillation

Page 13

HFn ME MEOH MG MGn NTSM W


%i x

poly(oxymethylene) hemiformals with n formaldehyde segments index for methanol methanol methylene glycol poly(oxymethylene) glycol with n formaldehyde segments number of theoretical stages per meter water overall mass fraction of component i

References

[1] [2] [3]

Ullmanns Encyclopedia of Industrial Chemistry. Wiley-VCH, Weinheim (2002). J. F. Walker, Formaldehyde. ACS Monograph, 3rd ed., Reinhold, New York (1964). M. Maiwald, H. H. Fischer, M. Ott, R. Peschla, C. Kuhnert, C. G. Kreiter, G. Maurer and H. Hasse, Quantitative NMR Spectroscopy of Complex Liquid Mixtures: Methods and Results for Chemical Equilibria in Formaldehyde-Water-Methanol at Temperatures up to 383 K. Ind.
Eng. Chem. Res., 42 (2003), pp. 259266.

[4]

I. Hahnenstein, H. Hasse, C. G. Kreiter and G. Maurer, 1H and 13C NMR Spectroscopic Study of Chemical Equilibria in Solutions of Formaldehyde in Water, Deuterium Oxide, and Methanol, Ind. Eng. Chem. Res. 33 (1994), pp. 10221029.

[5]

A. L. Balashov, S. M. Danov, A. Yu. Golovkin, V. L. Krasnov, A. N. Ponomarev and I. A. Borisova, Equilibrium Mixture of Polyoxymethylene Glycols in Concentrated Aqueous Formaldehyde Solutions. Russ. J. Appl. Chem. 69 (1996), pp. 190192.

Ott et al.: Formaldehyde Distillation

Page 14

[6]

A. L. Balashov, S. M. Danov, V. L. Krasnov, A. Yu. Chernov and T. A. Ryabova, Association of Formaldehyde in Aqueous Alcoholic Systems. Russ. J. Gen. Chem. 72 (2002), pp. 744747.

[7]

E. L. Piret and M. W. Hall, Distillation Principles of Formaldehyde Solutions, Liquid-Vapor Equilibrium and Effect of Partial Condensation. Ind. Eng. Chem. 40 (1949), pp. 661672.

[8]

B. Olsson and S.-G. Svensson, Formalindestillation. I III (1972), D. Eng. Thesis, Lund Institute of Technology.

[9]

B. Olsson and S.-G. Svensson, Formalin Distillation: Vapour-Liquid Equilibria and Tray Efficiencies. Trans. Instn Chem. Engrs. 53 (1975), pp. 97105.

[10]

S. Dilfanian, Simultaneous Chemical Reaction and Distillation of Formaldehyde. PhD Thesis (1978), University of Aston in Birmingham, Birmingham.

[11]

B. Davies, J. D. Jenkins and S. Dilfanian, Distillation with Chemical Reaction The Distillation of Formaldehyde Solutions in a Sieve Plate Column. Inst. Chem. Eng. Symp. Ser.
56 (1979), pp. 4.2/654.2/79.

[12]

L.F. Zilnik and J. Golob, Analysis of Separation of Water Methanol Formaldehyde Mixture. Proceedings of the International Conference on Distillation and Absorption (2002), Baden-Baden, ISBN 3-931384-37-3, VDI Gesellschaft Verfahrenstechnik und Chemieingenieurwesen GVC, Dsseldorf.

[13]

G. Maurer, Vapor-Liquid Equilibrium of Formaldehyde- and Water-Containing MultiComponent Mixtures. AIChE J. 32 (1986), pp. 932948.

[14]

H. Hasse, Dampf-Flssigkeits-Gleichgewichte, Enthalpien und Reaktionskinetik in formaldehydhaltigen Mischungen. PhD Thesis (1990), Universitt Kaiserslautern, Kaiserslautern, Germany.

[15]

Y.-Q. Liu, H. Hasse and G. Maurer, Enthalpy Change on Vaporization of Aqueous and Methanolic Formaldehyde Solutions. AIChE J. 38 (1992), pp. 16931702.

Ott et al.: Formaldehyde Distillation

Page 15

[16]

M. Albert, Thermodynamische Eigenschaften formaldehydehaltiger Mischungen. PhD Thesis (1998), Universitt Kaiserslautern, Kaiserslautern, Germany.

[17]

M. Albert, B. C. Garcia, C. G. Kreiter and G. Maurer, Vapor-Liquid and Chemical Equilibria of Formaldehyde-Water Mixtures. AIChE J. 45 (1999), pp. 20242033.

[18]

M. Albert, B. C. Garcia, C. Kuhnert, R. Peschla and G. Maurer, Vapor-Liquid Equilibrium of Aqueous Solutions of Formaldehyde and Methanol. AIChE J. 46 (2000), pp. 16761687.

[19]

S. Brandani, V. Brandani and I. Tarquini, Vapor-Liquid Equilibrium of Formaldehyde Mixtures Containing Methanol. Ind. Eng. Chem. Res., 37 (1998), pp. 34853489.

[20]

I. Hahnenstein, M. Albert, H. Hasse, C. G. Kreiter and G. Maurer, NMR Spectroscopic and Densimetric Study of Reaction Kinetics of Formaldehyde Polymer Formation in Water, Deuterium Oxide, and Methanol. Ind. Eng. Chem. Res., 34 (1995), pp. 440450.

[21]

M. Ott, H. H. Fischer, M. Maiwald, K. Albert and H. Hasse, Kinetics of Oligomerization Reactions in Formaldehyde Solutions: NMR Experiments up to 373 K and Thermodynamically Consistent Model. Chem. Eng. Proc., submitted paper

[22]

H. Hasse, Thermodynamics of Reactive Separations, K. Sundmacher and A. Kienle, Reactive Distillation. Wiley-VCH, Weinheim (2003), pp. 6596.

[23]

E. Scholz, Karl-Fischer-Titration. Methoden zur Wasserbestimmung. Springer (1984)

Ott et al.: Formaldehyde Distillation

Page 16

List of Figures Figure 1: Two types of technically important formaldehyde distillations. Figure 2: Vapor - liquid equilibrium in the system formaldehyde - water - methanol. Figure 3: Distillation lines in the system formaldehyde water methanol at p = 1 bar. Figure 4: Laboratory distillation column. Figure 5: Experimental and predicted concentration profiles of experiment 1 (base case, methanol

removal). Symbols: experimental data (open: column, full: feed), lines: prediction.
Figure 6: Experimental and predicted concentration profiles of experiment 10 (methanol removal).

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


Figure 7: Experimental and predicted concentration profiles of experiment 11 (base case,

formaldehyde removal). Symbols: experimental data (open: column, full: feed), lines: prediction.
Figure 8: Experimental and predicted concentration profiles of experiment 14 (formaldehyde

removal). Symbols: experimental data (open: column, full: feed), lines: prediction.
Figure 9: Experimental concentration profiles of experiment 14 (formaldehyde removal) compared

to a simulation with fitted NTSM numbers. Symbols: experimental data (open: column, full: feed), lines: prediction.

Ott et al.: Formaldehyde Distillation

Page 17

Methanol Removal

Formaldehyde Removal

MEOH + (FA +W)

MEOH + FA +W

FA + W + MEOH

FA + W + MEOH

FA + W

Fig. 1

vapor

FA + W FA + MEOH FA W MEOH MG

MG HF HF

FA FA + W

MEOH

MG

HF

MG MG n + W HF HF n + MEOH

MG n-1 + MG FA + MEOH

HFn-1 + HF
liquid

Fig. 2

Ott et al.: Formaldehyde Distillation

Page 18

Solid precipitate

p = 1 bar

Low boiling azeotrope 97C

100C

65C

Fig. 3

Ott et al.: Formaldehyde Distillation


PIC

Page 19

Ambient pressure or vacuum


T

FI

LC

Distillate
WIC

PdI

Feed

WIC

LC

Electrical reboiler Bottom product


WI

Fig. 4

Ott et al.: Formaldehyde Distillation

Page 20

3.5 3 2.5

Methanol Formaldehyde Water

Packing height / m

2 1.5 1 0.5 0 0 0.1 0.2 0.3 0.4 0.5 0.6


1

0.7

0.8

0.9

Mass fraction / g g

Fig. 5

3.5 3 2.5

Methanol Formaldehyde Water

Packing height / m

2 1.5 1 0.5 0 0 0.1 0.2 0.3 0.4 0.5 0.6


1

0.7

0.8

0.9

Mass fraction / g g

Fig. 6

Ott et al.: Formaldehyde Distillation

Page 21

3.5 3 2.5

Methanol Formaldehyde Water

Packing height / m

2 1.5 1 0.5 0 0 0.1 0.2 0.3 0.4 0.5 0.6


1

0.7

0.8

0.9

Mass fraction / g g

Fig. 7

3.5 3 2.5

Methanol Formaldehyde Water

Packing height / m

2 1.5 1 0.5 0 0 0.1 0.2 0.3 0.4 0.5 0.6


1

0.7

0.8

0.9

Mass fraction / g g

Fig. 8

Ott et al.: Formaldehyde Distillation

Page 22

3.5 3 2.5

Methanol Formaldehyde Water

Packing height / m

2 1.5 1 0.5 0 0.5 1 0 0.1 0.2 0.3 0.4 0.5 0.6


1

0.7

0.8

0.9

Mass fraction / g g

Fig. 9

Ott et al.: Formaldehyde Distillation

Page 23

List of Tables

Table 1: Overview of the distillation experiments of the type "methanol removal". Table 2: Overview of the distillation experiments of the type "formaldehyde removal".

Ott et al.: Formaldehyde Distillation

Page 24

Tab. 1

Methanol removal

Number 1 2 3 4 5 6 7 8 9 10

Varied parameter base case feed flow rate feed flow rate reflux reflux 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

Ott et al.: Formaldehyde Distillation

Page 25

Tab. 2
Formaldehyde removal

Number 11 12 13 14 15 16 17 18 19 20 21

Varied parameter base case feed flow rate feed flow rate reflux reflux 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

You might also like