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Holger Becker1 Herbert Vogel1

1

Full Paper

Department of Chemistry, Ernst-Berl-Institute of Technical Chemistry and Macromolecular Science, TU Darmstadt, Darmstadt, Germany.

Phenothiazine as Stabilizer for Acrylic Acid

For the safe and trouble-free operation of a manufacturing plant and the safe storage of acrylic monomers a sufficiently effective polymerization inhibitor is necessary. As stabilizers different radical interceptors are used. Hydroquinone monomethyl ether (MeHQ) and phenothiazine (PTZ) are the standard stabilizers. In this paper, the decomposition kinetics of PTZ was investigated under process conditions. In acrylic acid a linear PTZ consumption was detectable under process conditions, whereby five different decomposition products were formed. The PTZ consumption was caused by thermal decomposition and by radical and oxidation reactions. With increasing temperature the portion of the total PTZ consumption caused by radical reactions decreased rapidly (68 % at 60 C 38 % at 90 C) and the part of the oxidation reactions of the inhibitor increased (27 % at 60 C 54 % at 90 C). Comparative investigations in air and nitrogen atmosphere resulted in different values for PTZ consumption and radical formation rates. Measurements of oxygen and PTZ consumption in air atmosphere showed a ratio of 2:1 mol mol1 (60 C) which increased with temperature up to 4:1 mol mol1 (90 C). The data showed that in acrylic acid stabilized with PTZ the oxygen consumption could not be totally prevented. This indicates that one part of the oxygen is consumed by the oxidation of PTZ while another part reacts directly with the primary radicals which are not trapped by the inhibitor. With the results of this work it is possible to optimize the PTZ stabilization of acrylic acid under process conditions in the presence and absence of oxygen.
Keywords: Acrylic monomers, Decomposition, Polymerization Received: February 6, 2006; revised: March 28, 2006; accepted: April 9, 2006 DOI: 10.1002/ceat.200600056

Introduction

Acrylic acid, the simplest unsaturated monocarbonic acid, is an intermediate produced on an industrial scale. This monomer is extremely reactive and easy to polymerize so that, during synthesis, storage, transport and reprocessing, many safety guidelines must be followed [1]. Acrylic acid is mainly used for the production of acrylic esters (53 %), superabsorber polymers (31 %) and washing agents (6 %). The rest is used for a wide range of special applications (10 %) [2]. During the production of acrylic acid the inadvertent polymerization in the chemical reprocessing via rectification is an important problem. The polymerization is caused by radicals formed by impurities, UV or cosmic radiation. The exothermal polymerization with a reaction enthalpy of 76 kJ mol1 re-

Correspondence: Dr.-Ing. H. Vogel (vogel@ct.chemie.tu-darmstadt.de), TU Darmstadt, Department of Chemistry, Ernst-Berl-Institute of Technical Chemistry and Macromolecular Science, Petersenstr. 20, D-64287 Darmstadt, Germany.

flects a significant security risk during the handling of this monomer. On the one hand, the liberation of reaction enthalpy can cause deflagrations and explosions and, on the other hand, the polymers can lead to blockages causing interruptions, higher costs and loss of production. Therefore, acrylic acid is produced in the presence of polymerization inhibitors (PTZ, MeHQ and/or oxygen) in different plant units [3]. Under production process conditions PTZ is used. It can react directly with primary radicals or with peroxide radicals formed during the reaction of primary radicals with molecular oxygen. The presence of oxygen is not essential for PTZ inhibition. In this work, the consumption of PTZ and molecular oxygen during the inhibition period was investigated. The consumption rates were measured in different solvents (acrylic acid, acetic acid) and under different atmospheres (air, nitrogen). By comparing the results obtained the portion of the different decomposition reactions of PTZ (radical, oxidative and thermal decomposition) can be calculated. With the consumption kinetics of PTZ and oxygen the start of polymerization can be predicted. In addition, a more precise dosage of PTZ is possible, which reduces the raw material costs for PTZ.

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O S + N H O S + N H ROOH N H O S + ROH ROOH N H O S + ROH

Chem. Eng. Technol. 2006, 29, No. 8, 931936

75 % (L L1) acetonitrile und 25 % (L L1) water (volume flow rate 0.5 mL min1). The injection volume of the auto injector was varied depending on the PTZ concentrations of the samples.

2.3

Chemicals and Equipment Used

Scheme 1.

In the absence of inhibitors the copolymerization (acrylic acid monomer + O2) and the normal polymerization (polymer + monomer) are opposing reactions [4]. If the oxygen concentration is high enough the primary radicals react with oxygen to peroxide radicals and a copolymer with alternating monomer/oxygen units is formed [57]. In the presence of PTZ the radical chain is interrupted by the direct reaction of primary or peroxide radicals with PTZ. Further PTZ consumption is caused by the oxidation with dissolved oxygen or by the reaction with peroxides formed [8] (see Scheme 1). In the investigated system oxygen, PTZ and the monomer were present at the beginning and during the reaction peroxides were formed. This means that all the above radical and oxidation reactions are possible and influence the inhibition period of acrylic acid.

The investigations were carried out with pure acrylic acid from BASF AG, Ludwigshafen, Germany. For the purification and elimination of the storage stabilizer the monomer was distilled and recrystallized three times. After the cleaning process PTZ was added to the unstabilized acrylic acid. The monomer was either directly used or stored at 20 C to avoid side reactions such as the formation of diacrylic acid. The chemicals and equipment used are listed in Tab. 1 and Tab. 2.

Table 1. Equipment and producers.

Equipment O2 Sensor (electrochemical) Pumps Producer Aero2-Mat 4125, Fa. Syland Scientific GmbH, Heppenheim, Germany PTFE-Minidosierer BF 411, (0...60 mL/min), Fa. Telab, Dosiertechnik & Handelsgesellschaft GmbH, Duisburg, Germany Airflow Memory AM-2, Fa. Airflow Lufttechnik GmbH, Rheinbach, Germany Julabo HC 5, Fa. Julabo Labortechnik GmbH, Seelbach, Germany MFC 5850 TR, N2 from 05 L/min, Fa. Brooks Instrument B. V., Veenendaal, The Netherlands HP 1090 Series L Liquid Chromatograph Varian Star 5.3

AD transducer

Thermostats

2
2.1

Experimental
Mass-Flow Controller

Measuring Devices
HPLC system HPLC software

The measurements were made in a modified experimental plant described in earlier works [4, 7]. Directly after the O2 measurements the sampling of acrylic acid was conducted and PTZ concentration was analyzed via HPLC. Furthermore, a continuous stirred tank reactor, described in [1], was used. To simulate the real conditions, all measurements were made without the addition of radical starters. The different oxygen partial pressures in the acrylic acid were directly adjusted in the feed tank by gassing the liquid monomer with a defined oxygen/nitrogen mixture.

Table 2. Chemicals used.

Chemical Purity Company

2.2

PTZ Analysis

Acrylic acid purum > 99.5 % BASF AG Ludwigshafen (D) stabilized with 200 ppm (g g1) MeHQ Acetic acid MeHQ PTZ Nitrogen 99100 % > 98 % > 99 % 99.999 % (N2 5.0) Riedle-de Haen AG, Seelze (D) Fluka Chemie AG, Buchs (CH) Acros, Neuss (D) Linde AG, Wiesbaden (D) Fisher Chemicals (D) TUD, Darmstadt (D)

For analyzing PTZ and the decomposition products a HPLC system (Hewlett-Packard, Model HP 1090 Series L Liquid Chromatograph) was used. The UV-VIS detector (HP filter photometric detector) works at 254 nm where PTZ has its absorption maximum. As chromatographic column a modified RP 18 material with the model name NC-03 (250 3.0 mm) PRONTOSIL 1203-C18-AQ 3.0956 m was used. The column was tempered to 50 C. The mobile phase was a mixture of

Acetonitrile 99.99 % Water bidistilled

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Figure 1. Chromatogram of PTZ in acrylic acid und air atmosphere (90 C) at the beginning and after 52.5 h (75 % acetonitrile/ 25 % H2O, 254 nm, 0.5 mL/min, T(HPLC) = 50 C). Peak 1: O5-PTZ(3.972), peak 2: O4-PTZ(4.508), peak 3: O3-PTZ(4.704), peak 4: O2-PTZ(4.893), peak 5: O1-PTZ(5.102), peak 6: PTZ(5.259).

3
3.1

Results and Discussion

HPLC Results

The investigated samples have a PTZ concentration between 0 and 200 ppm (g g1). The main peak at a retention time of 2.57 min is caused by the excess of acrylic acid and cannot be analyzed quantitatively (see Fig. 1). The measurements show that during the reaction of PTZ in acrylic acid five not identified decomposition products (O1 PTZ, O2 PTZ, O3 PTZ,...) are formed.

3.2

PTZ Consumption

Figure 2. Decrease of PTZ concentration as a function of retention time (RT) at different temperatures: PTZ in acrylic acid with air (a), PTZ in acetic acid with air (b).

Die measurements of PTZ consumption were made in acrylic acid (AA) and acetic acid (HAc). Acetic acid was used as a polymerization inert reference solvent. In both solvents the consumption kinetics under air (21 vol.-% O2) and under nitrogen (0 vol.-% O2) atmosphere was investigated. The results show a linear PTZ decrease as a function of retention time (see Fig. 2). Under air atmosphere the PTZ consumption rates in acrylic acid and acetic acid are higher than under nitrogen atmosphere. Between 40 and 100 C these consumption rates of the linear consumption curves are represented graphically in Fig. 3. With the linear Arrhenius plots (see Fig. 4) the PTZ consumption rates could be extrapolated to temperatures beyond the measuring range. Under air atmosphere the activation energy of PTZ decomposition is lower in acrylic acid (67 kJ mol1) than in acetic acid (87 kJ mol1). One possible explanation could be that in acrylic acid many radicals are formed by instable copolymers and peroxides which react with PTZ and consume the stabilizer.

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Figure 3. PTZ consumption rates in acrylic acid (a) and acetic acid (b) as a function of temperature under air () and N2 atmosphere (): (a) EA = 67 kJ mol1 (), EA = 12 kJ mol1 (); (b) EA = 87 kJ mol1 (), EA = 90 kJ mol1 ().

Figure 4. Arrhenius diagrams of PTZ consumption rates in acrylic acid (a) and acetic acid (b) under air () and N2 atmosphere ().

3.3

Discrimination of PTZ Consumption in Three Partial Reactions

In acrylic acid PTZ is consumed at least by three decomposition reactions [9]: reaction with the formed radicals (PTZ R), oxidation with dissolved oxygen (PTZ Ox), thermal decomposition at higher temperatures (PTZ T). With the following assumptions it is possible to calculate the radical formation rates in acrylic acid with the PTZ consumption measured in acrylic acid and acetic acid: In the presence of O2 all three decomposition reactions take place. In acetic acid PTZ consumption by radical reactions is negligible. In N2 atmosphere no oxidative decomposition is possible. The solvents acetic acid and acrylic acid are comparable in their pH value, polarity and O2 solubility. With the differences in PTZ consumption rates in acrylic and acetic acid under the influence of the two atmospheres (air and nitrogen) the amount of the different PTZ decomposition reactions could be estimated. The results show that with

increasing temperature the amount of oxidative PTZ consumption also increases (27 % at 60 C 54 % at 90 C). In the temperature range between 90 and 100 C the oxidation represents the greatest part, whereas at temperatures below 90 C the radical reactions represent the greatest part (68 % at 60 C 38 % at 90 C) of PTZ consumption. The thermal decomposition of PTZ is of secondary importance and only at temperatures 90 C is the part of PTZ consumption greater than 10 % (see Fig. 5). On the assumption that for the consumption of one PTZ molecule one radical is necessary the radical formation rates in acrylic acid under air/N2 atmosphere can be calculated from the inhibitor consumption rates. Hereby, it is noticeable that the radical formation rates correspond between 50 and 60 C under nitrogen and air atmosphere. Above 70 C a sharp slope of the radical formation rate in air is detectable. By constrast, the radical formation rate under N2 atmosphere is approximately constant (see Fig. 6). One probable explanation is the start of the decomposition of peroxides formed by the oxygen and monomer during the inhibition period. Hereby, the additional radical sources could increase the radical formation rates at higher temperatures ( 70 C).

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3.4

Correlation between O2 and PTZ Consumption

The parallel measurements of the O2 and PTZ consumption in the continuous stirred tank reactor should yield a more precise overview of the inhibition processes. If PTZ were oxidation-resistant and effective enough to immediately trap all primary radicals formed, no oxygen would be consumed. In reality, oxygen is consumed by the oxidation of PTZ and by the reaction of O2 with the formed radicals. The consumption rates could be calculated using the concentrations of O2 and PTZ in the stationary operation state at different retention times. The ratio of these total consumption rates is kges (O2 AA)/ kges (PTZAA) and increases slightly with increasing temperatures from 1.7 to 2.1 (see Fig. 7). For the direct comparison of the concurrent reactions of O2 and PTZ with primary radicals the oxidative part must be calculated from the total consumption rates of O2 and PTZ. Estimation is possible, assuming that for the oxidation of 1 mol PTZ 1 mol O2 is necessary and the percentage of the partial reactions in Fig. 7. With this correction the ratio of the partial consumption rates kR (O2 AA)/kR (PTZAA) increases from 2.2 at

Figure 5. Rate constants of PTZ partial reactions (a) and their percentage on total PTZ consumption (b) in acrylic acid with air (for details, see text).

Figure 6. Radical formation rates (PTZ R) in acrylic acid under air () and N2 atmosphere (). Figure 7. PTZ () and O2 () consumption rates (a) and the corresponding ratio of O2/PTZ (b) in the continuous stirred tank reactor (VR = 5079 mL, RT = 820 h, T = 6090 C).

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60 C to 4.0 at 90 C (see Fig. 8). This indicates that the capability of PTZ to directly react with primary radicals decreases at higher temperatures and will be overcompensated by the reaction of oxygen with primary radicals. It seems that at higher temperatures the formation of peroxide and copolymer radicals again plays a role before these radicals react with PTZ.

Conclusions

The investigation of PTZ consumption kinetics in acrylic acid shows that under air atmosphere oxygen is consumed. This O2 consumption could be explained by the oxidation of PTZ and by the reaction of oxygen with primary radicals during the inhibition period. This is why only one part of the formed primary radicals is directly intercepted by PTZ whereas the other part first reacts with oxygen. It is only after this has taken place that the formed peroxide radicals can react with PTZ. Therefore, under process conditions, the PTZ and oxygen concentrations should be constantly measured to guarantee that both stabilizers are present in adequate concentrations. At temperatures 80 C PTZ oxidation increases, and this must be taken into consideration under production conditions. In plant units with higher temperatures (130 C) a higher PTZ concentration is necessary to inhibit polymerization. With the extrapolation of the inhibitor consumptions in acrylic acid an early warning system is possible which calculates the end of the inhibition period as a function of PTZ concentration. This extrapolation only yields relatively good results in the temperature range between 80 and 100 C, at temperatures below 80 C it fails (see Fig. 9). With the results of this work it is possible to adjust an optimal PTZ concentration to avoid polymerization of acrylic acid in the different reprocessing steps. For example, the PTZ consumption rates in a rectification column could be calculated. With some measuring points in a rectification column optimization of the PTZ concentration could be achieved. This reduces raw material costs and breakdowns in production plants.

Figure 8. Corrected ratio of O2/PTZ in continuous stirred tank reactor (VR = 5079 mL, RT = 820 h, T = 6090 C).

Acknowledgement
Financial support by the BASF AG Ludwigshafen, Germany, is gratefully acknowledged.

Figure 9. Calculation of inhibition period (IP) by extrapolation of PTZ consumption rates (white, gray) in comparison to measured inhibition period (black).

References
[1] S. Schulze, H. Vogel, Chem. Eng. Technol. 1998, 21, 829. [2] Markets & Economics, Acrylic Acid Chemical Week, Jan. 2001, 3. [3] W. Kurze, F. Raschig, Ullmanns Enzyklopdie der Technischen Chemie, Antioxidantien, Vol. 8, VCH, Weinheim 1975, 19.

[4] H. Becker, H. Vogel, Chem. Eng. Technol. 2002, 25, 547. [5] P. Gladyshev, D. K. Kitaeva, V. A. Popov, E. I. Penkov, Proc. of the Acad. Sci. USSR 215, 1974, 354. [6] J. J. Kurland, J. Polym. Sci. Polym. 1980, 18, 1139. [7] H. Becker, H. Vogel, Chem. Eng. Technol. 2004, 27 (10), 1122. DOI: 10.1002/ceat.200302114 [8] W. Kurze, F. Raschig, Ullmanns Enzyklopdie der Technischen Chemie, Antioxidantien, Vol. 8, VCH, Weinheim 1975, 19. [9] H. Roseboom, J. H. Perrin, J. Pharm. Sci. 1977, 66, 1392.

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