Kinetic Study of Reactions of Aniline and Benzoyl ... - ACS Publications

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Kinetic Study of Reactions of Aniline and Benzoyl Chloride Using NH3 as Acid Absorbent in a Microstructured Chemical System Peijian Wang, Jisong Zhang, Kai Wang, Guangsheng Luo,* and Pei Xie The State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China S Supporting Information *

ABSTRACT: NH3 was used as acid absorbent to intensify the reactions between aniline and benzoyl chloride in a microstructured chemical system in this work. By suppressing the side reaction, the addition of NH3 could reduce the reaction time needed for 99% reactants conversation to less than 1/10 of the condition without NH3. Furthermore, a complete kinetic model containing two rapid main reactions and two reversible consecutive side reactions was established, and six reaction rate constants and their corresponding activation energies and pre-exponential factors as well as confidence intervals were determined precisely. The accuracy of the obtained parameters was verified by comparing the calculated data with experimental data at extensional temperature. The kinetic model was used to optimize the intensification operating conditions, and effects of reactants concentration, temperature, NH3 addition amount, and NH3 feed methods were discussed based on the simulation results. This work proves that the microstructured chemical system not only provides an effective intensification ability but also develops a reliable platform for kinetic studies.

1. INTRODUCTION Kinetic study of the reactions between aniline (AL) and benzoyl chloride (BC) is of significant importance for it reveals the intrinsic rules of reactions between aromatic amines and aromatic acid chloride, which have been widely applied in the fields of organic synthesis and polymerization process, for example, synthesis of intermediates for the production of insecticides, spice, and medicine,1,2 and preparation of aramid fibers.3,4 As a significant reaction, the kinetic study of the reactions between aniline and benzoyl chloride has attracted wide interest of researchers.5−8 Borkent et al. studied the effect of substituents of the aromatic amines and acid chloride in the reactions using a stopped-flow spectroscopy method in hexamethylphosphoric triamide,6 but the kinetic parameters might not be very accurate since five parameters were estimated from a single curve as the author admitted. Wamer et al. studied the kinetics and mechanism of the reactions in a two-phase system of aqueous aniline and benzoyl chloride in chloroform.7 The reaction rate was limited by the mass transfer rate of aniline from the aqueous phase to the organic phase as the researcher concluded. Our previous works have found that there is a reversible consecutive side reaction between the byproduct HCl and aniline besides the reaction between aniline and benzoyl chloride in the process, as shown in Figure 1.5 The reaction between aniline and benzoyl chloride is so fast that more than 85% yield can be reached in less than 1 s. However, because of the side reversible reaction between HCl and aniline and the slow decomposition rate of aniline hydrochloride, it takes over 10 min for the yield to increase from 85% to 99%. © XXXX American Chemical Society

Figure 1. Reactions between aniline and benzoyl chloride.

Suppression of the side reversible reaction is an effective way to improve the entire reaction rate.9,10 Because the side reversible reaction is caused by acidic by-produced HCl and the alkaline reactant amine group, it is easy to think of the addition of a base as acid absorbent to neutralize HCl, accordingly to reduce the reaction between HCl and aniline. Different kinds of bases, including NH3, CaH2, pyridine, and so on, were used to adsorb HCl in the preparation of PPTA by researchers, and the reactions were intensified to some degree.11,12 Meanwhile, the reactant benzoyl chloride is acidic13 and could react with base added in the system. Figure 2 shows the possible overall reactions when a base is added into the reaction system. Bases with different alkalinity could have varied reaction rates with HCl and benzoyl chloride. Compared with the main reaction rate, k3 and k4 could be far less than, nearly equal to, or far more than k1. Since values of k1 and k2 have been obtained in our previous work, yields for the residence time of 1 s could Received: February 4, 2016 Revised: May 4, 2016 Accepted: May 17, 2016

A

DOI: 10.1021/acs.iecr.6b00506 Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX

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Industrial & Engineering Chemistry Research

addition of NH3 as acid absorbent to intensify reaction process in a microstructured chemical system. In this article, NH3 has been used as acid absorbent in the reaction between aniline and benzoyl chloride in a microstructured chemical system. The objective of this work is to suppress the side reaction in the process and intensify the overall reaction rate. A kinetic model has been established for the complete reaction network after the addition of NH3 as acid sorbent. All the kinetic parameters, including reaction rate constants, activation energies and pre-exponential factors as well as their confidence intervals, in the reaction network after addition of NH3 have been obtained by designing elaborate experiments in the microstructured chemical system.

Figure 2. Reaction network after addition of base as acid absorbent.

be obtained using a numerical calculation by assuming the relative values of k3 and k4 with k1, as shown in Supporting Information, Figure S1. There are nine possible yield curves for the residence time of 1 s when different amount bases are added in the system corresponding to different k3 and k4 values. In the figure, every row has the same k3, and every column has the same k4. From the calculated result, we could see that if the alkalinity of the added base is much stronger than that of aniline (k4 ≫ k1), the instantaneous yields decrease sharply because of the rapid reaction rate between added base and benzoyl chloride, which contradicts with the purpose to improve the entire yield. As a result, it is appropriate to add a kind of base with relatively weak alkalinity to intensify the process on the basis of optimization of the base amount, residence time, and so on. NH3 is a highly promising choice as the acid absorbent among all the weak bases, for its low price, extensive availability, easy reserve, and so on.14 The reaction network after the addition of NH3 in the reaction system is shown in Figure 3, and this mechanism has been versified in

2. EXPERIMENTAL SECTION 2.1. Materials. Aniline (AL, 99.5%), benzoyl chloride (BC, 99%), and benzanilide (BA, 98%) were from J&K Scientific Ltd. (Beijing); N-methyl-2-pyrrolidone (NMP, > 99%) was purchased from Aladdin Industrial Inc. (Shanghai). The trace water in NMP was removed by adding molecular sieve and CaH2 before the experiments. NH3 was purchased from Beiwen Gas Manufacturer (Beijing). 2.2. Equipment. The schematic diagram of the microchemical system is shown in Figure 4. The aniline/NH3/NMP

Figure 4. Schematic overview of the experimental setup.

solution and the benzoyl chloride/NMP solution were delivered using two metering pumps (Beijing Satellite Co. Ltd.). The two solutions were preheated to reaction temperature in stainless steel capillaries (316 stainless steel) before they mixed violently in the microsieved dispersion mixer (316 stainless steel). The inner diameter of all the capillaries is 2 mm while the outer diameter is 3 mm. The schematic diagram of the microsieved dispersion mixer is shown in Figure 5. The

Figure 3. Reaction network after addition of NH3 as acid absorbent.

Figure S2. To intensify the reaction process effectively, it is necessary to optimize the amount of NH3 as acid absorbent and study the kinetics of the process. Microstructured chemical system has been widely used in the field of kinetic study in recent years,15−17 for its enhanced mixing ability,18 high heat transfer efficiency,19 precise residence time control,20 less consumption of reactants,21 inherent safety,22 and so on. Taking advantages of the above characterizations, more accurate kinetic parameters are expected when using a microstructured chemical system.23,24 Plenty of studies have been conducted successfully in a microstructured system, such as cyclohexanone ammoximation over TS-1 catalyst,25 fast exothermic premixing reactions,23 dehydrochlorination of dichloropropanol,26 and so on. Our previous kinetic study of the reactions between aniline and benzoyl chloride was also conducted in a microstructured chemical system.5 This paper is the first time to report the

Figure 5. 3-D structure diagram of the micromixer.

mixing performance of the micromixer was reported in our previous work.27 The pore in the micromixer is a square with side length of 0.4 mm and the cross-flow channel is 10 mm in length, 0.4 mm in width, and 0.4 mm in height. The residence time of the reaction was controlled by changing the length of the delay loop which connected directly to the outlet of the micromixer. The reaction mixture was quenched using enough B


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3.2. Determination of k3 and k4. To intensify the process effectively, a kinetic model is expected to be built so that every influence factor could be optimized. There are some considerations which are thought to bereasonable in building the kinetic model: (1) Ideal mixing is achieved when the flow rate is larger than 20 mL/min, which has been proven in our previous work.28 (2) The decomposition rate of the product of benzoyl chloride and NH3 is near to that of aniline hydrochloride, so this reaction could be ignored in the time span of around 1 s, just as the decomposition of aniline hydrochloride. This assumption could been certified when each rate constant is obtained. (3) All the reactions are in first-order with respect to each reactant.6 So the kinetic model in the time span of around 1 s is as follows:

ultrapure water in the microneutralizer which has the same construction as the micromixer. All the preheat exchange units, the micromixer, and the delay loop were immerged in a water bath to maintain the reaction temperature. 2.3. Analysis. The sample contents were analyzed using a high performance liquid chromatography (HPLC, Agilent 1100) with an ultraviolet detector under the following conditions: C18 chromatographic column; 60% HPLC acetonitrile and 40% ultrapure water as mobile phase; mobile phase flow rate 1 mL/min; detection wavelength at 280 nm. The yield of benzanilide (Y) is calculated by the following equations: Y=

C BA × Ft CAL × FAL

(1)

where CBA (mol/L) is the concentration of benzanilide in the collected sample; Ft (mL/min) is total flow rate including aniline solution, benzoyl chloride solution and ultrapure water; CAL (mol/L) is the initial concentration of aniline solution; FAL (mL/min) is the flow rate of aniline solution. The relative measurement error of the yield was decreased to 1% by repeating the reactions three times under the same condition.

3. RESULTS AND DISCUSSION 3.1. Reactions Intensification by NH3. The effect of addition of NH3 as acid absorbent in the reaction system is shown in Figure 6. From this figure, the addition of NH3 has

dCA = −k1CAC B − k 2CAC D dt

(2)

dC B = −k1CAC B − k4C BC F dt

(3)

dC C = k1CAC B dt

(4)

dC D = k1CAC B − k 2CAC D − k 3C DC F dt

(5)

dC E = k 2CAC D dt

(6)

dC F = −k 3C DC F − k4C BC F dt

(7)

dC G = k 3C DC F dt

(8)

dC H = k4C BC F dt

(9)

where, the subscripts A, B, C, D, E, F, G, and H stand for aniline, benzoyl chloride, benzanilide, HCl, aniline hydrochloride, NH3, ammonium chloride, and the product of benzoyl chloride and NH3, respectively. Reaction rate between NH3 and HCl is 11.4 m3·mol−1·s−1 in gas phase29,30 which is extremely fast. Although the reaction system is in NMP in this paper, it could be too rapid to obtain the reaction rate between HCl and NH3 directly. However, since we have obtained the values of k1 and k2 in our previous work, k3 and k4 could be obtained if the relative values of k3, k4 and k1 are determined. We have designed experiments by addition of different amounts of NH3, which could reflect the relative values of k3, k4, and k1, as shown in Figure 7. From this figure, the regression values of k3 and k4 at 0 °C are 2.97 × 103 L·mol−1·s−1 and 47.3 L·mol−1·s−1, respectively, and the calculated data fit well with the experimental data. The values of k3 are in the same order of magnitude with the literature results29 although they were conducted in different systems, gas phase, and NMP phase, respectively. Similarly, the effect of temperature has been studied by conducting the experiments at different temperatures, as shown in Figure 8. The values of k3 and k4 at different temperatures are shown in Table 1. After obtaining the values of k3 and k4 at different temperatures, the activation energies and pre-exponential factors have been determined by using the Arrhenius equation,

Figure 6. Effects of the addition of NH3 in the reactions system. Results with NH3 were conducted in the microstructured chemical system under the conditions of 0.05 mol/L reactants concentration, each solution 50 mL/min flow rate and temperature at 40 °C. The results without NH3 were calculated using the kinetic model obtained in our previous work,5 under the conditions of 0.05 mol/L reactants concentration and temperature at 40 °C.

two kinds of opposite effects. On the one hand, NH3 could react with benzoyl chloride reversibly, and the yield in the residence time of 1 s decreased from nearly 85% to about 75%. On the other hand, NH3 could react with HCl and suppress the side reaction between HCl and aniline, and the yield of reaction increased faster than that without the addition of NH3. Since high reactants conversion are always desired in most reactions between aromatic amine and aromatic acyl chloride, the addition of NH3 could indeed intensify the reactions and reduce the residence time needed for high reactants conversion. Detailed intensification results of the reactions by the addition of NH3 will be discussed later in this paper. C


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as shown in Figure 9. The values of activation energies and preexponential factors as well as their confidence intervals are listed in Table 2. Table 2. Values and Confidence Intervals of the Activation Energies and Pre-Exponential Factors of k3 and k4

Figure 8. Effects of temperature on yields. Experiments were conducted in the microstructured chemical system under the conditions of 0.05 mol/L reactants concentration, residence time of 1 s, and each solution at 50 mL/min flow rate.

Table 1. Values of k3 and k4 at Different Temperatures temp (°C) 0 10 20 30 40

−1 −1

values of k3 (L·mol ·s )

values of k4 (L·mol ·s )

× × × × ×

47.3 58.0 66.3 75.5 86.1

2.97 3.86 4.67 5.61 6.72

103 103 103 103 103

values

confidence intervals

14.3 1.66 × 106 10.4 4.72 × 103

13.1−15.6 9.91 × 105 to 2.78 × 106 9.16−11.7 2.82 × 103 to 7.92 × 103

3.3. Determination of k−4. After getting the values of k3 and k4 at different temperatures, the decomposition rate constant of the product of NH3 and benzoyl chloride k−4 should be determined before an integral reaction network kinetics is established. By extending the time span to several minutes, the whole kinetics network is completed as follows:

Figure 7. Yield curve with different amounts of NH3 addition in the time span of around 1 s. Experiments were conducted in the microstructured chemical system under the conditions of 0.05 mol/L reactants concentration: each solution, 50 mL/min flow rate; residence time, 1 s; and temperature at 0 °C.

−1 −1

factors E3 (kJ/mol) A3 (L·mol−1·s−1) E4 (kJ/mol) A4 (L·mol−1·s−1)

dCA = −k1CAC B − k 2CAC D + k −2C E dt

(10)

dC B = −k1CAC B − k4C BC F + k −4C H dt

(11)

dC C = k1CAC B dt

(12)

dC D = k1CAC B − k 2CAC D − k 3C DC F + k −2C E dt

(13)

dC E = k 2CAC D − k −2C E dt

(14)

dC F = −k 3C DC F − k4C BC F + k −4CH dt

(15)

dC G = k 3C DC F dt

(16)

dC H = k4C BC F − k −4C H dt

(17)

where, the subscripts A, B, C, D, E, F, G, and H stand for aniline, benzoyl chloride, benzanilide, HCl, aniline hydrochloride, NH3, ammonium chloride, and the product of benzoyl chloride and NH3, respectively. In the above kinetic model, k−4 is the only undetermined parameter, and it could be obtained using the benzanilide yield

Figure 9. Reaction rate constants at different temperature: (a) k3 at different temperature; (b) k4 at different temperature. D


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Table 3. Values and Confidence Intervals of k−4 at Different Temperatures

at different residence times after the addition of NH3, as shown in Figure 10. From this figure, the regression value of k−4 at 0

temp (°C) 0 10 20 30 40

values of k−4 (s−1) 6.59 8.78 1.16 1.55 2.33

× × × × ×

−3

10 10−3 10−2 10−2 10−2

k−4 confidence intervals (s−1) 3.11 4.72 6.32 7.99 1.66

× × × × ×

10−3 10−3 10−3 10−3 10−2

to to to to to

9.92 1.27 1.69 2.30 3.01

× × × × ×

10−3 10−2 10−2 10−2 10−2

Figure 10. Yields in time span of several minutes. Experiments were conducted in the microstructured chemical system under the conditions of 0.05 mol/L reactants concentration, each solution at 50 mL/min flow rate, and temperature at 0 °C. The reactions were not terminated in the microstructured chemical system, and the reaction mixtures were kept in a conical flask to the set residence time before the reactions were terminated by adding in enough ultrapure water. Figure 12. Reaction rate constant k−4 at different temperature.

°C is 6.59 × 10−3 s−1. Similarly, values of k−4 at different temperatures could be obtained by conducting the experiments at different temperatures, as shown in Figure 11. The values

Table 4. Values and Confidence Intervals of the Activation Energy and Pre-Exponential Factor of k−4 factors

values

confidence intervals

E−4 (kJ/mol) A−4 (s−1)

21.9 9.90 × 101

17.3−26.6 1.44 × 101 to 6.82 × 102

The values of k1, k2, and k−2 at different temperatures have been already obtained in our previous work, as shown in Table S1. All the kinetic parameters have been obtained by now, and the accuracy of these parameters are verified by comparing the calculated data with experimental data at the extensional temperature of 50 °C, as shown in Figure 13. The calculated data fit well with the experimental data, which means the kinetic parameters we obtained are accurate. 3.4. Simulation of Reaction Process Based on the Kinetic Model. The object of the addition of NH3 as acid sorbent is to intensify the overall reaction rate. The kinetic model has been used to optimize the specific operating conditions to intensify the process. High reactants conversion is always wanted in either organic synthesis or polymerization process, especially in the polycondensation process, such as the preparation of PPTA. We have used the kinetic model to calculate the residence time needed for 99% reactants conversion at different conditions, as shown in Figure 14. From this figure, the optimal amount of NH3 is the molar ratio of NH3 and aniline equal to 1. Higher reactants concentration is beneficial for process intensification, but the effect of concentration is no longer significant when the concentration is higher than 0.005 mol/L. Meanwhile, increasing temperature always has a great effect on the residence time needed for 99% reactant conversion. It needs less residence time when the temperature is higher. As a whole, the influence of the addition of NH3 is the most important in the process. For example, 99% reactant conversion needs more than 20 min at 0.01 mol/L and 80 °C, but the time is reduced to less than 2 min when equal molar NH3 is added into the system which is less than 1/10 that of the former, as shown in Figure 14b. Hence, the addition

Figure 11. Yield curves in time span of several minutes at different temperature. Experiments were conducted in the microstructured chemical system under the conditions of 0.05 mol/L reactants concentration and each solution at 50 mL/min flow rate. The reactions were not terminated in the microstructured chemical system, and the reaction mixtures were kept in a conical flask to the set residence time before the reactions were terminated by adding in enough ultrapure water.

and confidence intervals of k−4 at different temperatures are listed in Table 3. Compared with the reaction rates of the reaction between aniline and benzoyl chloride and the reaction between HCl and NH3, the decomposition rate of the product of benzoyl chloride and NH3 is quite slow, which could prove that the second consideration in building the kinetic model is reasonable. Activation energy and pre-exponential factor of this decomposition reaction have been determined by using the Arrhenius equation regression, as shown in Figure 12. The values of activation energy and pre-exponential factor as well as their confidence intervals of the decomposition reaction are listed in Table 4. E


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Figure 15. Simulation results of residence time needed for 99% reactants conversion using different feed methods. Conditions are temperature at 0 °C and 0.001 mol/L, 0.01 mol/L reactants concentration.

Figure 13. Parameters verification by comparing calculated data with experimental data at extensional temperature of 50 °C. Experiments were conducted in the microstructured chemical system under the conditions of 0.05 mol/L reactants concentration, each solution at 50 mL/min flow rate, and temperature at 50 °C. The reactions were not terminated in the microstructured chemical system, and the reaction mixtures were kept in a conical flask to the set residence time before the reactions were terminated by adding in enough ultrapure water.

of the amount of NH3 addition, its effect on the early selectivity of the reaction becomes more important, and adding NH3 after 85% benzoyl chloride is a better choice. With further increase of NH3 addition amount, the effect on the early selectivity gets smaller compared to the whole process, and the two feed methods become closer. As a whole, adding NH3 after 85% benzoyl chloride reacted could reduce the residence time needed for 99% reactants conversion at some NH3 addition amount, but the overall effect is not significant. Considering the convenience of feed method, adding NH3 at the beginning may be a better choice.

of NH3 as acid absorbent is quite an effective way to intensify the overall process. In the above analysis, because NH3 could react with HCl and suppress the side reaction in the process, the addition of NH3 as acid absorbent could reduce the residence time needed for 99% reactants conversion significantly. In fact, the addition of NH3 could have two kinds of opposite effects. On the one hand, the addition of NH3 could react with HCl and suppress the side reaction and promote the overall process. On the other hand, the addition of NH3 could react with benzoyl chloride and hinder the process, which is the main reason why bases with strong alkalinity are not suitable acid absorbents in this process. To avoid the negative effect of the addition of NH3, an idea is that NH3 is added into the system after most of the benzoyl chloride has been reacted. For example, NH3 could be added into the system after 1 s when more than 85% benzoyl chloride has been reacted, so the reaction between NH3 and benzoyl chloride would reduce sharply. Effects of these two feed methods, adding NH3 at beginning or adding NH3 after 85% benzoyl chloride has been reacted, are shown in Figure 15. From the simulation results, when the amount of addition of NH3 is small, it has little effect on the early selectivity of the main reaction, and most of the NH3 reacts with HCl, so adding NH3 at beginning is a better choice. However, with the increase

4. CONCLUSIONS In this work, NH3 has been added into the reactions of aniline and benzoyl chloride as acid absorbent to intensify the reaction process by suppressing the side reaction in a microstructured chemical system for the first time. The addition of NH3 could promote the reactions effectively, and residence time needed for 99% reactants conversation could be reduced to less than 1/ 10 of the original. Moreover, a complete kinetic model which contains two rapid main reactions and two reversible consecutive side reactions has been established. By designing the residence time at a time span of 1 s and several minutes elaborately, reaction rate constants which are of a difference of 5−6 orders of magnitude have been determined precisely. Activation energies and pre-exponential factors of each reaction as well as their confidence intervals have been obtained by using the Arrhenius equation regression after getting reaction

Figure 14. Simulation results of residence time needed for 99% reactants conversion: (a) at different concentration; (b) at different temperature. Conditions: (a) temperature at 0 °C and different reactant concentrations; (b) 0.1 mol/L reactants concentration and different temperatures. F


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rate constants at different temperatures. The accuracy of the obtained parameters has been verified by comparing the calculated data with experimental data at the extensional temperature. After the kinetic model was established, it was used to optimize the operating conditions to intensify the process. Effects of reactants concentration, temperature, amount of NH3 addition, and NH3 feed methods have been discussed using the simulation results of the kinetic model. Furthermore, the complete kinetic model is expected to guild more organic synthesis and polymerization processes that contain aromatic amines and aromatic acyl chloride in our future work.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.iecr.6b00506. Calculated results of yield curves with the addition of different bases; infrared spectra of the reaction system; values of k1, k2, and k−2 (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We gratefully acknowledge the support of the National Natural Science Foundation of China (No. U1463208 and 91334201) on this work.

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REFERENCES

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