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Contents lists available at ScienceDirect

Education for Chemical Engineers

journal homepage: www.elsevier.com/locate/ece

1 Mass & energy balances coupling in chemical

2 reactors for a better understanding of thermal
3 safety

4 Q1 Sébastien Leveneur a,b,∗ , Lamiae Vernieres-Hassimi b , Tapio Salmi a

5
a Laboratory of Industrial Chemistry and Reaction Engineering, Johan Gadolin Process Chemistry Centre,
6 Åbo Akademi University, Biskopsgatan 8, FI-20500 Åbo/Turku, Finland
7
b Normandie Univ, INSA Rouen, UNIROUEN, LSPC, EA4704, 76000 Rouen, France

9 a r t i c l e i n f o a b s t r a c t
10

11 Article history: Process safety is an important topic in the curriculum vitae of a chemical engineer. It can be a
12 Received 26 January 2016 difficult course for the students and professors, because it is a frontier course between chem-
13 Accepted 7 June 2016 ical engineering and safety. How to introduce this course? We think that this course should
14 Available online xxx be introduced during the chemical reaction engineering, and more particularly during the
15 mass and energy balances lectures. Thus, the students can more easily understand the con-
16 Keywords: cept of isoperibolic mode, secondary reactions, heat-flow rate due to chemical reactions,
17 Chemical reaction engineering Semenov curves, etc. In this manuscript, we propose a pedagogical method to introduce
18 Introduction to thermal safety of this concept by using numerical simulation. In the first section, the roots of energy bal-
19 chemical processes ance for the different reactors is derived. In the second section, mass and energy balances
20 Applied numerical methods coupling is derived for the different chemical reactors. In the third section, the different
21 Mass & energy coupling thermal modes, i.e., isothermal, isoperibolic and adiabatic are described. Then, a tutorial
by using a batch reactor with several exothermic reactions is treated and corrected. At this
moment of the course, the instructor can introduce the last section about safety criteria
by using the zero-order approximation. The rigorous mass and energy balances coupling
should be introduced to the students before the current approximation made by the safety
community, i.e., zero order, in process safety.
© 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction A chemical engineer should appreciate the risk of ther- 31

mal runaway which can cause a pressure elevation and an 32

22Q3 The introduction of safety and risk assessment during a explosion of the vessel. The evolution of heat-flow rate due to 33

23 chemical engineering curriculum is recommended by differ- chemical reactions should be known, thus kinetics and ther- 34

24 ent associations (Favre et al., 2008; Shallcross, 2013; Perrin modynamics of the chemical system should be determined. 35

25Q4 and Laurent, 2008; Dee et al., 2015; Spicer et al., 2013). Process When the behavior of the heat-flow rate due to chemical reac- 36

26 safety for chemical engineers can be a difficult course for the tions is known, the chemical engineers could design a system 37

27 students and for the professors, because it includes several to remove the excess of heat to diminish the risk of thermal 38

28 concepts from thermodynamics, reaction kinetics, chemical runaway. For that reason, different Chemical Reaction Engi- 39

29 reaction engineering, process design, accident scenario devel- neering (CRE) books have integrated one chapter on process 40

30 opment and even sociology. safety or on thermal stability of reactor (Coker, 2001; Fogler,

∗
Q2 Corresponding author at: Laboratory of Industrial Chemistry and Reaction Engineering, Johan Gadolin Process Chemistry Centre, Åbo
Akademi University, Biskopsgatan 8, FI-20500 Åbo/Turku, Finland. Tel.: +33 618844859.
E-mail address: sebastien.leveneur@insa-rouen.fr (S. Leveneur).
http://dx.doi.org/10.1016/j.ece.2016.06.002
1749-7728/© 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002
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41 2016; Rawlings and Ekerdt, 2013; Villermaux, 1999). We should did not simulate the evolution of the pressure in the reactors 85

42 also mention the book of Francis Stoessel on thermal process head space during this course. During the lecture, we men- 86

43 safety assessment (Stoessel, 2008). By segregating this lecture tion that pressure increase can be due to the evaporation of 87

44 of thermal safety from CRE, students could use some formulae the reaction mixture and decomposition reactions producing 88

45 to calculate safety criteria based on zero-order reaction. non-condensable products. We think that this part can be seen 89

46 We are also convinced that this course can be introduced during the safety course and particularly during practices. As 90

47 as a chapter in chemical reaction engineering (CRE) courses. illustrated by Willey et al. (2011), the example of an industrial 91

48 More particularly, during the lectures on mass and energy bal- accident can be used by using VSP 2 technology. 92

49 ances. During our lectures of CRE and reactor stability at Åbo The course (around 20 h) includes the following main top- 93

50 Akademi University or at INSA Rouen, we have noticed that we ics: 94

51 should spend more time to illustrate properly the strong cou-

52 pling of mass and energy balances. Thus, students learn how - Mass and energy balances (3 h) 95

53 to determine the different heat-flow rates in a chemical reac- - Different thermal mode (3 h) 96

54 tor which illustrates the dynamic of the system. The thermal - Tutorials based on numerical simulation (5 h) 97

55 safety criteria are often introduced with a static approach: by - Thermal safety assessment (4 h) 98

56 assuming full accumulation, adiabatic conditions, single reac- - Project (5 h) 99

57 tion and zero-order reaction. The main drawback with that

58 approach is those students do not study properly the deter- The first 6 h of the course are dedicated to lectures of mass 100

59 mination of heat-flow rate under different thermal modes in & energy balances in chemical reactors and the different ther- 101

60 presence of multiple reactions. This static approach, based mal modes. This introduction is fundamental for students, 102

61 on the worst case scenario, could lead to some confusion for because they can understand why there is a strong mass & 103

62 the future chemical engineers. The different concepts of time energy balances coupling and the importance of the thermal 104

63 to maximum rate under adiabatic conditions TMRad , or adia- mode. The personal student work is between 3 and 6 h. 105

64 batic temperature rise Tad during process safety lectures can The next part of the course (5 h) is dedicated to practice to 106

65 be abstract to understand and handle (Stoessel, 2008). Based simulation by using Matlab. The instructors should explain the 107

66 on our experience, we have developed a pedagogical strat- skeleton of the Matlab code and the exercises. The instructor 108

67 egy including numerical simulation to ease the understanding can individually adapt the proposed exercises to the students. 109

68 of such concept during a CRE course for undergraduate and The students must solve out the different exercises by using 110

69 master students (Antunes et al., 2011; Lindfors, 1971; Taipa Matlab (2 or 1 student per computer). This part of the course 111

70 et al., 2015). The use of simulation is an efficient pedagogical can be the most demanding for the students and the instruc- 112

71 tool to understand the dynamic of a chemical reaction system tors. It is essential that the students feel familiar with the code 113

72Q5 (Coker, 2001; Finlayson, 2006; Fogler, 1999; Law, 2013; Rawlings to understand the effect of initial reaction and jacket tempera- 114

73 and Ekerdt, 2013; Salmi et al., 2010). However, the instructors ture, initial concentrations, thermal parameters and thermal 115

74 should spend time to explain correctly the program to the stu- mode on the evolution of heat-flow rate, concentration dis- 116

75 dents. Furthermore, due to the introduction of simplification, tribution and temperature with reaction time. The personal 117

76 the results of the simulation should be viewed with caution, student work is important for this part. Depending on student 118

77 essentially during the stage of design (Levenspiel, 1999). computing capacity, the personal can be estimated to 5–10 h. 119

78 The main objective of this manuscript is to propose a The lecture concerning the thermal safety assessment is a 120

79 dynamic view of safety criteria by using simulation. Fig. 1 illus- lecture, and the personal student work is typically 4 h. 121

80 trates the pedagogical approach. It is not a course on process The project should be done by the students. Several con- 122

81 safety, which should take place after this course. Some arti- figurations have been tested: personal, pair or group project; 123

82 cles have modeled some accidents or scenarii, but these case liberty for the student to choose their partners or the instruc- 124

83 studies are for master or post-graduate students (Eizenberg et tor defines a system to make the groups. Based on our 125

84 al., 2006; Willey et al., 2011; Dixon and Kohlbrand, 2015). We experience, the pedagogical results are better when students 126

work by pair and when they choose their partners. The com- 127

puter room is reserved for the students one time per week. 128

They have 3 weeks to finish that project. 129

Due to the space limitation of the journal, we have decided 130

to put as supplementary information different elements of 131

the course. For the sake of simplicity, only a batch reactor is 132

described in this manuscript. 133

2. Remind of mass balance and kinetics in

a reactor

Energy balance for chemical reactors is strongly linked to mass 134

balance. Hence, it is important to refresh the fundamentals of 135

mass balances for chemical reactors. Indeed, this course is 136

after the first course of CRE, where the different ideal reactors 137

were described. The instructor should insist on the fact that 138

mass and energy balance are done on a delimited zone (liquid 139

reaction, gas phase). For example, in case of liquid mono- 140

phase reaction systems, we should pay attention to the fact 141

Fig. 1 – Schematic view of the pedagogical approach. that the mass balance is derived for the liquid phase. It is quite 142

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002
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Fig. 2 – Mass balance for chemical reactors.

143 obvious to state this, but in case of temperature increase, such explain each terms in the energy balance. The roots of energy 173

144 as a thermal runaway, evaporation and decomposition reac- balance in a chemical reactor can be found in supplementary 174

145 tions producing non-condensable products could occur, and information (S1) inspired from the book of James B. Rawlings 175

146 make the mass balance more complex. and John G. Ekerdt (2013). 176

147 For undergraduate or master students, it is important to By neglecting enthalpy changes due to phase transfer, 177

148 treat liquid reaction systems under high pressure (inert gas) to energy balance for any chemical reactors is given by 178

149 neglect evaporation phenomenon. The instructor should show 179

some examples neglecting secondary reactions, i.e., reac-

dPR  dnj
150

tions with high activation energy producing non-condensable

  dTR
151
VR · R · ĈPR + minsert .ĈPinsert . − ˛ · TR · VR · + H̄j 180
152 products. The reason of this simplification is the complexity dt dt dt
j
153 to describe the pressure evolution in the gas-phase during
154 decomposition reactions occurring in the liquid-phase. The = Ḣin − Ḣout + Q̇exch + ẆS (2) 181

155 resolution of such system (liquid-phase reactions producing

156 non-condensable products) should be reserved for advanced 182

157 CRE courses. However, this simplification should really be where mR and minsert are the reaction mixture and insert mass, 183

158 emphasized during the lectures. Indeed, the thermal risk ĈPR and ĈPinsert are constant–pressure specific heat capacities 184

159 comes from the thermal runaway, which could lead to an over- of reaction mixture and insert, respectively, TR is the reac- 185

160 pressure due to secondary reactions and liquid vapor pressure. tion temperature, Ḣin and Ḣout are the inflow and outflow 186

161 Fig. 2 presents the mass balance expressions for the differ- enthalpies. The term ẆS is shaft power due to the stirring. 187

162 ent chemical reactors. An other important reminder from the The term Q̇exch (also written qexch in the literature) is the 188

163 first course of CRE is the difference between steady-state and exchanged heat-flow rate with the surroundings. 189

164 unsteady-state regime. The first term of Eq. (2) represents the accumulation of 190

165 The mass balance for a compound in an ideal batch reactor the heat-flow rate, the second one represents the variation 191

166 is usually written as of heat-flow rate due to the variation of pressure and the third 192

one is the heat-flow rate due to the chemical reactions. 193

dCj 
nr
dnj 
nr For the accumulation term, the thermal inertia of the 194
167 = ij · Ri or = VR · ij · Ri (1) inserts can be neglected. 195
dt dt
i=1 i=1 The accumulation term dnj /dt from Eq. (1) is inserted in Eq. 196

(2). 197
168 where, j refers the compound, ij is the stoichiometry coeffi- In a batch reactor, the inflow and outflow enthalpies are 198
169 cient of compound j for reaction i, Ri is the reaction rate and equal to zero, thus Eq. (2) becomes 199
170 VR is the reaction volume.

dPR  
nR
  dTR
VR · R · ĈPR + minsert · ĈPinsert . − ˛ · TR · VR · + H̄j . ij · Ri · VR = Q̇exch + ẆS
dt dt
j i=1
   (3) 200

with ij H̄j = Hf,j − Hf,j = HRi

j Products Reactants

The energy balance for a batch reactor can be defined as 201

202

3. Mass and energy balance coupling in a

  
nR

chemical reactor VR · R · ĈP + minsert · ĈPinsert ·

dTR
− ˛ · TR · VR .
dPR
+ HRi · Ri · VR 203
dt dt
i=1
171 This part might be the most difficult to absorb by the students,
= Q̇exch + ẆS (4) 204
172 and it is worth to come back to the traditional blackboard to 205

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002
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Fig. 3 – Energy balance for chemical reactors.

206 The instructor should insist on the fact that stoichiomet- isothermal, isoperibolic and adiabatic mode can be explained 244

207 ric coefficients disappeared in Eq. (4) and the reaction rates by using the following simplified equation: 245

208 are used and not the generation rates. Some simplification
209 regarding the pressure can be introduced (S2). It is important Q̇acc = Q̇rx + Q̇exch
210 to emphasize on the fact that temperature is a global signal
dTR  nR
(6) 246
211 and we assume no temperature gradients for an ideal reactor. ⇔ mR · CPR · =− Ri · VR · Hr + U · A · (Tj − TR )
212 The instructor could present the different ways to deter- dt
i
213 mine the thermal parameters. For example, heat capacity
214 can be determined by using differential scanning calorime- The instructor should remind to the students that the sym- 247
215 ter (Stoessel, 2008) and the global heat transfer coefficient can bol of heat-flow rate can be written as Q̇ or q. The term 248
216 be measured by using a calibration probe providing an elec- Q̇exch represents the heat-flow rate exchanged between the 249
217 trical power to the mixture (Leveneur et al., 2012). The energy reaction mixture and the surroundings, i.e., head space and 250
218 balances for the other reactors are described in Fig. 3. heat carrier circulating in through the jacket reactor. If the 251
219 The heat-flow rate due to the chemical reactions is given heat losses due to liquid evaporation and vapor condensation 252
220 by the relation: can be neglected, then the heat-flow rate exchanged can be 253

expressed as Q̇exch = U · A · (Tj − TR ). 254


nR
A is the heat-transfer area. U is the global heat-transfer 255
221 Q̇rx or qrx = Ri · HRi · VR (5) coefficient. This parameter depends on the geometry of the 256
i=1 reactor and the nature of the reaction mixture and heat carrier. 257

The instructor could speak about the importance of these two 258

222 Eq. (5) is fundamental to understand the concept of proba- parameters for the scale-up and for the safety issues. He/she 259

223 bility and severity, which is the definition of risk. The reaction can also introduce the concept of Wilson plot to determine 260

224 enthalpy represents the severity of a chemical reaction. The evolution of the parameter U (Lavanchy, 2005). The instruc- 261

225 instructor should insist on the fact that the product reaction tor should mention that the global heat-transfer coefficient 262

226 kinetics times reaction enthalpy represent the thermal risk. depends also on the stirring speed. 263

227 The instructor can give the example of hydrogen peroxide Under isothermal conditions, the accumulation term of Eq. 264

228 decomposition in acidic copper sulfate solutions (Mlasi et al., (6) is equal to zero. The heat-flow rate originating from chem- 265

229 2015). Mlasi et al. (2015) have shown that in absence of copper ical reactions and exchanged between reaction mixture and 266

230 sulfate, i.e., catalyst, the adiabatic temperature rise is lower surroundings are the same. Consequently, Eq. (6) becomes: 267

231 than 1 ◦ C.
nr
i
Ri · VR · Hr
Tj = + TR (7) 268
4. Consideration of different thermal mode U·A

Eq. (7) is solved with the ordinary differential Eq. (1). 269
232 From a safety viewpoint, it is essential to present the three
Under isoperibolic conditions, jacket temperature is main- 270
233 thermal modes. Usually, the students can differentiate the
tained constant due to a very rapid circulation of the heat 271
234 isothermal and adiabatic mode. However, confusion can occur
carrier. Then, one should solve the coupled Eqs. (1) and (6). The 272
235 for the isoperibolic conditions. As illustrated in chapter 2 of the
instructor should propose an appropriate numerical method. 273
236 book Thermal Safety of Chemical Processes: Risk Assessment
In this case, the ODEs are typically stiff, and a proper solver 274
237 and Process Design (Stoessel, 2008), the confusion between
such as a Rosenbrock method should be used. 275
238 isoperibolic and isothermal mode could have detrimental con-
Under adiabatic mode, heat-flow rate exchanged is equal 276
239 sequences on a process. Numerical applications can help the
to zero. Thus, Eq. (6) becomes 277
240 students to differentiate the three thermal modes.
241 For the sake of clarity, one should simplify the equation nR
by assuming negligible the shaft work (due to stirring) and dTR − i
Ri · VR · Hr
242
= (8) 278
243 by operating under isobaric mode. The difference between dt mR · CPR

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002
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Fig. 4 – Illustration of different thermal modes for a batch reactor.

279 As in the case of isoperibolic mode, the ODEs (1) and (8) should Wi and ĈPi are weight percent and specific heat capacity of 310
280 be solved out with the appropriate numerical solver. Fig. 4 compound i. For the sake of simplicity, this parameter will 311
281 illustrates the different thermal modes for a batch reactor be considered constant, i.e., 2000 J/(kg K) which is the average 312
282 based on Eq. (6) value for an organic solvent. 313

5. Tutorial with numerical approach

- Heat-losses due to evaporation and condensation are 314

neglected, 315
283 Even if it is not a lecture of numerical methods, the instruc-
- It is very important to emphasis the scale-up issue with the 316
284 tor should spend time to explain the different part of the
determination of A. 317
285 computer code (supporting information S3). The presence of
286 stiff ordinary differential equations should be highlighted. It
287 is important to give a simplified exercise, which neglects the 5.1. Tutorials 318

288 evaporation and the presence of secondary reactions lead-

289 ing to the production of non-condensable gaseous products. As a representative example, the following reaction system 319

290 Thus, there is no liquid–gas mass transfer to be considered. can be considered 320

291 Some parameters (Cp , density and UA) are assumed to be con- A + B → C (R1 ) 321

292 stant. The instructor should take time to explain the following B → D (R2 ) 322

293 assumptions: A researcher has decided to perform this chemical process 323

in a batch reactor with the following thermal modes: isother- 324

mal, isoperibolic and adiabatic modes. 325

294 - Evaporation is neglected and a low vapor pressure reaction
The reaction mass is mR = 0.3 kg and the liquid density is 326
295 mixture was selected, otherwise one should include this in
R = 1 kg/L. The initial concentrations of the different com- 327
296 the mass balance and take into account the evolution of the
pounds are CA = CB = 2 mol/L and CC = CD = 0 mol/L. 328
297 pressure in the head space of the reactor,
Kinetic data and thermodynamic constants for both reac- 329
298 - There are no secondary reactions, which would have led to
tions are given below 330
299 the formation of non-condensable gaseous products inter-
R1 = k1 ·[A]·[B]k1 = 0.2 × 10−2 L/(mol min) at 40 ◦ C 331
300 fering with the mass balance of the liquid-phase. But also to
Ea1 = 60 kJ/mol 332
301 highlight that in case of thermal runaway, evaporation can
HR1 = −60 kJ/mol 333
302 act as a safety barrier,
R2 = k2 ·[B]k2 = 0.6 × 10−7 min−1 at 40 ◦ C 334
303 - The instructor should speak about the fact that evaporation
Ea2 = 200 kJ/mol 335
304 is an endothermic phenomenon interfering with the energy
HR2 = −150 kJ/mol 336
305 balance of the liquid phase,
The process lasts for 6 h 40 min. 337
306 - The heat exchange capacity of the reaction mixture can be
The following tasks can be given during the tutorials: 338
307 determined from the heat exchange capacities of the com-
308 pounds present in the reaction mixture.
1. Study the effect of reaction temperature on the concentra- 339


N tion of the different species and on the heat-flow rate due 340
309 ĈPR = Wi · ĈPi (9) to chemical reactions and exchanged between the reac- 341

i=1 tion mixture and the heat carrier under isothermal mode. 342

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
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Fig. 5 – Presentation of the problem at the blackboard.

343 Different reaction temperature from 50 to 100 ◦ C can be

344 tested. The value of UA is 5 W/K.
345 The Matlab code is given in supporting information S3.
346 2. Study the effect of the global heat transfer coefficient (UA)
347 on the jacket temperature for a reaction temperature of
348 90 ◦ C in isothermal conditions.
349 3. Study this system under adiabatic mode with an initial
350 reaction temperature of 50 ◦ C, 70 ◦ C and 100 ◦ C. What is
351 the effect on reaction heat-flow rates, reaction temperature
352 and on the evolution of the concentration of D?
353 4. Study this system under isoperibolic conditions at differ-
354 ent jacket temperatures 50 ◦ C, 70 ◦ C and 100 ◦ C. What can
355 you conclude about the heat-flow rates of reactions and
356 exchanged between reaction mixtures and exchanged?
357 5. What should be the value of A to maintain the reactor in
358 isothermal conditions at 100 ◦ C with different reaction vol- Fig. 6 – Effect of reaction temperature on the concentration
359 ume: 5, 10 and 100 L? For this question, we wish to have of compound C and D.
360 the same evolution of Tj than for a volume reaction of 0.4 L.
361 The value of U is 700 W/(K m2 ).
362 6. A discussion must take place on the fact that an exothermic
363 reaction does not imply fast reaction heat-flow rates.

364 5.2. Tutorial pedagogy strategy

365 The instructor should push the students to draw a picture of

366 the different system and the different equations associated to
367 solve out this exercise such as the one represented in Fig. 5.
368 Response to question 1
369 The code (S3-isothermal) allows to follow the concentra-
370 tion of the different species, jacket temperature, and heat-flow
371 rates due to chemical reactions and exchanged with the heat
372 carrier. Students should use the value of kinetic parameters,
373 initial concentrations and reaction temperature. By running Fig. 7 – Effect of reaction temperature on jacket temperature
374 the program code at a higher reaction temperature, it can be under isothermal conditions.
375 noticed that the second reaction starts to be more and more
376 important (Fig. 6). Students can also notice that by using the the temperature increases, the heat-flow rate due to chem- 383

377 same value for the global heat transfer coefficient UA and by ical reactions increases. One of the most important aspects 384

378 increasing the reaction temperature, the jacket temperature to highlight is the difference of dynamics between reaction 385

379 decreases (Fig. 7). concentration evolution and the heat-flow rate. The instruc- 386

380 From Fig. 8, one can conclude that the heat-flow rate due tor should emphasize that heat-flow rate essentially occurs at 387

381 to chemical reactions is the same as the one exchanged. This the beginning of the reaction. 388

382 is a way to check whether there are mistakes in the code. As Response to question 2 389

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
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160 qrx (UA = 5 W/K & Tr=100°C)

qrx (UA = 5 W/K & Tr=80°C)
120
qrx (UA = 5 W/K & Tr=50°C)
qexch (UA = 5 W/K & Tr=100°C)
80
qexch (UA = 5 W/K & Tr=80°C)
qexch (UA = 5 W/K & Tr=50°C)
40
qrx (W)

0
0 2 4 6 8 10 12 14 16 18 20

-40 Time (min)

-80

-120

-160

Fig. 8 – Effect of reaction temperature on heat-flow rate under isothermal conditions.

Fig. 10 – Logarithm of heat-flow rate of reactions evolution

at different initial reaction temperature.
Fig. 9 – Effect of UA on the jacket temperature under
isothermal condition with Tj = 90 ◦ C.
Eq. (8) should be used for this problem. Under these con- 399

ditions, it is more evident for the students that the heat-flow 400

390 During this question, the instructor can suggest to the stu- rate is a dynamic phenomenon strongly linked to the initial 401

391 dents to vary UA from 5 to 20 W/K. Students should observe conditions (Fig. 10). 402

392 that the concentration distribution and the heat-flow rate Figs. 11A and B shows the concentration evolution of C and 403

393 should not change, but the jacket temperature will be lower at D with different initial temperature. It can be noticed that as 404

394 higher UA (Fig. 9). The instructor should explain that the reac- the reaction temperature increase, as the concentration of D 405

395 tion temperature and the jacket temperature can be similar in increases. 406

396 case of exothermic reactions under isoperibolic conditions if From Fig. 12, it is possible to determine some safety criteria 407

397 UA is high enough. such as the final temperature reached by the system and the 408

398 Response to question 3 time to reach this final temperature. 409

Fig. 11 – (A) Evolution of the concentration of C with different initial reaction temperatures. (B) Evolution of the
concentration of D with different initial reaction temperature.

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
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Fig. 13 – Evolution of temperature in case of neglecting the

Fig. 12 – Reaction temperature evolution with different
second reaction.
initial reaction temperatures.

One should plot the evolution of the reaction and jacket 428

410 It can be worth to give additional exercises such as to temperatures (Fig. 14) and the evolution of the concentration 429

411 investigate the same system under adiabatic conditions by distribution (Fig. 15). 430

412 neglecting the second reaction. The goal of this additional The goal of Figs. 14 and 15 is to highlight the difference 431

413 exercise is to demonstrate that the difference (Tr (Final) − Tr (0)) between these thermal modes. 432

414 is the same for a single reaction (Fig. 13). The concepts of adia- Response to question 5 433

415 batic temperature rise Tad and time to maximum rate under By running the program code at 100 ◦ C and with a reac- 434

416 adiabatic condition TMRad can be introduced. The goal of this tion volume of 0.4 L, it is possible to determine the difference 435

417 additional exercise is to highlight the case of a multiple reac- (Tj − Tr ). Then, it is possible to plot the graph in Fig. 16 and to 436

418 tion system. Students should be aware that in the presence know the needed surface area (slope of each curve) for each 437

419 of a single reaction, the adiabatic temperature rise Tad is the volume. 438

420 same at any initial reaction temperature. This is not the case The objective of this exercise is to illustrate the scale-up 439

421 in presence of composite reactions. issue. Cylindrical batch reactors as illustrated by Fig. 17 are 440

422 Response to question 4 considered. 441

423 At this moment, one can understand the difference From Table 1, it can be noticed that for a pilot batch reactor 442

424 between isothermal and adiabatic modes. At the end of this the external surface area is not big enough to ensure isother- 443

425 question, one should ask to the students to compare the same mal conditions, and the addition of an internal cooling coil 444

426 system under isothermal mode at 90 ◦ C, under adiabatic mode might be considered. 445

427 with Tr(0) = 90 ◦ C and under isoperibolic mode with Tj = 90 ◦ C. Response to question 6 446

Fig. 14 – Evolution of concentration for the three modes.

Fig. 15 – Evolution of temperature for the three modes.

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Table 1 – Features of the different reactors.

Volume (L) Diameter (m) Height (m) Surface area (m2 ) Required surface area (m2 )

0.4 0.04 0.29 0.04 0.01

5 0.15 0.30 0.16 0.18
10 0.15 0.60 0.30 0.36
100 0.30 1.50 1.48 3.57

that when UA is equal to 90 W/K, the reaction temperature 456

increase is not significant, thus one can consider the system 457

as isothermal. 458

The other discussion is how to vary the value of UA from 459

a design point of view. The instructor should first remind that 460

the heat exchange surface area can be increased by using some 461

internal coils, where the heat carrier fluid circulates. The value 462

of U depends of the nature of the reaction mixture (composi- 463

tion, temperature, conductivity) and of the heat carrier fluid 464

(conductivity, composition, temperature, velocity) (Lavanchy, 465

2005). 466

6. Introduction to thermal safety

assessment
Fig. 16 – Determination of the surface area.
At this moment of the course, students have a good knowledge 467

of the coupling of mass and energy balances; they know how to 468

determine the heat-flow rate and how to simulate quantitative 469

results, i.e., the progress of concentrations and temperature in 470

the reactor. Furthermore, they understand the methodology 471

Height
in case of composite exothermic reactions. This is the per- 472

fect timing to introduce some concepts of thermal safety as 473

described in the book of F. Stoessel (2008): 474

Diameter
- -thermal runaway with Semenov diagram, 475
Fig. 17 – Reactor dimension.
- -influence of UA, 476

- -critical temperature, 477

- -concept of TMRad and Tad . 478

- -Tnr 479

It is wiser to introduce these concepts with the corre- 480

sponding approximation after the lecture on mass and energy 481

balances coupling. Indeed, several safety criteria have been 482

determined by using zero order approximation (Leveneur et 483

al., 2015), which is considered to be the worst case scenario. 484

In case of thermal runaway, the heat-flow rate released by 485

chemical reactions is higher than the heat-flow rate absorbed 486

by heat carrier. The instructor should insist that some chem- 487

ical systems can evolve under these conditions (adiabatic or 488

isoperibolic) because the secondary reactions are not trigger 489

Fig. 18 – Influence of UA on reaction temperature under and/or the reactor was designed for such conditions. 490
isoperibolic mode with Tj = 90 ◦ C. It is easier to understand the Semenov curves by using 491

a zero-order reaction under isoperibolic mode (Fig. 19). A 492

447 This discussion should take place because it can be stable region occur when qrx < qexch . The students should 493
448 the source of misunderstanding. Indeed, a process can be observe that the heat-flow rate due to chemical reac- 494
449 performed under an isoperibolic mode and the reaction tem- tions increases exponentially, whereas the heat-flow rate 495
450 perature can be stable. There are two reasons for that: exchanged increases linearly. 496

When a reactor is operated at a critical cooling medium 497

451 - Reaction heat-flow rate, which is the product of reaction rate temperature (Tc ), an infinitely small increase of the cooling 498

452 times reaction enthalpy, is low, medium temperature leads to a runaway situation. This could 499

453 - The global heat transfer coefficient is high enough. have a dramatic effect if the secondary reactions are triggered. 500

Students should be aware that if heat transfer coefficient (UA) 501

454 By keeping the same reaction system, one can increase diminishes, due to fouling or inappropriate scale-up, then a 502

455 the global heat transfer coefficient (Fig. 18). It can be noticed runaway situation can appear. 503

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ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002
 ECE 121 1–12
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constant (isothermal mode), and at the end of the process, the 523

reaction mixture is cooled down. In case of a cooling failure, 524

the system can shift from isothermal to adiabatic mode. The 525

first temperature increase is due to the synthesis reactions 526

(desired and un-desired) and the second temperature increase 527

is due the secondary reactions producing non-condensable 528

products. If the secondary reactions are trigger, there is a risk 529

of explosion due to the overpressure inside the reactor. For 530

this reason, it is recommended to use a reflux condenser or a 531

rupture disk. 532

There are several kinds of calorimeters to study a chemical 533

system under adiabatic conditions allowing to follow the evo- 534

lution of the pressure in the gas phase. To model such system, 535

one should consider the liquid–gas mass transfer, the vapor 536
Fig. 19 – Semenov curves.
liquid equilibrium, and the kinetics of secondary reactions. 537

504 At the critical temperature, we obtain The knowledge of secondary reactions can be difficult and 538

requiring the use of on-line analytical techniques (Leveneur 539

dqrx dqexch et al., 2007). 540

505 = (10)
dt dt At this moment of the lecture, the instructor can present a 541

slide showing the different type of calorimeter and how these 542
506 For a zero-order reaction, the stability is reached if parameters can be measured or determined. 543

From Fig. 20, there are different messages to deliver: 544

R · Tcrit
2
507 Tcrit = Tcrit − TR ≥ with Tcrit
Ea
   - TMRad and Tad represent the probability and severity of 545
Ea 4 · R · T0 the risk,
508 = 1± 1− (11) 546
2·R Ea - The time and period of cooling failure can lead to different 547

consequences, if the cooling failure occur at the beginning 548

509 Students should be aware that in the presence of a complex of the reaction, then the severity can be high, 549

510 reaction system, a numerical approach is inevitable. - Fig. 20 is a pedagogic image, there is not a distinct plateau 550

511 The other important concept is the time of no return (Tnr). between the synthesis and secondary reactions. 551

512 If the system shifts to adiabatic conditions due to a failure for a - On a reactor system, there is some rupture disk to avoid the 552

513 period of time, then even if the cooling system is coped, there overpressure or some emergency relief system. 553

514 is no possibility to return to the initial thermal mode.

515 A proper way to introduce the different safety criteria such
An example will be treated to illustrate this figure for the 554
516 as TMRad or Tad is by using the example of an exothermic
project. 555
517 chemical system in a batch reactor under isothermal condi-
By assuming a zero-order reaction, one can calculate the 556
518 tions.
TMRad as: 557
519 Fig. 20 illustrates the different safety criteria during a cool-
520 ing failure, e.g., circulation of the heat carrier is stopped. Under
Cp · R · Tref
2
521 normal conditions, reactants are heating until the desired TMRad = (12) 558
522 temperature, after which the reaction mixture is maintained qrx,ref · Ea

Fig. 20 – Cooling failure scenario for an exothermic reaction system in a batch reactor.

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002
 ECE 121 1–12
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A + B → C (R1 ) 591

B → D (R2 )C + C → E (R3 ) 592

Kinetic data and thermodynamic constants for both reac- 593

tions are listed below 594

R1 = k1 ·[A]·[B]k1 = 0.2 × 10−4 L/(mol min) at 40 ◦ C 595

Ea1 = 60 kJ/mol 596

HR1 = −60 kJ/mol 597

R2 = k2 ·[B] 598

k2 = 0.6 × 10−9 min−1 at 40 ◦ C 599

Ea2 = 80 kJ/mol 600

HR2 = −100 kJ/mol 601

R3 = k3 ·[C]2 k3 = 1.0 × 10−13 L/(mol min) at 40 ◦ C 602

Ea3 = 260 kJ/mol 603

HR3 = −250 kJ/mol 604

The company purchased a cooling system to maintain the 605

reaction temperature at 130 ◦ C with UA = 5 W/K. In case of mal- 606

function, there is another cooling system working at 130 ◦ C. 607

The initial concentrations of A and B are 3 mol/L; and the con- 608

centrations for the other compounds are 0 mol/L. 609

1. Determine the reaction time to reach the maximum pro- 610

duction of compound C under isothermal conditions and 611

plot the evolution of the reaction and jacket temperature. 612

Fig. 21 – Reactor system. 2. The maximum temperature for technical reasons is 300 ◦ C. 613

Determine the adiabatic temperature rise and TMRad for 614

559 The two other safety criteria important to be introduced this system for the worst case scenario. 615

560 are: 3. During the process under normal conditions at 130 ◦ C, 616

under isothermal conditions, a cooling failure occur at time 617

10 000 s for 1700 s. The operator manages to fix the heat car- 618
561 - MTT is the maximum temperature for technical reason,
rier fluid circulation problem, but the cooling system still 619
562 which is linked to the resistance of the reactor structure.
did not work. Thus, the jacket temperature was constant 620
563 This criteria is usually the boiling point of the reaction mix-
and equal to 130 ◦ C at time 11 700 s. In such conditions, is it 621
564 ture.
possible to have an explosion if the process is schedule to 622
565 - TD24 is the temperature at which TMRad is 24 h. This criterion
last 300 min? 623
566 is complicated to determine accurately and need the use of
4. Based on the previous accident, determine with these oper- 624
567 low ϕ-factor calorimeter. For that reason, Eq. (12) is often
ating conditions the time of no return. 625
568 used.
5. Which are the consequences of the incident on the product 626

distribution? Due to the space limitation of the journal, the 627

569 By knowing all these criteria, it is possible to rank the ther-
responses to the problem are provided in supplementary 628
570 mal risk of a chemical process (Stoessel, 2008). One should
(S4). 629
571 really insist on the fact that usually worst case scenario is
572 considered, i.e., full reactant accumulation, batch reactor and
573 adiabatic conditions. 8. Conclusion
574 Introducing this approach without a complete upgrading of
575 mass and energy balances can lead the future chemical engi- We presented a pedagogical approach to present the strong 630
Q6 neers to make some wrong assessment or decision (Fig. 21).
576
coupling between mass and energy balances. It is important 631
577 Based on this introduction on process safety, the process for undergraduate or master students to take into account 632
578 safety course can start by discussing about the different ther- the different heat-flow rates at stake in a chemical reactor 633
579 mal techniques to determine the safety criteria, the Stoessel and to differentiate the different thermal modes before to 634
580 criticality classes, the calculation of vent size, the early detec- start a course on process safety. We have used some exercises 635
581 tion, etc. The study of different industrial accidents can be based on numerical methods where the students should plot 636
582 done (Al-shanini et al., 2014). the evolution of the reaction temperature, jacket temperature 637

and the heat-flow rates exchanged with the hat carrier and 638
7. Thermal risk project released by the chemical reactions. 639

For the students, this pedagogical approach is time- 640

583 The following project can be introduced at the end of the depending. Indeed, they have to be familiar with the code 641

584 course to master the numerical and the safety aspects. environment and understand the phenomenology. However, 642

585 A company wants to produce a compound C from A and B the 3-weeks project give them the time to test the code and 643

586 under isothermal conditions in a batch reactor. to understand the project. We have also noticed that the stu- 644

587 The total mass of the reaction mixture is 6 kg for a volumet- dents were thinking to develop some safety barrier such as the 645

588 ric mass of 1 L/kg. The heat capacity of the reaction mixture is introduction of an emergency cooling system. 646

589 constant during the process (2 kJ/(kg K)). The knowledge of the different notions taught in this 647

590 However, two other side reactions appear in the process: course will help the undergraduate or master students to 648

Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002
 ECE 121 1–12
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649 understand and to be critical vis-à-vis of the simplification Law, J.V., 2013. Numerical Methods for Chemical Engineers Using 691

650 done during the risks assessment of a chemical process. Excel, VBA and MATLAB, 1st ed. CRC Press. 692

651 The process safety course can start by presenting the dif- Leveneur, S., Estel, L., Crua, C., 2015. Thermal risk assessment of 693
vegetable oil epoxidation. J. Therm. Anal. Calorim. 122, 694
652 ferent thermal equipment and calorimeters used to determine
795–804, http://dx.doi.org/10.1007/s10973-015-4793-8. 695
653 the safety criteria, how to take into account the evolution Leveneur, S., Salmi, T., Musakka, N., Wärnå, J., 2007. Kinetic study 696
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Please cite this article in press as: Leveneur, S., et al., Mass & energy balances coupling in chemical reactors for a better understanding of
ECE 121 1–12
thermal safety. Education for Chemical Engineers (2016), http://dx.doi.org/10.1016/j.ece.2016.06.002