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Article

Cite This: Ind. Eng. Chem. Res. 2017, 56, 14771−14780 pubs.acs.org/IECR

Development of Adiabatic Criterion for Runaway Detection and Safe


Operating Condition Designing in Semibatch Reactors
Zichao Guo,* Liping Chen, and Wanghua Chen
Department of Safety Engineering, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, Jiangsu
210094, China
*
S Supporting Information

ABSTRACT: To prevent the occurrence of thermal runaway


accidents in semibatch reactors (SBRs), it is desirable and
practicable to develop criteria that can distinguish between the
safe and runaway operating regions. In this article a new safety
criterion, namely, the adiabatic criterion, has been developed
for SBRs in which liquid homogeneous as well as liquid−liquid
heterogeneous reactions with arbitrary reaction orders occur. It
states that an SBR is operated in the potential runaway
situation if the value of the adiabatic criterion exceeds zero at a
segment of the reaction path. Numerical results show that the
adiabatic criterion is more conservative than the two other
criteria (divergence criterion and target temperature criterion). However, the adiabatic criterion is not suitable to reactions with
autocatalytic behaviors. Also knowledge of activation energies and reaction enthalpies is necessary to utilize the adiabatic
criterion.

1. INTRODUCTION target temperature profile, three operation scenarios in


In the fine chemical and pharmaceutical industries, exothermic isoperibolic SBRs, namely, no ignition, thermal runaway, and
reactions are usually conducted in the semibatch reactors QFS, could be observed. The accumulation of the dosed
(SBRs) to prevent the occurrence of thermal runaway events. component in QFS scenario could be identified as harmless
By tuning the dosing rate of reactants, the heat release rate can because the temperature profile of the reaction mass was
be controlled to match the cooling capacity of reactor jackets or smooth. On the basis of this consideration, they developed a
coils. However, incidents of loss of temperature control in SBRs series of boundary diagrams to help designing thermally safe
still occur from time to time, mainly resulting from improper operating conditions for isoperibolic SBRs.5,6 However, these
design of the operating conditions or maloperation. boundary diagrams did not include the information on the
To prevent thermal runaway incidents in SBRs, designing the triggering of the second reactions. To solve this problem, Ni
right operating conditions should be considered first.1 In the and co-workers7,8 developed the modified boundary diagrams
last decades, many works have been devoted to this issue. The in their recent series of works, in which the information on the
pioneers are Hugo and Steinbach2 who observed that an maximum allowable temperature had been included.
accumulation of the dosed component at too low reactor In addition, another important sort of safety criterion9,10 was
temperature was the cause of the runaway in homogeneous developed on the basis of parametric sensitivity. This criterion
SBRs. The ideal safe behavior of SBRs can be identified as that predicted a parametrically sensitive or runaway region, which
the dosed reactant immediately reacts with the component might be called “generalized” because the maximum temper-
initially present in the SBRs, indicating that completely no ature became simultaneously sensitive to small changes to any
accumulation can be observed. However, it is not possible to of the model inputs.
avoid accumulation completely in a realistic case. As an In a practical SBR, a basic safety principle is that MTSR (the
alternative solution, it is desirable and practicable to develop maximum temperature of synthesis reaction) should be lower
criteria to distinguish between the safe and runaway operating than a maximum allowable temperature (MAT), which
regions. generally refers to the onset decomposition temperature of
Hugo and Steinbach3 determined empirically from their reaction mixture (TD) or the maximum temperature for
calculations that as long as the Damköhler number Da = kcB0tdos technical reason (MTT).11,12 This basic safety principle has
was smaller than the modified Stanton number St = (UAtdos/
VCpρ), which was renamed as the Westerterp number in 2010,4 Received: October 8, 2017
the SBRs could be considered to be performed in a safe way. Revised: November 27, 2017
Steensma and Westerterp5,6 stated that resulting from Accepted: November 27, 2017
comparison of the reaction mass temperature profile with a Published: November 27, 2017

© 2017 American Chemical Society 14771 DOI: 10.1021/acs.iecr.7b04181


Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

Table 1. Expression of the Reactivity Enhancement Factor, RE, and of the Function, f, for Homogeneous and Heterogeneous
SBRs in Which Slow or Fast Reactions Occur in the Dispersed or Continuous Phase
Homogeneous SBRs
RE (vB/vA)1−n
f (θ − X)n(1 − X)m/(1 + εθ)n+m−1
Heterogeneous Liquid−Liquid SBRs
reactions in the dispersed (d) phase reactions in the continuous (c) phase
REslow,c/d (vB/vA) mmB
1−n
(vB/vA) mmA
1−n

REfast,c/d (6/db,0)mB(m+1)/2CB,0(1−n−m)/2(vB/vA)(1−n)/2[2DL,B/((m + 1)k)]1/2 (6/db,0)mA(n+1)/2CB,0(1n−m)/2(vB/vA)(1−)/2[2DL,A/((n + 1)k)]1/2


fslow,c/d (θ − X) (1 − X) /(εθ)
n m n−1
(θ − X)n(1 − X)m/(εθ)n
f fast,c/d [(θ − X)n/2(1 − X)(m+1)/2(εθ)n−1]/[1 + 2.5εθ/(1+εθ)] [(θ − X)(n+1)/2(1 − X)m/2(εθ)(1−n)/2]/[1 + 2.5εθ/(1 + εθ)]

been widely utilized in chemical industries.13,14 Along this line, In general, when a thermal runaway event occurs, qr(t) must
Maestri and Rota developed the temperature diagrams to have been higher than qex(t); consequently, the reaction
predict the maximum temperature reached for the isoperibolic temperature increases and then promotes the heat generation
SBRs.15 rate in return. With respect to qex, though it always increases
Online monitoring the SBRs is another important way to with reaction temperature increasing, its rising rate cannot keep
ensure safety in SBRs. Hub and Jones16 proposed a simple pace with the rising rate of qr when thermal runaway occurs.
criterion, which stated that the SBRs were in a runaway From the above analysis, it can be reasonably expected that
situation once the first and second derivatives of the reactor SBRs can be remained in stable state if the first derivative of qex
temperature were positive simultaneously. Zaldivar. ́ and co- to time is always higher than that of qr at any instant, namely
workers17,18 proposed a more advanced divergence criterion,
which was derived from characterization of chaotic attractors in dqr dqex
<
dynamical systems. This divergence criterion states that when dt dt (3)
the divergence of the dissipative reactive systems exceeds zero
at a segment of the reaction path, the reaction is under a As mentioned previously, qex will increase before thermal
potential risk of thermal runaway. Recently, Maestri and runaway occurs, in other words, dqex/dt must be positive. We
Rota19−21 proposed a kinetic-free SBR monitoring method can reasonably expect that if the value of dqr/dt is negative over
based on the concept of X number that did not require any the entire reaction course, the reaction temperature can be
kinetic characterization of the system, but only the much more certainly controlled and no runaway event occurs.
straightforward estimation of the reaction heat. They have Before deducing the expression of dqr/dt, let us assume that a
successfully applied their kinetic-free method to both single and single exothermic reaction is performed in a stirred SBR
consecutive side reactions. equipped with the cooling jacket:
In addition, we recently developed an adiabatic criterion for vA A + vB B → C + vDD (4)
runaway detection in SBRs in which homogeneous exothermic
reactions were handled.22 This adiabatic criterion states that if where A and B are the reactants, C is the desirable product, and
the value of adiabatic criterion is lower than zero, then both the D is the side product, vi is the stoichiometric coefficient of the
second derivatives of conversion and reaction temperature to components. The number of vi for C is assumed to be equal to
time are lower than zero even in the undesirable case of 1. In addition, reactant B is supposed to be loaded into the
complete cooling failure. Regretfully, the previous work only reactor initially and reactant A is dosed at a constant rate until
took into account the homogeneous reactions. It is well-known the stoichiometric amount of A is added.
that many strongly exothermic reactions belong to liquid− Before we proceed the discussion, some assumptions can be
liquid reaction systems, such as nitration, oxidation, sulfonation, stated as follows:
and so forth. Hence, it is necessary to extend the adiabatic (1) The reaction mass is perfectly macromixed.
criterion to liquid−liquid situations. Moreover, how to employ (2) The influence of the chemical reaction on the reaction
this criterion to design thermally safe operating conditions for volume is negligible.
SBRs will be discussed in this work. (3) No phase inversions occur during the reaction duration
for liquid−liquid reactions.
2. DEVELOPMENT OF THE ADIABATIC CRITERION (4) The chemical reaction takes place only in one of the two
For SBRs in which single-step liquid homogeneous or liquid− liquid phase: this situation is very common in industrial
liquid heterogeneous exothermic reactions occur, to prevent the processes (such as nitration and oxidations), in which the
occurrence of thermal runaway, two safety constraints should catalyst (typically a strong acid) is present only in one
be fulfilled generally:23 phase.
qr(t ) ≤ qex,max (t ) (5) Heat dissipation by the agitator or mixing effect is
(1) negligible relative to the reaction heat; consequently, the
heat effects are only associated with the chemical
Tcf (t ) ≤ MAT (2) reaction.
where qr is the heat release rate by the exothermic reactions, qex (6) The physicochemical properties of all the components
is the heat exchange rate through cooling devices, Tcf is the are constant and additive during the whole reaction.
temperature reached when complete cooling failure occurs, the On the basis of the above assumptions, for SBRs in which
subscript of “max” means maximum. strongly exothermic liquid homogeneous or liquid−liquid
14772 DOI: 10.1021/acs.iecr.7b04181
Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

heterogeneous reactions are carried out, qr can be formulated as liquid−liquid heterogeneous reactions, dqr/dt can be ensured to
follows be negative as long as the following two equations are fulfilled
nB0ΔHr dXB ⎧ ΔT ·E n + (m + 1)θ − (n + m + 1)XB
qr = ⎪ 2
− <0
tdosvB dθ (5) ⎪ RTr (1 − XB)(θ − XB)

⎪ for fast reactions in the dispersed phase
where nB0 is the initial amount of B in SBRs, ΔHr is molar ⎨
reaction enthalpy, tdos is the dosing period of the dosed ⎪ ΔT ·E n + 1 + mθ − (n + m + 1)XB
component A, XB is the conversion of reactant B, θ = t/tdos is ⎪ 2
− <0
RT
⎪ r (1 − XB)(θ − XB)
the dimensionless form of time. The conversion rate for single ⎪ for fast reactions in the continuous phase
⎩ (13)
exothermic homogeneous and liquid−liquid heterogeneous
reactions in SBRs can be expressed in a general dimensionless ΔT ·E n+m+1
form as follows − <0
RTr 2 (1 − XB) (14)
dXB
= vA ·Da ·RE·f
(6) Equation 13 is suitable in the dosing period, and if θ ≥ 1, eq 14

needs to be employed.
where Da is the Damköhler number and RE is the reactivity In general, the accumulation of component B that is initially
enhancement factor. The expressions of Da, RE, and f in eq 6 added in the SBRs can be defined as follows
are summarized in Table 1.
From eqs 5 and 6, dqr/dt at any time can be derived as Xac = θ − XB (15)
follows After substituting eq 15 into eqs 11 and 12, we can get
dqr n ΔH ⎡ dT E ΔT ·E n − mθ + (n + m)Xac
= B0 r ⎢vADa RE f r − <0
dt tdosvB ⎣ dt RT 2 RTr 2
(1 + Xac − θ )Xac (16)
dX n + mθ − (n + m)XB ⎤ ΔT ·E n+m
− vADa RE f B ⎥ − <0
dt (1 − XB)(θ − XB) ⎦ (7) RTr 2 1 + Xac − θ (17)
where n and m are the reaction orders with respect to From eqs 16 and 17, it is apparent that as the values of ΔT
component A and B respectively. and/or E increase, the allowable accumulation decreases.
dTr/dt in eq 7 can be expressed as follows In addition, because the temperature rise rate for exothermic
dTr dX reactions under adiabatic conditions is linearly proportional to
= ΔT B qr, namely
dt dt (8)
dT q
ΔT in eq 8 can be formulated as follows = r
dt mCp (18)
nB0ΔHr 1
ΔT =
(CpρV )0 1 + RHεθ Thus the second derivatives of temperature must be negative as
(9)
long as eqs 11−14 are fulfilled. Hence, the combination of eqs
where RH = (ρCp)A/(ρCp)B is ratio of the volumetric heat 11−14 is called the adiabatic criterion in this article.
capacities of the dosed component A and B, ε = Vdos/V0 is the
relative volume increase at the end point of the feed period, ρ is 3. VALIDITY OF THE ADIABATIC CRITERION
density, Cp is specific heat capacity, and the subscript of 0 In this part, only kinetically controlled liquid−liquid reactions
represents initial state. that occur in the continuous phases are taken as an example to
Substituting eqs 6 and 8 into eq 7 gives show the validity of the adiabatic criterion because the same
nB0ΔHr ⎛ dXB ⎞ ⎡ ΔT ·E n + mθ − (n + m)XB ⎤
dqr 2 tendency can be observed in liquid homogeneous as well as
= ⎜ ⎟⎢ − ⎥ liquid−liquid heterogeneous reactions occurring in isoperibolic
dt tdosvB ⎝ dt ⎠ ⎣ RTr 2 (1 − XB)(θ − XB) ⎦ SBRs.
(10) 3.1. Comparison with Other Criteria in Isoperibolic
Apparently, dqr/dt in eq 10 must be negative as long as SBRs. In this part, the adiabatic criterion will be validated
through comparisons with the divergence criterion and the
ΔT ·E n + mθ − (n + m)XB target temperature criterion in isoperibolic SBRs. The general
− <0
RTr 2
(1 − XB)(θ − XB) (11) dimensionless form of the mass balance equation of component
B for liquid homogeneous as well as liquid−liquid heteroge-
where E is the activation energy and R is the gas law constant. neous reactions can be expressed in the form of eq 6. The
It is worthwhile to note that eq 11 is suitable only during the general dimensionless heat balance equation reads
dosing period, namely θ < 1. If θ ≥ 1, eq 11 should be rewritten
as dτ 1 ⎡ dXB
= ⎢⎣Δτ0 − ε(Wt(1 + εθ )(τ − τj)
ΔT ·E n+m dθ (1 + εθRH) dθ
2
− <0 ⎤
RTr (1 − XB) (12) + RH(τ − τdos))⎥
⎦ (19)
It is notable that eqs 11 and 12 are suitable to both liquid
homogeneous and kinetically controlled liquid−liquid hetero- With respect to the target temperature criterion, the value of
geneous reactions. With respect to single diffusion controlled target temperature can be obtained by
14773 DOI: 10.1021/acs.iecr.7b04181
Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

Figure 2. Isoperibolic SBRs profiles at τj = τdos = 0.948: (a)


dimensionless temperature profile; (b) criteria values profiles. vADa RE
= 1.8, ε = 0.4, γ = 38, Wt = 10, RH = 1, Δτ = 0.6, n = 1, m = 1.

∂(dXB/dθ ) ∂(dτ /dθ )


div = +
∂XB ∂τ (21)

The comparison of the three criteria for isoporibolic SBRs


are illustrated in Figures 1−3. Some more examples are listed in
the Supporting Information.
According to the target temperature criterion and the
Figure 1. Isoperibolic SBRs profiles at τj = τdos = 0.92: (a) divergence criterion, the case in Figure 1a can be identified
dimensionless temperature profile; (b) criteria values profiles; (c)
definitely to be a thermal runaway event. In Figure 1b, the value
dτ/dθ profile for two criteria. vADa RE = 1.8, ε = 0.4, γ = 38, Wt = 10,
RH = 1, Δτ = 0.6, n = 1, m = 1. of the adiabatic criterion surpasses zero at time of θ = 0.05,
indicating that the adiabatic criterion can also identify the
⎧ Wt (1 + εθ)τj + RHτdos Δτad,0 runaway event. In addition, from Figure 1a,b, the time at which
⎪ + 1.05 the values of the three criteria start to be positive can be ranked
⎪ Wt (1 + εθ) + RH ε(Wt (1 + εθ) + RH)
⎪ as adiabatic criterion < divergence criterion < target temper-
⎪ θ≤1
τta = ⎨ ature criterion, which implies that the adiabatic criterion can
⎪ Wt (1 + ε)τj + RHτdos Δτad,0 identify the thermal runaway event at the earlier stage.
⎪ + 1.05
⎪ Wt (1 + ε) + RH ε(Wt (1 + ε) + RH) To vividly show the physical meaning of the adiabatic
⎪ criterion, the comparison of the first derivatives of temperature
⎩ θ>1
(20) profiles between the adiabatic criterion and the divergence
criterion, with the assumptions that cooling failure event occurs
The target temperature criterion state that the SBRs are in as well as the dosing event stops once the values of adiabatic
the thermal runaway situation if the reaction mass temperature criterion and the divergence criterion equal to zero, are
surpasses the target temperature. If the reaction mass illustrated in Figure 1c. Apparently, the values of dτ/dθ for the
temperature is lower than the target temperature, the value of adiabatic criterion are continuously decreasing after the point at
target temperature criterion is negative. which the value of the adiabatic criterion is equal to zero. That
The values of divergence for the isoperibolic SBRs can be is to say, the value of d2τ/dθ2 under adiabatic conditions must
calculated through the following equation be negative as long as the adiabatic criterion is negative, just like
14774 DOI: 10.1021/acs.iecr.7b04181
Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

Figure 4. Comparison of the adiabatic criterion to the target


temperature criterion: (a) variable of Δτad,0; (b) variable of γ. vADa RE
= 1.8, ε = 0.4, Wt = 13, RH = 1, n = 1, m = 1.

Figure 3. Isoperibolic SBRs profiles at τj = τdos = 0.958: (a)


dimensionless temperature profile; (b) criteria values profiles; (c) d2τ/
dθ2 profile under adiabatic condition for the adiabatic criterion.
vADa RE = 1.8, ε = 0.4, γ = 38, Wt = 10, RH = 1, Δτ = 0.6, n = 1, m = 1.

the profile in Figure 3c. In contrast, the value of the dτ/dθ Figure 5. Comparison of the accumulation profiles in Figures 1−3.
profile for the divergence criterion presents an increasing vADa RE = 1.8, ε = 0.4, γ = 38, Wt = 10, RH = 1, Δτ = 0.6, n = 1, m = 1.
tendency at the initial stage after the point at which the value of
the divergence criterion is equal to zero. In Figure 2a, the
temperature profile is identified to be QFS by both the target are negative, hence the temperature profile in Figure 3a
temperature criterion and the divergence criterion, whereas the undoubtedly corresponds to QFS situation. From the above
adiabatic criterion still states that the case in Figure 2a is in a results, we can reasonably expect that as long as the values of
potential runaway situation, indicating that with the adiabatic adiabatic criterion are negative, the values of the target
criterion, conservative assessment results will be obtained. In temperature criterion and divergence criterion must be also
Figure 3, it can be seen that the values of all the three criteria negative. In other words, the adiabatic criterion is conservative
14775 DOI: 10.1021/acs.iecr.7b04181
Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

Figure 7. Isothermal SBRs profiles at τj = τdos = 1.055: (a) τcf and Xac
profile; (b) value profile of adiabatic criterition. vADa RE = 1.8, ε = 0.4,
γ = 38, Wt = 10, RH = 1, Δτ = 0.6, n = 1, m = 1.

indicates that the adiabatic criterion is more conservative


checking whether the isoperibolic SBRs are in QFS situation.
In addition, to illustrate the reactor productivity, the
accumulation profiles within the dosing period are shown in
Figure 5. It is generally considered that the lower the maximum
accumulation, the higher the reactor productivity. Obviously,
when the adiabatic criterion is lower than zero within the whole
dosing period, there is the lowest accumulation, which means
that the reactor productivity is relatively high if the value of
adiabatic criterion is achieved.
3.2. Validity in Isothermal SBRs. The validity of the
adiabatic criterion in isothermal SBRs will be presented in the
Figure 6. Isothermal SBRs profiles at τj = τdos = 0.96: (a) τcf and Xac following. The results are shown in Figures 6 and 7.
profile; (b) value profile of adiabatic criterition; (c) dτ/dθ profile. To design isothermal SBRs, one important aspect of the
vADa RE = 1.8, ε = 0.4, γ = 38, Wt = 10, RH = 1, Δτ = 0.6, n = 1, m = 1. safety assessment is to determine at which instant the
accumulation is at a maximum. In general, as for isothermal
reactions that obey N-order kinetics, the maximum accumu-
for checking whether the isoperibolic SBRs are in QFS lation Xac,max appears at the instant when the stoichiometric
situation. amount of the dosing reactant is added and consequently the
An interesting phenomenon can be found in the Figures 2b maximum value of τcf(θ) also appears at the dimensionless time
and 3b that the profiles of the adiabatic criterion and of the of θ = 1, as shown in Figures 6a and 7a. Herein, τcf(θ) denotes
divergence criterion almost overlap, which imply that the the temperature obtained if complete cooling failure occurs at
overlapping occur when SBRs are operating in QFS situation. any instant of θ and the dosing stops simultaneously.
The above discussion is based on only one set of the model From the safety view of point, the value of Xac,max should be
parameters, as shown in the captions of Figures 1−3. To further low enough; otherwise, the accumulated reactants, if cooling
verify the validity of the adiabatic criterion, comparison of the failure event occurs at this instant, would autoaccelerate the
adiabatic criterion and the target temperature with a reaction rate and ultimately render the reaction to risk situation,
tremendous amount of simulation work is conducted, as such as temperature jump and too high temperature that even
shown in Figure 4. Obviously, the adiabatic criterion indicates a could triggers subsequent dangerous decomposition reactions.
higher τc relative to the target temperature criterion to operate Therefore, determination of the acceptable Xac,max is of high
within the inherently safe region QFS. This trend undoubtedly importance in isothermal SBRs.
14776 DOI: 10.1021/acs.iecr.7b04181
Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

Figure 8. Temperature profiles for isoperibolic SBRs in cases that τj is variable: (a) τj = τdos = 1.055; (b) τj = τd = 1.065; (c) τj = τd = 1.075; (d) τj =
τd = 1.085. vADa RE = 1.8, ε = 0.4, γ = 38, Wt = 10, RH = 1, Δτ = 0.6, n = 1, m = 1.

To deal with this problem, Stoessel and co-workers11,12 potential runaway situation. To prevent the potential runaway
suggest that the value of Xac,max is acceptable as long as MTSR is accidents, the simplest response is stopping dosing the reactant
lower than MAT. This idea has been widely used in chemical once the value of the adiabatic criterion exceeds zero. For better
industries. However, on the basis of our experiences, this idea is understanding, let us assume that the dosing event is stopped at
a little conservative in some cases. In our opinion, the adiabatic θ = 0.085 in Figure 6. One can observe in Figure 6c that the
criterion can be utilized as an alternative option. To illustrate first derivatives of temperature profile under cooling failure
this opinion, the case of isothermal SBR, in which kinetically condition is continuously decreasing with time going on.
controlled liquid−liquid reactions that occur in the continuous 3.3. Relationship between Isothermal and Isoper-
phases, is taken as an example. ibolic SBRs. From the above analysis, we can reasonably
As shown in Figures 6 and 7, the isothermal SBRs are expect that if the values of the adiabatic criterion in the case of
simulated at two different dimensionless temperatures, i.e., 0.96 isothermal SBRs are negative over the whole the process, then
and 1.055. The other parameters required can be found in the isoperibolic SBRs with the initial temperatures equal to or
figure captions. The value of Xac,max in the first case is 0.59. higher than the corresponding reaction temperature in
Obviously, this Xac,max is significantly higher than that at the isothermal SBRs must be operated in the QFS situation. In
relatively high temperature, that is, 0.59 > 0.13. Therefore, the fact, we find that as long as the value of the adiabatic criterion at
first case can be considered to be in a more risky situation than θ = 1 in the isothermal SBRs is negative, the corresponding
the later one. This judgment is explicitly evidenced by the isoperibolic SBRs belong to QFS operation as well. For better
adiabatic criterion profiles in Figures 6b and 7b. The values of understanding, an example is illustrated in Figure 8, in which
the adiabatic criterion in Figure 6b exceed zero after the initial temperatures of the four isoperibolic SBRs profile are
dimensionless time θ = 0.085; in contrast, the values of the equal to or higher than the reaction temperature in Figure 7. It
adiabatic criterion in Figure 7b are negative over the whole is obvious that all the cases in Figure 8 belong to QFS
dosing period. According to the physical meaning of the situations. This phenomenon can be interpreted theoretically as
adiabatic criterion, it can be expected that the first derivatives of follows: the reaction temperatures in isoperibolic SBRs must be
the temperature profiles under cooling failure condition for the higher than that in isothermal SBRs, as a result of which the
second case in Figure 7 must be always negative. With respect reaction reactivity is higher in isoperibolic SBRs and
to the first case in Figure 6, it can be considered to be in a subsequently the accumulation is lower. Consequently, the
14777 DOI: 10.1021/acs.iecr.7b04181
Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

Figure 9. Temperature profiles for isoperibolic SBRs in cases that Wt is variable: (a) Wt = 5; (b) Wt = 10; (c) Wt = 20; (d) Wt = 40. vADa RE = 1.8,
ε = 0.4, γ = 38, RH = 1, Δτ = 0.6, τj = τdos = 1.055, n = 1, m = 1.

values of the adiabatic criterion must be negative in isoperibolic overall coefficient of heat transfer, U, reaction enthalpy. Here, it
SBRs. is worthwhile to highlight that the second method can also be
On the basis of the above analysis, we can make another considered as a useful tool to safely monitor the exothermic
expectation that regardless of the values of Wt, isoperibolic reactions that are operated in the SBRs. This application has
SBRs must be in QFS situation as long as the initial been in detail interpreted in the recent series of papers that
temperature is not less than the reaction temperature in Figure published by Maestri.19−21
7. One example is illustrated in Figure 9. The values of initial Moreover, the information on the adiabatic temperature rise
temperature and dosing period are equal to that in Figure 7. (ΔT) and activation energy (E) are also essential for
Four values of Wt are taken for the sake of example: 5, 10, 20, application of the adiabatic criterion. In practice, these two
and 40. It is obvious that all the four cases in Figure 9 are in
parameters can be conveniently determined with the
QFS situation, indicating that this tendency is independent of
calorimetric tools, such as reaction calorimeter (RC1),
the values of Wt indeed.
differential scanning calorimeter (DSC), accelerating rate
4. MORE DISCUSSION calorimeter (ARC).
In fine chemical industry, isoperibolic SBRs are probably the
This adiabatic criterion can be used to detect the potential risk simplest and most widely used reactors. The task of designing
situation and design thermally safe operating conditions for the right operating parameters for these SBRs should start from
SBRs. Nevertheless, its application necessitates the information
laboratory scale stage. In this stage, we suggest the adiabatic
on temperature of reaction mixture and conversion of the
criterion should be taken into account. For a given reaction
reactants. In practice, the reaction temperature could be
conveniently measured by temperature sensor, whereas recipe, initial reaction temperature and dosing period are the
obtaining real-time conversion information is difficult. For the two key parameters to be designed. The main purpose in
best of our knowledge, two types of methods to deal with this laboratory scale is to design a right set of these two parameters
problem are available: online spectroscopy, for example, FTIR to ensure that the values of the adiabatic criterion is negative.
and Raman, and balance based monitoring.19−21,24 The first Then provided that the mixing effect could be neglected, the
one is independent of process control but requires high cost two parameters can be scaled up to industrial scale. With the
and calibration effort. The second one is cost-efficient and knowledge about the overall coefficient of heat transfer and
virtually independent of process control but requires advanced reaction enthalpy, Tta,max in the industrial scale plants can be
knowledge of process and plant parameters, for example, the calculated through eq 22.
14778 DOI: 10.1021/acs.iecr.7b04181
Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

Wt(1 + ε)Tj + RHTdos C = instantaneous concentration, mol·m−3


Tta,max = + 1.05 Cp = specific heat capacity, J·kg−1·K−1
Wt(1 + ε) + RH
Da = Damköhler number at the reference temperature (TR),
ΔTad,0 Da = kRtdosCB,0
ε(Wt(1 + ε) + RH ) (22) DL = diffusion coefficient
E = activation energy, J·mol−1
Because the values of the maximum reached temperature f = function of the dimensionless time and conversion of
(Tmax) must be lower than that of Tta,max in QFS situation, the component B
designed operating parameters can be considered as the right Ha = Hatta number
option as long as the value of Tta,max is lower than MAT. k = kinetic rate constant, m3·mol−1·s−1
kL = mass transfer coefficient
5. CONCLUSION m = distribution coefficient or mass
In summary, a new safety criterion named adiabatic criterion is MAT = maximum allowable temperature, K
developed for runaway detection and safe operating condition nB = number of moles of the component B
designing in SBRs in which liquid homogeneous as well as r = instantaneous reaction rate, mol·m−3·s−1
liquid−liquid heterogeneous reactions with arbitrary reaction RH = ratio of the volumetric heat capacities of the dosed
orders occur. It states that an SBR is operated in the potential component A and B, RH = (ρCp)A/(ρCp)B
runaway situation if the value of the adiabatic criterion exceeds RE = the reactivity enhancement factor
zero at a segment of the reaction path. Simulation results St = Stanton number St = (UAtdos/Vcpρ)
evidence that the adiabatic criterion is more conservative in t = time, s
checking whether the isoperibolic SBRs are in QFS situation T = temperature, K
relative to target temperature criterion and divergence criterion. Tta = target temperature, K
The physical meaning of the adiabatic criterion is that the value U = overall heat transfer coefficient, W·m−2·K−1
of d2τ/dθ2 under adiabatic conditions must be negative as long V = actual volume of the reactor content, m3
as the value of adiabatic criterion is negative. In isothermal Wt = Westerterp number, Wt = (UA)0tdos/(ε(ρCp)0V0)
SBRs, the adiabatic criterion can be utilized as an alternative X = conversion
option for the widely accepted criterion of MTSR < MAT. In Greek Symbols
addition, we numerically demonstrate that if the values of the γ = dimensionless activation energy, γ = E/RTR
adiabatic criterion are negative in isothermal SBRs, isoperibolic ε = relative volume increase at the end point of the feed
SBRs must be conducted in QFS situation as long as the initial period
temperature is not less than the reaction temperature of θ = dimensionless time, θ = t/tdos
isothermal SBRs, regardless of the values of Wt. κ = dimensionless reaction rate constant, κ = exp(γ(1 − 1/
In the end, we underline that the adiabatic criterion τ))
developed in the article is not suitable to semibatch processes ν = stoichiometric coefficient
with autocatalytic behaviors. Also knowledge on activation ρ = density of the reaction mixture, kg·m−3
energy and reaction enthalpy of the reactions are necessary τ = dimensionless temperature, τ = T/TR
when the adiabatic criterion is utilized. ΔHr = enthalpy of the reaction, J·mol−1

■ ASSOCIATED CONTENT
* Supporting Information
S
ΔTad,0 = adiabatic temperature rise at initial conditions,
ΔTad,0 = (−ΔHr)nB,0/(νB(ρCp)0V0), K
Δτad,0 = dimensionless form of ΔTad,0, Δτad,0 = ΔTad,0/TR
The Supporting Information is available free of charge on the Subscripts and Superscripts
ACS Publications website at DOI: 10.1021/acs.iecr.7b04181.
ac = accumulation
Isoperibolic SBR profiles for omogeneous and liquid− ad = adiabatic condition
liquid heterogeneous reactions to validate the adiabatic A, B, C, and D = components
criterion (PDF) c = continuous phase

■ AUTHOR INFORMATION
Corresponding Author
cf = cooling failure
d = dispersed phase
dos = dose
*Z. Guo. E-mail: guozichaotju@163.com. Tel: +86 25 ex = exchange
84315526. Fax: +86 25 84315526. 0 = initial
f = final
ORCID
j = jacket temperature
Zichao Guo: 0000-0002-2288-1174 max = maximum
Notes min = minimum
The authors declare no competing financial interest. r = reaction

■ ACKNOWLEDGMENTS
R = reference
ta = target temperature


This work has been financially supported by the Fundamental
Research Funds for the Central Universities. REFERENCES

■ NOMENCLATURE
A = heat exchange surface area, m2
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14779 DOI: 10.1021/acs.iecr.7b04181


Ind. Eng. Chem. Res. 2017, 56, 14771−14780
Industrial & Engineering Chemistry Research Article

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14780 DOI: 10.1021/acs.iecr.7b04181


Ind. Eng. Chem. Res. 2017, 56, 14771−14780