Chemical Engineering and Processing 44 (2005) 13–21

A pollution reduction methodology in reactor design

Qishi Chen, Xiao Feng∗
Department of Chemical Engineering, State Key Laboratory of Multi-Phase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049, China

Received 20 January 2003; received in revised form 18 March 2004; accepted 26 March 2004
Available online 18 May 2004

Abstract

An algorithm for waste and pollutants reduction in reactor design is presented in this paper. This algorithm use potential environmental
impact balance (PEI) and PEI rate-law expression to track the generated PEI throughout reaction process within a reactor; and study how
reaction conditions (temperature, pressure, concentration, etc.) and various engineering factors (heat and mass transfer, and back-mixing and
so on) affect process environmental performance. The form of PEI rate-law expression should be consistent with the method for calculating
the overall PEI of mixtures of chemicals inside reactors. The algorithm can be used as a tool to aid in designing chemical reactors with
environmentally friendliness processes. The use of the methodology is illustrated with the reaction system of allyl chloride production.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Reactor design; Potential environmental impact; Chemical reaction engineering; Impact analysis

1. Introduction To address the ideal including environmental impact con-

There is currently a great deal of interest in the devel-
opment of methods that can be used to prevent or at least
reduce the generation of pollution, because it may result in
lower operating costs due to better utilization of raw mate-
rials and energy and reduced waste treatment and disposal
costs. Researches have shown that the most opportunities
of environmental impact minimization exist in the process
research and development and design stage of chemical pro-
cesses [1,2]. Waste and pollutant generation in many chemi-
cal manufacturing process can be traced back to the reaction
system, where reaction pathways that produce high yields
may also generate toxic byproducts or use environmentally
unfriendly raw materials, solvents, and catalysts—which
must be dealt with downstream at a significant cost [3];
and the size, configuration, and composition of the reactor
are very important factors controlling the ‘greenness’ of a
process [4]. Therefore, the design of new reactor is a very
important element in preventing pollution at the source.
siderations into process design, Cabezas et al. [5] introduced
a potential environmental impact (PEI) balance as an amend-
ment of the Waste Reduction Algorithm [6]. However, this
algorithm is simply a tool to be used to aid in evaluating the
environmental friendliness of a process [7].
Making clear the effects of reaction conditions such
as temperature, pressure and concentration as well as en-
gineering factors involving back-mixing, heat and mass
transfer and so forth, on the performances of reaction pro-
cess is one of critical bases for benign reactor design. In
this paper, potential environmental impact balance and PEI
rate-law expression are proposed as a tool to be used to
effectively discover these effects on environmental perfor-
mance of a reaction process. With this methodology, the
PEI of waste and pollutants could be tracked throughout
reaction process within reactors, and appropriate reactor
type and reaction conditions, which could lead to envi-
ronmentally benign reaction processes, could be selected
expediently.

Abbreviations: CSTR, continuous stirred-tank reactor; EIM, environ- 2. The potential environmental impact of a
mental impact minimization; NP, non-products; PEI, potential environ-
mental impact; PFR, plug-flow reactor
chemical process
∗ Corresponding author. Tel.: +86-29-82668980;

fax: +86-29-83237910. In the algorithm [5–9], the potential environmental im-

E-mail address: xfeng@mail.xjtu.edu.cn (X. Feng). pact of a certain quantity of a certain material and energy

0255-2701/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.03.006
14 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21

is defined as the effect that this material and energy would conditions and engineering factors and the like on the gen-
have on the environment if they were to be emitted into the eration of waste or pollutant is very important. However,
environment. For a steady-state process, the balance equa- studying each of wastes and pollutants within reactor is
tion is as follows: time-consuming and cost-consuming and the results may be
conflicting or competing, that is to say that reducing one pol-
İin − İout + İgen = 0 (1)
lutant or waste may increasing the others. In addition, this
where İin and İout are the input and output rates of PEI, research method does not address the impact of the pollu-
respectively, and İgen denotes the PEI generation rate inside tion generated within a reactor. For example, reactor A may
the processes. produce 50 kg/h of pollutants while reactor B may produce

(in)
100 kg/h. However, the pollutants generated within reactor
İin = ṁj xkj Ψk + · · · (2) A may be much more environmentally unfriendly than those
j k generated within reactor B. Thus, the strategies for reduc-

(out)

ing pollutants and wastes generated from reaction process
İout = ṁj xkj Ψk + · · · (3) should be studied through their PEI rather than their mass
j k or concentrate, the results would be, then, scientific and be-
(in) (out) yond conflicting.
where ṁj is the mass flow rate of input stream j, ṁj Traditionally, the foundation of reactor design is the equa-
the mass flow rate of output stream j, xkj the mass fraction tions such as reaction rate equation, mass, energy and mo-
of chemical k in stream j, and Ψ k the overall potential envi- mentum balances as well as the model describing the fluid
ronmental impact (PEI) of chemical k. flow within reactors. With these equations, reactor designers


Ψk = αl ψkl
s
(4) can track compositions of chemicals, pressure and tempera-
l
ture throughout reaction process and discover the effects of
reaction conditions as well as engineering factors on these
where ψkls is the specific potential environmental impact of
parameters, and then, an appropriate reactor with profitable
chemical k for environmental impact category l, in units of processes can be designed. Nevertheless, this kind of design
PEI/kg of chemical k. Details of the method for calculat- method does not consider environmental perspective of pro-
ing ψkl
s appeared in reference [7]. The impact categories in-
cesses effectively.
volved in this theory fall into two general area concerning If the PEI generated within reactors could be tracked
with four categories in each area: throughout the process, the influence of reaction conditions
(1) The global atmospheric categories: and engineering factors on the generated PEI could also
• Global warming potential (GWP). be clarified, and then reactors that generate the minimum
• Ozone depletion potential (ODP). amount of PEI would be easily obtained. The above thinking
• Acidification and acid-rain potential (AP). can be implemented by using the PEI balance and the PEI
• Photochemical oxidation or smog formation potential rate-law expression in reactor design. In this way, the design
(PCOP). method is similar to the traditional reactor design method
based on balance equation and reaction rate equation.
(2) The local toxicological impact categories:
• Human toxicity potential by ingestion (HTPI).
• Human toxicity potential by either inhalation or der- 3.1. PEI rate-law expression
mal exposure (HTPE).
• Aquatic toxicity potential (ATP). The PEI transformation rate of chemical k can be defined
• Terrestrial toxicity potential (TTP). as:

In Eq. (4), αl is a relative weighting factor for impact type dIk

rPEI,k = (5)
l independent of chemical k, and represent the value that V dt
society places on particular types of environmental impact
where Ik represents PEI of chemical k, Ik = mk Ψk , mk
[8]. This factor allows Eq. (4) to be customized to specific
is the mass of substance k, Ψ k the overall PEI per unit
or local conditions. The suggested procedure is to initially
mass of chemical k in units of PEI/kg, and V the reaction
set all αl to a value of one, and allow users to vary indi-
volume. According to Eq. (2), the PEI transformation rate
vidual αl from 1 to 10 according to local needs and polices
of a reaction system rPEI , in units of PEI/(L s), is:
[5,8].



rPEI = rPEI,k = rk ψk Mk × 10−3 (6)
k k
3. The algorithm
where Mk denotes molecular weight of chemical k in units
In order to perform waste reduction and pollution pre- of g/mol, and rk the rate of appearance of chemical k in units
vention in reactor design, studying the effects of reaction of mol/(L s).
 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21
Such an expression, which shows how the rate depends on
the concentrations of reactants, is called PEI rate-law expres-
sion. Note, PEI rate-law expression should be consistent with
the method for calculating the overall PEI in Eqs. (2) and
(3), which ignore the combinational impacts that could be
associate with mixtures of chemicals which accounts for the
additional terms not included into those equations. It should
be realized that if the method for calculating the overall PEI
of mixtures in reactors improve or adopt other method, the
form of the PEI rate-law expression should be adjusted ac-
cordingly.
Obviously, rPEI can be expressed in terms of reaction tem-
perature and concentration or partial pressure of chemicals
and so on. Therefore, the PEI rate-law expression can be
helpful to analyze the effect of concentrations and temper-
ature on the PEI transformation rate, rPEI , and to study the
influence of back-mixing on process environmental perfor-
mance. At least, the PEI rate-law expression can reveal the
factors that control the transformation rate of PEI, so as to
provide guidance for the selection of reactor type and opera-
tion conditions, and the inner structure of the reactor, which
produce desired products while creating minimum undesired
potential environmental impact.
3.2. PEI balance
Since desired products are the substance we desire and the
objective of this paper is to present a methodology of waste
reduction, that is the primary concern is reducing the impact
and the amount of the non-products, the Ψ k of the desired
products is not considered in PEI balance. This insures that
the user or producer is not directly penalized for producing
a chemical that has a high PEI value. Auxiliary materials
(catalyst, solvent and so on) used in reaction processes must
leave the production process completely as waste or emis-
sion [10], so the PEI of the auxiliary materials should be
considered. Raw materials that if possible shall be entirely
processed into the desired product are not as a rule com-
pletely converted into the product. The losses that arise are
the cause of generated waste and emission [10], thus their
potential environmental impact should be taken into account.
To sum up, the PEI balance of reaction system under steady
state is:
İgen
NP
= İout
NP
− İin
NP
(7)
where the superscript “NP” represents materials except de-
sired products, that is, non-products. İout
NP and İ NP are input
in
and output rates of PEI caused by non-products, and İgen NP
the rate at which impact is generated in a reactor.
For a differential flow reactor, dV, we write a PEI balance
equation over the reactor:
dİgen = rPEI dV (8)
With PEI balance Eq. (7), combining with other equations,
designers can reveal how PEI change with reaction time or
axial and radial direction inside reactors, i.e. can track the
15
changing of PEI throughout reactors; using Eq. (8) combin-
ing with other rate equations, the influence of operation pa-
rameters such as temperature, concentration, pressure and
reaction time, etc. on environmental metrics of a chemical
process could be analyzed facilely, and then, reactors gen-
erating a minimum of PEI could be designed easily.
4. Case study
In this case study, we use the environmental impact indices
below, which can be derived from Eq. (1), to characterize
environmental performance of reaction processes [7,8]:
(1) Potential environmental impact generation rate by non-
products İgen
NP .
(2) Specific potential environmental impact due to non-
products ΦPEI .
İgen
NP
ΦPEI =  (9)
p ṗp
where ṗp is the mass flow rate of product p, and ΦPEI has
units of potential environmental impact per mass of prod-
ucts. Obviously, the smaller the values of İgen NP and Φ
PEI ,
the more environmental friendly the process, and all others
factors such as economics being equal, the more desirable.
İgen
NP would be useful in comparing different designs on an
absolute basis, while ΦPEI would be useful in comparing
different designs independently of plant size [8].
These indices characterize some aspects of the genera-
tion of PEI within a reaction process. They are very useful
in addressing questions related to the ability of the reactor
to produce desired products while creating a minimum of
undesired potential environmental impact.
To illustrate the use of the algorithm, a case of allyl chlo-
ride manufacturing was used. Allyl chloride is manufactured
by means of non-catalytic chlorination of propylene. Con-
sider the following reaction system.
The principle reaction is:
Cl2 + CH2 =CH–CH3 → CH2 =CH–CH2 Cl + HCl (10)
The main secondary reaction is further chlorination of allyl
chloride to 1,3-dichloropropene:
Cl2 + CH2 =CH–CH2 Cl → ClCH=CH–CH2 Cl + HCl (11)
Another important side-reaction is the additive chlorination
of propene to 1,2-dichloropropane:
Cl2 + CH2 =CH–CH3 → CH2 Cl–CHCl–CH3 (12)
This reaction system is a kind of complex van de vusse
reaction, a typical reaction process involving consecutive
and parallel reactions. It is, therefore, sufficiently complex
to illustrate the algorithm. Due to the limit to the space of
the article, we only select temperature, concentration and
back-mixing to be the object of research to illustrate the use
of the algorithm.
16 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21

The following calculations and curves drawing can be ac- respectively.The differential PEI balance of PFR reactors
complished by mathematical software such as Mathcad2000 is:
or Matlab.
dİgen = rPEI dV (19)
4.1. Preconditions Dividing Eq. (18) by Eq. (17), then integrate, we obtain:

The kinetics of the reaction system [11] are: b 1−a a

(CC )PFR = (CB − CB,0 CB ),
a−1
r 1 = k1 C A C B (13)
k2 k1
a= , b= (20)
r2 = k2 CA CC (14) k1 + k 3 k1 + k 3
r3 = k3 CA CB (15) Dividing Eq. (19) by Eq. (17), and then integrate this, we
obtain:
where r1 , r2 , and r3 represent the rates of the reactions  CB
rPEI
in reaction Eqs. (10)–(12), respectively, expressed in (İgen )PFR = v0 dCB (21)
terms of mol/(L s), and k1 = 1.5 × 106 e−66271/RT , k2 = CB,0 rB
4.4 × 108 e−99410/RT and k3 = 100 e−33140/RT . Letters A–F
represent Cl2 , propylene, allyl chloride, hydrogen chloride, 4.2.2. Continuous stirred-tank reactors (CSTR)
1,3-dichloropropene and 1,2-dichloropropane, respectively. For CSTR reactors, the mass and PEI balances are:
Since the purpose of this case study is only to illustrate v0 CC = rC V (22)
the use of PEI balance and PEI rate-law expression, not
a practical reactor design, we might as well suppose the v0 (CB,0 − CB ) = −rB V (23)
reaction process is isovolumetric.
For all cases in this case study, the inlet concentrations İgen = rPEI V (24)
of all chemicals are CA,0 = CB,0 = 0.024 mol/L, CC,0 = From Eqs. (23) and (24), we obtain:
CD,0 = CE,0 = CF,0 = 0 mol/L. The volumetric flow rate rPEI
of the reaction feed at the reactor inlet is v0 = 325 L/s. İgen = (CB − CB,0 )v0 (25)
rB
The specific potential environmental impact values for
each impact category for the chemicals involved in the pro- From Eqs. (22) and (23), we obtain:
cess are shown in Table 1. Details of the method for calcu-    
rC CC CC
lating these data appear in reference [7]. Using these data, = =a −b
the overall PEI of each chemical can be obtained according rB CSTR CB − CB,0 CB
to Eq. (4). Solving this equation, we can get:

4.2. Mathematical models of ideal reactors bCB (CB,0 − CB )

(CC )CSTR = (26)
a(CB,0 − CB ) + CB
4.2.1. Plug-flow reactors (PFR)
The differential mass balances of PFR reactors are: 4.3. The effect of back-mixing on environmental
v0 dCA = rA dV (16) performance

v0 dCB = rB dV (17) It is well known that PFR represents reactors without

v0 dCC = rC dV (18) back-mixing, CSTR represents reactors with the maximum
back-mixing, we can therefore study effect of back-mixing
where −rA = r1 + r2 + r3 , −rB = r1 + r3 , and rC = r1 − r2 . on process environmental aspect by studying these two kinds
rA , rB and rC are the rate of appearance of A, B and C, of reactor.

Table 1
The specific potential environmental impact values for each category for the chemicals used in this case study [9]
Compound HTPI HTPE ATP TTP GWP PCOP AP

A 0 5.4 × 10−4 22 0 0 0 0
B 0 0 3.1 × 10−2 0 0 2.1 0
C 0.51 5.4 × 10−4 0.10 0.51 0 0 0
D 0.78 2.3 × 10−4 4.6 × 10−4 0.78 0 0 0.86
E 1.1 0 0.014 1.1 0 0 0
F 0.61 0 0.0059 0.61 0 0 0
Values are in PEI/kg.
 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21 17

4.3.1. The effect on İgen

4.3.1.1. αl = 1. When αl = 1, namely, the importance of

the above eight environmental impact categories is deemed
the same, and the PEI of each non-product is considered,
the PEI rate-law expression due to non-products is:

rPEI = −1.6k1 CA CB − 1.5k3 CA CB − 1.2k2 CA CC (27)

rPEI has units of PEI/(L s). The value of rPEI is negative be-
cause the overall PEI of the reactant A is far greater than that
of each reaction products, in addition, the PEI of product C Fig. 1. Curves of rPEI /rB vs. CB , rPEI /rB in units of PEI/mol. The solid
curve is for PFR, the dashed for CSTR.
is not considered. Suppose reaction temperature T = 530 K,
and at the outlet of reactor, CB,out = 0.007 mol/L. Substi-
4.3.1.2. Not considering PEI of A. To illustrate the use of
tute Eqs. (20) and (26) into rPEI /rB , respectively, and then
the algorithm effectively, suppose ΨA = 0 PEI/kg, and the
graph them in Fig. 1, respectively.
weighting factor for each impact type is likewise 1, and the
rPEI 1.6k1 + 1.5k3 + 1.2k2 (CC /CB ) PEI of each non-product except Cl2 is also considered. Note
= (28)
rB k1 + k 3 that this case is probably impractical in real manufacturing
processes. The PEI rate-law expression, rPEI , in units of
According to Eq. (25), İgen of CSTR is: PEI/(L s), is:

İgen = −[AABCD + 1.5(0.024 − 0.007)]v0 rPEI = −1.1 × 10−3 k1 CA CB + 0.049k3 CA CB

+ 0.33k2 CA CC (29)
where AABCD is the area of rectangle ABCD in Fig. 1. Ac-
cording to Eq. (21), İgen of PFR is: rPEI 1.1 × 10−3 k1 − 0.049k3 − 0.33k2 (CC /CB )
= (30)
  rB k1 + k 3
İgen = − AA
BCD
+ 1.5(0.024 − 0.007) v0
Using the same method as mentioned previously, we can
where AA
BCD
is the area of curved trapezoid A
BCD
(the obtain the curves describing the changing of −rPEI /rB of
shaded region) in Fig. 1. Obviously, when the outlet concen- PFR and CSTR with CB at various reaction temperature, as
tration CB,out is identical for both reactors, AABCD is greater shown in Figs. 2 and 3, respectively.
than AA
BCD
, thus, lower İgen will be achieved by using According to Eq. (21), if the inlet and outlet concentration
CSTR. The calculation results show that, when CB,out = of B are 0.024 and 0.007 mol/L, respectively, İgen of PFR
0.007 mol/L, and v0 = 325 L/s, İgen of CSTR is −3.7 × equals the area of the region below the curves in the range
104 PEI/h, and İgen of PFR is −3.3 × 104 PEI/h. Apparently, of CB = 0.007–0.024 mol/L in Fig. 2 multiplied by v0 . For
İgen of CSTR is about 12% lower than that of PFR. example, when reaction temperature T = 450 K, İgen of

Fig. 2. Curves of −rPEI /rB vs. CB of PFR ignoring the overall PEI of A. −rPEI /rB in units of PEI/mol. The numbers 1–7 denote the reaction temperatures
of 450, 470, 490, 500, 510, 520 and 530 K, respectively.
18 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21
Fig. 3. Curves of −rPEI /rB vs. CB of CSTR ignoring the overall PEI of A. rPEI /rB in units of PEI/mol. The numbers 1–7 denote the reaction temperatures
of 450, 470, 490, 500, 510, 520 and 530 K, respectively.
PFR equals the area of the shaded region multiplied by v0 .
From Eq. (25), İgen of CSTR is the product of v0 and the
area of the corresponding rectangle in Fig. 3. For example,
when reaction temperature is 450 K, İgen of CSTR equals
the area of the rectangle in Fig. 3 multiplied by v0 . In such
case, the value of İgen is positive number. Comparing Fig. 2
with Fig. 3, it can be found that lower İgen will be obtained if
we adopt PFR and lower reaction temperature. For example,
when reaction temperature is 500 K, and v0 is 325 L/s, İgen
of PFR is 4.8 × 101 PEI/h, while for CSTR, İgen = 1.1 ×
103 PEI/h, which is 2.3 times that of PFR.
4.3.2. The effect on ΦPEI
From Eqs. (9), (21) and (25), we obtain the formulas for
calculating ΦPEI . Suppose v0 is 325 L/s, then for PFR:

İgen 13.0 CB rPEI
ΦPEI = = dCB (31)
v0 CC,out MC × 10−3 CC,out CB,0 rB
for CSTR:
İgen 13.0 rPEI
ΦPEI = = (CB − CB,0 )
v0 CC,out MC × 10−3 CC,out rB
(32)
where CC,out is the outlet concentration of C.
According to Eqs. (31) and (32), using the curves about
rPEI /rB versus CB and corresponding area, the superior-
ity in environmental index ΦPEI about PFR and CSTR
can be discovered. When αl = 1, the outlet concentration
CC,out = 0.011 mol/L and reaction temperature T = 500 K,
using CSTR will obtain lower ΦPEI than using PFR. In
this case, for CSTR, ΦPEI = −31 PEI/kg; for PFR, ΦPEI =
−26 PEI/kg. Nevertheless, if not considering ψA , for the
same CC,out and T, using PFR will obtain lower ΦPEI
than using CSTR, for PFR, ΦPEI = 0.30 PEI/kg, while for
CSTR, ΦPEI = 0.80 PEI/kg, which is 2.6 times that of PFR.
4.4. The effect of temperature on environmental
performance
4.4.1. The effect on İgen
When αl = 1, from Eq. (27), it can be seen easily that the
value of rPEI decreases (its absolute value increase) as the
reaction temperature rises, that is, İgen can be lowered by
increasing reaction temperature. For example, when reaction
temperature increases from 500 to 600 K, and the outlet
concentration CB,out = 0.007 mol/K, and v0 is also 325 L/s,
İgen of PFR and CSTR would decrease from −3.2×104 and
−3.5×104 to −3.7×104 and −4.2×104 PEI/h, respectively.
The effect of reaction temperature on İgen can also be found
from Figs. 2 and 3.
When not considering the PEI of Cl2 , from the PEI
rate-law expression, expressed in Eq. (29), we can find that
in the initial stage of the reaction, the determining part
in the right side of Eq. (29) is −1.1 × 10−3 k1 CA CB +
0.049k3 CA CB , due to the concentration of C is very low
while the concentrations of A and B are relatively high.
Comparing the magnitudes of the two activation energies
in the two terms, we conclude that the value of this part
decreases as the reaction temperature increases. Thus, in
the early stage of this reaction process, to lower the value
of rPEI , the reactor should operate at relatively high tem-
perature. As the reaction proceeds, the concentration of C
is increasing while CA and CB is decreasing, so that the
influences of the third term, 0.33k2 CA CC , is becoming sig-
nificant. Since the magnitude of activation energy in this
term is the maximum, operating at relatively low temper-
ature would result in a relatively low value of rPEI in this
stage. Accordingly, for the reaction system in this case, a
PFR operating at higher temperature first and then lower
temperature must generate lower value of İgen than that sim-
ply operating at a corresponding uniform temperature. The
 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21
curves in different temperature in Fig. 2 intersect each other,
this fact also indicate this result. For example, when the inlet
and outlet concentrations of B are 0.024 and 0.007 mol/L,
respectively, and v0 is 325 L/s, for PFR operating at reaction
temperature of 450K, İgen = 3.9 × 101 PEI/h, and for PFR
at 530 K, İgen = 6.7 × 101 PEI/h. While for a two-stage
PFR, in which the first stage operates at 530 K, and the
second stage operates at 450 K, the inlet concentration of B
of the second stage is 0.018 mol/L, İgen = 3.4 × 101 PEI/h.
Obviously, it is 13% lower than that of the PFR simply
operating at reaction temperature of 450 K, and 49% lower
than that of the PFR simply operating at 530 K.
4.4.2. The effect on ΦPEI
Known from Eqs. (31) and (32), rPEI /rB can be used to
study the effect of the reaction temperature. When αl = 1,
it is not difficult to find that increasing reaction temperature
would decrease the values of −rPEI /rB , accordingly the value
of ΦPEI also decreases. For example, for CSTR operating at
500 K, if its outlet concentration CC,out = 0.011 mol/L, and
v0 is 325 L/s, the value of ΦPEI is −31 PEI/kg, while for
CSTR operating at 530 K and with the same CC,out , the value
of ΦPEI is −36 PEI/kg, that is, this CSTR reduced the value
of ΦPEI by 16%. Similar to this example, for the case of not
considering the potential environmental impact of Cl2 , one
can also conclude the effect of temperature on ΦPEI .
4.5. The effect of concentration on environmental
performance
We here only study the effect of concentration on ΦPEI .
Similar to previous method in Section 4.4.2, one can also use
rPEI /rB to study the effect of concentration. From Eqs. (31)
and (32), it can be found that for a particular outlet concen-
tration of C the value of ΦPEI would be decreased by in-
creasing the value of rPEI /rB . When αl = 1, from Eq. (28),
the value of rPEI /rB can be increased by augmenting CC and
decreasing CB within a reactor. Since C is a product whereas
B is a reactant, using CSTR will lead to higher CC and lower
CB within a reactor than using PFR. Therefore, in this case,
using CSTR would result in lower value of ΦPEI than using
PFR operating at the same reaction conditions. When not
considering the potential environmental impact of Cl2 , from
Eq. (30), decreasing CC and increasing CB within a reactor
will increase the value of rPEI /rB , accordingly, using PFR
would result in lower ΦPEI than using CSTR. These results
are also concluded in Section 4.3.2.
5. Discussion
In the case study, the indexes involved are İgen and ΦPEI .
However, these two indexes only express the situation of
PEI generation within processes. The environmental perfor-
mance of a process also relates to its emission of PEI. There-
fore, in the WAR algorithm, the output rate of PEI, İout , and
19
the total PEI per mass of product streams leaving the system,
Îout , are another category of indices to characterize some
aspects of emission of PEI from a manufacturing process.
According to Eq. (1):
İout = İin + İgen (33)
Îout is obtained by dividing İout by the output of products to
give:
İout İin + İgen
Îout =  =  (34)
p ṗ p ṗ
Substituting Eq. (9) into Eq. (34), we obtain:
İin
Îout =  + ΦPEI (35)
p ṗ
For the case study, it is not difficult to obtain that İin =
4.6 × 104 PEI/h, i.e. İin is a constant. Therefore, when the
feed condition of a reaction process is fixed, back-mixing
and reactiontemperature affect İgen and İout in the same
way. Since p ṗ = v0 CC,out MC × 10−3 , it is not difficult
to find that, when the feed condition and CC,out are spec-
ified, back-mixing and reaction temperature influence Îout
and ΦPEI in the same way, too.
Thus, in Section 4.3, when αl = 1 and the reaction pro-
cess is operated in the specified conditions, the results that
İgen and ΦPEI of CSTR are less than those of PFR indicate
that using CSTR can obtain lower İout and Îout than us-
ing PFR. That means at the given conditions, back-mixing
make the emission of potential environmental impact de-
crease. By contrast, when not considering the PEI of A, the
results are converse, i.e. using PFR would gain lower PEI
generation rate than using CSTR; and the value of ΦPEI of
CSTR that operate at reaction temperature 500 K and out-
let concentration CC,out = 0.011 mol/L is 2.6 times that of
PFR. The results indicate that at the given reaction condi-
tions, back-mixing will increase the emission of potential
environmental impact of the reaction processes, accordingly,
reactor designers should try to avoid it in such case.
In Section 4.4, when αl = 1, the results show that a higher
reaction temperature is favorable for the decrease of İgen
and ΦPEI in the giving conditions. Therefore, increasing the
reaction temperature will lead to the decrease of İout and
Îout . When not considering the PEI of Cl2 , PFR operating
at a high temperature in the first section and low tempera-
ture in the remainder section can result in lower generation
and emission of PEI than that operating at a corresponding
uniform temperature.
To study the effects of concentration on environmental
performance of reaction processes, two analyses are intro-
duced in Section 4.5. The results show that when αl = 1,
operating at relatively low concentration of B and high
concentration of C is favorable for decreasing the poten-
tial environmental impact created in manufacturing a unit
mass of the product C. This also is true for total PEI leav-
ing the system per mass of product streams according to
20 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21

the relations about these two categories of indexes. By
contrast, when neglecting the PEI of Cl2 , the results are
converse.
In the cases study, we have only studied the effects of
back-mixing on the environmental performance. Whereas
the phenomena of back-mixing is only one of engineering
factors, which still involve pre-mixing, heat and mass trans-
fer, thermostability and so on. However, the effects of those
engineering factors not involved in the case study on envi-
ronmental performance can also be simulated and therefore
well studied through a combination of reactor mathematical
model, which relates to corresponding engineering factors,
with PEI balances. As for the effects of other reaction con-
ditions not involved in the case study, such as space time,
pressure, compositions of feeds and so on, which may af-
fect the environmental performance of reaction processes
significantly in some cases, can also be studied with the
help of corresponding PEI balances and the PEI rate-law
expressions, because we can ultimately simulate the change
of the environmental indexes with these reaction conditions
through PEI balance and PEI rate-law expression.
The reaction system involved in the case studied is a kind
of relatively complex van de vusse reaction, nevertheless the
reaction system in real manufacturing process may involve
more reaction types and, therefore, is more complex than
that one. One can, however, simulate the change of envi-
ronmental indexes within a reactor by combining traditional
reactor mathematical model with the PEI balance, and may
also discover the effects of reaction conditions and engineer-
ing factors on environmental performance by PEI rate-law
expression and/or combinations it with other reaction rate
equations as well as other related equations in reactor math-
ematical models.
Note that assuming αl = 1 and not considering the PEI of
Cl2 are just for illustrating the algorithm, these assumptions
may be inappropriate for a real reactor design. Other users of
this methodology may choose to weight effects differently
to reflect local needs and polices where the plants locate [8].
In the case study, the quantitative environmental impact
assessment and the PEI indexes are cited from the WAR al-
gorithm, it is worth noting that, however, quantitative impact
assessment and environmental indexes are likely to improve
with time, and that these improvements can be incorporate
into this methodology as they become available. It is suggest
that either the WAR algorithm’s assessment method and the
PEI indexes, another similar method and indexes, or even a
more sophisticated and comprehensive method and indexes
be used to this pollution reduction methodology.
In the case study, the calculations of the impact indexes
should be accurate to no more than one significant figure
[12]. But two significant figures are used in order to allow
readers to reproduce the calculations if necessary. It is also
worth noting that, even being accurate to one significant
figure, one can still discern significant differences in the
index between different cases.
6. Conclusions
To perform pollution prevention in the process of reac-
tor design, studying the effects of reaction conditions such
as temperature, pressure and concentration as well as vari-
ous engineering factors on environmental performance of a
reaction process is very important. In this paper, potential
environmental impact balance and PEI rate-law expression
are proposed as a tool to be used to carry out this work. The
form of PEI rate-law expression should be consistent with
the method for calculating the overall PEI of mixtures of
chemicals inside reactors. The effectiveness of the method
has been demonstrated through the reaction of allyl chlo-
ride production. From the processes of the analyses in the
case study, analyzing with PEI balance and PEI rate-law ex-
pression combining with other corresponding equations and
some mathematic knowledge can give important insights
into how reaction conditions as well as engineering factors
affect the environmental performance of reaction processes.
This kind of study is one of the bases for developing chem-
ical reactors with environmental benign processes.
Acknowledgements
Financial support provided by the National Natural Sci-
ence Foundation of China under Grant No. 20176405 and
the Major State Basic Research Development Program un-
der Grant No. G2000026307 is gratefully acknowledged.

Appendix A. Nomenclature

A–F chlorine, propylene, allyl chloride, hydrogen chloride, 1,3-dichloropropene and

1,2-dichloropropane, respectively
CA , CB , etc. concentration of chemicals A, B, etc. (mol/L)
CA,0 , CB,0 , etc. initial concentration of chemicals A, B, etc. (mol/L)
CB,out , CC,out , etc. outlet concentration of chemicals B and C, etc. (mol/L)
dV, dC, dİgen differential V, C and İgen
İgen potential environmental impact generation rate (PEI/h)
İgen
NP potential environmental impact generation rate of non-products (PEI/h)
 Q. Chen, X. Feng / Chemical Engineering and Processing 44 (2005) 13–21 21

İin potential environmental impact input rate (PEI/h)

İin
NP potential environmental impact input rate of non-products (PEI/h)
Ik potential environmental impact of chemical k (PEI)
İout potential environmental impact output rate (PEI/h)
İout
NP potential environmental impact output rate of non-products (PEI/h)
(in)
ṁj mass flow rate of stream j into a process (kg/h)
(out)
ṁj mass flow rate of stream j out of a process (kg/h)
mk mass of chemical k
mk,0 mass of chemical k at initial state of reaction
mk, out mass of chemical k at reactor exit or at the moment of reaction termination
ṁp mass flow rate of desired product p (kg/h)
Mk molecular weight of chemical k (g/mol)
rA , rB , etc. the rate of appearance of chemicals A, B, etc. (mol/(L s))
rPEI total PEI transformation rate (PEI/(L s))
rPEI,k PEI transformation rate of chemical k (PEI/(L s))
S area of a certain figure
T reaction temperature (K)
v0 volume flow rate entering a reactor (L/s)
xkj mass fraction of chemical k in stream j

Greek letters
αl weighting factor for impact category l
ΦPEI generated PEI per unit mass of all desired products (PEI/kg)
ψkl
s the specific PEI of chemical k for environmental impact category l (PEI/kg of chemical k)
Ψk overall PEI of chemical k (PEI/kg of chemical k)

References
[1] H.T. Kohlbrand, From waste treatment to pollution prevention and
beyond: opportunities for the next 20 years, AIChE Symp. Ser.
94 (320) (1998) 117–121.
[2] A.P. Rossister, Waste Minimization Through Design, McGraw-Hill,
New York, 1995.
[3] J.A. Dyer, K.L. Mulholland, Prevent pollution via better reactor
design and operation, Chem. Eng. Prog. 94 (2) (1998) 61–66.
[4] A.D. Curzons, D.J.C. Constable, D.N. Mortimer, So you think your
process is green, how do you known? Using principles of sustain-
ability to determine what is green—a corporate perspective, Green
Chem. 3 (2001) 1–6.
[5] H. Cabezas, J.C. Bare, S.K. Mallick, Pollution prevention with chem-
ical process simulator: the generalized waste reduction (WAR) algo-
rithm, Comput. Chem. Eng. 21 (1997) S305–S310.
[6] A.K. Hilaly, S.K. Sikdar, Pollution balance: a new methodology for
minimizing waste production in manufacturing process, J. Air Waste
Manage. Assoc. 44 (1994) 1303–1308.
[7] D.M. Young, H. Cabezas, Designing sustainable process with simu-
lation: the waste reduction (WAR) algorithm, Comput. Chem. Eng.
23 (1999) 1477–1491.
[8] H. Cabezas, J.C. Bare, S.K. Mallick, Pollution prevention with
chemical process simulator: the generalized waste reduction (WAR)
algorithm—full version, Comput. Chem. Eng. 23 (1999) 623–
634.
[9] D.M. Young, R. Scharp, H. Cabezas, The waste reduction (WAR)
algorithm: environmental impacts, energy consumption, and engi-
neering economics, Waste Manage. 20 (2000) 605–615.
[10] W. Schramm, New findings on the generation of waste and emissions,
and a modified cleaner production assessment approach—illustrated
by leather production, J. Cleaner Prod. 5 (4) (1997) 291–300.
[11] B. Pahor, Z. Kravanja, N.I. Bedenik, Synthesis of reactor networks
in overall process flowsheets within the multilevel MINLP approach,
Comput. Chem. Eng. 25 (2001) 765–774.
[12] S. Mallick, H. Cabezas, J.C. Bare, et al., A pollution reduction
methodology for chemical process simulator, Ind. Eng. Chem. Res.
35 (11) (1996) 4128–4138.