CHAPTER 3

An Intelligent Simulation-Optimization
Framework for Sustainable Process Operations
Design and operation of chemical plants always involves a combination of
synthesis, analysis and evaluation of different alternatives. Such activities have
traditionally been driven by economic factors first, followed by engineering, safety,
and environmental considerations, in that order. However, the situation has changed
much during the recent past. Chemical companies have embraced the concept of
sustainable development as part of their core business values. This means that the
feed materials and energy must be renewable, products non-toxic and biodegradable,
and wastes minimized or even eliminated at source. Such need for sustainable
development has challenged the chemical process industries to seek new approaches
to tackle the waste problem. This includes exploitation of popular, commercial tools
such as process simulators to evaluate process retrofit options. While process
simulators are useful, one main shortcoming of their application to the waste
minimization is the lack of decision support for the non-expert user. The inherent
capability of process simulators is limited to predicting the behavior of the process
in response to changes in one or more variables. When used for waste minimization,
the overall outcome of the study is still very much dependant on the insight, skill,
27
and expertise of the user in diagnosing the traits of waste generation in that specific
case, identifying the relevant features (root causes) that control them, exploring and
generating different alternatives, and tuning the necessary variables to optimize the
process. This shortcoming of the process simulator-based approaches has indeed
been highlighted during a joint workshop organized by the US Environmental
Protection Agency, the Department of Energy, and the Center for Waste Reduction
Technologies (Eisenhauer and McQueen, 1993). Their recommendation was to
develop an integrated framework comprising of an expert system and process
simulator. The rationale behind this is that since waste minimization is a
multifaceted problem, its analysis requires the application of different computational
tools, each providing a different perspective.
In this work, a framework comprising of an expert system, process simulator,
and multi-objective optimization is proposed for both qualitative and quantitative
waste minimization analysis. The qualitative approaches of expert system are
practical, easy to use even by a non-expert and require less precise process
information. However, they only provide broad direction for improving the process.
On the other hand, quantitative approaches through process simulation and
optimization can provide precise actions for retrofitting. However, they need
specialized process knowledge. In this chapter, an intelligent framework that
combines the strength of each approach is proposed. In the following sections, each
element of the framework will be discussed but before that, a literature case study
that illustrates the different components of the framework is first described.




28
29
3.1 Hydrodealkylation (HDA) Process of Benzene from Toluene
The flowsheet of HDA process is shown in Figure 3.1 (Douglas, 1988).
Fresh toluene and hydrogen are initially mixed with a recycle stream containing
hydrogen, methane, benzene and toluene. The feed mixture is first heated in a
furnace before being passed to an adiabatic reactor (PFR-100) for the
hydrodealkylation reaction. In the reactor, toluene and hydrogen react to form
benzene product, accompanied by the generation of byproduct methane and waste
diphenyl. The reactor effluent comprising the products and unreacted hydrogen and
toluene is next condensed in a cooler (E-100), followed by separation in a flash
separator (V-100) to remove the aromatics from the non-condensable hydrogen and
methane. A fraction of the vapor stream leaving the top of the separator which
contains significant amount of methane and hydrogen is recycled and mixed with the
raw material streams while the rest is purged as waste. The liquid from the flash
separator is split into two. The first stream is mixed with the reactor effluent and
recycled back to the cooler. The second stream is passed through a series of
distillation columns (stabilizer T-100, benzene column T-101 and toluene column T-
102) to separate the benzene product and the methane byproduct from the other
components. Benzene product is obtained at 99% (mol) purity from T-101. The
distillate stream from T-102 contains high purity toluene and is recycled, while the
diphenyl stream from the bottom of the column becomes waste. The process
currently incurs an environmental impact of 1473 and an operating cost of $1504 per
hour. The objective in this case study is to retrofit the process to make it
environmentally benign reduce waste material and energy while being
economically attractive.


3
0



13

Furnace








Figure 3.1 Flowsheet of hydrodealkylation process
E-Cond101
E-Cond100
E-Reb100
E-Reb101
Benzene-
product
Fuel-gas
17
18
T-100
T-101
16
Sep-bottoms
TEE-100
12
RCY-1
TEE-101
Purge
15
V-100
Sep_inlet
E-100
E-Cooler
14
Diphenyl-waste
E-Reb102
T-102
E-Cond102
Toluene-
byproduct
P-101
E-P101
Toluene-
recycle
RCY-3
MIX-102
9 10 11
E-Reactor
E-102 PFR-100
E-Furnace
Toluene-feed
P-100
E-P100
6
MIX-101
1
2
Recycle-gas
K-100
E-Compressor
5
7
8
H2-feed
MIX-100
RCY-2

3.2 Overview of the WAR Algorithm
The WAR algorithm was first developed by Hilaly and Sikdar (1994), who
introduced a concept of pollution balance based on the mass balance of pollutants.
Cabezas et al. (1999) developed a generalized WAR algorithm based on the
potential environmental impact (PEI) balance of pollutants, as an improvement upon
the original WAR algorithm. From the PEI balance calculation, a relative indication
of the environmental friendliness of the chemical process can be compared.
In the WAR algorithm, a potential environmental impact
.
I , of a chemical k
in a non-product (NP) stream of j of a process is expressed as:
.
I
NP
=
.
M
j
(3.1)
where
NP
kj
x
k
.
M
j
is the mass flowrate of stream j, is the mass fraction of chemical k in
the non-product stream j and is defined as the overall potential environmental
impact of chemical k, which is developed using the following expression
NP
kj
x
k


k
=

l
s
l k l ,
o

(3.2)
where o
l
is a relative weighting factor for impact category type l independent of
chemical k and is the specific potential environmental impact of chemical k for
an environmental impact type l which includes the following categories: global
warming, ozone depletion, acid rain, smog formation, human toxicity, aquatic
toxicity and terrestrial toxicity (see Table 3.2). The relative weighting factor o
s
l k,

l

allows the environmental impact of a chemical k,
k
, to be customized to specific or
local conditions. The recommended value is between 0 to 10 according to local
needs and policies. Throughout this thesis, o
l
is set to 1. Chemical impact scores
k
31

of several chemicals have been quantified using this expression. A database
software containing the environmental impacts of various chemicals has also been
developed by the USEPA (Martin and Young, 2008).
Based on the steady state balance, the environmental impact of any processes
can be written as follows:
.
I
gen
=
.
I
out
-
.
I
in
(3.3)
where
.
I
in
is the input impact rate of stream entering the system,
.
I
out
is the output
impact rate of stream leaving the system and
.
I
gen
is the rate of impact generation by
the system. For balance involving only the non-product (NP) streams, the following
equation can be analogously written by adding the superscript non-product (NP) to
the above equation:
.
I
NP
gen
=
.
I
NP
out
-
.
I
NP
in
(3.4)
Using the terminology described in equation (3.1) and the impact balance of
equation (3.4), the potential environmental impact
.
I
gen
generated by the non-
product stream can thus be described as:
.
I
NP
gen
=

j
out
j
M
.

k
k
NP
kj
x -

j
in
j
M
.

k
k
NP
kj
x (3.5)
To account for the product stream of the process, an index
.
I
NP
gen
, is introduced as
follows:
NP
gen
=

p
p
NP
gen
P
I
.
.
(3.6)
.
I
where
.
I
NP
gen
is defined as a measure of the potential impact created by all non-
product streams in producing all of the products
.
P produced by the system.
32

By setting the potential environmental impact
k
of all product streams to
zero, which means no environmental impact generated by the product streams and
setting all the non-product streams
k
to one, the following index can be deduced
from equation (3.5) and (3.6):
NP
gen
=

p
p
k
NP
kj
j
in
j
k
NP
kj
j
out
j
P
x M x M
.
. .
(3.7)
.
M
where
.
M
NP
gen
is a measure of the mass inefficiency of the process, i.e. it gives the
ratio of mass converted to an undesirable form to mass converted to a desirable
form.
One main drawback of the WAR algorithm arises due to the difficulty,
ambiguity and subjectivity involved in assigning the impact factor
k
of each
chemical in relation to the different environmental impacts potentially generated by
the process. Nevertheless, the algorithm provides a useful basis for comparing the
environmental friendliness of each process modification applied to the process.

3.3 Intelligent Simulation-Optimization Framework for Sustainable
Process Design
In practice, a waste minimization study is done by a team of experts in a two-
stage review (Allen and Rosselot, 1997). During the preliminary stage, the team
would assess the different parts of the process and derive several possible
alternatives to reduce the waste generated within the process. Since source reduction
gets a higher priority, it is explored first before recycling options are considered. All
the alternatives, which are generally available in qualitative form, are assessed in
more detail in the next stage of the study. At this stage, process simulators may be
33

used to evaluate the resultant changes in the product and waste streams.
Environmental and economic impacts would also be calculated for short-listing
promising alternatives. Finally, optimization would be performed to find the best
alternative(s) that minimize environmental impact and cost. This optimization is
typically performed through trial-and-error by adjusting the process variables to
obtain reduction in waste subject to economic boundaries. Any resulting trade-offs
between different alternatives would be highlighted and taken into consideration
when implementing the modifications in the plant.
A thorough waste minimization analysis is therefore knowledge-intensive,
laborious, time consuming, and expensive. Given the complex and multifaceted
nature of such analysis, a systematic method of identifying and evaluating suitable
design alternatives is thus essential. In this section, a framework that mimics the
two-stage waste minimization review is introduced for generating waste
minimization alternatives to chemical processes. The framework has been developed
by combining different process systems engineering (PSE) methodologies into one
coherent simulation-optimization framework for the sustainable process operations
problem.
Figure 3.2 shows the proposed framework for conducting sustainability study
which involves the following elements:
(1) process information representation,
(2) waste source diagnosis,
(3) knowledge-based alternative generation,
(4) quantitative assessment of alternatives, and
(5) multi-objective optimization.
34

A process graph-based scheme is used for diagnosing the waste sources in the
process. The hierarchical design approach of Douglas (1992) is used to derive
heuristic alternative design solutions that address the origin of waste. The efficacy of
each solution is measured based on simulation conjoined with economic and
environmental impact calculations. As conflicting effects between environmental
and economic factors are commonly encountered, multi-objective stochastic
optimization is then employed to identify solution design strategies that concurrently
satisfy the different objectives. Each of these is described in detail next.
























35


USER INPUT
Material
classification
Environmental
impact data
(WAR)
Economic data Stream status
Process flowsheet
E































Figure 3.2 Proposed intelligent simulation-optimization framework
EN NV VO OP PE EX XP PE ER RT T
IF-THEN
heuristic rules
P-graph model
Functional
model
Simulation engine
Multi-objective
Simulated Annealing
QUANTITATIVE ANALYSIS
WASTE MINIMIZATION SOLUTIONS
Heuristic Solutions Pareto-optimal Solutions
705
710
715
720
725
730
735
78300 78800 79300 79800 80300
Operating Cost ($)
E
n
v
i
r
o
n
m
e
n
t
a
l

I
m
p
a
c
36

37
3.3.1 Process Information Representation
The first step in performing waste minimization in any process plant is to
extract appropriate knowledge about that process including the flowsheet, reaction
chemistry, and material and energy balances. If a simulation of the process already
exists, such information can be extracted easily using industrial standards such as
eXtensible Markup Language or XML. XML is a text-based markup language for
distributing documents over the web. Similar to HyperText Markup Language
(HTML), the XML syntax consists of a set of tags, i.e., identifiers enclosed in angle
brackets (Kokkonen et al., 2003). The starting-tag, ending-tag and parsed character
data in between the tags form an element of an XML document. Additional
information can also be embedded inside a tag as pairs of attributes and values. A
parent element can contain many child elements to form a hierarchical structure.
Various XML schema customized to chemical process modeling have been
reported including CapeML (von Wedel, 2002), Logical data model (Karhela, 2002),
and HYSYS-XML (Hyprotech, 2003). However, no universally agreed-upon XML
schema currently exists for modeling and simulation purposes. In this work, HYSYS
is used as the simulator and therefore use its XML schema for importing process
information. The XML document of a simulation contains all the building blocks of
the case study, includes the list of materials, list of unit operations, stream and unit
operation connections, reaction kinetics, thermodynamic model, and values of
operating variables or process parameters. An extract from the XML document for
the HDA case study is shown along with the HYSYS-XML schema in Figure 3.3.


<FSO OwnerType="FlowShtObject"
OwnerName="Main" Type="ParamSet">
<FSOName OwnerType="FlowShtObject"
OwnerName="Main" Type="Param">
<Value>Toluene-feed</Value>
</FSOName>
<Icon OwnerType="FlowShtObject"
OwnerName="Main" Type="Param">
<Value>MaterialStream</Value>
</Icon>
<X OwnerType="FlowShtObject"
OwnerName="Main" Type="Param">
<Value>838.718143</Value>
</X>
<Y OwnerType="FlowShtObject"
OwnerName="Main" Type="Param">
<Value>-371.314925</Value>
</Y>
</FSO>
Case definition
Case
description
File name
Software version
Model type
Date
Basis
Component list
Reaction package
Fluid package
Component name
Reaction name
Reaction type
Property
coefficient
Thermodynamic
model
Flowsheet objects Flowsheet
Stream or
unit name
Variable and
parameter
Material stream name
Pressure
Temperature
Composition
Energy stream name
Energy flow
Unit operation name
Feed stream list
Product stream list
Energy stream list
Design parameter
Flow diagrams
Stream or unit position
X and Y coordinates
XML Data
XML Data
<ComponentName OwnerType=
FluidPkgMgrObject" OwnerName=""
Type="Param">
<Value>Hydrogen</Value>
<Status>Specified</Status>
</ComponentName>
<ComponentName
OwnerType="FluidPkgMgrObject"
OwnerName="" Type="Param">
<Value>Methane</Value>
<Status>Specified</Status>
</ComponentName>











Figure 3.3 Hierarchical representation of process flowsheet in XML document
3
8



In addition to these, other data needed for the sustainability study are the
classification of material components into raw material, utility, waste or product (see
Table 3.1); status of each material component in output streams desirable or
detrimental; environmental impact factors of the different materials (Table 3.2);
economic data (Table 3.3), and bounds on the decision variable (Table 3.4).
Table 3.1 Classification of material components in the HDA process
Status in Stream Component Purpose
Purge Fuel-gas Benzene-
product
Diphenyl-
waste
Toluene

raw-material

desirable

detrimental

detrimental

detrimental

Hydrogen

raw-material

desirable

detrimental

detrimental

detrimental

Benzene

product

desirable

detrimental

desirable

detrimental

Methane

product

desirable

desirable

detrimental

detrimental

Diphenyl waste-
byproduct
desirable

detrimental

detrimental

desirable


Table 3.2 Environmental impact indexes (per mass basis) of chemicals in HDA process
Index \ Pollutant Hydrogen Methane Benzene Toluene Diphenyl
HTPI
(Human Toxicity Potential by Ingestion)
0 0 0.12 0.078 0.12
HTPE
(Human Toxicity Potential by Exposure)
0 0 0.092 2.20E-06 0.0016
ATP
(Aquatic Toxicity Potential)
0 0.057 0.09 0.065 0.88
TTP
(Terrestrial Toxicity Potential)
0 0 0.12 0.078 0.12
GWP
(Global Warming Potential)
0 0.0035 0 0 0
ODP
(Ozone Depletion Potential)
0 0 0 0 0
PCOP
(Photo Chemical Oxidation Potential)
0 0.014 0.39 1.2 0
ARP
(Acid Rain Potential)
0 0 0 0 0
Total impact 0 0.0745 0.812 1.421 1.1216
Source : Fu et al. (2000)
39


Table 3.3 Economic information for HDA process
Description Cost

Raw material ($/kmol)
Hydrogen
Toluene

Waste treatment ($/kmol)
Purge
Diphenyl waste

Energy ($/kWh)
Furnace
Compressor
Pump
Cooler
Condensor (distillation)
Reboiler (distillation)
Reactor

2.50
14.00


0.7
1.8


0.05
0.07
0.07
0.10
0.004
0.02
0.02


Table 3.4 Initial values and bounds for decision variables in HDA process
Process variables Initial Minimum Maximum

H
2
feed (kmol/h)
Toluene feed (kmol/h)
Energy of furnace (kJ/h)
Energy of compressor (kJ/h)
Energy of cooler (kJ/h)
Energy of pump P-101 (kJ/h)
222.4
123.8
2.4710
7
6.1410
4
3.010
7
7172
220
120
2.4710
7
6.110
4
3.010
7
7150
223
124
2.4810
7
6.210
4
3.110
7
7200


3.3.2 Qualitative Waste Source Diagnosis
Once the required process information is available, the sources of wastes in
the process can be diagnosed. For this, the process graph (P-graph)-based approach
proposed by Halim and Srinivasan (2002a) is adopted. P-graph originates from the
work of Friedler et al. (1994) who demonstrated a special directed bipartite graph for
representing process structure suitable for the synthesis problem. In the P-graph
40

model, a material stream is represented by a circle, an operating unit by a bar and
connections between material streams and operating units by directed arcs. The flow
of material in the process is succinctly represented in the P-graph. Halim and
Srinivasan (2002a, 2002b) showed that the P-graph for a continuous process can be
derived automatically from the process flowsheet. They also reported methods for
identifying the sub-graph of streams and unit operations that contribute to the
presence of different material components in each waste stream. Figure 3.4 shows
the P-graph model for the HDA process. The flow paths of methane and benzene
(highlighted) have been traced from the diphenyl-waste and the benzene and fuel-
gas product streams, in the upstream direction until the input streams.
In general, five sources can be identified through P-graph analysis:
(1) useless material in inlet stream,
(2) excessive feed of useful material in inlet stream,
(3) useful material transformed at low conversion rate,
(4) useless material produced from reaction or phase change phenomena, and
(5) ineffective separation of useful material.
The term ineffective separation is used to describe a separation that causes an escape
of non-waste materials into a waste stream. Waste generating operations are
identified based on information of the status of the material. The presence of a
product material in the waste stream, for example, is detrimental. Likewise, a waste
material present in the product stream. An ineffective separation can be flagged if
there is a material that is detrimental in the waste stream, yet desirable in other
streams. The next step is to find the intersecting separation operation which leads to
the escape of such material into the former stream. In the example in Figure 3.4, the
41

42
stabilizer and benzene columns lead to the escape of desirable methane and benzene
into the waste streams can be identified as ineffective separators. Such analysis,
when performed on all components in the waste streams, reveals the following waste
sources in the HDA process:
(1) excessive raw materials in the H
2
and toluene streams leading to their presence
in the purge and waste streams,
(2) diphenyl by-product and low conversion of toluene and hydrogen in the reactor,
(3) inefficient methane separation in stabilizer column (T-100),
(4) inefficient benzene separation in benzene column (T-101), and
(5) inefficient toluene separation in toluene column (T-102).
The subsequent step after diagnosing the waste sources is to derive decision
solutions to eliminate them.

RECYCLE
GAS
Hydrogen
Methane
Toluene
Benzene

H2 FEED
Hydrogen
Methane


TOLUENE
FEED


FUEL-GAS
Methane
(desirable)
DIPHENYL
WASTE
Methane
Benzene
(detrimental)
BENZENE
PRODUCT
Benzene
(desirable)
Waste flow path
Intersecting unit




Intersecting unit

Figure 3.4 P-graph model of HDA process
4
3



3.3.3 Knowledge-Based Alternatives Generation
A set of design heuristics for minimizing waste generation and recovering
the valuable material from the waste stream has been identified (Halim and
Srinivasan, 2002b). These heuristics, which are based on Douglas (1992) and Smith
(1995), can be summarized below:
(1) If an impurity exists in a feed stream, then prevent it from entering the process.
(2) If a useful material in the feed stream exits through a waste stream, then prevent
excessive feed of that material.
(3) If a unit-operation generates waste, then eliminate or reduce that byproduct
formation.
(4) If an inefficient separation unit exists, then improve the separation process or
include another separation unit.
(5) If a useful material exists in a waste stream, then recover and recycle that
material.
By using these heuristics, various waste minimization solutions can be proposed.
For example, in the HDA process, the presence of toluene and hydrogen in the waste
streams can be eliminated or minimized through reducing their amounts in the feed
stream or material recycling. To eliminate diphenyl byproduct in the waste stream,
the solutions involve eliminating it during the reaction by changing the operating
conditions of the reactor. To prevent the escape of benzene product into the waste
stream, the operating conditions in the ineffective separator needs to be modified.
Table 3.5 shows the list of solutions derived for this HDA process.

44

Table 3.5 Qualitative waste minimization alternatives for HDA process
Stream/Unit
Name
Waste minimization solution
Toluene-feed Prevent excessive feed of toluene component in the toluene
stream
Use alternative material in the toluene stream
H
2
-feed Prevent excessive feed of hydrogen component in the hydrogen
stream
Use alternative material in the hydrogen stream
Purge Direct recycle or recovery-recycle of hydrogen, toluene,
methane, and benzene component
Use further separation system to recover the useful hydrogen,
methane and benzene
Diphenyl
waste
Direct recycle or recovery-recycle of hydrogen, toluene,
methane, and benzene component
Use further separation system to recover the useful hydrogen,
methane, toluene and benzene
Reactor
(PFR-100)
Increase conversion of toluene and hydrogen
Use alternative reaction route to eliminate diphenyl production
Optimize the operating condition in reactor to eliminate diphenyl
production
Stabilizer
column
(T-100)
Use further separation system to recover the useful methane
Optimize the operating condition in Stabilizer column (T-100) to
avoid the escape of methane
Benzene
column
(T-101)
Use further separation system to recover the useful benzene
Optimize the operating condition in Benzene column (T-101) to
avoid the escape of benzene
Toluene
column
(T-102)
Use further separation system to recover the useful toluene
Optimize the operating condition in Toluene column (T-102) to
avoid the escape of hydrogen, methane, toluene and benzene

The heuristics for diagnosing the source of waste using P-graph analysis and
generating the qualitative process alternatives to eliminate or minimize the sources
of waste has been implemented as a knowledge-based system, called ENVOPExpert,
using Gensyms G2 expert system shell (Halim and Srinivasan, 2002a; Halim and
Srinivasan, 2002b; Halim and Srinivasan, 2002c). It has been applied on several case
45

studies including a hydrocarbon separation and a chemical intermediate
manufacturing process and found to successfully emulate the decision making
process of human experts.
The heuristics provide potential solutions whose benefits to the plant can be
justified only when significant reduction in the waste amount can be demonstrated.
The analysis based on the P-graph model only suggests how a particular waste
source can be solved. It is not capable of specifically determining the variables that
should be manipulated and the extent of the resulting benefits in quantitative
terms. For example, consider the alternative optimize the reactor condition to
eliminate diphenyl production; there are many ways of improving the reaction,
such as changing the temperature, pressure and flow of the reactants. These
alternatives cannot be evaluated by using the P-graph model. For example, consider
the alternative optimize the reactor condition to eliminate diphenyl production;
there are many ways of improving the reaction, such as changing the temperature,
pressure and flow of the reactants. These alternatives cannot be evaluated by using
the P-graph model. Thus, the next step in the sustainable design framework is to
perform quantitative analysis using the simulator.

3.4 Quantitative Analysis
The connection between the qualitative results of ENVOPExpert and the
quantitative assessment of the alternatives using the process simulator is through a
list of decision variables which have to be optimized to enhance sustainability. This
procedure is described as follows.

46

3.4.1 Intelligent Identification of Decision Variables
Based on the qualitative solutions, a subset of variables to be manipulated
and optimized can be identified. This short-listing of variables is enabled by
functional models that capture the functional interactions between the constituent
elements of the process (Modarres, 1993). In this case, each of the unit operations in
the plant is classified according to its function. Following the terminology of Lind
(1994), each unit operation is considered to serve one or more of the following basic
flow functions:
(1) Source a supply of mass and energy to the process, e.g., feed stream, reactor,
heater, and cooler
(2) Sink an end point for mass and energy flow, e.g., product stream or waste
stream
(3) Storage accumulator as well as distributor of mass and energy, e.g.,
separation tank
(4) Balance acts as a balance between the incoming and outgoing flow of mass
and energy, e.g., stream mixer and splitter
(5) Barrier prevents transfer of mass and energy between two flow functions, e.g.,
valve
(6) Transport transfers mass and energy between the two flow functions, e.g.,
pump and compressor
Main and supporting variables that influence that function are also defined for each.
The term main variable is used to describe those variables that directly affect the
flow function of a unit. For example, temperature is the main variable for coolers or
heat exchangers and pressure for pumps or compressors. On the other hand,
47

48
supporting variables directly or indirectly influence the main variable. These
variables may be within the same unit or be associated (main or supporting
variables) with upstream units. Consider a cooler as an example. The cooling energy
would be the supporting variable as it directly impacts the main variable cooler
temperature. The energy of a compressor that is connected upstream of the cooler
would also be a supporting variable as this energy influences the compressor
temperature, which in turn affects the cooler temperature. Thus, given a process
flowsheet, the entire chain of functional interactions between the units can be
identified.
Figure 3.5 shows the functional model for the HDA process from the
perspective of main variables of each process unit. This reveals that the hydrogen
and toluene feed, heating-energy of furnace, and the energy of compressor, cooler
and pump (P101) are relevant variables (degrees of freedom) that control the flow
and concentration of diphenyl waste stream. These six variables thus become the
decision variables for optimization. Thus functional interactions enable us to
automatically shortlist the set of variables that are relevant to a design alternative
and link the qualitative analysis of ENVOPExpert with the simulation-optimization
procedure described next.





K-100
Pressure
4
9


TRANSPORT









Figure 3.5 Functional model of HDA process
SOURCE
SOURCE
SOURCE SOURCE
SOURCE
SOURCE
SINK
TRANSPORT
TRANSPORT
STORAGE
STORAGE STORAGE
STORAGE BALANCE
BALANCE
BALANCE
BALANCE
MIX-102
E-102
Temperature
Furnace
Temperature
PFR-100
Temperature
Concentration
T-102
Concentration
Pressure
Temperature
V-100
Concentration
Pressure
Temperature
T-100
Concentration
Pressure
Temperature
T-101
Concentration
Pressure
Temperature
Toluene-feed
Concentration
H2-feed
Concentration
Diphenyl-waste
TEE-101
TEE-100
E-100
Temperature
P-101
Pressure
P-100
Pressure
MIX-101
MIX-100
BALANCE


3.4.2 Quantitative Assessment of Alternatives
Numerous indicators have been developed to set the performance targets and
measure the effectiveness of implementing sustainable alternatives. Azapagic and
Perdan (2000) proposed categorizing sustainability indicators into different metrics
for environmental, economic, and social performance. The environmental indicators
include impacts such as global warming, ozone depletion, and ecotoxicity as well as
efficiencies (such as material recyclability, product durability), and measures of
compliance to environmental management system. These are calculated following
the products life-cycle. The UK IChemE produced a more complete set of indicators
to measure the three components of sustainable development (Tallis et al., 2002).
Schwartz et al. (2002) under the sponsorship of AIChEs Centre for Waste
Reduction Technology introduced five basic indicators to measure the
environmental sustainability of a process: material intensity, energy intensity, water
consumption, toxic emissions and pollutant emissions. The term material intensity is
used as a measure of waste material per unit product and this is calculated by
subtracting the product outputs from the raw material inputs (excluding utilities). In
the same way, energy intensity is a measure of fuel consumption per unit of
production. These indicators are used to benchmark different production alternatives
and guide improvements in the operations. As it is not possible to set up a
standardized sustainability indicator that is applicable to every process, Krajnc and
Glavic (2003) used indicators from different sources (such as IChemE and AIChE)
and combined them with additional metrics that they proposed.
In this work, environmental and economic indicators are used as the
sustainability measure as they are the most practical to the operation of process
plants. For the former, pollutants are used as the measure of environmental impact
50

although the other metrics can be additionally used as well. In this case, the WAste
Reduction (WAR) algorithm, as described in section 3.2, has been implemented as
the environmental impact indicator due to its wide database of chemical compounds,
although other impact indicators such as those by Heijungs et al.(1992), Wright et
al.(1997), or Koller et al. (2000) can also be used. The economic objective is
calculated based on the costs of raw material, waste treatment, and energy
consumption.
In WAR, each process material is assigned an index value to indicate its
potential impacts to different environmental categories. Based on this index, the total
impact of a waste stream in the plant can be calculated as the sum of each material
index of the waste stream weighted by its flowrate. The total environmental impact
of a process is thus calculated as the sum of the environmental impact of all the
waste streams in the process. The flowrates for the economic impact calculation and
the costs are calculated using the process simulator.
Like other design problems, the environmental impacts and economic
aspects of the proposed alternatives may conflict one another. For example,
increasing the reactant flowrate to reduce the byproducts formation and thus the
environmental impact would lead to higher operating costs. Thus the next step
would be to perform multi-objective optimization to identify and resolve the trade-
offs.

3.4.3 Multi-Objective Optimization using Simulated Annealing
Although multi-objective simulated annealing algorithm is used for
optimization method in this work, other techniques such as genetic algorithm
51

(Srinivas and Deb, 1994) or tabu search (Cavin et al., 2004) can be used as well. The
basic principle of simulated annealing is derived from the statistical mechanics of
annealing of metals. In contrast to greedy search which moves in the direction of
improving objective function values and is hence susceptible to local optima,
simulated annealing seeks to reach the global minimum energy state by temporarily
accepting even poorer solutions, with a probability P (Kirkpatrick et al., 1983). In
other words, given a prior solution x' and a new solution x'' for the optimization
problem min ( ) f x , x'' would be accepted with a probability P:

( ) ( )
( ) ( )
1
f x f x
T
if f x f x
P
e Otherwise
'' '

'' ' <

(3.8)
where T is the annealing temperature. The classical simulated annealing algorithm
was designed for single objective optimization. However, it has recently been
extended to multi-objective optimization problems, where it is used to identify the
Pareto set. A solution to a multi-objective problem is deemed as Pareto-optimal or
non-dominated, if no other solution is found to dominate it (Smith et al., 2004). As
an illustration, consider the optimization problem involving minimization of
environmental impact (f
env
) and operating cost (f
eco
) :
Min { } ) ( ), ( x f x f
eco env
(3.9)
where x is the vector of decision variables, and f
env
and f
eco
are the two objective
functions. For two solutions x' and x'' , x' is said to dominate x'' if f
env
( x' ) is no
worse than f
env
( x'' ) and f
eco
( x' ) no worse than f
eco
( x'' ). x'' would be Pareto-optimal
solutions if x'' is better than x' in exactly least one of the two objective functions.
The set of all Pareto-optimal solutions is termed as the Pareto set, which represents
the possibly optimal trade-offs between different objectives.
52


Suppapitnarm et al. (2000) proposed an extension of the simulated annealing
to the multi-objective case using the concept of archiving solutions. As applied to
the sustainable design case, it consists of the following steps:
(1) Specify the elements of the solution vector x , the various decision variables that
control the sustainability profile of the process. Specify the minimum and
maximum values for each. Use the values from the base-case design as the initial
solution vector x' .
(2) Initialize the Pareto set with the triplet ) ( ), ( , x f x f x
eco env
' ' ' as its element.
(3) Using the candidate solution vector, simulate the process to obtain the
environmental and economic objective function values.
(4) Specify an initial annealing temperature T .
(5) Perform random perturbation to generate a new solution vector x'' in the
neighborhood of x' and evaluate its objective function values f
env
( x'' ) and
f
eco
( x'' ) using the simulator.
(6) Compare objective values of x'' with all solutions in the Pareto set. If
x'' dominates any element of the Pareto set, replace that element with x'' . If x'' is
Pareto-optimal with all the elements in the set, then include it in the set.
(7) If x'' is dominated, temporarily accept it as the current solution vector with a
probability P defined as
min 1, exp .exp
env eco
S S
P
T T
A A | | | |
=
`
| |
\ . \ . )
(3.10)
53

where
( ) ( )
( ) ( )
env env env
eco eco eco
S f x f x
S f x f x
'' ' A =
'' ' A =
(3.11)
(8) x'' is accepted as the new solution, i.e., x x ' '' iff P > P
rand
a random number
in [0 1]; otherwise the earlier solution vector is retained.
(9) To escape from local optima, periodically, x' is replaced with a randomly
selected solution from the Pareto set.
(10) For convergence, periodically the annealing temperature T is reduced using a
problem dependent temperature reduction factor
t
R :

t
T T R

(3.12)
(11) Steps (3) to (10) are repeated for a predefined total number of iterations N
Total
.
The above multi-objective simulated annealing algorithm as implemented by Suman
(2004) has been used to serve as the optimizer in the proposed framework.
Both the steps described above have been automated so that the various tasks
for sustainable design are transparent to the user. The automated procedure starts
with ENVOPExpert extracting the information about the process from the HYSYS
model. This is done by converting the flowsheet information into an XML file,
parsing it into ENVOPExpert and creating corresponding objects, connections, and
relations in G2. Once all the relevant information is available, P-graph diagnosis is
performed by ENVOPExpert and qualitative waste solutions derived. HYSYS is
also used for the quantitative assessment of the process. A bridge between G2 and
HYSYS has been developed using G2-ActiveXLink and the HYSYS-Browser
components. The former enables communication between G2 and the COM
(Component Object Model)-compliant applications such as Microsoft Excel. The
54

latter allows connection between HYSYS and Excel through VisualBasic for
Applications (VBA). This two-way connection is used to send the values of decision
variables to HYSYS, which simulates their effects and returns the results back to
G2. Environmental and economic evaluation is performed in ENVOPExpert using
these results. The multi-objective simulated annealing algorithm has also been
embedded in ENVOPExpert, so it plots the next random move of the decision
variables and sends them again to HYSYS for simulation. This cycle is repeated for
a number of iterations to obtain the complete Pareto solution set.

Table 3.6 Multi-objective optimization results for HDA process
Pareto Optimal Solutions
Description
Base
case
1 2 3 4
Decision variables
H
2
feed (kmol/h) 222.44 221.42 220.58 221.26 221.44
Toluene feed
(kmol/h)
123.83 120.99 121.39 121.01 120.82
E-Furnace
(10
7
kJ/h)
2.47 2.47 2.48 2.48 2.48
E-Compressor
(10
4
kJ/h)
6.142 6.163 6.164 6.163 6.163
E-Cooler
(10
7
kJ/h)
3.000 3.08 3.06 3.05 3.07
E-Pump101 (kJ/h)

7172

7168 7177 7174 7174
Objectives

Operating cost
($/h)
1504 1495 1486 1489 1493
Total impact 1476 1197 1218 1214 1205

Table 3.6 shows the complete Pareto solution set for the HDA case study.
Among the optimal solutions, the environmental impact ranges from 1197 to 1218
and the operating cost from 1486 to 1495. Compared to the base case, this signifies a
reduction of up to 19% for environmental impact and 1% for costs. The same case
55

study has been previously used by Fu et al. (2000) for optimization using four
decision variables: hydrogen and toluene flowrate, furnace temperature and reaction
conversion. In their approach, the optimization problem was solved as single
objective optimization with respect to economic and four environmental categories
HTPI / TTP, HTPE, GWP and PCOP. (In this work, HTPI and TTP have been
classified as one environmental category as both share the same material indexes.
ODP and ARP have also been eliminated from assessment due to their zero
indexes.) Table 3.7 presents the optimization results for the five different objective
functions. The table shows that the environmental impact of this process is
dominated by PCOP followed by ATP; in fact the two contribute to 93% of the total
environmental impact. The table also shows a reduction in both environmental
impact and operating cost compared to the base case. However, it also reveals a
trade-off between cost and environmental impact (See Min cost and Min
PCOP). Compared to their approach, where the analysis and formulation had to be
done manually, the proposed approach is completely automated. In addition, Table
3.7 also reveals that the multi-objective optimization yields better results than
solving any single objective optimization. All the single-objective results are
dominated by the multi-objective solutions, as shown in Figure 3.6. This further
highlights the advantage of the proposed methodology.





56

Table 3.7 Comparison of HDA design alternatives

Description
Base
case
1
Min
Cost
2
Min HTPI,
TTP
3
Min
HTPE
4
Min
GWP
5
Min
PCOP
Decision variables
H
2
feed (kmol/h) 222.44 221.125 220.718 220.912 221.751 221.22
Toluene feed
(kmol/h)
123.83 121.274 121.365 121.743 120.936 121.279
E-Furnace
(10
7
kJ/h)
2.47 2.476 2.476 2.477 2.474 2.474
E-Compressor
(10
4
kJ/h)
6.142 6.152 6.263 6.165 6.160 6.151
E-Cooler
(10
7
kJ/h)
3.000 3.028 3.063 3.075 3.063 3.068
E-Pump101
(kJ/h)
7172

7178

7174

7179

7175

7173

Objectives
Operating cost
($/h)
1504 1486 1489 1493 1496 1494
HTPI 89 77 75 75 75 75
TTP 89 77 75 75 75 75
HTPE 2 1 1 1 1 1
ATP 369 369 371 371 365 368
GWP 7 6 6 7 6 6
PCOP 920 723 691 700 706 703
Total impact 1476 1253 1219 1229 1228 1228









1190
1200
1210
1220
1230
1240
1250
1260
1484 1486 1488 1490 1492 1494 1496 1498
Operating cost ($/hour)
E
n
v
i
r
o
n
m
e
n
t
a
l

i
m
p
a
c
t
Pareto plot of multi-
objective solution
Figure 3.6 Single- vs. multi-objective optimization results
57

3.5 Case Study: Biodiesel Production
In this section, the application of ENVOPExpert to a biodiesel production
plant is illustrated. Different routes for biodiesel production have been developed
including alkali-catalyzed transesterification and acid-catalyzed process using virgin
or waste oil (Zhang et al., 2003a). The process considered here is based on acid-
catalyzed processing of waste canola oil. It consists of a transesterification reaction
followed by a series of separation steps involving waste oil (represented by triolein),
methanol, sodium hydroxide, water, glycerol and biodiesel (methyl oleate). Figure
3.7 shows the flowsheet of the process (Zhang et al., 2003a), which involves the
following operations:
(1) Transesterification: Initially, a stream of fresh methanol and sulfuric acid is
mixed with the recycled stream for reaction with waste oil (triolein). The
reaction, which is carried out at 80

C and 400 kPa pressure, converts 97% (mass

basis) of oil into biodiesel (methyl oleate) and glycerol byproduct:
Triolein + 3 Methanol 3 Methyl Oleate + Glycerol
(2) Methanol recovery: The reaction product is cooled prior to separation in a
vacuum tower to recover the excess methanol. In this process, 94% of methanol
is recovered and recycled back to the reactor. The bottom stream is again cooled
and sent to the acid removal unit.
(3) Acid removal: In this step, sulfuric acid is neutralized by adding calcium oxide
(CaO) to produce CaSO
4
and water. This is followed by settling to remove
CaSO
4
. The reaction is assumed to fully remove the acid component.
58

59
(4) Water washing: The purpose of this operation is to separate the biodiesel from
the glycerol, methanol and acid catalyst. This is done through washing with
water in an extraction column.
(5) Biodiesel purification: In the final stage, the biodiesel product is distilled further
under vacuum to obtain the required purity of 99.6% (mass basis).

The process currently generates four waste streams: bottom liquid of the acid
neutralization column, washwater waste of the extractor column, vent gas of the
purifier column, and reboiler liquid. As the vent flowrate is negligible compared to
the other waste streams, it is thus ignored during analysis. Table 3.8 shows the cost
and environmental data for this process. The process generates a total environmental
impact of 126.9 as calculated from the three waste streams. The economic objective
is represented by the operating cost including costs of raw material, waste
treatment and energy and is $728.4/hour for the base case. Thus, with a throughput
of 3 kmol/hour and a biodiesel selling price of $170/kmol (Zhang et al., 2003b), a
loss of $218.4 per hour of operation is incurred. The process can be made more
efficient to lower the loss through better utilization of raw material and energy; this
is indeed the goal of the current plant waste minimization study.


Recycle
Recycled-methanol
6
0


Vent-gas










Figure 3.7 Flowsheet of biodiesel production process
Reactor-feed
Waste-vapor
Washed-mixture
Waste-oil
Water
Settler
Neutralized-mixture
Neutralizer
Vent-gas2
Biodiesel-bottom
Methanol-
pump
E-pump2
Methanol-top
Methanol-
column
E-cooler1
Reactor-product
Reactor
E-reactor
Oil
Recycled-feed
Pumped-feed
E-pump1
Feed-pump
Feed-mixer
Fresh-feed
H2SO4
Methanol
Top-mixture
Reactor-mixer
Product-cooler
Cooled-product
E-condenser1
E-reboiler1
Bottom-cooler
E-cooler2
Cooled-mixture
CaO
E-neutralizer
E-condenser2
Biodiesel-product
E-settler
CuSO4-waste
Extractor
Bottom-Waste
Waste-mixer
Waste-water
Purifier
E-reboiler2


Table 3.8 Cost and environmental data for biodiesel process
Description Value Description Value

Cost of raw material ($/kmol)
Methanol
H
2
SO
4
Triolein
Water
CaO

Price of product ($/kmol)
Biodiesel

Cost of waste stream ($/kmol)
Waste vapor
Waste water

Cost of energy ($/kWh)
Pump
Cooler
Reactor
Condensor (distillation)
Reboiler1
Reboiler2
Neutralizer

5.77
5.88
177.09
0.18
2.24


170.08


10.46
7.23


0.062
0.003
0.003
0.003
0.31
0.45
0.062
Environmental impact
(per mol basis)*
Methanol
Triolein
Methyl-oleate
Glycerol
H
2
SO
4

Water
CaO
CaSO
4




11.95
67.29
20.46
7
62.77
0
43.24
42.2
*Source: Martin and Young (2008)
Using the P-graph based approach, the following waste sources were first
diagnosed by ENVOPExpert:
(1) Waste byproducts (glycerol and CuSO
4
) which are formed in the reactor and the
neutralizer.
(2) Inefficiencies in the extraction and purification columns that lead to the escape
of biodiesel into the waste water stream.
(3) Excessive feed of methanol, H
2
SO
4
and oil cause the presence of those
components in the waste water and the waste vapor stream. However, as the
waste vapor flowrate is small, it can be ignored.
(4) Excessive use of CaO and water as the neutralizing and extraction agent lead to
waste water stream. However, as CaO is assumed to be fully converted, its
61

presence in the waste water stream is assumed negligible.
Subsequently, the design modifications listed in Table 3.9 were proposed. Six
variables feed streams of waste oil, methanol, H
2
SO
4
, the energy of the two
coolers, and water flowrate are selected as the decision variables and their values
varied in the ranges shown in Table 3.10. Such ranges of the variables have been
decided to ensure that flowsheet convergence can be attained during the
optimization run. This is particularly important as changes, even small ones, in these
variables could lead to failed convergence, especially in the column operation. For a
process without column operation, a wider range of variables can always be used.
Like in the HDA case, the objective in this process is to minimize both the
environmental impact and the operating cost.
Figure 3.8 shows the Pareto optimal set. Compared to the base design, the
maximum reduction in the environmental impact and operating cost is found to be
4% and 1.5%, respectively. This finding thus confirms the benefits of implementing
waste minimization to the plant. Figure 3.8 also shows the trade-off between the
objectives. Overall, about 80% of the environmental impact is due to the presence of
un-recovered methanol and H
2
SO
4
in the waste stream; about half of the operating
cost comes from energy consumption. Therefore, decreasing the amount of methanol
and CaSO
4
in the waste by reducing the feed amounts leads to lower raw material
and waste treatment cost, but the energy needed increases since the efficiency of
methanol- H
2
SO
4
separation has to increase. It should also be noted that, in this case
study, glycerol has been considered as a waste byproduct and its contribution to the
overall environmental impact is about 6%. Thus from the decision-makers
standpoint, it would be desirable to find a beneficial use for glycerol, so that it can
become a product.
62


Table 3.9 Waste minimization alternatives for biodiesel process
Source Stream/Unit
name
Waste minimization alternative
Methanol
H
2
SO
4
Feed
stream
Oil
Prevent excessive feed
Substitute with other material
CaO Utility
stream Water
Prevent excessive feed
Substitute with other material
Reactor product Reactor
Neutralized
mixture
Increase the reactant conversion
Use alternative reaction route to
eliminate byproduct
Optimize reaction condition to
minimize byproduct
Bottom waste Separator
Waste oil
Add another separation unit to
recover useful material
Optimize separation condition to
recover useful material
Waste water Waste
stream Waste vapor
Direct recycle or recovery recycle
of useful material



Table 3.10 Initial values and bounds for decision variables in biodiesel process
Decision variables

Base case Minimum Maximum
Oil (kmol/h)
Methanol (kmol/h)
H
2
SO
4
(kmol/h)
Water (kmol/h)
Energy of Cooler 1 (kJ/h)
Energy of Cooler 2 (kJ/h)
1.15
6.66
1.54
5.92
65600
17500
1.1
6.5
1.4
5.5
64000
17000
1.2
6.8
1.7
6.5
67000
19000

63

64
121
122
123
124
125
126
127
128
129
130
131
716 718 720 722 724 726 728 730
Operating cost ($/hour)
Base case (728.4, 126.9)
E
n
v
i
r
o
n
m
e
n
t
a
l

I
m
p
a
c
t

Figure 3.8 Optimization results for biodiesel production

To sum up this chapter, an advanced version of ENVOPExpert system has
been proposed for synthesizing waste minimization analysis generic to any chemical
processes operating on continuous mode. It consists of three elements a knowledge
base for identifying the root cause of waste generation in a process, a heuristic
design method for generating alternative designs and a simulation-optimization
algorithm for manipulating the decision variables optimally to improve the
environmental and economic objectives. In the next chapter, extension of
ENVOPExpert framework to batch operations is described. Unlike continuous
process, batch operation delivers its product in discrete amount. Consequently any
process wastes generated from batch operation would vary with time. To
accommodate this type of operation, the operating procedure has to be analyzed to
both diagnose the source of waste generation as well as identify process
modifications that will eliminate it.