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INTRODUCTION
concentrated on technological alternatives with predetermined chemistry (Linninger et al., 1995; DouReaction path synthesis is a very large and comglas, c1994).
plex problem. In order to identify promising reaction
routes, reaction path synthesis tools must deal with a The central ideas behind our procedure are to relarge number of alternative chemistries and sufficient duce the size of the reaction path synthesis problem by decomposing it into a series of steps, each
information to evaluate each one.
Traditional approaches to reaction path synthesis of which is approached in a guided way, and to inhave concentrated on generating chemistries (Corey corporate environmental considerations in the route
and Wipke, 1969; Ugi and Gillespie, 1971; Rotstein et selection exercise in order to exploit the earliest opal. 1982). Agnihotri and Motard (1980) divided these portunities for waste reduction. We adopt a group
methods into two categories - logic-based systems, based approach to reaction path synthesis, achieving
with their roots in mathematics and information- problem size reduction principally by introducing a
based systems, with their roots in chemistry. How- raw material and co-product design step, exploiting
ever, the relationships between the desired product the relationship between these compounds and the
and the raw materials and stoichiometric co-products desired product. Our procedure includes both logic
(which we will refer to collectively as co-materials) and information-based chemistry representation syshave not been exploited so that within these tools, tems in a way which capitalises on the advantages of
the co-materials are not developed in a systematic both.
way. Furthermore, there is a trade-off between the Aspects of the Methodology for Environmental Imgenerality of the tools (the ability to represent many pact Minimization, MEIM (Pistikopoulos et al.,
alternatives) and their predictive power (the ability to 1994) provide the framework for the environmental
represent specific distinct reactions in detail) (Govind evaluation of alternatives. Using this approach, we
and Powers, 1981), according to the representation incorporate environmental considerations and prinsystem employed.
ciples from life cycle analysis in the route selection
Recently, the issue of route selection, with or with- problem, so that the wastes associated with the inout explicit environmental objectives, has come puts to a process (raw materials, energy consumpto the forefront (Crabtree and E1-Halwagi, 1994; tion, capital, etc.) as well as the conventional process
Fornari and Stephanopoulos, 1994; Knight, 1995; emissions are accounted for. This is achieved by (i)
Mavrovouniotis and Bonvin, 1995). However, the expanding the conventional process boundary to inpotential of environmental evaluation of alternative clude all processes associated with raw material manreaction routes has not been fully explored. Other ufacture and energy generation, (ii) defining a set of
synthesis approaches for waste minimization have pollution metrics (such as air, water pollution, global
*To whom correspondence should be addressed; e-marl: e.pistikopoulos@ic.ac.uk
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Determine a set of candidate reaction routes and corresponding process technologies for the production
of a fixed amount of the desired product which are
promising both economically and in terms of minimum environmental impact.
This problem has two key elements: (i) the generation of a set of alternative reaction routes with corresponding technologies and (ii) the evaluation of these
routes and the selection of a subset of economically
attractive, environmentally benign candidates. Each
of these subproblems is very large because of the
many alternative reaction routes and corresponding
alternative process configurations which may be employed to produce the desired product.
It is desireable to solve the subproblems simultaneously. However, this is difficult to achieve, as the traditional reaction path synthesis tools have revealed.
Therefore, we propose a structured, stepwise procedure in which we decompose the reaction path synthesis problem in order to deal with its size.
OUTLINE OF PROCEDURE
The steps of our methodology are as follows for a fixed
desiredproduct: (i) select co-material groups, (ii) determine a set of candidate co-materials using group
based molecular design techniques, (iii) identify a set
of promising candidate stoichiometries using a logicbased representation system and an optimization selection procedure incorporating aspects of the MEIM,
(iv) generate corresponding mechanisms using functional group transformations and so introduce competing reactions, (v) evaluate the mechanism steps in
detail using the MEIM to make a final selection.
The key to our procedure is the introduction of the
co-material design steps. Recognising that much organic chemistry essentially consists of reorganising
functional groups (through additions, substitutions
and eliminations), we expect our co-materials to contain (at least) the group structures present in the desired product. Accordingly, we systematically design
our candidate co-materials according to the group
structure of the product, the types of chemistries we
wish to consider (e.g. aliphatic or aromatic) and other
considerations (such as property constraints) using a
group based computer aided molecular design technique.
We use groups, rather than atoms, as our molecular building blocks for several reasons. First of all,
this considerably reduces the combinatorial size of
the molecular generation problem without much loss
of generality - very many organic compounds can be
constructed using only a small number of groups.
Secondly, with appropriate group bonding restrictions (see Co-Material Desi#n) such a method provides a short cut to structurally and chemically feasible molecules, so significantly reducing molecular
screening requirements. Finally, a suitable choice of
groups gives direct access to the thermodynamic and
environmental properties we need through group contribution methods.
With the co-materials and product known the reaction path synthesis problem is no longer open ended
and is therefore considerably reduced. Now we must
bridge the gap between these materials with feasible stoichiometries and corresponding reaction mechanisms and then make our final route selection.
The first step towards this is to identify feasible overall stoichiometries, without mechanisms, involving
our co-materials and leading to our product. In order to achieve this we employ a logic-based chemistry
representation system and an optimization based procedure, incorporating aspects of MEIM, to identify
good candidate stoichiometries among the alternatives according to economic, thermodynamic and environmental impact criteria (see Stoichiometry Selection).
Now we have a set of promising stoichiometries involving some of our candidate raw materials, our
product and some stoichiometric co-products. From
this position we can employ an information based approach in order to generate the underlying reaction
mechanisms using functional group transformations
based on real chemistry. We can then use the MEIM
in its full form to analyse our candidate routes within
an optimization framework and make the final selection.
In this work we concentrate on the identification of
economically attractive and environmentally benign
candidate stoichiometries, divorced from any process
technology. In future publications we will consider
the problem of determining the underlying chemical
mechanisms and the optimal process configurations
corresponding to our candidate stoichiometries.
CO-MATERIAL DESIGN
Co-material design is the key in reducing the reaction
path synthesis problem to a manageable size. Our
aim is to select a set of co-material groups (see New
Rules for Co- Material Design) and then to generate a
set of structurally and chemically feasible co-materials
from these groups with the minimum screening requirement. We must also introduce additional structural restrictions which are pertinent to the reaction
path synthesis problem.
We employ the molecular design algorithm within the
CAMD approach of Gani et al. (1991), later updated
by Constantinou et al. (1995), incorporating some
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Additional Molecules
During addition, substitution and elimination reactions some simple molecules which do not feature in
CAMD may be generated or consumed. We introduce
the following set of additional co-material molecules
from which we may select a subset to be included in
our stoichiometries.
a) H20
b) O2
c) H2
d) CO2
e) HCI
SELECTION
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Stoichiometry Determination
The first step - stoichiometry determination - can
be achieved with a linear formulation. We write an
atom balance for our co-materials and product as a
system of linear equations (Rotstein et al, 1982) of
which the solutions are vectors of stoichiometric coefficients. We then employ guided enumeration to extract stoichiometries from this system.
From a process point of view we are more interested
in simple stoichiometries, with few reactants and coproducts, than in complex ones. Clearly, the more
molecules we have the more complex the reaction
and particularly the separation processes must become. Accordingly, we formulate the stoichiometry
determination problem as an optimization problem
in which our objective is to minimise the sum of the
magnitudes of the stoichiometric coefficients and we
impose a (case dependent) upper limit on the number
of molecules to be involved in the stoichiometries.
We introduce constraints so that the stoichiometric
coefficients take whole number values, integer cuts
to exclude side reactions and we solve the problem
iteratively, introducing integer cuts to exclude previous solutions as we go. In this way, we enumerate
the stoichiometries starting with the simplest first.
This formulation represents our guided enumeration
approach.
following the Bhopal disaster. UCIL's process involved the raw materials 1-naphthol and methyl isocyante, a toxic substance with a PEL of 0.02ppm.
Under disputed circumstances, 45 tons of methyl isocyanate underwent a chemical reaction and were released, killing approximately 2,500 people in the vicinity of the plant and resulting in some 300,000 additional casualties.
The search for a production route involving more
innocuous reactants is the motivation for this case
study (Crabtree and E1-Halwagi, 1994).
Group Pre-selection
Carbaryl can in fact be made with or without methyl
isocyanate (Worthy, 1985). The two alternative industrial chemistries are shown below (Figures 1 and
2).
CH3NH2
"J"
COCI2
Methyl Amine
Phosgene
"{-
"J"
2 HCI
Methyl Isocysaate
CH3-- N~CffiO
O--H
O--C ~ ~CH 3
n
O .
I-Naphthol
Stoichiometry Evaluation
The second step - stoichiometry evaluation - involves
equilibrium analysis of each reaction stoichiometry.
Since the stoichiometries are now known, this reduces
to a non-linear programming (NLP) problem. Our
objective is the minimization of the environmental
impact associated with each stoichiometry, subject
to the aforementioned cost and thermodynamic constraints. In order to estimate the impact we assume
5% loss of reactor effluent by unavoidable leakage.
We measure the impact in terms of the critical water
mass (CTWM, Pistikopoulos et al., 1994).
We solve the problem to determine the equilibrium
composition and reaction temperature which correspond to the minimum environmental impact for each
stoichiometry. The thermodynamic and environmental properties we require are calculated from group
contributions (Van Krevelen et al., 1951; Gao et al.,
1992).
Finally we rank our stoichiometries according to economics and environmental impact in order to identify
the most promising candidates. The mathematical
details of our approach are reported elsewhere (Buxton et al., 1996).
COCI~
O--H
+
_
It
O
"t-
HCI
O--C ~CI
II
O
1-Naphthalenyl Chloroformate
CI
CH3Nll:2
H
l
O _ C ~ N~CH3
fl
O
Carlmryl
Co-Material Design
(earbarvl contains 14 groups), (iii) we allow only monosubstituted aromatic molecules (since the product is
monosubstituted), (iv) we eliminate all molecules of
which the carbon skeleton must be altered in order
to achieve the product (e.g. we reject all benzyl (single ring) structures since we do not wish to be concerned with contructing the naphthyl (double ring)
group). By applying these criteria we reduce our set
of molecules to fifteen in total (see Figures 3 and 4).
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in any feasible stoichiometry. Thirteen stoichiometries meet this constraint, these routes are shown in
Table 1, ranked according to their economic potential.
The original Union Carbide industrial chemistry and
one of the routes generated by Crabtree and E1Halwagi (1994) were reproduced, the other two routes
put forward by Crabtree and E1-Halwagi were eliminated by our cost constraint.
CI
a)
OH
b)
H~N~cH3
d)
c)
_ C ~ OH
n
O
O_c~CI
II
O
13
e)
~ ~. ~ ~ t.- ~. ~ ~. ~ .~ ~ e~ "~
O--C ~ ~CH 3
II
O
g)
CI2
CH3C |
CH3OH
CI--C~ H
a)
b)
c)
d)
H-- C ~ N ~ CH 3
II
CH3NH2
CI~C_. O
CI
e)
CH3-- N = C = O
f)
,.7
"7"7"7"7
"77
"7,
"7,
h)
g)
1
2
3
4
Additional Molecules
We introduce four additional co-material molecules:
a) H 2 0
b) 02
c) H2
d) HC1
6
7
8
9
10
Oxygen
Hydrogen
Hydrogen Chloride
1-Naphthol
Chloroformate
Methyl Formamide
Water
Methylamine
Phosgene
Methyl Isocyanate
1-Naphthol
11
12
13
14
15
16
17
18
19
Carbaryl
Naphthalene
1-Chloronaphthalene
N-methyl-l-Naphthyl
Amine
1-Naphthalenyl
Hydroxyformate
Chlorine
Chloromethane
Methanol
Chloromethanal
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APPENDIX
REFERENCES
Agnihotri, R.B. and R.L. Motard (1980). Reaction
Path Synthesis in Industrial Chemistry. Compu-