Pergamon

Computers" chem. Engng, Vol. 21, Suppl., pp. $965-$970, 1997

~ 1997 Elsevier Science Ltd All fights reserved Printed in Great Britain

PII:S0098-1354(97)00174-9

0098-1354/97 $17.00+0.00

Chemical Process Route Selection Based On Assessment of Inherent Environmental Hazard

S. R. Cave and D. W. Edwards
Department of Chemical Engineering, Loughborough University, Loughborough, LE11 3TU, UK. Abstract - At the preliminary stages of chemical plant development and design the choice of the chemical process route is the key design decision. In the past, economics were the most important criterion in choosing the chemical process route. Safety and environmental issues have now become important considerations. Methods are lacking for assessing chemical process routes for environmental friendliness. The Environmental Hazard Index (EHI) ranks routes by the estimated environmental impact of a total release of chemical inventory. The EHI is a function of the environmental effects of the chemicals and the estimated inventory thereof in a plant that, if designed and built, would implement the route. The lower the EHI the more environmentally friendly is the route. The EHI has been tested on six potential and established routes to Methyl Methacrylate (MMA). These results have been compared with those for the Inherent Safety Index for the same chemical process routes. An expression has been derived which relates the EHI to an estimated fish kill.

INTRODUCTION An environmentally friendly chemical plant is one that has a small impact on the environment during normal operation and in the event of unexpected incidents. An inherently environmentally friendly chemical plant would have small levels of actual and potential environmental impact, which could not be compromised, The environmental friendliness of a plant can be assessed byestimating:

The chemical process route, hereafter called simply the route, is defined as the raw material(s) and the sequence of reaction steps that convert them to the desired product(s) (Edwards and Lawrence, 1993). The choice of route fixes the chemicals present in the plant. Route selection is therefore an early design decision that is key to the environmental friendliness of a plant. The possible routes to a specific product are identified and developed in the Research and Development and Preliminary design phases of a project. The 'best' route was historically chosen on the basis of predicted plant economics. Nowadays other issues, such as safety and environmental impact, influence the decision. The Inherent Safety Index, ISI, devised by Edwards and Lawrence (1993), allows routes to be ranked by inherent safeness. There are no methods for assessing routes for inherent environmental friendliness. This paper develops a methodology for the assessment of the environmental hazard of a route by the Environmental Hazard Index (EHI). This is the first step to assessing the overall enviromental friendliness of a route. The subsequent steps are to develop a methodology for assessing the operational environmental impact of a route and then combine the two methodologies to give the overall environmental friendliness. The EHI is compatible with the ISI since it uses a similar method for inventory estimation and is intended to be used in conjunction with it. The EHI $965

'worst' possible unplanned environmental impact that could occur during plant operation. This is defined as a total loss of chemical containment:
Environmental H a z a r d - T h e Operational Environmental Impact The

environmental impact due to day to day plant operation. This includes a diverse range of impacts, such as chemical emissions and social effects. The earlier the environmental friendliness of a proposed chemical process plant is considered the better. This is because decisions made in the initial stages of the development and design process have the most impact upon the final plant design and it is also easier to make changes to a design in the early stages. As the project proceeds down the design path the opportunity for incorporating inherently environmentally friendly design features and make design changes diminishes. At the same time the cost of changingthedesign increases,

$966

PSE '97-ESCAPE-7 Joint Conference The EHI of a route is calculated by evaluating the effects and exposure of each chemical in the route. The environmental effect of a chemical is represented by the Specific Environmental Hazard Index (SEHI). The exposure of a chemical is the amount of the chemical available for release, that is the total inventory of the chemical in the plant, Q. The EHI is based upon the following assumptions: * * The damage to the environment of a chemical is directly proportional totheamountreleased. The damage due to the release of a mixture of chemicals is additive. This is the simplest assumption that can be made for assessing the overall toxic effects of a mixture of chemicals (Calamari and Vighi, 1993).

and ISI share a similar calculation method which allows both indices to be quickly evaluated, BASIS OF T H E E H I An environmental hazard is a potential to cause harm to the environment. Chemical plants are environmentally hazardous because they typically contain large inventories of ecotoxic chemicals. For example, in 1986 over 10 tonnes of a mixture of pesticides were washed into the Rhine during a fire in a pharmaceutical plant. The fire occurred in a warehouse storing large quantities of pesticides, solvents and other organics. The Rhine was rendered lifeless for 200 kilometres and half a million fish were killed (Capel, 1988). The plant had a high environmental hazard due to its large inventory of environmentally harmful chemicals. Using only data about a route the EHI estimates the maximum environmental harm which could be caused by a total loss of containment on a plant which implements the route. Using the EHI alternative chemical process routes can be ranked, or screened if an acceptable threshold limit is set. The EHI is a dimensionless number which indicates the potential environmental hazard of a route; the higher the EHI, the higher the hazard. The EHI is also a measure of the inherent environmental friendliness of a route, because a more environmentally friendly route would have a lower inventory of environmentally hazardous chemicals associated with it. The EHI is not location specific and does not consider the circumstances leading to the release. It is acknowledged that these factors would influence the impact of the release, however they would not be known at the route selection stage. The EHI is not intended to be extremely accurate because at the route selection stage much data is lacking and must be estimated. Rather it is intended as a guide to allow the selection of routes based on environmental considerations. A full nomenclature for equations is given at the end of the text. D E F I N I T I O N O F T H E EHI The hazard to the environment due to a chemical has been defined as a function of two elements (BroRasmussen and Christiansen, 1983): 1. The damage that the chemical could do to the environment following a loss of containment, that is the effects of the chemical. The quantity of chemical involved, that is the exposure of the chemical,

The EHI of a route is calculated by: EHI = Y, Qi i ffilion

X

SEHI i

[1]

C H E M I C A L E F F E C T S ASSESSMENT, S E H I The detrimental environmental effects of a chemical caused by a loss of containment are measured using the Specific Environmental Hazard Index (SEHI). The Environment can be considered to be composed of a set of different compartments each with similar properties. For example, Mackay & Paterson (1990, 1981) have defined a typical environment to be made up of six compartments: * Air, Water, Biota (aquatic life), Soil, Sediment and Suspended sediment.

The six compartments are illustrated in figure 1.

AIR~

, I, BIOTA

SOIL/ WATER/

~ ~ ~ /
/ , . . -* ** I

SSEDD UPNE
SEDIMENT ~---- SEDIMENT

Figure 1: Environmental Compartments The SEHI is calculated with reference to one tonne of the chemical and is defined by the following equation:

2.

PSE '97-ESCAPE-7 Joint Conference SEHIi = f (Environmental concentrationof one tonneof chemical i in differentenvironmentalcompartments, Toxicityof chemical i to the speciespresentin the differentenvironmentalcompartments) [2] In the event of a loss of containment, the aquatic and terrestrial ecosystems are most affected (LindgaardJOrgensen & Bender 1994; Welsh 1992). The predominant route of environmental exposure has been found to be through the liquid phase (LindgaardJCrgensen & Bender 1994). Therefore, in order to evaluate the effects of a chemical to both ecosystems following a loss of containment two indices have been developed. The Specific Water Hazard Index (SWHI) represents the hazard to the aquatic ecosystem associated with one tonne of a chemical. The Specific Terrestrial Hazard Index (STHI) represents the hazard to the terrestrial ecosystem through food and water intake due to one tonne of the chemical. The SEHI is the sum of the SWHI and STHI. SEHI i = SWHI i + STHI i [3]

$967

Time Period
The time basis for the calculation is taken as 4 days (96 hours). This is because there is a better availability of data and estimation techniques for a 96 hour period (Hermens, 1989; Reinert, 1987; Blum & Speece, 1990). Also 96 hours is within the period of 1 hour to 1 month during which the effects of a sudden release are generally felt (Vighi and Calamari, 1992). This also takes into acount that there is usually a period of time before any remedial action is carried out and the beneficial effects are felt (LindgaardJcrgensen & Bender, 1994).

ChemicalDistribution
In order to assess the effect of the chemical toxicity upon the ecosystem it is necessary to calculate how the chemical distributes in the environment. Predicted environmental concentrations (PEC)for the water and soil compartments are calculated using Mackay's fugacity model (Mackay & Paterson 1990, 1981), which gives the equilibrium concentration of a chemical in the different environmental compartments. The PEC of the chemical is calculated for a 1 km 2 area surrounding the plant. An affected area of 1 km 2 corresponds to a 0.6 km radius circle around the plant. This radius is within the range of 0.001 to 5 km over which the effects of a sudden chemical release are generally felt (Vighi and Calarnari, 1992). This area is assumed to represent the region where the chemicals released would be most concentrated and consequently the effects most severe.

An Atmospheric Hazard Index has not yet been developed, The SWHI and STHI are based on the three parameters described below,

Toxic Effects
It has been found that the immediate environmental implications of a loss of containment are mainly due to toxic effects. Wheras other properties such as carcinogenicity and bioaccumulation are important for long term effects CLindgaard-JCrgensen & Bender, 1994). The toxic effects are assessed using toxicity to animal species beacause vegetation toxicity data is rarly available. Acute toxicity data, such as LDSO and LCSo, have been chosen as the basis for the environmental hazard indices for the following reasons: For a one-off loss of containment acute data is more pertinent than chronic toxicity data. Acute data is much more widely available than chronic data (Weis, 1990). Methods exist for the estimation of acute toxicity data from chemical properties using Quantitative Structure Activity Relationships (Hermens, 1989; Reinert, 1987; Blum & Speece, 1990).

Calculation of SWHI and STill

SWHI and STHI are calculated from the following equations: PEC wi x 106 LCso i [4]

SWHI i =

The SWHI is calculated with reference to the aquatic organism with the lowest toxicity value. [(TDI wx PEC wi)+ (TDI ,x PEC si)] LDS0 xi Wt x [5] The STHI is calculated for each terrestrial species (for example mammals, birds etc) for which LDS0 data is available. The most sensitive species has the highest value of STHI. This value is taken to represent the ecosystem. In the calculation of the STHI the following assumptions are made :

STHI i = d

x 109

The toxicity of the chemical to the most sensitive species based on available toxicity data is taken to represent theecosystem(Weise, 1990).

$968

PSE '97-ESCAPE-7 Joint Conference RESULTS Figure 2 shows the results of the EHI calculation for the routes to MMA. The routes are ranked according to their environmental hazard in Table 1.

The food and water intake of all the species is from the contaminated area. The concentration of the chemical in the food is assumed to be equal to that in the soil. LDS0 can be used to estimate a total lethal dose over a 4 day period.

Sample daily intake data for a variety of different laboratory test species can be found in Sax, 1989. The calculation methods for SWHI and STHI are based on the CMU-ET (Hovarth, 1995) and I1 (Vighi and Calamari, 1992) indices which were both developed to assess the environmental hazard of a chemical. In both cases a score is assigned which is proportional to the quantity of chemical and the potential environmental damage of the chemical.
EXPOSURE ASSESSMENT, Q

EHI iK40, it20, 100

80

106.2

~ 1 ~ 6 0
14.5

60 40 20 0

0.81
TBA i/C4

Chemical Process Route Separation

C3

C2/MP C2/PA ACH Storage

Reaction

The larger the inventory of a chemical plant, the higher the volume of chemicals available to escape to the environment and therefore the higher the associated hazard. At the route selection stage it is impossible to calculate the inventory of all the equipment, such as vessels, pipework etc., which would make up the plant that implemented the route. This calculation cannot be attempted until the detailed design stage. However, an estimate can be made for the major items of equipment which would most likely have the largest capacity. These are assumed to be the storage vessels, reactors and separators. A mass balance is compiled for the route block diagram, with assumptions made about likely recycles, reactor conversions and separator efficiency. Then, with some further assumptions about residence times for reactors, separators and storage, the plant chemical inventories may be estimated, EXAMPLE The Environmental Hazard Index has been tested on six potential or established chemical process routes to Methyl Methacrylate (MMA). These routes exhibit a diverse range of environmentally hazardous chemicals. Also, these routes have been compared by inherent safeness using the ISI (Lawrence, 1996). The six routes considered were: Tert-butyl alcohol, TBA. Isobutylene, i/C4. Propylene, C3. Ethylene via methyl propionate, C2/MP. Ethylene via propionaldehyde, C2/PA. Acetone cyanohydrin, ACH.

Figure 2: EHI for Chemical Proeesss Routes to MMA

Highest Hazard 1" I I I Lowest Hazard

Process Chemical Route ACH C2/PA C3 C2/MP TBA i/C4

Table l:MMAChemiealProcessRoutesRankedBy
Estimated Inherent Environmental Hazard

The EHI calculations indicate that the ACH route has the largest environmental hazard and the i/C4 route the lowest. The ACH route has the largest number of reaction steps (6) and uses the most environmentally hazardous chemicals, such as: hydrogen cyanide, acetone cyanohydrin, sulphuric acid and ammonia. It is not surprising that it presents the largest hazard. The C2/PA chemical process route represents the largest hazard to the environment due to chemical storage alone. This hazard is mostly due to the formaldehyde stored. This would suggest that in order to minimise the associated hazard with a plant based upon this route the storage time should be reduced as much as possible. The EHI associated with the storage of chemicals represents a large proportion of the total EHI. This is due to the large inventories of chemicals in storage. The residence time of chemicals in storage is often over 300 times that of reaction and separation stages. The ACH and C3 routes do not have a high environmental hazard associated with storage. This is

Detailed data for the routes can be found in Edwards and Lawrence, 1993.

sntointoiatinro 'i
because environmentally hazardous chemicals are le,] The three routes with the lowest EHI values, TBA, C2/MP and i/C4 all had EHI scores of a similar order of magnitude. Whereas, the methods used for estimating inventory and physical properties have accuracies which are often no better than an order of magnitude. Therefore, it is not possible to say categorically which of these is the best. ~t ~ ~EI ~ ~ ~E0
1E-1

PSE '97-ESCAPE-7 Joint Conference

$969

40

1E-2
1E-3 1E-2 IE-1 lEO 1E1 1E2 1E3

Comparison With ISI

The Inherent Safety Index devised by Edwards and Lawrence ranked the same six routes to MMA for inherent safety, as shown in table 2 (Lawrence,
1996):

EHI I--Equate,iSle7,.~,~.~ I

Figure 3: EHI for Environmental Incidents involving a Chemical Release

Process Chemical Route Least Safe

$

I
[

ACH C2/PA c3 C2/MP i/C4 TBA

Equation 5 was used to quantify the potential environmental impact of the six routes to MMA in terms of their predicted fish kill. The results are shown in Table 3. Estimated Fish Kill in the event of a total loss of containment (tonnes) 6
8

Safest

Table 2 : MMA Chemical Process Routes Ranked By Estimated Inherent Safety (Lawrence, 1996)

i/C4
TBA

The ranking order for the ISI is very similar to that for the EHI. The only difference is in the order of i/C4 and TBA. This similarity is to be expected as both indices are fundamentally based on the inventory of the routes and the hazard of the chemicals involved. The Inherent Safety Index (ISI) defines the hazard as the potential loss of human life due to explosiveness and toxicity. Whereas the EHI defines the hazard as the loss of life of species in the ecosystem due to toxicity. It was also found that the storage steps contributed the most to the ISI total. PHYSICAL I N T E R P R E T A T I O N O F THE EHI In order to relate the EHI score to the possible consequences of a total loss of containment a number of environmental incidents involving a loss of containment were investigated. The EHI was calculated for each incident using equation 1. The results are plotted in figure 3. Equation 5, shown in figure 3, was derived from this data by regression to relate fish kill (tonnes) to an EHI score. Only three data points were used to derive the expression due to the absence of data on chemical spills and their environmental effects. Therefore, the accuracy of the expression is questionable, Log FK = 1.41 Log EHI + 1 [5]

C2/MP C3 C2/PA ACH

8 425 3115 6865

Table 3: Estimated Fish Kill of the routes to MMA in

the event of a total loss of containment

The predicted environmental impacts of complete losses of containment from plants implementing the ACH and C2/PA routes are estimated to be worse than that of incident 1. The TBA, i/C4 and C2/MP plants are predicted to have the least impact, with a complete loss of containment resulting in an estimated fish kill of approximately 10tonnes. CONCLUSIONS The Environmental Hazard Index can be used to assess the environmental hazard of a chemical process route, based on the predicted environmental impact of a total loss of containment. The method has been tested on six routes to MMA and was found to be quick, simple and make effective use of the available data. Plant chemical inventory is one of the major parameters needed to calculate EHI. The inventory estimation method relies on many broad assumptions. Further work is required to improve this method and quantify its accuracy. The validity of the EHI has been tested by applying the methodology to documented chemical releases

$970

PSE '97-ESCAPE-7 Joint Conference Bro-Rasmussen and Christiansen, 1983, Hazard Assessment-A Summary of Analysis and Integrated Evaluation of Exposure and Potential Effects from toxic environmental chemicals. Ecol. Mod. 22, 67-84. Calamari, D. & Vighi, M. (1993). Scientific Basis for

which resulted in damage to the environment. The EHI was calculated for incidents with a reported fish kill. From this data an expression was derived which showed that the higher the EHI, the greater the damage to the environment in terms of fish kill. The expression was derived using only three data points due to the inadequate reporting of environmental incidents in the literature. There is therefore scope for a more detailed study of environmental incidents. It would be useful to test the index on other chemical process routes, including batch processes. Additional case studies may yield a maximum score for the EHI above which the environmental hazard associated with the route is too great for the plant to be viable. The next step to deducing the environmental friendliness of a chemical process route is to assess its continuous impacts. This will be extremely complex as any method must consider a number of different impacts such as energy use and daily chemical emissions. NOTATION d EHI FK LC50~ = = = = Time period, days = 4 days Environmental Hazard Index Estimated Fish kill as a result of a chemical release, tonnes Concentration of Chemical i in water which kills 50% of a test population of the most sensitive species over a 96 hour period, mg/dm 3 Lethal Dose of chemical i that kills 50% of the test population of species x, mg/kg number of chemicals involved in a route Predicted specific environmental concentration of chemical i in the soil compartment per tonne released, m 3 Predicted Environmental Concentration of Chemical i in the water compartment per tonne released, m_3 Quantity of chemical i, te Specific Environmental Hazard Index of chemical i, te 1 Specific Terrestrial Hazard of chemical i , te q Specific Water Hazard Index of chemical i, te -1 Daily Food intake of species x, m3/day Daily Fluid Intake of Species x, m3/day Weight of Species x, kg

the Assessment of Several Chemical Substances in combination at low level. EEC. Luxemborg.
Capel, P. D., 1988, Accidental input of Pesticides into the Rhine River, Envir. Sci. & Tech., 122(9): 992-996. Edwards, D. W. and Lawrence, D., 1993, Assessing the Inherent safety of Chemical Process Routes : Is There a Relation Between Plant Costs and Inherent Safety?, Trans lChemE, 71 (B): 252-258 Hermens, LL.M., 1989, Quantitative StructureActivity RelationshipsofEnvironmentalPollutants.

The Handbook of environmental Chemistry (Reactions andProcesses),2E 111-162

Hovarth, A., Hendrickson, C.T., Lave, L. B., McMichael, F. C., & Wu, T., 1995, Toxic Emission Indices for Green Design and Inventory. Env. Sci. and Tech., 29(2) 86-91 Lawrence, D., 1996, Quantifying Inherent Safety For The Assessment Of Chemical Process Routes. PHD THESIS. Loughborough Universisty. Unpublished. Lindgaard-JCrgensen, P & Bender, K. ,1994, Review of Environmental Accidents and Incidents, Wat. Sci.

and Tech., 29(3) 165-172.

Mackay, D. and Paterson, S., 1981, Calculating Fugacity. Environ. Sci. Technol. 15(9) 1006-1014. Mackay, D. and Paterson, S., 1990, Fugacity Models. in Karcher, W. & Devillers, J. (ed.). Practical

LDS0xi

n PECsi

= =

Applications of Quantitative Structure-Activity Relationships (QSAR) in Environmental Chemistry and Toxicology, Kluwer, London
Reinert, K.H. , 1987, Aquatic Toxicity of Acrylates and Methacrylates: Quantitative Structure Activity Relationships based on Kow and LC5o, Regulatory Toxicology and Pharmacology, 7 384-389. Sax, N., I. & Lewis, R., J., 1989, Dangerous Properties of Industrial Materials. Vol 1 ed 7. Vighi, M. and Calamari, D. ,1992, Ecotoxicolocal Risk Indices in Environmental Impact Assessment (Colombo, A. G. ed). Kluwer Accademic Publishers. Dordecht. Weise, E., 1990, UUmann's Encyclopedia of Industrial Chemistry. Weinheim. Welsh, S., 1992, Assessment and Management of Risks to the Environment. in Major Hazards Onshore and Offshore, Symposium Series No 130. IChemE.

PECwi

Qi SEHII STHIi SWHIi TDIfx TDIwx Wtx

= = = = = = =

REFERENCES Blum, D.J.W. & Speece, R.E. ,1990, Determining Chemical Toxicity to Aquatic Species. Environ. Sci. Technol, 24(3) 284-293