Describe the method and sequence of calculation/modeling, process/equipment

design.

I. Method and sequence of calculation/modeling.

Once the process flowsheet has been constructed and energy and mass efficiency
measures implemented, it is appropriate to conduct a thorough environmental impact
study. The environmental metrics (indexes) representing the main environmental impacts
or risks of the entire process will be the final product of the impact evaluation. To
account for possible harm to human health as well as to numerous significant
environmental media, multiple indices are required. Additionally, there are three groups
into which the environmental impact assessment steps fall:

First, quantitative risk assessment evaluates the rates of release for each chemical in
the process. Secondly, the calculation of environmental fate and transport and
environmental concentrations. Thirdly, the accounting for multiple measures of risk using
toxicology and inherent environmental impact information.

1. Quantitative risk assessment:

Finding the emission rates of each chemical used in the process is the first
step. This provides a baseline for additional impact assessments by quantifying the
contaminants that process operations discharge into the air, water, and soil.
This assessment shows that impacts are a function of dose, that dose is a
function of concentration, and that concentration is a function of emission rate.
Thus, the main piece of data needed for impact evaluation is emissions from a
process design flowsheet. The location, chemical and physical characteristics of
the contaminants, as well as their emissions, determine their concentrations in the
various environmental compartments (air, water, and soil).
When evaluating the environmental performance of different chemical
process designs, carry out a quantitative risk assessment. This method works best
when the source and receptor are clearly identified and localized, but it is not
appropriate for industrial releases, which frequently have an impact on not just the
local environment but also the regional and global ones. Furthermore, even the
biggest chemical manufacturer would struggle to execute a quantitative risk
assessment for every release source and receptor due to the computational
resources required. Giving up on quantitative risk assessment and switching to an
assessment of possible health and environmental hazards is a more practical
strategy. Materials that develop approaches for analyzing the potential for
environmental impacts of chemical processes and their designs are presented. The
 establishment of the possible impacts of chemical releases is sufficient for
comparing the environmental hazards of chemical process designs.

2. Environmental Fate and Transport Modeling:

This step focuses on understanding how chemicals move through and react
within different environmental compartments post-release. It covers two main
modeling approaches:

a. Single-compartmental models (SCMs) concentrate on transport and fate processes

within a single environmental compartment (e.g., air, water, or soil).
+ Advantages: They use minimal computer resources to get results that are quite
reliable and require little information particular to chemicals and environments.
+ Disadvantages: When considering numerous environmental impacts, they have a
major restriction in that they only provide concentration information in one
compartment. It is possible to connect many single-compartment models to
produce multi-compartmental (multimedia) insights into the destiny and transit of
the environment. Regrettably, routine chemical process evaluation is difficult to
perform practically due to the high computational requirements.

b. Multi-compartmental models (MCMs) forecast chemical concentrations

simultaneously in several environmental compartments, providing a more
thorough picture of the environmental impact with minimal data input. Moreover,
they predict in response to a continuous emission into an environmental region of
defined volume, the steady-state concentrations of a chemical in four
environmental compartments (air, surface water, soil, and sediment).
+ Advantages: They accommodate several intermediate transport pathways and
degradation, are very simple and computationally efficient, and require little in the
way of data input.
+ Disadvantages: a widespread misconception that they can only provide estimates
of the order of magnitude of environmental concentrations and a general lack of
experimental data that can be utilized to confirm their accuracy

When selecting an environmental fate and transport model, two key

considerations are accuracy and ease of use. Accuracy relies on how closely the
model describes mass transport and reaction while taking environmental factors
into account. Ease of use the computational and data requirements that the model
places on the environmental evaluation.
 Reaction expressions and prominent intermediate transport mechanisms
should be incorporated into the model.

- Fugacity and Fugacity capacity: Fugacity is a thermodynamic property of a chemical

that describes mass transfer and reaction processes. It is defined as the chemical's
"escaping tendency" from a specific environmental phase, such as air, water, soil organic
matter (soil phase), etc.

 In air phase: The fugacity f = y ϕ P T ≈ P

{
y :the mole fractionof the chemical∈the air phase
where ϕ : the fugacity coefficient (for non−ideal behavior)
PT :the total pressure ( Pa)

At the relatively low pressures (1 atm) encountered in the environment, ϕ=1 ,

making the fugacity equal to the partial pressure (P) of the chemical in air. The
concentration is related to partial pressure (and fugacity) by the ideal gas law:

n P f
C 1= = = =f Z 1
V RT RT

{
3
n: moles of chemical∈a volume V (m )
R :the gas constant
where T :the absolute temperature ( K )
−4 moles
Z 1 :the air phase capacity , has a value of 4.04 10 at 25 C
m3 Pa

 In water phase: The fugacity f =x P s

where

{ {
x :the mole fraction
:the activity coefficient∈the Raoul t ' s law convention
s s
P :the saturation vapor pressure of pure liquid chemical at the systemtemperature(Pa) P :the saturation

It can be demonstrated that the activity coefficient is typically constant (i.e., does
not fluctuate with concentration (x)) in scenarios involving diluted concentrations
characteristic of environmental concerns. As a result, f and concentration in
 aqueous solution, C2 (moles/m3), have a linear relationship. The desire
relationship is obtained by rearranging the previous equation:
x f f f
C 2= = = =
P H Z2
s
w

{
3
m
−5
w :the molar volume of solution(water , 1.8 10 )
mole
where ' Pa m3
H :the Henr y s law constant for thechemical ( )
mole
Z 2 : the water fugacity capacity for each chemical

 In soil phase (soil organic matter): Chemicals associated to the sediment or soil
phases are typically in equilibrium with the concentration of the water phase and
have absorbed into the soil's organic matter.

C s=K d C 2

{
moles
C s :the sorbed concentration( )
kg
moles
where C 2 : the aqueous concentration( )
L solution
L solution
K d :the quilibriumdistribution coefficinet ( )
kg solids

Since carbon makes up the majority of natural organic matter, the distribution
coefficient and the amount of organic carbon in the soil or sediment are correlated
by:
Kd
K oc =
❑3

{
L
K oc :the organic carbon−based distribution coefficient( )
kg
where
g organic carbon
❑3 : themass fraction of organic carbon ∈the soil phase ( )
g soil solids

The fugacity can be calculated by multiplying the concentration per volume of the
sorbed phase ( C 3 for soil solids) by the phase density ( ❑3, kg solid/m3 solid), and
then using Henry's Law constant (H) to relate C 2 to partial pressure (fugacity):
 1 f
❑3 C s= K oc ❑3 3 =Z 3 f
H 1000
(the factor of 1000 is used ¿ convert L ¿ m )
3

 In other phase which make up the four environmental compartments.

- Intermedia Transport

Chemicals travel through both diffusive and non-diffusive mechanisms to migrate

between environmental compartments.

 Diffusion processes such as volatilization from water to air or soil to air, can occur
in multiple directions and depending on the sign of the fugacity difference
between compartments.The diffusive rate of transfer Nij (moles/h) from
compartment I to compartment J:
moles
N ij =Dij ( f i ) ( )
h

where

{ ( )
Dij :an intermedia transport parameter for diffusion ¿compartment i¿ j mole ¿ f :the fugacity ∈compartment i¿
¿ Pa hr i

 Non-diffusive (one-way) transport transfer across compartments. Examples of this

type of transport include sediment deposition and re-suspension, rain washout, and
the wet/dry deposition of air particles to soil and water. This transport can be
described by:
moles
N=GC =GZf =Df ( )
h

{
3
m
G: volumetric flow rate of the transported material ( )
h
where moles
C : phase concentration( 3
)
m

The intermediate transport parameters can be further classified into categories,

such as air/water transport, air/soil transport, water/sediment transport, soil/water
transport, advective transport.

 Air/Water transport ( D12∧D21 ¿

Transport from air to water involves three processes: diffusion (absorption),

 washout by rain, and wet/dry deposition of aerosols.

 Diffusion (absorption)
1
DVW =
1 1
+
u1 A w Z 1 u2 A w Z 2

{
A w :theinterfacial area between the atmosphere∧the surface water
m
u1 : air−side mass transfer coefficient (5 )
where h
m
u2 : water −side mass transfer coefficient(0.05 )
h

 Rain washout
D R W =u 3 A w Z2

m −4 m
where u3 : a rainfall rate, is assumed equal to 0.876 (10 ¿
yr h

 Wet and dry deposition of aerosols

DQW =u4 A w Z 7
−10 m
where u 4: wet/dry aerosol deposition velocity (6×10 ¿
h

 The air-to-water transport (since mechanisms operate in parallel)

D12=DVW + D RW + DQW

 The water-to-air transport (the reverse of the absorption mechanism)

D21=DVW

 Air/Soil transport ( D1 3∧D31 ¿

1
DVS=
1 1
+
DS D SW + DSA

- DS =u5 A s Z 1
 {
m
u5 : soil air phase diffusion mass transfer co e fficient (0.02 )
where h
A s :the air∧soil interface area

- DSW =u6 A s Z 2

{
m
u6 :s oil air phase diffusion mass transfer coefficient (5 )
where h
A s :the air∧soil interface area

- DS A=u7 A s Z 1

{
m
u7 : soil air surface mass transfer co e fficient (0.02 )
where h
A s :the air∧soil interface area

 The air-to-soil transport

D1 3=DV S + DQS + D RS

where { DQS : wet ∧dry deposition

D R S : rainwashout

 The soil-to-air transport

D3 1=DVS

 Water/Sediment transport ( D24∧D 42 ¿

 The water-to-sediment transport
D24=u 8 A W Z 2+ u9 A W Z 5

{
−4 m
u8 :sediment water diffusion mass transfer coefficient (10 )
h
m
where u 9 : suspended sediment deposition velocity(5 ×10−7 )
h
AW :the surface ( 1010 m2 )
Z5 :the Z value for the suspended sediment

 The sediment-to-water transport

D42=u 8 AW Z 2+u 10 AW Z 4

where u10 :sediment resuspension velocity ¿ )

 Soil/Water ( D3 2 ¿
D32=u11 A s Z 2+ u12 A s Z 3

{
m −5
u11 :soil water run−off water velocity (5 ×10 )
h
−8
u 12 :soil suspended solids run−off velocity (10 )
where A s : the soil surface area
Z 2 :the Z value for the water
Z 3 :the Z value for the soil solid

An additional non-diffusive transport mechanism which removes chemical

from the sediment is burial:
D4 =uB A W Z 4

−7 m
where u B is the sediment burial rate (2 ×10 )
h
 Advective transport
 Chemicals from outside the model region may enter compartments directly
through emissions and advective inputs. The overall input rate for each
compartment:
I i=Ei +G Ai C Bi

{
moles
E i :the emision rate( )
h
m
3 moles
where G Ai :the advective flow rate( ) compartment i( )¿
h m3
C Bi :the background concentrationexternal
¿

 Chemicals leave the model domain through advective (bulk flow) processes from
compartments. The transfer values:
D A i =G Ai ZC i
where ZCi : the compartment I fugacity capacity
- Reaction Loss Processes (with the environments include biodegradation, photolysis,
hydrolysis, and oxidation)
moles
The rate of reaction loss for a chemical in a compartment N R i( ¿:
h

N Ri =k Ri V i Ci=k Ri V i Z i f =D Ri f

{
1
k R i(k R):1st order rate constant ( )
h
where V i :the compartment volume (m3)
moles
Ci :the molar concentration of the chemical ( )
m3
The relationship for a first order reaction between t 1/ 2(half-life) and k R:

−ln ⁡(0.5)
k R=
t 1 /2

- Balance Equation

A steady-state balance between the rates of input from all emissions/bulk flow and
intermedia transport and the rates of output from the processes of intermediate transport,
advection, and response loss in each compartment. For each compartment, we create
mole balance equations, which are compiled in Table 11.2-4.
 c. Environmental Risk Assessment:

Tier 3 Metrics for Environmental Risk Evaluation of Process Design

This step evaluates possible dangers from chemical releases by combining

emissions data with information on environmental destiny and transportation. A
completed flowsheet for a chemical process design will be quantitatively evaluated using
this methodology, which will be applied in a systematic manner. In order to comprehend
the effects of chemical process designs on local, regional, and global scales, it entails the
calculation of various environmental and health-related indices. It also involves the
ranking of technologies, the optimization of in-process waste recycle/recovery processes,
and the evaluation of reactor operation modes. Both biotic and abiotic effect measures are
used into many indexing techniques:

+ Abiotic (global warming, stratospheric ozone depletion, acidification,

eutrification, and smog formation)

+ Biotic (human health and plant, animal, and other organism health)
 Additionally, in order to translate the concentration-dependent doses into
probabilities of risk, information regarding toxicity or inherent impact is needed.

In terms of long-term requirements for raw material consumption, resource-

depletion indices are indicative of challenges related to environmental and economic
sustainability. Several environmental metrics (indices) have been created by using
different parameters for an emitted chemical's inherent impact potential (IIP) and
exposure potential (EP), according to an analysis of several of these approaches:

(Dimensionless Risk Index)i=¿ ¿

Nine environmental and health-related indexes for chemical process impacts:

+ Abiotic Indexes (Global warming, Stratospheric ozone depletion, Acid

deposition, Smog formation)

+ Health-Related Indexes (Inhalation toxicity, Ingestion toxicity, Inhalation

carcinogenicity, Ingestion carcinogenicity)

+ Ecotoxicity Indexes (Fish Aquatic Toxicity)

The contributions for each chemical weighed by its emission rate must be added
together in order to estimate the index I for a certain impact category resulting from all of
the chemicals produced from a process:

I =∑ (Dimensionless Risk Index)i × mi

i

Environmental and health indexes which have been used to compare impacts of
chemicals, processes, or products:

 Global warming

Due to the action of hydroxyl radicals in the troposphere, the majority of

compounds of interest have such a short atmospheric half-life that they disappear (get
converted to CO2) long before any appreciable direct effect is felt. However, because
organic compounds derived from fossil fuels leak carbon dioxide into the atmosphere
and other environmental compartments during oxidation, these compounds will
indirectly contribute to global warming.
  Direct: the global warming potential (GWP), which measures the cumulative
infrared energy captured from the release of 1 kilogram of greenhouse gas relative
to that from 1 kg of carbon dioxide, is a commonly used indicator of global
warming (IPCC, 1991):
n

∫ ai Ci dt
0
GW P i (direct)= n
∫ aCO2 CCO 2 dt
0

{
−2
ai : the predicted radiative forcing of gas (Wm )
Ci :the prdeicted concentration∈the atmosphere( ppm) kg
where n :the number of years ( for C O2=120 years ) the entire process ( ) ¿
h
mi : themass emissionrate of chemical
¿

A group of experts formed under the Intergovernmental group on Climate Change

(IPCC, 1991 and 1996) put together a list of "best estimates" for GWPs based on these
model forecasts; these estimates have appeared on other lists (Heijungs et al., 1992;
Goedkoop, 1995).

The strength of a chemical's infrared radiation absorbance (band intensities) and

its tropospheric residence time are the primary factors influencing its ability to cause
global warming. These gasses are all incredibly flammable, insoluble in water, and
adsorbent to sediments and soils. Thus, once they are released from sources, they will
remain in the atmosphere. The equivalent emission of carbon dioxide, the benchmark
compound, is the product of the GWP and the mass emission rate of a greenhouse
chemical. This step will provide the equivalent process emissions of greenhouse
chemicals in the form of the benchmark compound, CO2. The total of the emissions-
weighted GWPs for each chemical makes up the global warming index for the entire
chemical process:

I GW =∑ GWPi ×mi
i

 Indirect: organic compounds with atmospheric reaction residence times less than
1/2 year:
M W CO2
GW P i (¿ direct)=N C
M Wi

where {N :the number

C of carbon atoms ∈the chemicali
MW :the molecular weights
  Ozone depletion
The predicted time- and height-integrated change … [O3] in stratospheric
ozone caused by the release of a particular quantity of a chemical relative to that
caused by the same quantity of a benchmark compound, trichlorofluoromethane
(CFC-11, CCl3F), is known as the chemical's ozone depletion potential (ODP)
(Fisher et al., 1990b).
[ O3 ]i
ODPi=
[ O3 ]CFC−11
Once released from sources, the compounds will almost entirely reside in
the atmosphere. The total contribution from all released chemicals multiplied by
their emission rates is the ozone depletion index for a complete chemical process.
The process's total equivalent CFC-11 emission:
I OD=∑ ODP i × mi
i

 Acid rain

Any substance's potential for acidification is determined by the ratio of H +¿¿ produced
to the amount of the compound released. This relationship can be found in the balanced
chemical equation:
+¿+¿ ¿
X +¿H

where ¿

Since acidification is typically expressed in terms of a mass basic, the H +¿¿ generated
per mass of substance emitted:
❑i ¿

where M W i: the molecular weight of the emitted substance (moles i/kg i).
The acid rain potential ( ARPi )of any emitted acid-forming chemical:
❑i
AR Pi =
❑S O 2

The total acidification potential of an entire chemical process:

I AR=∑ AR P i × mi
i
 Smog formation

VOCs in smog formation is to form radicals which convert NO to NO 2

The smog formation potential (SFP) is based on the maximum incremental

reactivity scale of Carter (Carter, 1994):
MIR i
SF Pi=
MIR ROG

MIR ROG : the average value for background reactive organic gases, the

benchmark compound for this index.

The process equivalent emission of ROG:

I S R=∑ SF Pi ×mi
i

 Toxicology (Non-Carcinogenic Toxicity and Carcinogenic Toxicity)

Chemical toxicity is a function of dose and response for both people and
ecosystems. The dose is dependent on a complex series of steps involving the manner
of release, environmental fate and transport of chemicals, and uptake mechanisms.

- Non-Carcinogenic toxicity
 The toxicity potential for ingestion route exposure:
 [ (2L)
( Ci , w ) d
70 kg
Rf Di
]
I NGTPi =

[ ( ) ]
2L
( C toluene, w ) d
70 kg
Rf Dtoluene

where

{
Ci , w ∧C toluene, w :the steady−state concentrations of the chemical∧the benchmark
kg
compound ( toluene ) ∈the water comparment after release of 10000 of each into
h ∧body weight
the water comparment
2L
∧70 kg :the standard ingestion rate(Pratt , et al .,1993)
d

The toxicity index for the entire process:

I ING=∑ INGTP i × mi
i

 The toxicity potential for inhalation exposure:

Ci , a
Rf C i
¿ H TPi=
C toluene, a
Rf C toluene
where:C i ,a∧C toluene ,a :the concentrations of the chemical∧the benchmark
kg
compound (toluene ) ∈the air comparment after release of 10000 of each into
h
the air comparment

The toxicity index for the entire process:

I ¿ H =∑ ¿ H TPi × mi
i

 The toxicity potential for inhalation exposure:

 Ci , a
Rf C i
INHTPi =
Ctoluene , a
Rf C toluene

- Carcinogenic toxicity
 The toxicity potential for ingestion route exposure:
Ci , w × S F i
¿ GC Pi=
Cbenzen e ,w × S F benzene
−1
mg
SF kg the cancer potency slope factor, is the slope of the excess
( ) :
d
cancer versus administered dose data.
The toxicity index for the entire process:
I C ING =∑ ING C Pi ×mi
i

 The toxicity potential for inhalation exposure:

Ci, a× S Fi
INGCPi=
C benzene , a × S F benzene
The toxicity index for the entire process:
I C INH =∑ INH C Pi × mi
i

II. Process/Equipment Design Implications:

The methodology highlights the importance of integrating environmental impact

assessment early in the process and equipment design phase. By quantitatively
assessing the environmental impacts through various indexes and metrics, designers
can make informed decisions to optimize processes for minimal environmental
footprint. This could involve selecting materials and processes with lower emissions,
designing for efficient waste recovery and recycling, and considering the full life
cycle impacts of the process operations. This comprehensive approach underscores
the critical role of environmental impact assessment in guiding the design and
operation of chemical processes. It demonstrates the interconnection between
emissions, environmental fate, and impacts, providing a framework for minimizing
the environmental footprint of chemical processes.

1. Design implications from environmental impact assessment: Integrating

environmental impact assessments early in the design phase is crucial. The
assessments guide decisions in process and equipment design towards minimizing
environmental impacts. This may involve selecting processes and materials that
lower emissions, optimizing waste recovery and recycling, and considering the life
cycle impacts of process operations.

2. Optimization for reduced environmental footprint: The design phase aims to

implement solutions identified during the assessment phase to reduce the
environmental footprint. This includes technological innovations, process
modifications, and the adoption of more sustainable practices and materials. This
structured approach not only ensures compliance with environmental regulations
but also aligns with sustainability goals by minimizing the ecological footprint of
chemical processes.

3. Software tools
- Environment fate and risk assessment tool (EFRAT)
- Waste reduction algorithm (WAR)