Design of the Wastewater Treatment Plant for Microelectronic Processes

Wastewater Using CHEMCAD® Process Simulator

R. W. Gaikwad
Department of Chemical Engineering, Jawaharlal Nehru Engineering College, Chh. Sambhajinagar, 431001 (MS) India
(PDLOUZJDLNZDG#JPDLOFRP0RELOH
Hemant S. Sadafale
Department of Chemical Engineering, Jawaharlal Nehru Engineering College, Chh. Sambhajinagar, 431001 (MS) India
Email: [email protected]

Abstract: The wastewater from the microelectronics sector is generating a lot of organic and inorganic contaminants,
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ZDVWHZDWHU DUH FODVVL¿HG DV TXDOLWDWLYH FRQWDPLQDQWV DOWKRXJK WKH\ DUH SUHVHQW LQ ORZ FRQFHQWUDWLRQV WKH\
SRVH D VLJQL¿FDQW KDUP WR SXEOLF KHDOWK DQG WKH HQYLURQPHQW 7KH GHVLJQ RI WKH ZDVWHZDWHU WUHDWPHQW SODQW IRU WKH
microelectronics industry wastewater using CHEMCAD® process simulator is accomplished by utilizing the process
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characteristics down to the CPCB of India’s limitations.
KeyWords: Microelectronics, wastewater, metal removal, design, CHEMCAD, simulations

1. INTRODUCTION a study done on the accumulation in river waters and bed

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The microelectronics industry is seeing exponential
increase in production speed due to the huge demand for manufacturers (Hsu et al. 2016).
electronics integrated circuits across multiple industries.
Applications for semiconductors include smart factories,
displays, robots, AI, and automobiles. Numerous hazards to
both humans and the environment are linked to the toxicity
of chemical chemicals employed in the semiconductor
manufacturing process (Mori et al. 2015). One of the
PDMRU LQGXVWULDO HIÀXHQWV VHPLFRQGXFWRU ZDVWHZDWHU
makes for 28% of all wastewater released untreated into
the environment (Mao et al., 2022). Researchers have
paid close attention to these wastes in terms of resource
recovery and zero-liquid discharge. The composition of the
YDULDQFHV LQ WKH JHQHUDWHG HIÀXHQWV SUHVHQWV WKH ELJJHVW
challenge (Cielik and Konieczka 2017).It is concerning
because the microelectronics sector contributes trash
that pollutes the environment negatively by generating Fig. 1. Prominent Chemical And Inorganic Pollutants
large amounts of wastewater that contain heavy metals, )RXQG,Q(৾XHQW)URP0LFURHOHFWURQLFV,QGXVWU\
SKRVSKDWH DQG ÀXRULGH 7KH PRVW SUHYDOHQW NLQG RI
contaminants from microelectronic waste is depicted in The etching procedure used to create integrated circuit chips
Figure 1. Figure 2 illustrates that the heavy metals utilized SURGXFHGWKHÀXRULGHFRPSRXQGZKLFKZDVVKRZQWRUDQJH
in the microelectronics industries most frequently include in concentration from 250 to 1500 mg/l in semiconductor
copper (14.29%), silicon (26.19%), and silver (27.38%). HIÀXHQW /LXDQG/LX/DFVRQHWDO :DVWHZDWHU
One of the metals that can be recovered and recycled from microelectronic devices is very different from that
IURPWKHPLFURHOHFWURQLFVLQGXVWU\¶VHIÀXHQWVLVVLOLFD 6L from other industries. These wastewaters are produced
residue (Noman, E.A et.al. 2024).The most often discovered by the emulsifying process used in the manufacturing of
elements were Pb2+, Cr2+, Cd2+, Zn2+, and Ni2+, according to ÀXRURSRO\PHUV DQG WKH\ FRQWDLQ EHWZHHQ DQG

July-September 2024 218 Journal of Indian Water Works Association

The production of waste occurs in a number of ways during
the microelectronics manufacturing process. When taken
into account separately, these wastes are rather common
and simple to handle. However, the different streams are
occasionally merged and held as a result of continuous
VWXG\ WR ¿QG WKH PRVW HIIHFWLYH WHFKQLTXH WR PDQDJH WKH
waste. This study focuses on one potential treatment train
for mixed waste streams.Recently CHEMCAD® simulator
has been used to model and simulate extensive variety
of processes, for instance: the simulation of an olive
pits fed rotary kiln pyrolysis plant installed in Southern
,WDO\ %HQDQWL HW DO WKH FRQFHSWXDO GHVLJQ RI DQ
acetaldehyde manufacturing plant(Eliasson, J. 2010),
the simulation of the biodiesel production process by
WUDQVHVWHUL¿FDWLRQRIYHJHWDEOHRLOV &KLOHY& 6LPHRQRY
E.2014). In this investigation, the theoretical design of
wastewater treatment.
plant for microelectronic processes wastewater
)LJ6LJQL¿FDQW+HDY\0HWDOV,Q(৾XHQW)URP using CHEMCAD® process simulator is carried out
Microelectronic Industry (Chemstations ,2002). This study aims to understand the
P0RISHUÀXRURRFWDQRLFDFLG 3)2$ DVZHOODVWR mass composition of the different streams involved in the
J/RI70$+WRJ/RIJO\FHURO±PJ/RI wastewater treatment process, so it is possible to determine
S\UD]ROH ± PJ/ RI DFHWRQH ± PJ/ RI WKH PDLQ GHVLJQ SDUDPHWHUV RI SURFHVV HTXLSPHQW WR
FDOFLXPÀXRULGH &D) ±PJ/RI.2+1+±1 FDOFXODWHWKHÀRZUDWHRIWKHGLIIHUHQWDX[LOLDU\FRQVXPHG
± PJ/ DQG WXUELGLW\ 178 ± 7KH S+ The outcomes attained in this simulation analysis will assist
UDQJHV DUH WR ± J/ RI WRWDO VROLG ± to design a wastewater treatment plant for microelectronic
PJ/RIVXVSHQGHGVROLG±PJ/RI&2'%2' processes wastewater and can be used to gain the essential
&2'EHWZHHQDQG±PJ/RIVXOSKDWHV methods to intensify the pollutant removal, get better
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DO 3RVW HW DO :DQJ HW DO 7HRZ HW DO well as to form the necessary details for forthcoming
2022). Wastewater from microelectronic industry contains optimization investigations.
Cu+2, Sn+2, Pb+2, HF, methyl methacrylate, methanol,
and acetone. As per the norms of Central Pollution 2. METHODOLOGY
Control Board, before discharged to the environment, Treatment of a wastewater stream from microelectronics
the Cu+2,Pb+2,and HF concentration has to be 3 mg/lit, manufacture obtained by CHEMCAD® simulator is
2 mg/lit, and 1 mg/lit respectively(https://cpcb.nic.in). depicted in Fig. 3.Stream 1 is where the waste stream
Environmental Protection Agency (EPA) has calculated a enters the process. It is made up of water that has been
Reference Concentration for methyl methacrylate of 0.7 polluted with trace levels of Cu+2, Sn+2, Pb+2, HF,
mg/m3( https://www.epa.gov). methyl methacrylate, methanol, and acetone. Low amounts
of the three metals are successfully eliminated from
Motivation for Design:
the waste by use of an ion-exchange procedure carried
There has been a lot of environmental criticism recently out in Equipment-1. There are twocolumns in the ion-
regarding the amount of wastewater created by the exchange process: one is being used, and the other is being
semiconductor industry. Millions of gallons of water are regenerated. Nitric acid is used as the column regenerant.
used every day in microelectronic operations to wash Although the precise content of the regeneration solution is
chemicals and microscopic debris off chip surfaces. These unknown, a 1 M HNO3 solution likely to work well. The
waste kinds cannot be disposed of on land unless they amount of nitric acid needed to regenerate the column is
have undergone pretreatment in accordance with Best known to be 250 moles. Based on the column capacity,
Demonstrated Available Technology (BDAT) guidelines. which has been sized for a loading period of one day and
Right now, cutting back on waste production is a top a regeneration time of up to one day, this is determined.
priority. However, the waste stream needs to be managed In contrast to vast quantities of sludge, which are more
until a more appropriate method of manufacturing is found. GLI¿FXOW WR GLVSRVH RI WKH UHJHQHUDWLRQ HIÀXHQW IURP WKH

Journal of Indian Water Works Association 219 July-September 2024

column, Stream 4, contains the metals that were originally ¿WV EHWWHU WKH WHPSHUDWXUH DQG SUHVVXUH UDQJHV KDQGOHG
taken from the wastewater with low volumes of scrap metal throughout the production process, and it’s also capable of
WKDW PD\ EH UHDGLO\ ODQG ¿OOHG )ROORZLQJ WKH UHPRYDO predicting satisfactorily the most important thermodynamic
of the metals, Equipment-4 receives the water stream, variables of all the chemicals used according to the
Stream 3. With the help of this reactor, lime is added to different existing phases. Using this model and the SRK
ZDVWHZDWHU WR QHXWUDOL]H +) DQG FUHDWH FDOFLXP ÀXRULGH
model (Soave-Redlich-Kwong) allows determining the
Since CaF is a solid, removing it from Stream 9 is simple
values of the equilibrium constant K and other important
DQG RQO\ UHTXLUHV ¿OWUDWLRQ ,Q (TXLSPHQW WKH SDUWLFOHV
are extracted from the water, readying the waste for the thermodynamic parameters. Additionally, it is taken
separations phase of the procedure. Only the organic waste, into account some useful recommendations provided by
or Stream 10, makes its way into the separations section of the simulator itself. PSRK (3UHGLFWLYH 6RDYH±5HGOLFK±
the process. Water and methyl methacrylate are separated Kwong) is an estimation method for the calculation of
IURP DFHWRQH DQG PHWKDQRO XVLQJ (TXLSPHQW WKH ¿UVW phase equilibria of mixtures of chemical components. The
distillation column. The acetone and methanol in Stream 12 original goal for the development of this method was to
are then separated using Equipment-7, and they leave the enable the estimation of properties of mixtures containing
system as Streams 14 and 15, respectively. In Equipment-8, supercritical components. This class of substances cannot be
methyl methacrylate is extracted from the water by carbon predicted with established models, for example UNIFAC.
adsorption. The “clean water” leaves the system through
As stated previously, the PSRK model is based on a
Stream 16. The carbon in the column is regenerated off-site
FRPELQDWLRQ RI WKH 6RDYH±5HGOLFK±.ZRQJ HTXDWLRQ RI
with steam. Table 1 shows an equipment description for the
SURFHVVÀRZGLDJUDP state with a mixing rule whose parameters are determined
by the UNIFAC method. The equation of state of Soave is
Thermodynamic model selection GH¿QHGDVIROORZV
In CHEMCAD, to simulate the majority of the process
using the SRK as a K-value model and NRTL as an
Enthalpy model. In this design, the ion exchange column
ZDV PRGHOHG DV D FRPSRQHQW VHSDUDWRU 7KH ¿OWHU ZDV
where P, T and nm are the system pressure, temperature
assumed to remove all solids while allowing 99% of the
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liquid to continue on to the rest of the process. The two
distillation columns were designed by using CHEMCAD. PSRK EoS.
The carbon adsorption column was also simulated as a
component separator and sized by hand. The Freundlich
isotherm model was used to determine the amount of
carbon required.
K-Value Model -/LTXLG SKDVH DFWLYLW\ FRHI¿FLHQWV DUH
calculated by NRTL equation. The Non Random Two
Liquid equation has the following form.
where Pc,i and Tc,i stand for the critical pressure and
FULWLFDOWHPSHUDWXUHRISXUHFRPSRQHQWLUHVSHFWLYHO\XLV
the acentric factor. The PSRK mixing rule is written as

Enthalpy Model
Peng-Soave-Redlich-Kwong vapor-phase associated where g0ELVH[FHVV*LEEVHQHUJ\WKHUHFRPPHQGHGYDOXH
thermodynamic model was selected to carry out simulation RI$LVLQWKH365.PRGHOWKHDFWLYLW\FRHI¿FLHQW
calculations in CHEMCAD® simulator. This model of component i, gi is calculated using the UNIFAC model.

July-September 2024 220 Journal of Indian Water Works Association

Table 1: Equipment Description With Stream Numbers of the critical point, and the dew and bubble lines of the
(Negative Sign Indicates Outlet Stream) liquid phase envelope. The operating condition of the plant
was located on the phase envelope diagram as well.
Equip- Description Stream Equip Description Stream
-ment Number -ment Number
ID ID 3. RESULT AND DISCUSSION
1 Component 2,-3,-4 5 Rotary 9,-10, The results of the simulation are shown numerically in
Separator 1 Drum Filter -11
WinWord window as shown Table 2. The results show
2 Mixer I 6, 1, -2 6 Distillation 10,-12,
Column 1 -13 PDVV ÀRZ UDWHV LQ HDFK VWUHDP WRJHWKHU ZLWK DQ RYHUDOO
3 Sedimentator 4,-5,-6 7 Distillation 12,-14, input/output balance. In stream number 1, around 0.014260
Column 2 -15 Kmol/h of acetone, 0.004730 methyl methacrylate Kmol/h
4 Reactor 7, -9 8 Component 13,-16, , 0.047300 HF Kmol/h was processed. In stream number
9 Mixer II 8, 3, -7 Separator II -17 DERXW .PROK FRSSHU K\GUR[LGH
Kmol/h lead hydroxide, and 0.000400 Kmol/h tin hydroxide
was processed. The Table 3,shows the chemicals and metal
removed from wastewater using simulation.

Table 3: Chemicals And Metal Removed From Wastewater

Stream Stream Name Molar Flow rate

No. Kmol/h
14 Acetone 0.0013822
15 Methanol 0.01222
17 Methyl methacrylate 0.046
11 Calcium Fluoride 0.02
5 Metals 0.0051
Phase Envelope: The phase envelope of the gas stream
Fig.3- Treatment Of A Waste Water Stream From Microelectronics
was generated by using the simulation software packages,
Manufacture Obtained By Chemcad® Simulator
as shown in Fig. 4. Bubble point which forms bubble line
Phase Envelope: in Fig. 4 is a point separating the liquid phase and the two
phases region, namely the liquid phase and the gaseous
Phase diagram or phase envelope is a relation between phase. Dew point which forms dew line in Fig.4 is a point
temperature and pressure that shows the condition of separating the gaseous phase and the two phases region,
equilibria between the different phases of chemical QDPHO\WKHOLTXLGSKDVHDQGWKHJDVHRXVSKDVH7KH¿JXUH
compounds, mixture of compounds, and solutions. Phase illustrates that the operating condition lies very close to
diagram is an important issue in chemical thermodynamics the dew line of the phase envelope. Thus, any movement
and solution reservoir. It is very useful for process along a straight line to the left or right (by changing the
simulation, reactor design, and petroleum engineering WHPSHUDWXUH UHVXOWVLQDFKDQJHRIWKHSKDVHLHLWUHVXOWV
studies. It is constructed from the bubble line, dew line, in a change in the rate of the gas production.
and critical point. Bubble line and dew line are composed
of bubble points and dew points, respectively. Bubble
SRLQWLVWKH¿UVWSRLQWDWZKLFKWKHJDVLVIRUPHGZKHQD
OLTXLG LV KHDWHG 0HDQZKLOH GHZ SRLQW LV WKH ¿UVW SRLQW
where the liquid is formed when the gas is cooled. Critical
point is the point where all of the properties of gases and
liquids are equal, such as temperature, pressure, amount
of substance, and others. Critical point is very useful in
processing and dissolution of certain chemicals. Michelsen
(1980), described the calculation of the phase envelope.
However, to determine the phase of the obtained liquid
stream, CHEMCAD was used to generate the phase
envelope of the liquid stream. The PSRK model refers to Fig.4- Phase Envelop For Methyl Methacrylate Removal
the thermodynamics package that was used in the creation Stream No.17

Journal of Indian Water Works Association 221 July-September 2024

7KHWHPSHUDWXUHDQGPROHIUDFWLRQVSUR¿OHVKDYHGLUHFWO\ Adsorbent (Carbon) requirement Calculation:
drawn using plot function in CHEMCAD, which is
The carbon adsorption column was also simulated as a
illustrated in Fig. 5.
component separator and sized by hand calculations. The
Sizing of Distillation Column Freundlich isotherm model was used to determine the
amount of carbon required. The following parameters were
The results of the simulation for sizing of distillation used.
column are shown numerically in WinWord window as
shown in Table 4.

Where x= mass of methyl methacrylate ,m = mass of

carbon, KF= Freundlich adsorption constant = 1.3, Ce
= concentration of methyl methacrylate in solution at
equilibrium, n = Freundlich exponent = 0.58. The carbon
was assumed to be regenerated by the manufacturer.

Data obtained after Simulation –

Mass of methyl methacrylate= 467.476 gm
Moles of methyl methacrylate = 4.669 mol/hr
9ROXPHWULFÀRZUDWHRIPHWK\OPHWKDFU\ODWH P3/hr
Fig. 5-7KH7HPSHUDWXUH$QG0ROH)UDFWLRQV3UR¿OHV0HWKDQRO
Acetone At 101.33 Kpa By Nrtl For Distillation Column 7 Therefore, concentration of methyl methacrylate,
ChemCad has successfully converged the design of the
wastewater treatment plant for Microelectronics Wastewater
Treatment. The material and energy complexities were
reduced to a greater extent. Different component of mixed Using Freundlich isotherm model,
waste stream were separated more or less to pure form. It
FDQEHYLVXDOL]HGIURPÀRZVXPPDULHVRIVWUHDPV6L]LQJ
of distillation column was done which gives the internal
GHWDLOV IRU IDEULFDWLRQ7KH WHPSHUDWXUH SUR¿OHV IURP WKLV
study are shown in Fig. 6. The goal was to identify a “good This calculation shows only 118.8 gm of carbon is needed
tray” for the temperature control system and to comprehend for the removal of 467.476 gm of methyl methacrylate,
the column’s sensitivity. The decision has been made to
4. CONCLUSION
choose a tray from the region shown in the illustration. Trays
10 through 12 have one thing in common: the temperature The current investigations are found effective for the
SUR¿OHVLQGLFDWHDQLQÀHFWLRQSRLQWDWWKLVORFDWLRQ7UD\ Design of the wastewater treatment plant for the removal
has been chosen to measure and regulate the temperature in of Cu+2, Sn+2, Pb+2, HF, methyl methacrylate, methanol,
the column’s lowermost part. and acetone, using CHEMCAD® process simulator. The
VLPXODWHGSODQWZDVDEOHWRUHGXFHWKHHIÀXHQWVWUHDPVWR
below the regulatory threshold established by the Central
3ROOXWLRQ &RQWURO %RDUG &3&% 7KH VWXG\¶V ¿QGLQJV
support the possibility that CHEMCAD® could serve as a
tool for environmental engineers and engineering students
to use while designing, running, and controlling processes
that must adhere to environmental limitations. Furthermore,
it shows that the SRK and NRTL model thermodynamics
SDFNDJH JLYHV WKH EHVW ¿W LQ WKH VLPXODWLRQ RI GHVLJQ RI
WWT plant, since the obtained results were comparable
to the measured values from real industrial data. Thus, it
FRQ¿UPVWKHYDOLGLW\RIWKHPRGHOZKLFKLVUHTXLUHGEHIRUH
completing any further study (e.g., sensitivity study or
)LJ7UD\7HPSHUDWXUH3UR¿OH,Q'LVWLOODWLRQ&ROXPQ optimization).

July-September 2024 222 Journal of Indian Water Works Association

Table 4- Simulation Results For Sizing Of Distillation 4. REFERENCES
Column (Equip. 6 & 7) For Wastewater Stream From %HQDQWL()UHGD&/RUH¿FH9%UDFFLR* 6KDUPD
Microelectronics Wastewater Treatment (Chemcad V, (2011) Simulation of Olive Pits Pyrolysis in a
Simulator Generated) Rotary Kiln Plant. Thermal Science, 15(1), 145-158.
Chemstations (2002), ChemCAD Professional® (Version
5.2.0). Houston, Texas: Chemstations Inc. Recovered
from www.chemstations.com
&KLOHY& 6LPHRQRY( 6LPXODWLRQRI%LRGLHVHO
3URGXFWLRQ E\7UDQVHVWHUL¿FDWLRQ RI9HJHWDEOH 2LOV
Journal of Chemical Technology and Metallurgy,
49(5), 479-486.
&LHĞOLN % .RQLHF]ND 3 $ UHYLHZ RI SKRVSKRUXV
recovery methods at various steps of wastewater
treatment and sewage sludge management. The
concept of “no solid waste generation” and analytical
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HY, Chen TY, Chang CF, Liu YT, Tzou YM (2016)
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DQGVHPLFRQGXFWRULQGXVWULHV6FL5HS ±
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IRU WUHDWPHQW RI KLJK ÀXRULGHFRQWHQW ZDVWHZDWHU -
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Michelsen, M.L, (1980) Calculation of phase envelopes
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(2015) Toxicity of tetramethylammonium hydroxide
to aquatic organisms and its synergistic action with
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al. (2024) An insight into microelectronics industry
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perspectives: a critical review. Appl Water Sci 14, 64.

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Table 2 - Simulation Results For Wastewater Stream
From Microelectronics Wastewater Treatment
(Chemcad Simulator Generated)

July-September 2024 224 Journal of Indian Water Works Association

Journal of Indian Water Works Association 225 July-September 2024