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5

Exergy and Exergoeconomic Analysis of Ethylene


Oxide / Ethylene Glycol Process at Start Run and
End Run

5.1 Introduction
Ethylene oxide (EO) is a very important intermediate product in the petrochemical
industry. EO is the second most important derivative of ethylene next to polyethylene. The
major portion of ethylene oxide is converted to ethylene glycol (EG). Mono Ethylene
Glycol (MEG) has the largest application in the manufacture of polyester staple fiber &
filament yarn. MEG is also used as automobiles anti-freeze and as stabilizers against gel
formation. EO is used for the production of Glycol, in dyes, pharmaceuticals,
ethanolamine production and as a disinfectant. EO/EG plants are one of the most profitable
plants in the petrochemical industry (Wang et al., 2013). This process is very vulnerable
due to high temperature, runaway reactions and very explosive gas mixture. Direct
oxidation of ethylene produces EO by using pure oxygen on the silver-based catalyst. The
quantity of EO formed depends upon the selectivity of the catalyst. A major hurdle in the
process is the deterioration of catalyst selectivity as production progress. The energy loss
due to non-selectivity of the top 10 petrochemical products was 138 PJ in the year 2000
(Neelis et al., 2007). EO production is at second number followed by Acrylonitrile in this
list. Due to the higher cost of ethylene and silver catalyst, EO process is economically
challenging to achieve higher profitability. Over the period, the cost of ethylene has been
increased, but catalyst with higher selectivity reduces overall consumption of ethylene and
compensates overall cost. In the present study, energy and exergy analysis are carried out
for the EO / EG process at start-run (higher selectivity for desired product) and end-run
(lower selectivity for desired product). Two different processes of EG are compared based
on exergy analysis. Finally, EXCEM method is used for exergoeconomic analysis of the
process to decide end run selectivity of the catalyst.
Exergy Analysis of Nitric Acid, Ethylene Oxide/Ethylene Glycol Processes and Methanol Reactor

5.2 Ethylene Oxide / Ethylene Glycol Production


Wurtz first produced EO by reacting ethylene chlorohydrin and potassium hydroxide
(Rebsdat et al. 2013). The direct oxidation process of ethylene and oxygen developed by
Lefort has replaced Wurtz’s process after 1931 as the first one is inefficient and causing
pollution. Either air or pure oxygen is required for the oxidation of ethylene. Conversion of
ethylene per pass is low; hence recycling of gases through the reactor is required. Nitrogen
enters into the system along with oxygen in the air-based process. The largest amount of
purging is required to maintain the concentration of nitrogen in recycling gases. An air
based process also requires two or three reactors in series for EO production to get the
required concentration of EO in the product gas. The oxygen based process is
advantageous over air based process due to more yield (McKettaet al, 1984). Although the
carbon dioxide removal system is not required in the air based process, its capital cost
requirement is more than oxygen-based process (Gunardsonet al, 1998).
In present study oxygen based process is analyzed due to its worldwide acceptance as an
efficient process. As more than half of EO produced is used in the production of EG,
petrochemical complexes are having integrated plants of EO and EG. A simplified flow
diagram of EO/EG plant is shown in Fig. 5.1. It is broadly divided into five sections – 1)
Ethylene oxidation 2) EO absorption 3) CO2 removal 4) EG reaction 5) EG separation.

5.2.1 Ethylene Oxidation


Ethylene is introduced into recycling gas going into the reactor. Oxygen is mixed at the
mixing station in a static mixer. Feed gas is sent to the reactor through the feed gas heater
(H-2). A tubular reactor (R-1) consists of several thousand tubes having an internal
diameter of 20-50 mm and a length of 6-13 m. Tubes are packed with silver catalyst.
Along with the formation of EO (reaction-1), combustion of ethylene into carbon dioxide
and water also take place (reaction-2) in the reactor. The fraction of EO further oxidizes to
form combustion products (reaction -3).

1. H2C = CH2 + ½ O2 → ΔHR,298 = -105.08 kJ/mol

2. H2C = CH2 + 3 O2 → 2 CO2 + 2 H2O ΔHR,298 = -1324.10 kJ/mol

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3. + 5/2O2 → 2 CO2 + 2 H2O ΔHR,298 = -1223 kJ/mol

Fig. 5.1 Process flow diagram of EO/EG process

The catalyst must maximize primary reaction-1 and minimize reaction 2 and 3. Selectivity
and activity are important parameters for EO catalyst. Different families of a catalyst like
high activity, high selectivity, hybrid catalyst are available in the market (ethylene oxide,
2013). High selectivity catalyst offers superior selectivity at initial stages, but have a
lower life span, whereas high activity catalyst offers a higher initial activity as well as long
term reasonable selectivity. Today average selectivity has been increased up to 90%,
which was only 65% in 1965. Hybrid catalyst and high performance catalyst are also
developed recently. In this process, high activity catalyst with 81% initial selectivity and
three year life is used. The reactor temperature is maintained at 506.15 K at start run and
528.15 K at an end run with an average pressure of 2.05 MPa. Heat generated in the
reactor is taken out by boiling water. Steam is produced at 2.15 MPa (489.15 K) in steam
generator by vaporizing 2 to 4 % of water by thermosyphon action. Ethylene conversion

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per pass is almost 12% in the reactor. Inlet and outlet compositions of EO reactor are
shown in Table 5.1. Values are reported for the amount of component per ton of ethylene
oxide produced.

Table 5.1 Inlet and outlet compositions of EO reactor


Start run (kg/t) End run (kg/t)
Component
Inlet Outlet Inlet Outlet
Nitrogen 126.99 126.99 127.14 127.14
Argon 4350.60 4350.60 4352.67 4352.67
Oxygen 2421.17 1535.93 2421.17 1442.87
Methane 6419.54 6419.54 6443.39 6443.39
Ethylene 6633.38 5844.01 6633.38 5816.81
Ethane 696.89 696.89 652.54 652.54
Carbon dioxide 4162.48 4641.17 4162.48 4726.50
Ethylene oxide 2.82 1002.79 2.91 1002.89
Water 40.04 235.99 39.79 270.67

Accumulation of argon and nitrogen is due to their presence in oxygen. All the
hydrocarbon gases entering and leaving the reactor are explosive. Ethylene oxide itself is
having a wide explosive limit in the range of 2.6% - 100%. Percentage of ethylene and
oxygen at the reactor inlet should be 40% and 9% by volume respectively for safe
operation (Coombs et al., 1997). Methane, which is less reactive than ethylene, is used as
ballast gas and acts as an inert in the system. Ballast gas is added to cycle gas loop, which
serves the dual purpose- 1) Both ethane and methane have higher specific heat and thermal
conductivity than nitrogen, which helps to rise flammable limit in the reactor gases
(Deveret et al., 2010) 2) To absorb & remove a part of heat of reaction from the reaction
zone. It also improves the yield of EO by reducing the hot spot effect (Papavassiliou and
Wagner, 1999). Methane ballast has an advantage over nitrogen ballast, as it gives higher
selectivity & power requirement of recycling compressor is less. Mixing of lean gas with
oxygen takes place at the oxygen mixing station (OMS). The gas mixture flows from the
gas- gas exchanger to the EO reactor. Outgoing product gas stream from EO reactor is
exchanging heat with incoming gas steam in the feed gas heater (H-2).

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5.2.2 EO Absorption
EO is separated from product gas by absorption in water (C-1). Along with EO, small
quantities of methane, ethylene and carbon dioxide is also absorbed. These gases are
removed in C-2 and C-3. EO along with water is taken out from finishing column (C-4).
Overhead gases from C-1 at 1.86 MPa are compressed in the compressor (K-1) and sent
back to the reactor. A small stream of recycled gas is purged to control the build-up of
nitrogen and argon. Reclaim compressor K-2 is used to compress gases coming out from
C-3 and C-4 along with methane that is used as ballast. A network of heat exchangers (H-3
to H6, H-17) is used to maintain the temperature of various streams.

5.2.3 CO2 Removal


A part of compressed gas from K-1 is sent to CO2 removal section where hot potassium
carbonate solution maintained at 393.15 K is used to absorb CO2. Potassium carbonate is
having a low heat of reaction, low volatility and non degradable. High pressure in the CO2
absorber (C-5) (2.20 MPa) increases driving force for absorption and push the reaction
forward. The overall reaction for CO2 absorption is (Kothandaraman, 2010)
4. CO2 + K2CO3 + H2O ↔ 2KHCO3
Potassium carbonate and potassium bicarbonate are both strong electrolytes and hence
reaction-4 is represented by
5. CO2 + CO32- + H2O ↔ 2HCO3-
Live steam and reboiler provide the energy required for CO2 desorber (C-6). The column
is operated at 0.19 MPa and 383.15 K. The energy requirement for desorber is less due to
lower pressure in the column. Gases from the top of C-5 are recycled to the reactor through
K-2. CO2 recovered from desorber is pure, hence having market potential.

5.2.4 EG Reaction
EO - water mixture from C-4 at 383.15 K is heated to 418.15 K in glycol feed heater (H-8)
and sent to the EG reactor (R-2). Glycol reactor is an adiabatic pipeline reactor designed to
produce the maximum amount of mono ethylene glycol (MEG) (reaction-6) with water to
EO ratio of 22:1 in reactor feed. Residence time in the reactor is about 6 to 10 minutes.
The Higher amount of water is necessary to reduce subsequent exothermic non-catalytic
reactions, which produces diethylene glycol (DEG) (reaction-7), tri-ethylene glycol (TEG)

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(reaction-8) and higher glycols. The formation of these byproducts is unavoidable due to
their faster rate of formation than MEG (Stein et al., 1999). Reactor effluent consists of
86% water coming out at 463.15 K. The reactions are

6. + H2O → HO-CH2-CH2-HO ΔHR,298 = -95.24 kJ/mol

7. + HO-CH2-CH2-HO → HO-CH2-CH2-O-CH2-CH2-OH
ΔHR,298 = -129.90 kJ/mol

8. + HO-CH2-CH2-O-CH2-CH2-OH →
HO-CH2-CH2-O-CH2-CH2-O- CH2-CH2-OH ΔHR,298 = -101.78 kJ/mol

5.2.5 EG Separation
The reactor effluent is sent to the evaporators. In the present study, two evaporators (EV-1,
EV-2) are used for removal of water. Medium pressure steam provides heat in the first
evaporator. The pressure in both evaporators is 1.86 MPa and 0.33 MPa respectively.
Almost 97% water is removed from evaporator train. Three columns - drying column (C-
7), MEG column (C-8) and DEG column (C-9) operate under vacuum. The separation
process is energy intensive due to large quantities of water present in the reactor effluent.

5.3 Energy Balance


Oxidation of ethylene is a highly exothermic reaction; hence it is net exporters of energy.
Ethylene oxide and excess water are reacted to produce EG. Large amount of heat is
required to remove this excess water during purification hence EG process is a net
importer of energy. EO/EG process is simulated by Aspen Plus process simulator using
SR-POLAR as property package. The calculations are presented based on per ton of EO,
as it is a key component in the plant. Oxygen supplied to the process is provided from
outside the battery limit. In the entire process ethylene, oxygen and water are the reactants
and MEG, DEG, TEG and CO2 are products. Makeup quantity of methane is required due
to its loss in a flare. EO production in the reactor is kept constant by supplying extra
ethylene after a drop in catalyst selectivity. Catalyst selectivity is 81 % at start run and
78% at end run.

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In possible heat integration, steam produced in the EO reactor is used in the first
evaporator and steam produced in the first evaporator is used in the second evaporator.
Condensate from the first evaporator at 488.15 K is used in glycol feed heater. Some
amount of steam is imported for other heat exchangers. At end run heat liberated in
ethylene oxidation is more than start run hence steam production also increases. A part of
high pressure steam from EO reactor is exported instead of laying down for other heat
exchangers. If steam pressure is reduced, exergy is lost; hence low pressure steam is
imported as per requirement. In complex petrochemical plants, there are various sources of
low to medium pressure steam. Total heat integration of petrochemical complex is out of
the scope of the present study. Only schematic representation of a possible steam circuit
for EO/EG plant is presented in Fig. 5.2 & 5.3.

Fig. 5.2 Steam circuit in EO/EG plant at start run

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Various factors like temperature in the reactor and cost of raw material limit end run value
of catalyst selectivity. Overall material balance for both runs of EO/EG process is shown
in Table 5.2 and 5.3. To get clear picture energy balance is calculated by considering HP,
MP and LP steam production and consumption. Heat integration is not considered hence
steam import and export values are shown.
The increase in ethylene consumption by 3.33% and CO2 emission by 15.12 % is due to
decrease in selectivity of the EO catalyst (Fig. 5.4). The temperature in the reactor must be
increased to maintain catalyst activity at lower selectivity. Inlet and outlet temperature at
different selectivity values of EO catalyst is shown in Fig. 5.5.

Fig. 5.3 Steam circuit in EO/EG plant at end run

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Table 5.2 Energy balance at start run

Flow rate
Temperature Pressure Energy
Component (kg/t of
(K) (MPa) (MJ/t of EO)
EO)
Input
Ethylene 796.97 303.15 2.84 33.48
Oxygen 887.43 303.15 2.84 2.04
Water 186.15 298.15 0.10 0.00
#
Nitrogen 0.17 303.15 2.84 0.00
Argon# 6.19 303.15 2.84 0.02
Methane 8.41 303.15 2.84 0.15
&
Ethane 0.91 303.15 2.84 0.05
Pumps and Compressors 678.14
Steam consumed 20.87 X 103
Heat of reaction (Oxidation) 9586.24
Heat of reaction (Glycol) 2215.68
Total 33.38 X 103
Output
Carbon dioxide 478.69 375.15 0.12 32.58
Mono ethylene glycol 1233.57 420.15 0.01 619.61
Di ethylene glycol 126.19 407.15 0.001 48.00
Tri ethylene glycol 22.32 458.15 0.005 8.29
Ethylene* 25.48
Oxygen*
Nitrogen*
310.60 1.86 0.12
Argon*
Methane*
Ethane*
Cooling water 8616.98
Steam produced 24.05 X 103
Total 33.38 X 103
*
Purge gas, #with oxygen, &with ethylene

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Table 5.3 Energy balance at end run

Flow rate
Temperature Pressure Energy
Component (kg/t of
(K) (MPa) (MJ/t of EO)
EO)
Input
Ethylene 824.43 303.15 29.00 34.63
Oxygen 980.43 303.15 29.00 2.16
Water 151.28 298.15 1.00 0.00
#
Nitrogen 0.18 303.15 29.00 0.00
Argon# 6.42 303.15 29.00 0.02
Methane 8.77 303.15 29.00 0.15
&
Ethane 0.89 303.15 29.00 0.05
Pumps and compressors 678.14
Steam consumed 20.87 X 103
Heat of reaction (oxidation) 10869.73
Heat of reaction (glycol) 2215.68
Total 34.67 X 103
Output
Carbon dioxide 564.02 361.15 0.12 31.16
Mono ethylene glycol 1233.62 421.15 0.015 624.96
Di ethylene glycol 126.19 407.15 0.001 11.02
Tri ethylene glycol 22.32 458.15 0.005 1.27
Ethylene*
Oxygen*
Nitrogen*
26.23 303.5 1.86 0.10
Argon*
Methane*
Ethane*
Cooling water 8999.26
Steam export 24.9 X103
Total 34.67 X 103
*
Purge gas, #with oxygen, &with ethylene

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590

570

550
kg/t of EO

530

510

490

470

450
77.50 78.00 78.50 79.00 79.50 80.00 80.50 81.00
Selectivity %

Fig. 5.4 CO2 production at different selectivity values

544

534

524
Reactor outlet
514
Temperature K

504

494

484

474

464 Reactor inlet

454
77.00 77.50 78.00 78.50 79.00 79.50 80.00 80.50 81.00
Selectivity %

Fig. 5.5 Inlet and outlet temperature of EO reactor at different selectivity values

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Table 5.4 Heat exchangers in process

Heat duty
Th,in Th,in Th,in Th,in
Tag Equipment (MJ/t of Utility
(K) (K) (K) (K)
EO)
Steam
Steam generator 7470.58 516.15 506.15 438.15 489.15
produced
Secondary steam Steam
H-1 501 506.15 495.15 165 489.15
generator produced
H-2 Feed gas heater 5760.38 495.15 358.15 316.15 458.15 -
Absorber solvent
H-3 4794.81 383.15 342.15 332.13 374.15 -
cooler-1
Steam
H-4 Stripper reboiler-1 480 467.15 467.15 406.15 408.15
required
Stripper overhead Cooling
H-5 893.18 380.15 333.15 306.15 316.15
cooler water
Reabsorber bottom Heating by
H-6 1660 467.15 343.15 335.15 418.15
heater condensate
Steam
H-7 CO2 desorber reboiler 1836.67 467.15 467.15 382.15 382.15
required
Heating by
H-8 Glycol feed heater 737.42 488.15 438.15 383.15 418.15
condensate
Steam
H-9 Evaporator reboiler-1 6340.28 488.15 488.15 479.15 482.15
required
Steam
H-10 Evaporator reboiler-2 2081.28 467.15 467.15 463.15 463.15
required
Dryer column Steam
H-11 101.18 467.15 467.15 443.15 443.15
reboiler required
Dryer column Cooling
H-12 9.6 356.15 356.15 306.15 316.15
condenser water

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Table 5.4 Heat exchangers in process (continued)

Heat duty
Th,in Th,in Th,in Th,in
Tag Equipment (MJ/t of Utility
(K) (K) (K) (K)
EO)
Steam
H-13 EG column reboiler 2971 488.15 488.15 473.15 473.15
required
Steam
H-14 EG column condenser 2682.81 419.15 419.15 373.15 408.15
generated
Steam
H-15 DEG column reboiler 138.62 467.15 467.15 458.15 458.15
required
DEG column Cooling
H-16 893.18 407.15 407.15 306.15 316.15
condenser water
Absorber solvent Cooling
H-17 3752.25 342.15 308.15 306.15 316.15
cooler water

The heat of complete combustion of ethylene is almost 13 times greater than partial
oxidation of ethylene. Heat generation in EO reactor will increase with the decrease in
catalyst selectivity. It is the only usable source of heat in the process. Cooling tower water
is used in various condensers (H-12, H-16), heat exchangers (H-5, H-17) and for product
cooling. Secondary steam generator (H-1) is used to remove the heat generated if post
reactor ignition occurs. Various heat exchangers with their inlet and outlet temperature are
shown in Table 5.4.
The heat of reaction for EO production is 9586 MJ/t and CO2 production 10869.73 MJ/t.
Heat taken by cooling water is higher in the end run. Low temperature streams are having
limited options for heat recovery; hence need to be cooled by cooling water.

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5.4 Exergy Balance

The energy balance of the system shows input energy is a sum of output energy and
accumulation. The case is not true for exergy balance because some part of exergy is lost
in the process. Exergy analysis is used as a tool for performance assessment of various
chemical industries (Nimkar and Mewada, 2014). In most of the processes, exergy
destruction is due to irreversibilities in the reaction. Both physical and chemical exergy
play an important role in EO/EG process. Production of EO is under higher pressure
compared to EG production. Almost 92% of total exergy input is chemical exergy in the
form of ethylene. Part of chemical exergy is converted into physical exergy in the reactor
due to its exothermic nature. Effective utilization of heat of reaction in exothermic
processes will be the key factor for exergy efficiency. Most of the heat is lost to the
cooling tower as temperature goes down. If low grade heat is converted into high grade
exergy like electricity, the efficiency of the plant will improve (Mewada and Nimkar,
2015). Chemical exergy of EO and EG is less than ethylene that indicates loss of
chemical exergy in the reactor. Low exergy products are formed in the reactor when
catalyst selectivity decreases. Exergy balance of EO/EG process at both runs is shown in
Tables 5.5 and 5.6. Exergy calculations for equipments are shown in Appendix-III.
Exergy efficiency of the process at SR is 74.59 % and 73.29 % at ER. Though steam
generation is more at ER, its exergy efficiency is less due to the production of low exergy
products like CO2 and water. Exergy destruction is 11 GJ/t at start run and 11.89 GJ/t at
end run.

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Table 5.5 Exergy balance at start run

Chemical Physical Total Chemical Physical Total


Exergy Exergy Exergy Exergy Exergy Exergy
Component Component
(MJ/t of (MJ/t of (MJ/t of (MJ/t of (MJ/t of (MJ/t of
EO) EO) EO) EO) EO) EO)
Carbon
Ethylene 38.66 X 103 223.02 38.88 X 103 216.12 8.33 224.45
dioxide
Mono
Oxygen 110.10 228.12 338.22 ethylene 23.98 X 103 101.28 24.08 X 103
glycol
Di ethylene
Water 98.18 0.00 98.18 2904.71 6.88 2911.59
glycol
Tri ethylene
Nitrogen# 0.00 0.05 0.06 541.34 1.64 542.98
glycol
Argon# 1.81 1.27 3.08 Ethylene*
Methane 436.01 4.27 440.27 Oxygen*
Ethane& 44.68 0.23 44.91 Nitrogen*
Pumps and
0.00 678.14 678.14 Argon* 239.23 7.53 246.76
compressors
Steam
0.00 7145.20 7145.20 Methane*
consumed
Ethane*
Cooling
625.12 625.12
water
Steam
7990.79 7990.79
produced
Total 47.63 X 103 Total 36.63 X 103
*
Purge gas, # with oxygen, & with ethylene

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Table 5.6 Exergy balance at end run

Chemical Physical Total Chemical Physical Total


Exergy Exergy Exergy Exergy Exergy Exergy
Component Component
(MJ/t of (MJ/t of (MJ/t of (MJ/t of (MJ/t of (MJ/t of
EO) EO) EO) EO) EO) EO)

3 3
Carbon
Ethylene 39.99 X 10 230.70 40.22 X 10 254.64 7.63 262.27
dioxide
Mono
3 3
Oxygen 121.64 252.03 373.67 ethylene 23.98 X 10 103.10 24.09 X 10
glycol
Di ethylene
Water 79.78 0.00 79.78 2906.02 6.88 2912.89
glycol
Tri ethylene
Nitrogen# 0.00 0.05 0.06 541.34 1.64 542.98
glycol
Argon# 1.88 1.32 3.21 Ethylene*
Methane 454.64 4.44 459.08 Oxygen*
Ethane& 43.88 0.23 44.10 Nitrogen*
Pumps and
0.00 678.14 678.14 Argon* 274.85 7.53 282.38
compressors
Steam
0.00 7145.20 7145.20 Methane*
import
Ethane*
Cooling
652.77 652.77
water
Steam export 8374.76 8374.76
3 3
Total 49.01 X 10 Total 37.12 X 10
*
Purge gas, # with oxygen, & with ethylene

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Table 5.7 Exergy destruction in various equipments

Start run End run


Equipment
Exergy destruction (MJ/t) % Exergy destruction (MJ/t) %
R-1 5083.59 46.19 5822.84 48.96
R-2 1296.81 11.78 1311.02 11.02
C-1 414.79 3.77 287.15 2.41
C-2 855.35 7.77 876.74 7.37
C-3 316.47 2.88 303.48 2.55
C-4 328.48 2.98 325.49 2.74
C-5 40.29 0.37 121.22 1.02
C-6 313.59 2.85 247.86 2.08
C-7 73.14 0.66 123.48 1.04
C-8 273.98 2.49 273.12 2.30
C-9 19.19 0.17 19.19 0.16
EV-1 297.78 2.71 315.36 2.65
EV-2 314.76 2.86 254.00 2.14
M-1 181.79 1.65 205.85 1.73
K-1 140.68 1.28 140.20 1.18
K-2 4.47 0.04 3.26 0.03
P-1 0.02 0.00 0.02 0.00
P-2 16.13 0.15 16.13 0.14
P-3 0.02 0.00 0.02 0.00
H-1 12.09 0.11 32.26 0.27
H-2 370.32 3.36 370.05 3.11
H-3 79.52 0.72 93.05 0.78
H-7 209.15 1.90 164.04 1.38
H-8 62.91 0.57 59.81 0.50
H-12 31.00 0.28 29.70 0.25
Remaining
270.46 2.46 496.73 4.18
HE
Total 11006.78 100.00 11892.07 100.00

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Table 5.7 shows the exergy destruction in various equipments. Exergy destruction
increases in both the reactors at end run. Exergy destruction in both reactors is more than
50% of total exergy destruction. EO reactor is the key equipment in the entire process.
Various studies have been carried out for optimization of reactor performance (Peschel et
al., 2012; Zahedi et al., 2011; Bayat et al., 2013; Luo et al., 2012; Rahimpour et al., 2011).
Input and output exergy will be different at different selectivity values of catalyst in EO
reactor. Physical and chemical exergy in EO reactor is shown in Fig.5.6 and 5.7. Physical
exergy in the reactor is used to produce steam. Exergy taken by steam is shown in Fig.5.8.
The difference in the temperature of the feed water and product gases causes exergy loss in
the steam generator. Exergy loss in the reactor is due to irreversibilities in the oxidation
reaction. Exergy destruction in EO reactor at different selectivities shown in Fig. 5.9.

700700

700650

700600
Total exergy MJ/t

700550

700500

700450

700400
77.50 78.00 78.50 79.00 79.50 80.00 80.50 81.00
Selectivity (%)

Fig. 5.6 Exergy input into EO reactor

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692800

692600

692400
Exergy out MJ/t

692200

692000

691800

691600

691400
77.50 78.00 78.50 79.00 79.50 80.00 80.50 81.00
Selectivity (%)

Fig. 5.7 Exergy output from EO reactor

3200

3150

3100
Exergy MJ/t

3050

3000

2950

2900

2850
77.50 78.00 78.50 79.00 79.50 80.00 80.50 81.00
Selectivity (%)

Fig. 5.8 Exergy taken by steam generator

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6000

5900

5800
Exergy destruction MJ/t
5700

5600

5500

5400

5300

5200

5100

5000
77.50 78.00 78.50 79.00 79.50 80.00 80.50 81.00
Selectivity (%)

Fig. 5.9 Exergy destruction in EO reactor

5.5 Alternate Process for MEG Production

MEG demand is increasing worldwide, compared to higher glycols due to its wide
application in the process industry. A considerable amount of di and tri-ethylene glycol is
produced due to the lower selectivity of MEG reaction. The Maximum production of MEG
will increase the profitability of the industry. Dilution of ethylene oxide by an excess of
water is the only way to raise the selectivity of MEG. However, the higher water ratio
causes lower MEG concentration in the production stream. It requires a large amount of
heat to separate MEG and water by evaporation and distillation. Various studies have been
carried out to increase the yield of EO hydration process using different catalysts (Van Hal
et al., 2007), but unable to get the commercial option.
In the new process developed by Mitsubishi Chemical Corporation, MEG is produced in
two steps using phosphonium salt as a catalyst (Kawabe, 2010). Process flow diagram (EG
production part) of the new process is shown in Fig.5.10. Detailed information about the
process parameters is not available in the literature because the technology is new and

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exclusively licensed. Required basic data for simulation of the new process is collected
from the open literature.

Fig. 5.10 Mitsubishi process for MEG manufacturing (Kewabe, 2010)

Evaporator train is eliminated in the new process due to less water requirement. Glycol
production takes place in two steps – first is carbonation of EO to produce ethylene
carbonate (EC) and second is hydrolysis of EC. EO is fed to the carbonation reactor with
carbon dioxide and water. A hydration reaction also proceeds simultaneously in the reactor
along with carbonation reaction.

9.

10.

Maximum EO will be converted into EC (reaction 9) and a small amount into EG. The
heat of reaction is recovered in the exothermic EC process. Unreacted CO2 is compressed
and recycled back to the reactor after purging a small amount. As both reactions are taking
place at low temperature, heating of raw material is not required like in conventional
processes.

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EG and CO2 are produced (reaction 10) after reacting EC and water. Water used for the
reaction is sufficient to complete the reaction. Alkali metal salts are also used along with
phosphonium salt to accelerate the reaction.
The product from hydrolysis reactor is fed to dehydrating column followed by purification
column. Excess water is removed from the product, using only one column compared to
evaporator train in the conventional process. A byproduct of higher glycol formation is
very limited due to higher selectivity (99%) of the process. Though more information is
not available about the operating conditions of the new process, various process
parameters are calculated using Aspen Plus simulator. Energy and exergy balance are
shown in Table 5.8 and 5.9.

Table 5.8 Energy balance of new process at SR


kg/t of kg/t of
Component MJ/t of EO Component MJ/t of EO
EO EO
Ethylene 796.97 33.48 CO2 478.69 32.58
Oxygen 887.43 2.04 MEG 1392.00 134.78
Water 208.46 0.00 DEG 12.40 1.08
Nitrogen 0.17 0.00 TEG 0.00
Argon 6.19 0.02 Ethylene 7.60 0.12
Methane 8.41 0.15 Oxygen 2.18
Ethane 0.91 0.05 Nitrogen 0.17
Pumps and Compressors 678.14 Argon 6.19
Steam consumed 12.53 X 103 Methane 8.41
CO2 Comp 207.17 Ethane 0.91
Heat of Reaction
9586.24 Cooling Water 12.28 X 103
(Oxidation)
Heat of Reaction (Glycol) 2644.53 Steam produced 12.74 X 103
Total 25.19 X 103 Total 1908.56 25.19 X 103

The exergy efficiency of the new process is 71.90 % at SR and 71.10 % at ER. In this
process exergy destruction in EG reactor is more as a reaction takes place in two steps. In
both the steps, destruction takes place due to the irreversibility of the reaction. The exergy
efficiency of the process is higher compared to conventional process due to more steam

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production considering additional 207.17 MJ/t electrical energy required to compress


carbon dioxide into EC reactor. Water used in stoichiometric proportion eliminates the
requirement of evaporators. The energy required in the process is mainly for separation of
MEG and DEG. Energy intensive process is required to separate MEG from DEG although
the quantity of the latter is smaller.

Table 5.9 Exergy balance of new process


SR ER SR ER
Component Component
MJ/t of EO MJ/t of EO
3 3
Ethylene 38.88 X 10 40.22 X 10 CO2 224.45 262.27
Oxygen 338.22 373.67 MEG 27.07 X 103 27.17 X 103
Water 109.93 91.51 DEG 277.58 284.45
Nitrogen 0.06 0.06 TEG 0.00 1.64
Argon 3.08 3.21 Ethylene
Methane 440.27 459.08 Oxygen
Ethane 44.91 44.10 Nitrogen
Pumps and
678.14 678.14 Argon 246.77 282.63
Compressors
Steam consumed 3629.90 3623.54 Methane
CO2 Comp 207.17 207.17 Ethane
Heat of Reaction
0.00 0.00 Cooling Water 359.98 673.61
(Oxidation)
Heat of Reaction
0.00 0.00 Steam produced 4425.25 5045.14
(Glycol)
Total 44.34 X 103 45.70 X 103 Total 32.71 X 103 33.72 X 103

5.6 Ethylene Recovery from Purge Gas


Purging is necessary from recycle gas to maintain the concentration of ethane and argon in
the reactor. These gases are accumulating in the reactor due to the presence of ethane in
ethylene and argon in oxygen. Valuable raw material like ethylene and methane are lost in
purging. The purge stream is normally used as fuel in the boiler. The commercial value of
ethylene that could be converted into EO is lost and the only heating value remains.
Recovery of ethylene can reduce the raw material cost of the process. A semipermeable

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membrane made up of silicone rubber is used to separate ethylene from the gas mixture
based on its solubility in membrane polymer (Baker, 2008). The membrane allows large
hydrocarbon molecules to permeate much faster than smaller molecules like argon.
A typical composition of purge stream is shown in Table 5.10. The purge gas stream enters
the membrane system at a higher pressure and lower temperature (Fig. 5.11). Ethylene rich
permeate and argon rich residue streams are separated. Ethylene rich stream is compressed
and recycled back to the reactor.

Fig. 5.11 Ethylene recovery unit

Table 5.10 Composition of purge gas


SR ER
Component
kg/t of EO % kg/t of EO %
Ethylene 7.60 29.85 7.86 29.95
Oxygen 2.18 8.57 2.13 8.10
Nitrogen 0.17 0.68 0.18 0.69
Argon 6.19 24.31 6.42 24.47
Methane 8.41 33.02 8.77 33.42
Ethane 0.91 3.58 0.89 3.38
Total 25.48 100 26.238 100.00

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The system can recover 75% ethylene from purge gas. Exergy analysis shows 0.72 %
reduction in ethylene consumption in feed after ethylene recovery. It improves exergy
efficiency of the plant up to72.47% for SR and 69.97% for ER. Table 5.11 shows the
comparison of exergy efficiencies of EO/EG plants in various situations. Approximately
1.06 M$/yr can be saved for the plant having an annual capacity of 150 kt of EO
(considering ethylene price is1200 $/MT). Ethylene recovery unit is installed in various
plants worldwide and observed payback period is less than 8 months (Jacobs and Billing,
2005).

Table 5.11 Comparison of exergy efficiency

Ethylene Requirement Purge gas Exergy


Description (kg/t of EO) (kg/t of EO) Efficiency (%)
SR ER SR ER SR ER
Conventional Process 796.97 824.43 25.48 26.23 74.59 73.29
Conventional Process with
791.26 818.53 19.77 20.34 75.17 73.88
ethylene recovery
Alternate Process for EG 796.97 824.43 25.48 26.23 71.90 71.10

5.7 Exergoeconomic Analysis

The design of the new process is based on higher efficiency and lower cost. Previously,
safety and economics were key parameters. In the present scenario, environmental impact
and resource consumption need to be addressed while working with new processes. It has
created challenges for engineers. Natural resources are limited and their uses cause
environment pollution. It is important to understand energy and resource consumption
while improving the system. Economic aspects of energy conversion system are studied on
the basis of prices. Sometimes it is found incorrect over a long term due to uncertainty in
future prices. If these are related to exergy, it will be helpful to find a more sound method.
Thus exergy is not only applicable to find efficiency, but also for the economic assessment
of the process. Due to its relation to the economy, it is helpful in engineering decisions and
optimization. Many researchers have developed methods of economic analysis using

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exergy. These are referred by names- thermoeconomics, second law costing,


exergoeconomics, EXCEM etc.
The objective of exergy costing is to study the relation between cost and operation system,
irrespective of the way of analysis. It will help to reduce inefficiency by proper
modification at the design stage and to assist in the decision making process in the plant
operation and maintenance (Groniewsky, 2013). Gaggioli and El-Sayed (1987) have
developed a methodology for thermoeconomic analysis of energy systems. Valero et al.
(1990, 1986) explained the theory of exergy cost which lies within the context of cost
allocation and functional relationship among thermoeconomic variables of energy systems.
The process of exergetic cost formation of product is the unalterable process of energy
degradation of resources (Lozano and Valero, 1993). Lagrange multiplier is useful for
thermoeconomic optimization of the energy system (Lozano et al., 1993). Exergoeconomic
analysis based on the specific exergy costing method applied to cement manufacturing
process shows that the cost rate of exergy destruction in the rotary kiln is the highest
among other equipments (Atmaca and Yumrutas, 2014 a & b). This method is also used
for the economic analysis of cogeneration plant (Kwon et al., 2001; Valero et al., 1987).
List of exergoeconomic applications is increasing and researchers are extending it to
various studies like chemical processes (Boyarskii et al., 1992; Tonon et al., 2006) and
ecological systems (Valero et al., 2010; Silveira et al., 2012).
In an economic study of EO/EG process, EXCEM method developed by Rosen (1986) is
used. This method is based on the quantities of exergy (EX), cost (C), energy (E) and mass
(M) (Rosen and Dincer, 2003a). It is useful to study the relation between energy loss,
exergy loss and capital cost for energy system like electricity generation. EXCEM method
is applied to power plants (Rosen and Dincer, 2003 b & c), hydrogen production (Orhanet
al., 2010), geothermal district heating system (Ozgener et al., 2007) to examine
thermodynamic and economic data for various devices and the correlations between capital
cost and exergy destruction.

5.7.1 Balancing Equations

EXCEM methodology is described by considering the balance equations for appropriate


quantities. A general balance equation is written as

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Input + Generation - Output - Consumption = Accumulation (5.1)


Input and output refer to the entering and exiting quantities through system boundaries.
Generation and consumption represent quantities produced and consumed in the system.
Build up of the quantity in the system is referred as accumulation. For a continuous
process, differential balance is applied and for batch process integral balance is used. As
per the first law of thermodynamics, energy can neither be created nor be destroyed. Hence
energy balance can be written as
Energy input – Energy output = Energy accumulation (5.2)
Unlike energy, exergy is consumed in the process due to irreversibilities. Its general
balance can be written as
Exergy input – Exergy output – Exergy consumption = Exergy accumulation (5.3)
Exergy output = Product exergy output + Waste exergy output (5.4)
Output quantities consist of energy or exergy in products and waste components. Cost is an
increasing, non conserved quantity. Its balance can be written as
Cost input + Cost generation - Cost output = Cost accumulation (5.5)
Where
Cost input = Cost associated with all input like raw material, utilities and operating cost
Cost output = Cost associated with all outputs like product cost, by product cost
Cost accumulation = Cost associated with accumulated material and energy
Cost generation = Cost associated with capital cost (Equipments, infrastructure) and its
maintenance. For cost balance profit margin is also considered as a part of cost generation.

5.7.2 Loss Rate and Capital Cost

Energy losses from various components of the system can be identified from energy
balance equation. Loss from accumulation is neglected. Energy loss from the system is
only associated with waste energy. The term energy loss rate Ĺen is presented as
Ĺen = Waste energy output rate (5.6)
In the case of exergy, the loss is from the waste stream as well as from irreversibilities.
Total exergy loss consists of loss from the waste stream and exergy destruction. Hence, the
term exergy loss rate is written as
Ĺex = Exergy consumption rate + Waste exergy output rate (5.7)

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For steady state process accumulation is zero, hence energy and exergy loss rate is
Ĺen = ∑inputs Energy flow rate - ∑products Energy flow rates (5.8)
Ĺex = ∑inputs Exergy flow rate -∑products Exergy flow rates (5.9)

K = Capital cost of equipment (5.10)

A parameter R is the ratio of thermodynamic loss rate to capital cost K.


R = Ĺ/ K (5.11)

The value of R depends upon either energy loss rate (Ren) or exergy loss rate (Rex)
Ren = Ĺen/ K (5.12)
and
Rex = Ĺex / K (5.13)

Exergy consumption is due to irreversibilities i.e. internal loss and due to loss associated
with waste i.e. external loss.
Ĺex = Ĺex-i + Ĺex-e (5.14)

Only capital cost is considered for simplification and it is a most significant contribution in
cost generation. This method is applied to a thermal power plant (Rosen & Dincer,
2003b,c) and geothermal power plant (Ozgener et al., 2007) to study the change in Rex for
different parameters like a change in fuel, change in dead state temperature, change in
brine flow rate.
In the present study, EXCEM method is applied to the EO/EG complex having an annual
capacity of 150 kt of ethylene oxide. The capital cost of the plant is estimated by using
CAPCOST (Appendix-III). All the cost and prices used for analysis are for the month of
May 2014. Ethylene cost is a major input cost in the process. Steam, electricity and
cooling tower water does not carry any mass into the system but carry cost, energy and
exergy. Purge gas going out of the plant is used in the boiler hence it has cost component.
Various parameter values are shown in Table 5.12. Exergy loss rate to capital cost is
highest for finishing column and lowest for reclaim compressor (Fig.5.12).

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18
16
End run
14
12 Start run
10
W/$

8
6
4
2
0

Fig. 5.12 Values of exergy loss rate to capital cost (Rex) for EO/EG plant at SR and ER

For any successful process design, the value of Rex approaches ideal value Rex* where the
appropriate trade-off between exergy losses and capital costs is observed. From Fig. 5.13 it
is found that if no investment is made, exergy loss is equal to input exergy and to achieve
zero exergy loss investment approaches to infinity. When Rex = Rex*, it is expected to
combine exergy loss and capital cost to get the optimal design. In EO/EG plant, energy
loss is through cooling water only. Each equipment contributes some exergy loss.
Approximately 46% of total exergy loss is taking place in an ethylene oxide reactor
followed by the ethylene glycol reactor. At the end of catalyst life, this value rises further.
Reaction irreversibility is the major cause of exergy loss in both reactors. A Higher value
of Rex is observed for finishing column followed by EG reactor. Exergy loss is distributed
over various heat exchangers of different capacities. Statistical analysis is carried out to get
generalized results. For power generation stations mean R value of the device is
approximately equal to overall station R value based on internal exergy loss (Rosen &
Dincer, 2003b). It is not true for EO/EG process as observed in Table 5.13.

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Table 5.12 Various parameters of EXCEM analysis of EO/EG plant.


SR ER
K
Equipment Code Ĺen Ren Ĺex Rex Ĺen Ren Ĺex Rex
6
10 $ kW W/$ kW W/$ kW W/$ kW W/$
EO Reactor with
R-1 9.10 0.00 0.00 26477.06 2.91 0.00 0.00 30327.30 3.33
Steam Drum
EG reactor R-2 0.40 0.00 0.00 6754.20 16.80 0.00 0.00 6828.24 16.99
EO Absorber C-1 7.06 0.00 0.00 2160.35 0.31 0.00 0.00 1495.55 0.21
EO Reabsorber C-2 1.06 0.00 0.00 4454.95 4.20 0.00 0.00 4566.38 4.31
EO Stripper C-3 0.13 0.00 0.00 1648.28 12.68 0.00 0.00 1580.64 12.16
Finishing
C-4 0.10 0.00 0.00 1710.85 18.01 0.00 0.00 1695.27 17.84
column
CO2 Absorber C-5 1.78 0.00 0.00 209.86 0.12 0.00 0.00 209.86 0.12
CO2 Stripper C-6 0.90 0.00 0.00 1696.00 1.88 0.00 0.00 1696.00 1.88
Recycle Gas
K-1 2.30 0.00 0.00 732.75 0.32 0.00 0.00 730.20 0.32
Compressor
Reclaim
K-2 0.59 0.00 0.00 23.26 0.04 0.00 0.00 16.88 0.03
Compressor
Evaporator-1# EV-1 1.02 0.00 0.00 1550.95 1.52 0.00 0.00 1642.48 1.61
Evaporator-2# EV-2 0.36 0.00 0.00 1640.00 4.52 0.00 0.00 1322.94 3.64
Secondary
H-1 1.79 0.00 0.00 63.00 0.04 0.00 0.00 168.00 0.09
Steam Generator
Dehydrator* C-7 1.34 48.52 0.04 388.84 0.29 560.00 0.42 643.00 0.48
MEG Column* C-8 0.56 0.00 0.00 1427.00 2.56 0.00 0.00 1422.51 2.55
DEG Column* C-9 0.21 854.16 4.13 328.49 1.59 854.41 4.13 327.82 1.59
P-
Pumps 0.33 0.00 0.00 49.00 0.15 0.00 0.00 51.00 0.15
1,2,3
Heat Exchangers 1.43 41291.12 28.87 6365.96 4.45 52139.79 36.46 9078.00 6.35
Total 30.47 42193.80 1.38 57680.80 1.89 53554.20 1.76 63802.07 2.09

* Including condenser and reboiler # Including reboiler


.

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Fig. 5.13 Illustration of the tendency of Rex for a device to approach Rex* the value of Rex
for which the ‘‘appropriate’’ trade-off between losses and capital costs is attained (Rosen
and Dincer, 2003b).

Table 5.13 Statistical data for thermodynamic loss rate to capital cost ratio values
SR ER
Based on Based on
Parameter Based on Based on
exergy energy
energy loss exergy loss
loss loss
Minimum, Rmin (W/$) 0.00 0.04 0.00 0.03
Maximum, Rmax (W/$) 28.87 18.01 36.46 17.84
Mean, R (W/$) 1.84 4.02 2.28 4.09
Standard Deviation, SD(R) (W/$) 6.62 5.56 8.34 5.54
Coefficient of Variation, CV(R) (%) 360.76 138.31 366.24 135.45

It is observed that the difference in the value of (Ren)min - (Ren)max is greater than (Rex)min -
(Rex)max. It indicates that relative spread in R for the different device is large when it is
based on energy and small when it is based on exergy. The mean value of Rex is double
than Rex value of the overall process. CV (R) is a measure of relative variation in a set of

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values about the mean. The above observation is supported by the difference between
CV(R) values.
CV(Ren) > CV(Rex) (5.15)
In power generation stations, only physical exergy plays a very important role, whereas
both physical and chemical exergy values are important in chemical process plants. Most
of the energy required in the plant is contained in the raw material itself. In a power plant,
most of the exergy destruction is taking place steam generator that is having an equal
capital cost as that of the turbine. In EO/EG plant EO reactor is key equipment. The silver
catalyst is required while operation is having almost equal cost as that of the reactor.
Catalyst loses its selectivity and needs to be replaced after a specific period. Hence, a new
analysis is developed on the basis of EXCEM which can be used to analyze EO reactor at
different catalyst selectivity values. A new indicator EGRex is proposed to decide end run
selectivity of the catalyst.

5.7.3 New Parameter EGRex Proposed for EO Reactor


Ethylene is oxidized in the presence of a silver catalyst. Due to the highly exothermic
nature of the reaction, a catalyst is placed in a tube. Heat is taken out by boiling water.
Product EO has a very wide explosive range. Hence the reactor design is important from a
safety point of view. Safety consideration and efficiency should be balanced while
operating the plant. The temperature in the reactor is increased to maintain EO output
constant at lower selectivity. Heat generation is increased at lower selectivity and it will be
utilized for steam generation. Energy and exergy values in EO reactor are shown in
Fig.5.14. The reactor gas flow rate is 466.01 t/hr at SR and 465.66 t/hr at ER for 150 kt
annual production of EO. Temperature maintained in the reactor is 506.15 K at SR and
528.15 K at ER. Catalyst cost depends on the price of silver. Fluctuation in the cost of the
catalyst is observed due to ups and down in silver price in last ten years.
EXCEM analysis of EO reactor is based on the catalyst selectivity (Fig. 5.15). Ethylene
consumption and steam production will increase as selectivity decreases. The cost of the
catalyst is constant for all selectivities as it is charged once in three years. For simplicity,
start run selectivity value is considered as 81% and end run selectivity value is 78 %. A
drop of 1 % in selectivity of catalyst per year (i.e. 0.5% per six months) is observed in a
catalyst cycle.

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Let us assume the cost of the catalyst is CC, the cost of ethylene is CE , the cost of steam is
CS and the product cost is CP. Total production cost per cycle is C
C = Catalyst cost per cycle + Ethylene cost per cycle + Operation cost per cycle (5.16)
The catalyst is charged only once at the starting of the cycle, hence its cost is fixed
throughout the cycle. Operation cost is also considered as a same throughout the cycle. For
simplification, only ethylene cost is considered because it is the dominant cost in the
process.
C = CE (5.17)
EO output is same throughout all selectivities but the steam generation will increase.
Therefore steam cost is considered.
Income generated per catalyst cycle (IEG) based on ethylene is
IEG = Product cost + Steam cost – Ethylene cost
IEG = CP + CS - CE (5.18)

47500

46500 Exerg

45500

44500

43500
kW

Energy
42500

41500

40500

39500

38500
77.5 78 78.5 79 79.5 80 80.5 81
Catalyst selectivity ( % )

Fig. 5.14 Energy and Exergy values in the EO reactor


Only exergy loss is taking place in the reactor hence ratio of the exergy loss rate to cost
(Ĺex(EO reactor)) is considered.
For ethylene glycol product, a new term EGRex is proposed.

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EGRex = Ĺex(EO reactor)/ IEG (5.19)


For 150 kt annual production of EO, exergy destruction in the reactor is shown in Table
5.14. Considering the use of produced steam for the various equipments, remaining steam
is exported.

Fig. 5.15 EXCEM analysis of EO reactor

Table 5.14 Ethylene requirement and steam export (150 kt/yr of EO production)
Steam Exergy Destruction
Selectivity (%) Ethylene (Mt)
Export (Mt) (MW)
75.00 63678.84 210254.72 17.67
75.50 63257.13 178832.82 16.94
76.00 62840.96 156791.44 16.83
76.50 62430.23 132342.20 16.19
77.00 62024.84 114407.39 16.03
77.50 61624.68 96275.95 15.54
78.00 61229.65 81190.23 15.16
78.50 60839.66 68949.45 14.94
79.00 60454.59 56998.70 14.34
79.50 60074.38 47929.30 13.95
80.00 59698.91 40605.02 13.56
80.50 59328.11 35357.28 13.32
81.00 58961.89 31962.00 13.23

The MEG production rate is 372.66 kmol/hr. Ethylene cost is considered 1200 $/Mt, MEG
cost 1100 $/Mt and steam cost 43.52 $/Mt (Appendix -III). EGRex is calculated considering
above values as shown in Table 5.15.

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In this analysis end run selectivity value is 78.50%. EGRex value at start run is 0.4085 and
at end run it is 0.4704. Total income generated for the entire catalyst cycle is 191.65 M$.
The average annual income is 63.88 M$. EGRex value for last operating year of the cycle is
0.9228 W/$. If the plant is to be operated for few more months after the present end run
selectivity, the annual income value must be maintained. As discussed in section 5.7.2,
profit can be generated by decreasing exergy destruction. Chemical exergy loss in the
reactor cannot be reduced because we cannot change the reaction route. Hence ethylene
consumption will remain same as per respective selectivity values. Only physical exergy
destruction can be reduced by recovering more heat from the reactor. If the temperature
difference between feed water and steam is minimized, or heat transfer area in the reactor
is increased by increasing the number of tubes (diameter of present tubes can be reduced to
increase the number of tubes) we can convert available exergy into steam. For this,
economic analysis calculations are carried out for 0.5% to 5% reduction in exergy
destruction that is shown in Table 5.16. Detailed calculations are shown in Appendix-III.

Table 5.15 EGRex value at different selectivity values.


Selectivity
CE (M$) CS (M$) IEG (M$) EGRex (W/$)
(%)
75.00 76.41 9.15 34.51 0.5123
75.50 75.91 7.78 33.64 0.5036
76.00 75.41 6.82 33.18 0.5073
76.50 74.92 5.76 32.61 0.4964
77.00 74.43 4.98 32.32 0.4962
77.50 73.95 4.19 32.01 0.4856
78.00 73.48 3.53 31.83 0.4764
78.50 73.01 3.00 31.76 0.4704
79.00 72.55 2.48 31.71 0.4524
79.50 72.09 2.09 31.77 0.4393
80.00 71.64 1.77 31.90 0.4251
80.50 71.19 1.54 32.12 0.4148
81.00 70.75 1.39 32.41 0.4085

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Table 5.16 EGRex values at different % reduction in exergy destruction values


Max
Catalyst Cycle Cycle Income CE Average IEG End run
EGRex
(Months) (M$) (M$) (M$/yr) Selectivity (%)
(W/$)
Reduction in exergy destruction = 0%
36 191.65 431.23 63.88 78.50 0.9228
42 223.48 504.70 63.85 78.00 0.9469
48 255.49 578.65 63.87 77.50 0.9620
54 287.81 653.08 63.96 77.00 0.9817
60 320.43 728.00 64.09 76.50 0.9926
66 353.61 803.41 64.29 76.00 1.0037
Reduction in exergy destruction = 0.5 %
36 191.72 431.23 63.91 78.50 0.9178
42 223.56 504.70 63.87 78.00 0.9417
48 255.59 578.65 63.90 77.50 0.9566
54 287.94 653.08 63.99 77.00 0.9761
60 320.58 728.00 64.12 76.50 0.9868
66 353.80 803.41 64.33 76.00 0.9977
Reduction in exergy destruction = 1 %
36 191.78 431.23 63.93 78.50 0.9128
42 223.64 504.70 63.90 78.00 0.9364
48 255.69 578.65 63.92 77.50 0.9512
54 288.06 653.08 64.01 77.00 0.9705
60 320.73 728.00 64.15 76.50 0.9811
66 353.99 803.41 64.36 76.00 0.9918
Reduction in exergy destruction = 1.5 %
36 191.84 431.23 63.95 78.50 0.9078
42 223.72 504.70 63.92 78.00 0.9312
48 255.79 578.65 63.95 77.50 0.9458
54 288.19 653.08 64.04 77.00 0.9649
60 320.89 728.00 64.18 76.50 0.9753
66 354.17 803.41 64.40 76.00 0.9858

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Table 5.16 EGRex values at different % reduction in exergy destruction values (Continued)

Max
Catalyst Cycle Cycle Income CE Average IEG End run
EGRex
(Months) (M$) (M$) (M$/yr) Selectivity (%)
(W/$)
Reduction in exergy destruction = 2 %
36 191.90 431.23 63.97 78.50 0.9028
42 223.80 504.70 63.94 78.00 0.9260
48 255.89 578.65 63.97 77.50 0.9405
54 288.31 653.08 64.07 77.00 0.9594
60 321.04 728.00 64.21 76.50 0.9696
66 354.36 803.41 64.43 76.00 0.9799
Reduction in exergy destruction = 2.5 %
36 191.96 431.23 63.99 78.50 0.8978
42 223.88 504.70 63.97 78.00 0.9208
48 255.99 578.65 64.00 77.50 0.9351
54 288.44 653.08 64.10 77.00 0.9538
60 321.19 728.00 64.24 76.50 0.9638
66 354.55 803.41 64.46 76.00 0.9739
Reduction in exergy destruction = 3 %
36 192.02 431.23 64.01 78.50 0.8928
42 223.96 504.70 63.99 78.00 0.9156
48 256.09 578.65 64.02 77.50 0.9297
54 288.56 653.08 64.12 77.00 0.9482
60 321.35 728.00 64.27 76.50 0.9581
66 354.74 803.41 64.50 76.00 0.9680
Reduction in exergy destruction = 3.5 %
36 192.08 431.23 64.03 78.50 0.8878
42 224.04 504.70 64.01 78.00 0.9105
48 256.19 578.65 64.05 77.50 0.9244
54 288.69 653.08 64.15 77.00 0.9427
60 321.50 728.00 64.30 76.50 0.9524
66 354.92 803.41 64.53 76.00 0.9621

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Table 5.16 EGRex values at different % reduction in exergy destruction values (Continued)

Max
Catalyst Cycle Cycle Income CE Average IEG End run
EGRex
(Months) (M$) (M$) (M$/yr) Selectivity (%)
(W/$)
Reduction in exergy destruction = 4 %
36 192.15 431.23 64.05 78.50 0.8828
42 224.11 504.70 64.03 78.00 0.9053
48 256.29 578.65 64.07 77.50 0.9191
54 288.81 653.08 64.18 77.00 0.9371
60 321.65 728.00 64.33 76.50 0.9466
66 355.11 803.41 64.57 76.00 0.9562
Reduction in exergy destruction = 4.5 %
36 192.21 431.23 64.07 78.50 0.8779
42 224.19 504.70 64.06 78.00 0.9001
48 256.39 578.65 64.10 77.50 0.9137
54 288.94 653.08 64.21 77.00 0.9316
60 321.81 728.00 64.36 76.50 0.9409
66 355.30 803.41 64.60 76.00 0.9504
Reduction in exergy destruction = 5 %
36 192.27 431.23 64.09 78.50 0.8729
42 224.27 504.70 64.08 78.00 0.8949
48 256.49 578.65 64.12 77.50 0.9084
54 289.06 653.08 64.24 77.00 0.9261
60 321.96 728.00 64.39 76.50 0.9353
66 355.49 803.41 64.63 76.00 0.9445

Maximum acceptable EGRex value for economical operation of the plant is 0.9228 W/$.
If the plant is operated after end run, average annual income increases slightly, but this
income is not sufficient for profitable operation. After reducing exergy destruction in the
reactor, steam recovery can be increased. It will increase cycle income by keeping ethylene
consumption constant at respective selectivity values. To decide end run selectivity
average annual income must be equal to or greater than 63.88 M$ and EGRex should be
less than 0.9228 W/$. From Table 5.16 it is observed that catalyst can be used for six more

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Exergy Analysis of Nitric Acid, Ethylene Oxide/Ethylene Glycol Processes and Methanol Reactor

months if 2% reduction is exergy destruction is achieved. A further six month extension is


possible if 4% reduction is achieved. This extension will reduce total downtime of the
plant in its entire life. It will increase MEG production and hence total profit. It will also
save the catalyst cost. Approximately 58.89 tons of catalyst worth 5.95 M$ is used for 150
kt of annual EO production. There is a slight increase in annual income for every six
month extension in catalyst cycle. EGRex is useful to decide the end point of that cycle at
various exergy destruction values as shown in Fig. 5.16. It shows that the relation between
the exergy loss rate and income generated becomes a useful to decide end run selectivity of
the catalyst in ethylene oxide/ethylene glycol process.

1.01
% reduction in exergy destruction
0%
0.99
1%
2%
0.97 3%
4%
EGRex (W/$)

5%
0.95

0.93

0.91

Maximum acceptable EGRex


0.89

0.87
76.00 76.50 77.00 77.50 78.00 78.50
Selectivity (%)

Fig. 5.16 EGRex values for various % of reduction in exergy destruction

5.7.4. Limitations of EGRex Calculation


Exergy loss rate to income ratio based on EXCEM analysis is useful for an immediate
decision, but more data is required for accurate analysis. In the present analysis 0.5 % drop
after every six months is considered. More precise EGRex value can be found out if the
monthly drop in selectivity is calculated.

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Exergy Analysis of Nitric Acid, Ethylene Oxide/Ethylene Glycol Processes and Methanol Reactor

EGRex does not consider the time value of money in the present analysis. Ethylene and
MEG cost are considered as constant throughout catalyst cycle. Increase or decrease in
ethylene cost depends on various factors like political situation, demand, etc. It may vary
average annual income.
Exergy recovery in EO reactor needs capital investment. No investment measures like a
change in temperature values will hardly improve exergy efficiency of the reactor.
Revamping of the reactor to increase the number of tubes for more heat recovery will need
considerable capital investment. The attractive payback period is necessary before
investing though this investment will save energy for the entire life of the reactor. This
investment is not considered while calculating generated income. Though all these
considerations will increase complications of calculations, we can get a more accurate
value of EGRex which enable optimization of catalyst cycle for more profit generation.

5.8 Conclusion
The present study provides insight into the relation between catalyst selectivity, exergy
loss, raw material cost and income generation. Energy and exergy analysis of EO/EG
process is carried out at start run and end run. Most important equipment in the entire
process i.e. ethylene oxide reactor is also studied from exergy point of view. Newly
developed process for MEG production is compared with the conventional process on the
basis of exergy. The ratio of the thermodynamic loss rate to capital cost is useful in
exergoeconomic analysis. The EXCEM method proposed by Rosen and Scot (1985) is
used for exergoeconomic analysis of EO/EG plant. There is no fixed trend of EO-EG
prices and even shutdown of one plant may cause a variation of prices in that region. To
get maximum profit in such situations exergoeconomic analysis is useful. New parameter
EGRex is proposed to decide end run selectivity of a catalyst cycle. It is the ratio of the
exergy loss rate to income generated. For improved reactor parameters based on exergy
EGRex is used to decide extension for catalyst use by keeping the same average annual
income.
The study results are summarized as follows:
 Exergy analysis pinpoints the true losses in the process and exergoeconomic
analysis shows the relation between exergy destruction and cost.

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Exergy Analysis of Nitric Acid, Ethylene Oxide/Ethylene Glycol Processes and Methanol Reactor

 The exergy efficiency of the process is higher (74.59%) at SR and lower (73.29%)
at ER.
 Highest exergy destruction is observed in EO reactor (46%) at SR and (47.53%) at
ER followed by EG reactor (11.8%) at SR and (10.70%) at ER. .
 The exergy efficiency of the new process is lower than the conventional process
but does not deteriorate at end run. Capital cost saving is the added advantage of
the new process.
 Ethylene recovery from purge gas will improve exergy efficiency of the entire
plant up to 75.17%.
 The temperature in the reactor, increase in the volume of gas and price of ethylene
are the limiting factor in deciding ER selectivity of the catalyst.
 Statistical data for thermodynamic loss rate to capital cost ratio values shows that
the relative spread in R for different devices is large when it is based on energy and
small when it is based on exergy.
 The relation between exergy loss and generated income will be helpful to
maximize profit in a catalyst cycle. Catalyst use can be extended in a cycle if
exergy efficiency of the reactor is increased.
 High activity catalyst can be used for six more months if exergy loss is reduced by
2% and one year more if exergy loss is reduced by 4%.
 High selectivity catalyst data can be used for future work to know the relation
between the thermodynamic loss rate and generated income. Further new processes
can be compared on the basis of exergoeconomic analysis.

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Exergy Analysis of Nitric Acid, Ethylene Oxide/Ethylene Glycol Processes and Methanol Reactor

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