Article

pubs.acs.org/IECR

Comparative Techno-Economic and Environmental Analysis of

Ethylene and Propylene Manufacturing from Wet Shale Gas and
Naphtha
Minbo Yang† and Fengqi You*,‡
†
Department of Chemical and Biological Engineering, Northwestern University, Evanston, Illinois 60208, United States
‡
Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, New York 14853, United
States
*
S Supporting Information

ABSTRACT: In this work, we perform a comparative techno-economic and environmental

analysis for manufacturing ethylene and propylene from naphtha and from shale gas with rich
natural gas liquids (NGLs). We first propose two novel process designs for producing
ethylene and propylene from NGLs-rich shale gas. These two designs employ steam co-
cracking of an ethane−propane mixture and an integration of ethane steam cracking and
propane dehydrogenation, respectively. For benchmarking, we also consider a conventional
process design in which ethylene and propylene are produced via steam cracking of naphtha.
Detailed process models are developed for all the three designs to obtain the mass and
energy balances of each unit operation. On this basis, techno-economic analysis and life cycle
analysis are conducted for each of the three designs in order to systematically compare the production costs and life cycle
environmental impacts of ethylene and propylene manufactured from shale gas and naphtha based on the same conditions. The
economic analysis indicates that manufacturing ethylene and propylene from NGLs-rich shale gas is more attractive than from
naphtha. The environmental impact analysis shows that manufacturing ethylene and propylene from NGLs-rich shale gas results
in lower life cycle water consumption but higher life cycle greenhouse gas emissions.

1. INTRODUCTION ethylene, He and You developed three process designs by

Ethylene and propylene are important building blocks for
manufacturing plastics, fibers, and other chemicals. In the
United States, ethylene is primarily manufactured via steam
cracking of hydrocarbons, including natural gas liquids (NGLs,
ethane, propane, butanes, etc.), naphtha, and gas oil.1 In
addition to ethylene, propylene is obtained as a byproduct in
steam crackers, which accounts for roughly half of the total
propylene production.2,3 In recent years, the successful
application of advanced extraction technologies resulted in a
boom of shale gas production in the United States and provides
extra NGLs at low costs for the chemical manufacturing
industry.4−8 As a result, manufacturing ethylene and propylene
from shale gas-based feedstocks (e.g., ethane and propane),
instead of from naphtha, is of growing interest.9 With different
feedstocks, ethylene and propylene may require different
production costs and result in different environmental impacts.
It is of great significance to investigate the economic and
environmental implications of ethylene and propylene
manufacturing from different feedstocks.10,11 Therefore, the
objective of this study is to compare the production of ethylene
and propylene from NGL-rich shale gas and naphtha in terms
of economics and life cycle environmental impacts.
There are some recent publications regarding the process
design and synthesis for shale gas processing and upgrading.12
Shale gas is considered as the feedstock to produce syngas,13
methanol,14 liquid fuels, and light olefins. For the production of
integrating shale gas processing with ethane steam cracking,
which could significantly increase the overall profitability.15
Later, an integrated process design combining the conversion
of methane, ethane, and propane and the dehydration of
bioethanol was proposed to improve the economics and
environmental impacts for ethylene production.16 Salkuyeh and
Adams proposed a polygeneration process design to produce
ethylene and electricity from shale gas via methane oxidative
coupling, which showed the ethylene production costs could be
close to those of steam cracking methods.17 However, these
publications only focus on the production of ethylene from
shale gas and do not explore the economics and environmental
implications of manufacturing propylene from shale gas. In
addition, some contributions were made to addressing the
water management in shale gas production,18optimal design of
shale gas supply chain,19 and uncertainty in shale gas supply
chain design and optimization.20
Environmental impacts of manufacturing chemicals from
shale gas are of particular interest. A recent concern associated
with shale gas production is the fugitive methane emissions,21
which may result in high greenhouse gas (GHG) emissions.22
Received: January 25, 2017
Revised: March 19, 2017
Accepted: March 22, 2017
Published: March 22, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.7b00354

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Figure 1. Block flow diagrams for the manufacturing of ethylene and propylene from shale gas and naphtha.
Several studies have examined the life cycle GHG emissions of
shale gas. Laurenzi and Jersey examined the life cycle GHG
emissions of Marcellus shale gas for power generation.23 Dale et
al. performed a process-based life cycle assessment (LCA) for
Marcellus shale gas.24 The upstream carbon footprints of shale
gas and conventional natural gas were also compared.25
Another concern of shale gas production is the considerable
water usage associated with horizontal drilling and hydraulic
fracturing.26 Shale gas production is reported to consume
notably more water than conventional natural gas.27 For olefins
production, the steam cracking of hydrocarbons (e.g., ethane,
propane, naphtha, etc.) is highly energy intensive and thus
produces significant amounts of GHGs.28 Besides, waste heat
needs to be discharged to the ambient environment, and this is
commonly performed by cooling water systems that consume a
considerable amount of water.1 To the best of our knowledge,
there are very limited studies focusing on environmental
impacts of manufacturing olefins from shale gas, except a recent
study on ethylene production from shale gas.29 However, it
remains inconclusive whether shale gas can be regarded as a
low-carbon feedstock for the production of ethylene and
propylene compared with naphtha.
In this work, we first develop two novel process designs for
producing ethylene and propylene from NGLs-rich shale gas. In
the first design, the ethane−propane mixture is sourced from
shale gas at first and then stream co-cracked to produce
ethylene and propylene. In the second design, ethane and
propane are derived from shale gas separately. Ethylene is
mainly produced via the steam cracking of ethane, and
propylene is mostly manufactured via the dehydrogenation of
propane. For the purpose of a systematic comparison, we also
model a conventional naphtha cracking process that produces
ethylene and propylene from naphtha. We develop detailed
process models for all three designs to obtain the mass and
energy balances. Next, we conduct a techno-economic analysis
and life cycle analysis for each of the three designs. Finally,
production costs, life cycle GHG emissions, and life cycle water
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consumption of ethylene and propylene manufactured from
shale gas and naphtha are investigated and compared.
The key contributions of this work are summarized as
follows: (1) two novel process designs for manufacturing
ethylene and propylene from NGLs-rich shale gas and (2)
systematic comparison of manufacturing ethylene and
propylene from NGLs-rich shale gas and naphtha based on
the same conditions from economics and environmental
perspectives.
The rest of the paper is organized as follows. Section 2
presents the description of each process design. Results of
process simulation, economic analysis, and environmental
analysis are provided and compared in Section 3. The
conclusion of this work is given in Section 4.
2. PROCESS DESCRIPTION
In this study, shale gas from the Marcellus region in the United
States is analyzed for the production of ethylene and propylene
because there is an increasing attention for producing olefins in
this region from the locally produced shale gas.30 Table S1 in
the Supporting Information gives the composition of the raw
shale gas considered in this study. Depending on the raw shale
gas composition, two process designs for manufacturing
ethylene and propylene from shale gas are proposed as
depicted in Figure 1(a) and (b), respectively. Each design
consists of two stages: shale gas processing and olefins
production.
In the co-cracking design shown in Figure 1(a), raw shale gas
is first fed into an acid gas removal unit to remove the acid
component. Then, the sweet gas is introduced into a
dehydration unit to reduce the water content. NGLs are
further recovered from the dry gas by a cryogenic separation
unit. The resulting methane-rich gas is pressurized and sent out
as pipeline gas, and the mixture of ethane and propane is sent
to produce ethylene and propylene. At the olefins production
stage, the ethane−propane mixture derived from shale gas and
the unreacted ethane and propane are steam co-cracked in the
steam cracking unit. After being cooled, pressurized, and
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Figure 2. Process flowsheets for the processing of Marcellus shale gas.
purified, the cracking gas is then sent to an olefin separation
unit and spilt into ethylene, propylene, hydrogen, methane,
ethane, propane, and other products.
In the technology-integrated design shown in Figure 1(b),
the shale gas processing stage is similar to that in the co-
cracking design. The difference between these two shale gas
processing stages is the NGLs fractionation unit for separating
the ethane−propane mixture into ethane and propane. The
olefins production stage considers the integration of ethane
steam cracking and propane dehydrogenation technologies.
Ethane is fed into the ethane steam cracking unit, while
propane is taken as the feedstock for the propane dehydrogen-
ation unit. The cracking gas and the effluent from the propane
dehydrogenation unit are sent to an olefins separation unit,
where they are separated into ethylene, propylene, and other
products.
In addition to the two novel process designs that we propose,
a conventional process design for manufacturing ethylene and
propylene from naphtha is modeled and analyzed for
comparing economic and environmental performances of the
products. As shown in Figure 1(c), naphtha is first steam
cracked in a stream cracking unit. Similarly, the cracking gas is
cooled, pressurized, and purified. After that, the cracking gas is
separated into ethylene, propylene, and other products in an
olefins separation unit. Details of each unit are given in the
following subsections.
2.1. Shale Gas Processing. Figure 2 shows the flowsheets
for the processing of Marcellus shale gas with the composition
given in Table S1. It comprises five units, namely, acid gas
removal, dehydration, NGLs recovery, compression, and NGLs
fractionation.
Since CO2 in shale gas could lead to solids formation in the
cryogenic separation process for NGLs recovery, the CO2
concentration should be reduced to less than 50 ppmv.31 As
show in Figure 2(a), a monoethanolamine (MEA)-based
absorption unit is employed for acid gas removal. Raw shale
gas is fed into the bottom of an absorber (T-101) and contacts
with a lean MEA solution from the top of absorber T-101. The
rich MEA solution from absorber T-101 bottom passes through
a pressure relief valve (VLV-101) followed by a flash tank (V-
101) to remove dissolved light hydrocarbons. After that, the
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rich MEA solution is depressurized via another valve (V-102)
and preheated in a heat exchanger (E-103), and then, it is fed to
a stripper (T-102). In stripper T-102, acid gas in the rich MEA
solution is stripped off, and the MEA solution is regenerated.
The lean MEA solution from stripper T-102 bottom is first
cooled in a heat exchanger (E-103) and then pumped to the
top of absorber T-101 along with the makeup MEA and water.
The gas effluent from the top of stripper T-102 enters a flash
drum (V-102) after being cooled. The liquid from flash drum
V-102 is pumped to the top of stripper T-102, and the gas from
flash drum V-102 is acid gas.
Since acid gas is removed in an amine-based unit, the sweet
gas leaving absorber T-101 is water saturated. Water must be
reduced to prevent hydrate formation in the cryogenic
separation process.31 Triethylene glycol (TEG) is the typical
choice in most instances for water removal from natural gas.31
A TEG-based dehydration unit is depicted in Figure 2(b). The
sweet gas enters an absorber (T-201) from the bottom and
contacts with a lean TEG stream. The rich TEG stream from
the bottom of absorber T-201 is depressurized via a valve
(VLV-201) and flashed in a flash tank (V-201) to remove most
hydrocarbons. Then, the rich TEG stream is fed into a
distillation tower (T-202) for TEG regeneration after being
preheated in a heat exchanger (E-203). Water and hydro-
carbons from the overhead condenser of tower T-202 are
purged, and the lean TEG stream from the tower bottom is
sent to a stripper (T-203) to further reduce the water content
in the TEG stream. A small portion of dry gas from the top of
absorber T-201 is used as strpping gas in stripper T-203. The
regenerated TEG stream mixed with the makeup TEG is
pumped to the top of absorber T-201 after being cooled in a
cooler (E-302).
After dehydration, shale gas is sent to a cryogenic separation
process for NGLs recovery. As shown in Figure 2(c), the dry
gas is first cooled in a heat exchanger (E-301), and then, it
enters a two-phase separator (V-301). The gas product from
separator V-301 flows through an expander (EX-301) to further
reduce the temperature before it is fed into another separator
(V-302). Liquid products from separators V-301 and V-302 are
introduced into a demethanizer (T-301). The gas product from
separator V-302 and that from the top of demethanizer T-301
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Figure 3. Process flowsheets of olefins production by steam co-cracking of ethane−propane mixture: (a) ethane−propane steam co-cracking and (b)
olefins separation.
are methane rich and mixed. The composition of the mixed
product has met the corresponding specifications of pipeline
gas, as shown from Table S1. After heat recovery in heat
exchanger E-301, a small portion of methane-rich gas is
consumed for steam generation, and the rest is introduced into
a gas compression unit as shown in Figure 2(d). The methane-
rich gas is pressurized to 6 MPa and sent out as pipeline gas.
Power generated by Expander EX-301 provides part of the
power for gas compression; additional power is provided by
steam turbines driven by the steam generated via the
combustion of methane-rich gas. In the co-cracking design,
the NGLs product (i.e., the ethane−propane mixture as shown
in Table S1) from the bottom of demethanizer T-301 is sent to
the olefins production stage. In the technology-integrated
design, the NGLs product is introduced into a deethanizer (T-
401), where the mixture is split into ethane and propane, as
illustrated in Figure 2(e). Then, ethane and propane are sent to
the olefins production stage.
2.2. Co-Cracking of Ethane−Propane. In the co-cracking
design, the mixture of ethane and propane coming from the
shale gas processing stage is steam co-cracked. Figure 3 shows
the process flowsheets of the olefins production stage in the co-
cracking design. Typically, a commercial steam cracking furnace
consists of convection and radiant sections.1 In the convection
section, hydrocarbons, dilution steam, and boiler feedwater are
heated. In the radiant section, hydrocarbons are cracked into
small molecules, such as ethylene, propylene, hydrogen,
methane, etc. For the sake of convenience, the steam cracking
furnace is simulated using a heater combined with the plug flow
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reactor (PFR) model.29 In this work, a mass-based hydro-
carbons-to-steam ratio of 1:0.4 is applied.32 The reaction
scheme for the steam co-cracking of an ethane−propane
mixture is given in Table S2 in the Supporting Information.
The cracking gas from the cracking furnace flows through a
heat exchanger (E-501) to generate high pressure (HP) steam
at 11 MPa, which is subsequently superheated in the cracking
furnace.1,33 The cracking gas is further cooled by another heat
exchanger (E-502) to preheat dilution steam and ultimately
cooled to 40 °C in a quench tower by contacting with cooling
water. After that, a five-stage compressor is employed to
pressurize the cracking gas to 3.7 MPa. The compression power
is provided by steam turbines driven by the superheated HP
steam. During compression, the temperature of the cracking gas
is controlled below 100 °C by intermediate coolers to prevent
olefin polymerization and subsequent equipment fouling.1 Acid
components in the cracking gas are removed in the caustic
tower after the third stage compression, according to reactions
1 and 2. The compressed cracking gas is introduced into the
olefin separation unit after the water content is reduced in a
molecular sieve dryer.
CO2 + 2NaOH → 2Na 2CO3 + H 2O (1)
H 2S + 2NaOH → 2Na 2S + 2H 2O (2)
In the olefins separation unit shown in Figure 3(b), the
cracking gas is first cooled to about −37 °C through two heat
exchangers (E-510 and E-504) and a cooler (E-505). Then, the
cracking gas enters a separator (V-501). The gas product from
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Figure 4. Process flowsheets of olefins production by the integration of ethane steam cracking and propane dehydrogenation: (a) ethane steam
cracking, (b) propane dehydrogenation, and (c) olefins separation. The steam cracking unit is similar to that in Figure 3, and the rest of the olefins
separation section is similar to that in Figure 3 excluding a debutanizer.
separator V-501 is introduced into a series of cold boxes. Liquid
products from separators V-501 to V-504 are fed into a
demethanizer (T-503) where methane and hydrogen in the
liquid phase are removed. The gas phase from separator V-504
is ultimately cooled to −165 °C in a heat exchanger (E-515)
and fed into separator V-505. The gas product from separator
V-505 is hydrogen rich, and the liquid product is methane rich.
These two streams serve as coolants for heat exchanger E-515
and for heat exchangers E-511−E514 along with the gas
product from demethanizer T-503. The bottom product of
demethanizer T-503 is nearly methane free and is introduced
into a deethanizer (T-504). After being preheated and mixed
with some hydrogen-rich gas, the gas product from deethanizer
T-504 is sent to a hydrogenator (R-501), where acetylene is
reacted with hydrogen and converted into ethylene or ethane,
according to reactions 3 and 4.
C2H 2 + H 2 → C2H4
C2H 2 + 2H 2 → C2H6
The separation of ethylene and ethane often requires large
distillation columns with 120−180 trays.34 The gas product
from hydrogenator R-501 is fed into a C2 splitter (T-509) with
120 trays, after being cooled in a heat exchanger (E-506). The
ethylene product with a purity of 99.9% is drawn from the ninth
tray of C2 splitter T-509. The gas product from the top of C2
splitter T-509 is ethylene rich and is further cooled in a cooler
(E-509) to reduce the amount of gas recycled to be
recompressed. The liquid product from separator V-506 is
routed to the first tray of C2 splitter T-509. Ethane from the
bottom of C2 splitter T-509 is depressurized and finally
recycled as a feedstock of cracking furnaces, after being heated
Article
in heat exchangers E-504 and E-511. A liquid stream is
extracted from the 99th tray of C2 splitter T-509 as a coolant in
heat exchanger E-510 and returned to the 101st tray. The liquid
product from the bottom of deethanizer T-504 is fed into a
depropanizer (T-505). The overhead product from depropan-
izer T-505 contains propane and propylene that are separated
in a C3 splitter comprising two distillation columns (T-506 and
T-507). Polymer-grade propylene with a purity of 99.5% is
obtained from the top of column T-506, and propane from the
bottom of column T-507 is fed into cracking furnaces. Last, a
debutanizer (T-508) is used to separate the bottom product
from depropanizer T-505 into a C4 mixture and C5+ mixture.
2.3. Integration of Ethane Steam Cracking and
Propane Dehydrogenation. The technology-integrated
design considers the integration of ethane steam cracking and
propane dehydrogenation. Figure 4 presents the process
flowsheets of the olefins production stage in the technology-
(3)
integrated design. Ethane sourced from shale gas along with the
(4)
recycled ethane is sent to the ethane steam cracking unit, which
is similar to the one described in Figure 3. The reaction scheme
used for ethane steam cracking is given in Table S3 in the
Supporting Information. Propane derived from shale gas and
the recycled propane are merged as the feedstock for the
propane dehydrogenation unit, as shown in Figure 4(b).
Meanwhile, hydrogen is injected into the propane feed to
reduce the coke formation on the catalyst with a mole-based
hydrogen-to-hydrocarbons ratio of 0.6:1.35 The reaction section
consists of four reactors (R-601−R-604) with fired heaters
(FH-601−FH-604).36 The mixture of propane and hydrogen is
introduced into the reactors after being heated to over 630
°C.35 In this work, reactors are modeled using the PFR model,
and the kinetic model for propane dehydrogenation is given in
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Figure 5. Process flowsheets of olefins production by the steam cracking of naphtha: (a) naphtha steam cracking and (b) olefins separation. The
olefins separation unit is similar to that in Figure 3.
Table S4 in the Supporting Information.35 The effluent from
reactor R-604 is cooled to 40 °C and compressed to 1.2 MPa,
and then, it is sent to an olefins separation unit, as shown in
Figure 4(c). In the separation unit, the product from the
propane dehydrogenation unit is further cooled and presepa-
rated in separators (V-601−V-603). Liquid products from
separators V-601−V-603 are introduced into a deethanizer (T-
601) to remove C2 and lighter components. The gas product of
the deethanizer T-601 is ethane rich and treated as a feed for
steam cracking. The liquid product containing C3 and heavier
components is introduced into a depropanizer. Note that the
rest of the olefins separation unit is similar to that described in
Figure 3 excluding a debutanizer. The gas product from
separator V-603 is hydrogen rich and is purified in a pressure
swing adsorption (PSA) unit. As aforementioned, a portion of
the purified hydrogen is injected into the propane feed.
2.4. Naphtha Steam Cracking. For the purpose of a fair
comparison, a conventional naphtha cracking design is
investigated in this work as well. Figure 5 presents the process
flowsheets of the naphtha cracking design for the production of
ethylene and propylene. Similar to the co-cracking of the
ethane−propane mixture, naphtha is preheated and steam
cracked in cracking furnaces. A steam-to-naphtha ratio of 0.5:1
is applied in this work.1 The reaction scheme used for naphtha
steam cracking is given in Table S5 in the Supporting
Information. After heat recovery in a heat exchanger (E-701),
the cracking gas is further cooled by contacting with cooling oil
in a quench oil tower. The resulting mixture is introduced into
a gasoline fractionator (T-701), where the cracking gas is
further cooled and the heavy fraction is condensed. Most of the
condensed fraction is split and recycled to the quench oil tower
and gasoline fractionator T-701 after being cooled, while the
rest is stripped by low pressure (LP) steam in a stripper (T-
702). The gas product from the top of stripper T-702 is routed
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to fractionator T-701, and fuel oil is obtained from the bottom.
Parallel to naphtha cracking furnaces, the recycled ethane and
propane are co-cracked in a separate furnace.37 The cracking
gas is cooled in heat exchangers E-707 and E-706. After that,
these two cracking gas streams merge into one and enter a
quench water tower (T-703), where the cracking gas is
ultimately quenched to 40 °C by contacting with cooling
water. The effluent from the bottom of tower T-703 consists of
heavy hydrocarbons and water, and it is separated by a three-
phase separator (V-701). The water stream along with the
makeup water is split and recycled to the quench water tower
(T-703) as cooling water and to generate dilution steam. The
hydrocarbon stream is spilt and introduced into fractionator T-
701 and another stripper (T-704). In stripper T-704, the
hydrocarbon stream is boiled to strip off the dissolved gas. Gas
products from quench water tower T-703, stripper T-704, and
separator V-701 are mixed and pressurized to 3.7 MPa via a
five-stage compressor. The condensation of water and hydro-
carbons from the former three stages is routed into separator V-
701, while the condensate from the last two stages is fed into a
condensate stripper (T-706). The gas product from stripper T-
706 is fed to the fourth stage of the compressor for
recompression, and the bottom effluent is introduced into a
depropanizer in the olefins separation unit for further
fractionation. After being dried by a molecular sieve, the
cracking gas is sent to the olefins separation unit, which is
similar to that described in Figure 3.
2.5. Power and Refrigeration Generation. Power
generation via steam turbines is operated on the Rankine
cycle.38 As shown in Figure 6, water is first pressurized and
heated to generate HP steam. At shale gas processing stages,
HP steam is generated via the combustion of methane-rich gas;
at olefins production stages, HP steam is generated by heat
recovery from the cracking furnaces and fired heaters. The HP
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Figure 6. Process flowsheet of power generation.38
steam is then expanded in steam turbines, where steam energy
is converted to mechanical power. Next, LP steam exiting steam
turbines is used to satisfy on-site thermal requirements or
condensed by cooling water. Finally, the condensed water is
recycled to the pump.
Refrigeration is used for NGLs recovery, NGLs fractionation,
and olefins separation. Figure 7 shows refrigeration cycles of
propylene, ethylene, and methane. In the propylene cycle,
propylene is first pressurized to 1.6 MPa via a multistage
compressor (K-1) driven by steam turbines.39 Propylene is then
condensed by cooling water and/or process streams. Depend-
ing on the process requirements, the condensed propylene is
depressurized to provide cold utilities with temperatures of −25
and −40 °C. Lastly, propylene gases are gathered and
recirculated to compressor K-1 for recompression. The
ethylene cycle is similar to the propylene cycle. Ethylene is
compressed to 2.0 MPa via compressor K-2 and then
condensed using cooling water and propylene refrigerant.39
Depending on the process requirements, ethylene is used to
provide cold utilities with temperatures of −75 and −102 °C.
In addition, methane is used to provide the cold utility with a
temperature of −135 °C.1 In the methane cycle, methane is
pressurized to about 2.8 MPa and condensed by the ethylene
refrigerant.
In this section, we present two novel process designs for
manufacturing ethylene and propylene from NGLs-rich shale
gas. The major difference between the two designs is the
technologies employed for converting ethane and propane into
ethylene and propylene. Also, a conventional process design for
the steam cracking of naphtha is introduced for the purpose of
a fair comparison in systems analysis.40 Therefore, three process
designs for the production of ethylene and propylene are
Figure 7. Process flowsheets of refrigeration generation: (a) propylene cycle, (b) ethylene cycle, and (c) methane cycle.
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modeled in detail to analyze and compare the economic and
environmental profiles of the products manufactured through
different feedstocks and routes.
3. RESULTS AND DISCUSSION
Following the Aspen HYSYS Customization Guide,41 all the
three process designs discussed in the previous section are
modeled and simulated in Aspen HYSYS V7.2. Detailed
operating parameters of important columns including dis-
tillation towers, strippers, and absorbers are listed in Table S6
in the Supporting Information. Heat integration of each process
design is extracted and investigated using Aspen Energy
Analyzer V7.2, according to the Aspen Energy Analyzer User
Guide.42
3.1. Mass and Energy Balances. In this study, we
consider a production scale of 1 Mt/yr ethylene for the three
designs following a recent report.30 The operating time is 8000
h/yr.29 The mass and energy information on each unit
operation in the three designs is determined by HYSYS
simulation, and the results are summarized in Table 1.
To meet the given ethylene production rate, the co-cracking
design consumes 969.5 million standard cubic feet per day
(MMSCFD) of raw shale gas. At the stage of shale gas
processing, pipeline gas is the main product. About 77.0% of
the energy content of raw shale gas remains in the pipeline gas
product, and 20.0% of that is taken by the mixture of ethane
and propane. Also, the methane-rich gas used for utility
generation occupies 2.7% of the energy content of raw shale
gas. At the olefins production stage, the steam cracking of the
ethane−propane mixture results in an ethylene yield of 63.4 wt
% of the feed and a propylene yield of 14.4 wt % of the feed. It
means that propylene and ethylene are produced with a ratio of
0.23. Typically, process energy use is expressed in terms of
specific energy consumption.34 The specific energy consump-
tion of the olefins production stage in the co-cracking design is
determined as 23.9 GJ/t ethylene, which is slightly higher than
the specific energy consumption for ethane steam cracking
reported in the existing literature.34
The technology-integrated design consumes 1242.0
MMSCFD of raw shale gas to satisfy the given ethylene
production rate. Similarly, at the shale gas processing stage,
pipeline gas is the main product, which takes 76.6% of the
energy content of raw shale gas. Ethane and propane totally
occupy 20.0% of the energy content of raw shale gas, and the
utility generation consumes 3.1% of the energy content of raw
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research Article

Table 1. Mass and Energy Balances for Manufacturing Ethylene and Propylene from Shale Gas and Naphtha
co-cracking design technology-integrated design naphtha cracking design
shale gas processing stage
input
shale gas (MMSCFD) 969.5 1242.0 −
shale gas (MMBTU/h)a 47628 61012 −
MEA (kg/h) 26.0 33.4 −
TEG (kg/h) 26.2 33.6 −
output
pipeline gas (MMSCFD) 820.2 1045.7 −
pipeline gas (MMBTU/h)a 36673 46754 −
ethane−propane (t/h) 197.3 − −
ethane (t/h) − 150.9 −
propane (t/h) − 101.8 −
direct emissions
CO2 (t/h) 78.0 111.8 −
utilities
power (MW)b 97.0 139.7 −
LP steam (125 °C) (GJ/h)b 58.7 165.2 −
MP steam (175 °C) (GJ/h)b 13.3 17.1 −
HP steam (250 °C) (GJ/h)b 13.8 17.6 −
recycling cooling water (kt/h)c 59.6 89.4 −
make up water (kt/h) 1.2 1.8 −
olefins production stage
input
ethane−propane (t/h) 197.3 − −
ethane (t/h) − 150.9 −
propane (t/h) − 101.8 −
naphtha (t/h) − − 368.0
NaOH (kg/h) 60.6 56.0 84.5
output
ethylene (t/h) 125.0 125.0 125.0
propylene (t/h) 28.4 87.1 51.3
C4s (t/h) 8.4 13.1 7.2
C5+ (t/h) 1.6 0 134.2
hydrogen (t/h) 10.8 17.7 8.3
utilities
power (MW)b 88.9 142.8 93.0
LP steam (125 °C) (GJ/h)b 414 1509 447
MP steam (175 °C) (GJ/h)b 0 0 5.9
total fuel consumption (GJ/h) 2992 3977 3341
external fuel demand (GJ/h) 1643 3397 −351
recycling cooling water (kt/h)c 54.5 122.9 90.6
make up water (kt/h) 1.1 2.5 1.8
direct emissions
CO2 (t/h) 148.3 169.8 164.0
a b c
High heating value (HHV) basis. Power and steam are generated on-site. MP steam: medium pressure steam. In cooling water systems,
evaporation loss rate = 0.00153 × cooling range; blow down loss = 1.5 × evaporation loss.43 Cooling range is equal to 5 °C in this analysis.

shale gas. At the olefins production stage, ethane and propane
are consumed with a total mass flow rate of 252.7 t/h. In terms
of mass flow rate, ethylene and propylene account for 49.5 and
34.5 wt % of the feed, respectively. It is found that the
technology-integrated design results in a propylene-to-ethylene
ratio of 0.70. The corresponding specific energy consumption is
determined as 31.8 GJ/t ethylene.
In the naphtha cracking design, naphtha is consumed with a
mass flow rate of 368.0 t/h to meet the given ethylene
production rate. The steam cracking of naphtha shows an
ethylene yield of 34.0 wt % of the feed and a propylene yield of
13.9 wt % of the feed. It means that propylene and ethylene are
produced with a ratio of 0.41. The corresponding specific
H DOI: 10.1021/acs.iecr.7b00354
energy consumption is identified as 26.7 GJ/t ethylene, which
meets the value reported in literature.34
Comparing shale gas processing stages in the two proposed
designs, the main difference is the NGLs fractionation unit for
the separation of the ethane−propane mixture. To separate the
ethane−propane mixture into ethane and propane, more
refrigeration and LP steam are needed. As a result, in the
technology-integrated design, slightly more methane-rich gas is
combusted and less pipeline gas is produced based on per unit
of raw shale gas.
The three olefins production stages rely on different
technologies and feedstocks. From Table 1, we can see that
more naphtha is consumed in the naphtha cracking design than
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Industrial & Engineering Chemistry Research Article

Table 2. Economic Evaluation Results of Shale Gas Processing Stages

designs co-cracking design technology-integrated design
raw shale gas cost (M$/yr) 1050.3 1345.5
other feeds cost (M$/yr) 3.4 3.9
plant overhead (M$/yr) 7.2 9.1
labor cost (M$/yr) 11.5 14.6
maintenance (M$/yr) 3.0 3.5
total capital cost (M$) 369.4 440.5
capital depreciation (M$/yr) 18.5 22.0
property taxes and insurance (M$/yr) 7.4 8.8
general expenses (M$/yr) 108.9 139.2
total production cost (M$/yr) 1210.2 1546.6

Table 3. Economic Evaluation Results of Olefins Production Stages

designs co-cracking design technology-integrated design naphtha cracking design
hydrocarbon feed cost (M$/yr) 350.1 451.2 1265.9
other feeds cost (M$/yr) 38.3 89.8 3.2
plant overhead (M$/yr) 3.9 5.2 4.3
labor cost (M$/yr) 2.9 3.6 3.2
maintenance (M$/yr) 5.0 6.8 5.5
total capital cost (M$) 912.6 1167.0 1042.8
capital depreciation (M$/yr) 45.6 58.4 52.1
property taxes and insurance (M$/yr) 18.3 23.3 20.9
general expenses (M$/yr) 45.9 63.1 134.0
total production cost (M$/yr) 510.0 701.4 1489.1

ethane and propane consumed in the other two designs in
terms of mass flows. This is because ethane and propane can
achieve higher ethylene yields compared with naphtha in steam
cracking. Besides, the technology-integrated design requires
more ethane and propane than the co-cracking design. The
reason is that ethylene is mainly produced via the steam
cracking of ethane in the technology-integrated design. From
the viewpoint of the production of ethylene and propylene, the
three designs could coproduce ethylene and propylene.
However, the co-cracking design results in a propylene-to-
ethylene ratio lower than the naphtha cracking design, meaning
that there exists a propylene gap if shifting feedstocks from
naphtha to an ethane−propane mixture for steam crackers. The
technology-integrated design could result in a propylene-to-
ethylene ratio higher than the naphtha cracking design. This
indicates that the propylene gap can be eliminated by the
integration of ethane steam cracking and propane dehydrogen-
ation. In terms of energy consumption, the olefins production
stage in the technology-integrated design consumes more
energy than those in the other two designs. The first reason is
that the propane dehydrogenation reaction is energy intensive
and requires fired heat. The second reason is that the
dehydrogenation product not only requires power for
compression but also needs refrigeration and steam for
separation. Note that the naphtha cracking design produces
excess fuel, as the stream cracking of naphtha results in high
methane yields.
3.2. Economic Analysis. The total annual production cost
can be estimated as the sum of direct manufacturing costs
(feedstocks, utilities, labor-related operations, and mainte-
nance), plant overhead, fixed costs (property taxes, insurance,
and capital depreciation), and general expenses.44 On the basis
of the obtained mass and energy balances, the total cost of
feedstocks and utilities can be determined by summing the cost
of each feedstock and utility, which is equal to the annual
I DOI: 10.1021/acs.iecr.7b00354
consumption quantity multiplied by the corresponding price.
Economic parameters for estimating costs of feedstocks and
utilities are listed in Table S7 in the Supporting Information.
Aspen Process Economic Analyzer V7.2 is used to estimate the
costs of labor, maintenance, and plant overhead.45 Capital
depreciation is estimated based on the total capital cost using a
straight-line method over the plant life, as given by eq 5.46 The
total capital cost of a process is also estimated using Aspen
Process Economic Analyzer V7.2 and based on existing sources
as given in Table S8 in the Supporting Information. The cost of
process equipment, units, or plants can be converted to current
value using the Chemical Engineering Plant Cost Index
according to eq 6.47 The property taxes and insurance are
estimated as 2% of the total project cost.46 General expenses
including selling expenses, research and development costs, and
administrative expenses are estimated as 9% of the total
production cost.48
TCC
DP =
ls (5)
⎛ CEPCI 2016 ⎞⎛ S ⎞ β
C2016 = C base⎜ ⎟⎜ ⎟
⎝ CEPCIbase ⎠⎝ S base ⎠ (6)
where DP is the capital depreciation; TCC is the total capital
cost; ls is the life span; C2016 is the cost in 2016; Cbase is the cost
in the base case; CEPCI2016 is the cost index in 2016; CEPCIbase
is the cost index in the base case; S is the actual capacity; Sbase is
the capacity in the base case; β is the cost scale factor.
To evaluate production costs of manufacturing ethylene and
propylene from the raw shale gas given in Table S1, costs for
producing ethane and propane are evaluated at first. The results
of the economic evaluation of shale gas processing stages are
given in Table 2. We find that raw shale gas cost dominates the
total production cost. The other notable contributions come
from the fixed costs and general expenses. At shale gas
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Industrial & Engineering Chemistry Research
processing stages, multiple products including pipeline gas,
ethane, and propane (or ethane−propane mixture) are
produced. Thus, cost allocation is employed to estimate costs
for producing ethane and propane from raw shale gas. In
general, methods for cost allocation include the physical
measure method, economic value method, and zero cost
method.49 The physical measure method is reasonable for cases
that the product market values are about the same, and the zero
cost method assigns all costs to the main product.49 Because
economic values of pipeline gas, ethane, and propane differ
greatly and pipeline gas is the main product at shale gas
processing stages, the physical measure method and the zero
cost method are not suitable. Therefore, the economic value
method is selected in this study. In the co-cracking design,
allocation factors for the pipeline gas and ethane−propane
mixture are determined as 71.0% and 29.0%, respectively. In the
technology-integration design, allocation factors for pipeline
gas, ethane, and propane are determined as 70.9%, 11.3%, and
17.8%, respectively. As a result, the production cost for the
ethane−propane mixture is estimated as $221.8/t, and
production costs for ethane and propane are estimated as
$145.8/t and $337.3/t, respectively.
Subsequently, costs for manufacturing ethylene and
propylene via the three designs are systematically evaluated.
Table 3 shows the economic evaluation results of olefins
production stages in the three designs. The olefins production
stage in the technology-integrated design requires the highest
capital cost because of investments in the propane dehydrogen-
ation unit and the expanded olefins separation unit. The steam
co-cracking of the ethane−propane mixture results in a lower
total capital cost than the steam cracking of naphtha. As shown
from Table 3, the naphtha cracking design requires the highest
total production cost. This is because the consumption quantity
and price of naphtha are higher than those of ethane and
propane. Similarly, the economic value allocation method is
employed to evaluate the production costs of ethylene and
propylene. For the co-cracking design, the technology-
integrated design, and the naphtha cracking design, allocation
factors of ethylene are determined as 62.3%, 41.9%, and 41.3%,
respectively, and those of propylene are determined as 18.5%,
38.0%, and 22.1%, respectively. On this basis, the production
costs of ethylene and propylene are determined and compared
as shown in Figure 8. It is shown that the production costs of
ethylene and propylene are dominated by the direct
manufacturing costs for all the three designs. The technology-
integrated design shows the best economic performance for
manufacturing ethylene and propylene. Manufacturing ethylene
and propylene via the naphtha steam cracking design results in
the highest production costs, which are about 1.9 times of those
Figure 8. Breakdown of production costs for the manufacturing of
ethylene and propylene via the three designs (2016 dollar value).
J DOI: 10.1021/acs.iecr.7b00354
Article
associated with the co-cracking design and 2.1 times of those
associated with the technology-integration design. Such results
indicate that manufacturing ethylene and propylene from the
considered shale gas is more cost effective than from naphtha.
3.3. Environmental Analysis. The environmental impacts
of manufacturing ethylene and propylene from NGLs-rich shale
gas and naphtha are systematically analyzed following the LCA
approach.50,51 The primary goal of this LCA study is to assess
and compare the life cycle environmental impacts of ethylene
manufactured from NGLs-rich shale gas and naphtha. The
functional unit is defined as 1 kg of ethylene produced at the
gate of plant. Because the use and end-of-life phases of the
ethylene products could vary significantly, a cradle-to-gate LCA
is considered in this study.52 This LCA encompasses the
environmental impacts during the acquisition of feedstocks and
the processing of shale gas (for manufacturing ethylene and
propylene from shale gas), as well as the manufacturing of
ethylene and propylene. The investigated life cycle impact
categories include GHG emissions and water consumption.
The life cycle inventory is calculated based on the mass and
energy balances provided in the previous subsections. Data
used to model GHG emissions and water consumption during
feedstocks acquisition are collected from publications and the
Ecoinvent database,53 as listed in Table S9 in the Supporting
Information. Because shale gas processing and olefins
production stages produce multiple products, the correspond-
ing mass and energy flows as well as the associated
environmental burdens must be allocated to each of the
products to accurately reflect their individual contributions to
the environmental impacts.54 In this study, coproduct allocation
is applied based on the mass allocation method and the
economic value allocation method.54 On the basis of the
coproduct allocation, the environmental impacts for the
production of propylene can be identified as well.
3.3.1. Life Cycle GHG Emissions. Figure 9 shows the
breakdown of life cycle GHG emissions of ethylene produced
from NGLs-rich shale gas and naphtha. For manufacturing
ethylene from shale gas, shale gas production and olefins
production stages are major contributors for GHG emissions,
while shale gas processing stages contribute less than 10% of
the total value. These observations are consistent with the
recent studies on shale gas environmental impact analyses.55−57
For manufacturing ethylene from naphtha, the production of
naphtha causes GHG emissions close to the downstream
olefins production stage. From Figure 9, it is shown that
ethylene manufactured by the steam cracking of naphtha shows
the least life cycle GHG emissions. Compared with ethylene
manufactured from naphtha, ethylene produced through the
technology-integrated design results in higher life cycle GHG
emissions by 19% using the economic value allocation method
or by 25% using the mass allocation method. Ethylene
manufactured via the co-cracking design causes the highest
life cycle GHG emissions, which are nearly 1.40 times of the life
cycle GHG emissions associated with the steam cracking of
naphtha. Such results imply that manufacturing ethylene from
the considered shale gas is not competitive in terms of GHG
emissions.
By employing coproduction allocation, we can also identify
the life cycle GHG emissions for manufacturing propylene from
NGLs-rich shale gas and naphtha, as shown in Figure 10. On
the basis of the economic value allocation, propylene produced
via the naphtha steam cracking design has the lowest GHG
emissions, which are 71.4% and 83.8% of the GHG emissions
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 9. Breakdown of life cycle GHG emissions of ethylene produced via the three designs.
Figure 10. Breakdown of life cycle GHG emissions of propylene
produced via the three designs.
of propylene produced via the co-cracking design and the
technology-integrated design, respectively. On the basis of the
mass allocation, propylene produced via the naphtha steam
cracking design shows lower GHG emissions than propylene
produced via the co-cracking design and the technology-
integrated design by 27.3% and 20.1%, respectively. Regarding
life cycle GHG emissions, naphtha is more attractive than the
considered shale gas for the manufacturing of propylene.
3.3.2. Life Cycle Water Consumption. Life cycle water
consumptions of ethylene manufactured from NGLs-rich shale
gas and naphtha are compared in Figure 11. For manufacturing
ethylene from shale gas, water consumed at the olefins
production stage dominates life cycle water consumption of
ethylene. However, for manufacturing ethylene from naphtha,
water consumption associated with the production of naphtha
is more important. As shown from Figure 11, ethylene
manufactured via the co-cracking design leads to the lowest
Figure 11. Breakdown of life cycle water consumption of ethylene
produced via the three designs.
K DOI: 10.1021/acs.iecr.7b00354
Article
life cycle water consumption. Compared with ethylene
manufactured via the co-cracking design, ethylene manufac-
tured via the technology-integrated design causes higher life
cycle water consumption by 29% based on the economic value
allocation or by 42% based on the mass allocation. The steam
cracking of naphtha results in notably higher life cycle water
consumption than the steam co-cracking of the ethane−
propane mixture by over 200%. Considering life cycle water
consumption, manufacturing ethylene from the considered
shale gas via the co-cracking design is more attractive than from
naphtha.
Similarly, the life cycle water consumption of propylene
manufactured via the three designs can be determined based on
coproduction allocation, as given in Figure 12. If coproduction
Figure 12. Breakdown of life cycle water consumption of propylene
produced via the three designs.
allocation is based on economic values, propylene produced via
the naphtha steam cracking design leads to significantly higher
water consumption than propylene produced via the co-
cracking design and the technology-integrated design by
207.5% and 137.6%, respectively. If coproduction allocation is
performed based on mass flows, propylene produced via the
naphtha steam cracking design still shows the highest water
consumption, which is 302.6% and 213.0% of the water
consumption of propylene produced via the co-cracking design
and the technology-integrated design, respectively. In terms of
life cycle water consumption, manufacturing propylene from
the considered shale gas is more competitive than from
naphtha.
3.4. Systematic Comparison. Figure 13 provides a
comprehensive comparison of production costs, life cycle
GHG emissions, and life cycle water consumption for
manufacturing ethylene and propylene from NGLs-rich shale
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 13. Relative cost and environmental impacts of ethylene and
propylene produced from shale gas and naphtha: (a) environmental
impacts based on economic value allocation and (b) environmental
impacts based on mass allocation.
gas via the two proposed designs and from naphtha via the
conventional naphtha cracking design. For each category, the
largest value is normalized to 1. Thus, each point represents the
relative value. Although the economic value allocation method
results in different life cycle environmental impacts for ethylene
and propylene, relative values considering ethylene and
propylene are the same. In each figure, a point closer to the
center indicates the better corresponding performance. We find
that the economic value allocation method and the mass
allocation method show similar results: (1) Ethylene and
propylene produced via the technology-integrated design have
the lowest production costs. (2) Ethylene and propylene
produced through the co-cracking design result in the least
water consumption. (3) Ethylene and propylene produced via
the naphtha cracking design lead to the lowest GHG emissions.
From Figure 13, we also find that manufacturing ethylene and
propylene from NGLs-rich shale gas is more attractive than
from naphtha considering production costs and water
consumption. However, manufacturing ethylene and propylene
from naphtha is more competitive than from NGLs-rich shale
gas in terms of GHG emissions.
3.5. Sensitivity Analysis. In order to better understand the
impacts of altering economic parameters on the economic and
environmental performance of manufacturing ethylene and
propylene from NGLs-rich shale gas and naphtha, a sensitivity
analysis is conducted. For illustration, Figure 14 presents the
sensitivity analysis result of ethylene production cost based on
economic value changes of raw shale gas, ethane, propane,
naphtha, ethylene, and propylene. It is shown that the feedstock
price and the ethylene price have great impacts on the ethylene
production cost. In the co-cracking design and the technology-
integrated design, changes in ethane and propane prices also
lead to notable effects on the ethylene production cost.
However, in the naphtha cracking design, price changes of
Figure 14. Sensitivity analysis of ethylene production cost: (a) co-cracking design, (b) technology-integrated design, and (c) maphtha cracking
design.
L DOI: 10.1021/acs.iecr.7b00354
Article
ethane and propane do not affect the ethylene production cost
because ethane and propane are neither feedstocks nor final
products. Also, we find that a high propylene price could result
in a low ethylene production cost, which is different from the
other prices analyzed in Figure 14. In the technology-integrated
design, the ethylene production cost is more sensitive to the
propylene price than those in the other two designs. This is
because the technology-integrated design produces more
propylene than the other two designs. It is noteworthy that
the naphtha cracking design still results in higher ethylene
production cost than the other two designs even the naphtha
price decreases by 40%. Such results indicate that NGLs-rich
shale gas is more attractive than naphtha for the production of
ethylene from the standpoint of economics.
As for environmental performance, economic parameters
could affect allocation factors when economic value allocation is
considered. Herein, we present effects of economic parameters
on life cycle GHG emissions of ethylene for illustration. From
Figure 15, we see that the ethylene price is most important for
life cycle GHG emissions of ethylene. The propylene price is
the second important factor after the ethylene price. Note that
the increase in propylene price decreases life cycle GHG
emissions of ethylene because both ethylene and propylene are
the products to which the GHG emissions are allocated. Ethane
and propane prices also affect life cycle GHG emissions of
ethylene in the co-cracking design and the technology-
integrated design, but they have little effect on the naphtha
cracking design. Additionally, we find that life cycle GHG
emissions of ethylene produced via the naphtha cracking design
are always lower than those of ethylene produced via the other
two designs under various changes.
4. CONCLUSION
This work addressed the comparison of manufacturing ethylene
and propylene from NGLs-rich shale gas and naphtha regarding
economic and environmental performance. For manufacturing
ethylene and propylene from shale gas, we proposed two novel
process designs. We also investigated a conventional design
considering the steam cracking of naphtha for the production of
ethylene and propylene. On the basis of process modeling and
HYSYS simulation, we conducted techno-economic analysis
and life cycle analysis for the three designs. The economic
analysis showed that manufacturing ethylene and propylene
from NGLs-rich shale gas via the co-cracking design and the
technology-integrated design resulted in lower production costs
than from naphtha by 48.2% and 52.3%, respectively. As for
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 15. Sensitivity analysis of life cycle GHG emissions of ethylene: (a) co-cracking design, (b) technology-integrated design, and (c) naphtha
cracking design.
environmental impacts, we assessed the life cycle GHG
emissions and life cycle water consumption for the manufactur-
ing of ethylene and propylene. On the basis of the economic
value allocation, ethylene and propylene manufactured from
NGLs-rich shale gas via the co-cracking design and the
technology-integrated design led to higher GHG emissions
than those produced from naphtha by 40.0% and 19.4%,
respectively. This indicated that naphtha could be regarded as a
low-carbon feedstock for the production of ethylene and
propylene compared with NGLs-rich shale gas. However,
manufacturing ethylene and propylene from naphtha caused
significantly higher water consumption than from NGLs-rich
shale gas via the co-cracking design and the technology-
integrated design by 207.5% and 137.6%, respectively. We also
obtained similar results by investigating the environmental
impacts based on the mass allocation method.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.7b00354.
Input data, reaction kinetics, and model parameters.
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Phone: (607) 255-1162. Fax: (607) 255-9166. E-mail: fengqi.
you@cornell.edu.
ORCID
Fengqi You: 0000-0001-9609-4299
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors acknowledge financial support from National
Science Foundation (NSF) CAREER Award (CBET-1643244).
This invited contribution is part of the I&EC Research special
issue for the 2017 Class of Influential Researchers.
■ REFERENCES
(1) Zimmermann, H.; Walzl, R. Ethylene. In Ullmann’s Encyclopedia
of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co.: Weinheim,
Germany, 2009.
(2) Zinger, S. The High Stakes Gamble In the Olefins Industry-
Market Risks and Rewards for New Petrochemical Construction.
http://lca.org/assets/doc/Wood_Mackenzie_Zinger_Risks_and_
Rewards_for_Petrochemical_Construction.pdf (accessed October 20,
2016).
M DOI: 10.1021/acs.iecr.7b00354
Article
(3) Allen, K. The Changing Dynamics and New Challenges Facing
the North American Petrochemical industry. http://www.slideshare.
net/14Balmoral/the-changing-dynamics-and-new-challenges-facing-
the-north-american-petrochemical-industry (accessed October 1,
2016).
(4) DeRosa, S. E.; Allen, D. T. Impact of natural gas and natural gas
liquids supplies on the United States chemical manufacturing industry:
production cost effects and identification of bottleneck intermediates.
ACS Sustainable Chem. Eng. 2015, 3, 451−459.
(5) Siirola, J. J. The impact of shale gas in the chemical industry.
AIChE J. 2014, 60, 810−819.
(6) Gao, J.; You, F. Design and optimization of shale gas energy
systems: Overview, research challenges, and future directions. Comput.
Chem. Eng. 2017, DOI: 10.1016/j.compchemeng.2017.01.032.
(7) Hughes, J. D. A reality check on the shale revolution. Nature
2013, 494, 307−308.
(8) Kerr, R. A. Natural Gas From Shale Bursts Onto the Scene.
Science 2010, 328, 1624−1626.
(9) Jenkins, S. Propylene production via propane dehydrogenation.
Chem. Eng. 2014, 121, 27−28.
(10) Foster, J. Can Shale Gale Save the Naphtha Crackers? https://
www.platts.com/IM.Platts.Content/InsightAnalysis/
IndustrySolutionPapers/ShaleGasReport13.pdf (accessed October 28,
2016).
(11) Gong, J.; You, F. Sustainable design and synthesis of energy
systems. Curr. Opin. Chem. Eng. 2015, 10, 77−86.
(12) Gong, J.; Yang, M.; You, F. A systematic simulation-based
process intensification method for shale gas processing and NGLs
recovery process systems under uncertain feedstock compositions.
Comp ut. Chem. Eng. 201 6, DOI: 10.1016/j.compche-
meng.2016.11.010.
(13) Martinez-Gomez, J.; Nápoles-Rivera, F.; Ponce-Ortega, J. M.; El-
Halwagi, M. M. Optimization of the production of syngas from shale
gas with economic and safety considerations. Appl. Therm. Eng. 2017,
110, 678−685.
(14) Julián-Durán, L. M.; Ortiz-Espinoza, A. P.; El-Halwagi, M. M.;
Jiménez-Gutiérrez, A. Techno-economic assessment and environ-
mental impact of shale gas alternatives to methanol. ACS Sustainable
Chem. Eng. 2014, 2, 2338−2344.
(15) He, C.; You, F. Shale Gas Processing Integrated with Ethylene
Production: Novel Process Designs, Exergy Analysis, and Techno-
Economic Analysis. Ind. Eng. Chem. Res. 2014, 53, 11442−11459.
(16) He, C.; You, F. Toward more cost-effective and greener
chemicals production from shale gas by integrating with bioethanol
dehydration: Novel process design and simulation-based optimization.
AIChE J. 2015, 61, 1209−1232.
(17) Khojasteh Salkuyeh, Y.; Adams, T. A., II A novel polygeneration
process to co-produce ethylene and electricity from shale gas with zero
CO2 emissions via methane oxidative coupling. Energy Convers.
Manage. 2015, 92, 406−420.
(18) Gao, J.; You, F. Optimal design and operations of supply chain
networks for water management in shale gas production: MILFP
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
model and algorithms for the water-energy nexus. AIChE J. 2015, 61,
1184−1208.
(19) Gao, J.; You, F. Game Theory Approach to Optimal Design of
Shale Gas Supply Chains with Consideration of Economics and Life
Cycle Greenhouse Gas Emissions. AIChE J. 2017, DOI: 10.1002/
aic.15605.
(20) Gao, J.; You, F. Deciphering and handling uncertainty in shale
gas supply chain design and optimization: Novel modeling framework
and computationally efficient solution algorithm. AIChE J. 2015, 61,
3739−3755.
(21) Alvarez, R. A.; Pacala, S. W.; Winebrake, J. J.; Chameides, W. L.;
Hamburg, S. P. Greater focus needed on methane leakage from natural
gas infrastructure. Proc. Natl. Acad. Sci. U. S. A. 2012, 109, 6435−6440.
(22) Howarth, R. W.; Santoro, R.; Ingraffea, A. Methane and the
greenhouse-gas footprint of natural gas from shale formations. Clim.
Change 2011, 106, 679−690.
(23) Laurenzi, I. J.; Jersey, G. R. Life cycle greenhouse gas emissions
and freshwater consumption of Marcellus shale gas. Environ. Sci.
Technol. 2013, 47, 4896−4903.
(24) Dale, A. T.; Khanna, V.; Vidic, R. D.; Bilec, M. M. Process based
life-cycle assessment of natural gas from the Marcellus Shale. Environ.
Sci. Technol. 2013, 47, 5459−5466.
(25) Weber, C. L.; Clavin, C. Life cycle carbon footprint of shale gas:
Review of evidence and implications. Environ. Sci. Technol. 2012, 46,
5688−5695.
(26) Yang, L.; Grossmann, I. E.; Manno, J. Optimization models for
shale gas water management. AIChE J. 2014, 60, 3490−3501.
(27) Clark, C. E.; Horner, R. M.; Harto, C. B. Life cycle water
consumption for shale gas and conventional natural gas. Environ. Sci.
Technol. 2013, 47, 11829−36.
(28) Ghanta, M.; Fahey, D.; Subramaniam, B. Environmental impacts
of ethylene production from diverse feedstocks and energy sources.
Appl. Petrochem. Res. 2014, 4, 167−179.
(29) He, C.; You, F. Deciphering the true life cycle environmental
impacts and costs of the mega-scale shale gas-to-olefins projects in the
United States. Energy Environ. Sci. 2016, 9, 820−840.
(30) Gonzalez, B.; Mehta, P. Ethylene Projects in the Ethane-Heavy
Northeast US. http://blogs.platts.com/2016/03/01/ethylene-projects-
ethane-northeast-us/ (accessed October 20, 2016).
(31) Kidnay, A. J.; Parrish, W. R.; McCartney, D. G. Fundamentals of
Natural Gas Processing, 2nd ed.; CRC Press, 2011.
(32) Sundaram, K. M.; Froment, G. F. Modeling of thermal cracking
kineticsI: Thermal cracking of ethane, propane and their mixtures.
Chem. Eng. Sci. 1977, 32, 601−608.
(33) Alizadeh, M.; Sadrameli, S. Modeling of Thermal Cracking
Furnaces Via Exergy Analysis Using Hybrid Artificial Neural
Network−Genetic Algorithm. J. Heat Transfer 2016, 138, 042801.
(34) Ren, T.; Patel, M.; Blok, K. Olefins from conventional and heavy
feedstocks: Energy use in steam cracking and alternative processes.
Energy 2006, 31, 425−451.
(35) Chin, S.; Radzi, S.; Maharon, I.; Shafawi, M. Kinetic model and
simulation analysis for propane dehydrogenation in an industrial
moving bed reactor. International Journal of Chemical, Molecular,
Nuclear, Materials and Metallurgical Engineering 2011, 5, 260−266.
(36) Gregor, J.; Wei, D. UOP Oleflex Process for Light Olefin
Production. In Handbook of Petrochemicals Production Processes;
Meyers, R. A., Ed.; McGraw-Hill Education: New York, 2004.
(37) Aly, S. Ethylene from Naphtha by Millisecond Cracking with
Front-End Demethanization. http://www.diquima.upm.es/old_
diquima/docencia/tqindustrial/docs/etileno.pdf (accessed October
15, 2016).
(38) Combined Heat and Power Technology Fact Sheet Series: Steam
Turbine; United States Department of Energy, 2016.
(39) Mafi, M.; Naeynian, S. M.; Amidpour, M. Exergy analysis of
multistage cascade low temperature refrigeration systems used in olefin
plants. Int. J. Refrig. 2009, 32, 279−294.
(40) Yue, D.; You, F.; Darling, S. B. Domestic and overseas
manufacturing scenarios of silicon-based photovoltaics: Life cycle
N DOI: 10.1021/acs.iecr.7b00354
Article
energy and environmental comparative analysis. Sol. Energy 2014, 105,
669−678.
(41) Aspen HYSYS Customization Guide; Aspen Technology, Inc.:
Burlington, MA, 2010.
(42) Aspen Energy Analyzer User Guide; Aspen Technology, Inc.:
Burlington, MA, 2009.
(43) Morvay, Z. K.; Gvozdenac, D. D. Cooling Tower. In Applied
Industrial Energy and Environmental Management; Wiley-IEEE Press,
2008.
(44) Seider, W. D.; Seader, J. D.; Lewin, D. R. Product and Process
Design Principles: Synthesis, Analysis and Evaluation, 3rd ed.; John Wiley
& Sons, 2009.
(45) Getting Started with Relative Economics in Aspen HYSYS; Aspen
Technology, Inc.: Burlington, MA, 2011.
(46) Anderson, J. Determining Manufacturing Costs. CEP Magazine,
January 2009; pp 27−31.
(47) Lozowski, D. Chemical engineering plant cost index (CEPCI).
Chem. Eng. 2016, 123, 96.
(48) Peters, M. S.; Timmerhaus, K. D. Cost Estimation. In Plant
Design and Economics for Chemical Engineers; McGraw-Hill: New York,
1991.
(49) Tayyari, F.; Parsaei, H. R. Joint Cost Allocation to Multiple
Products: Cost Accounting v. Engineering Techniques. In Economics of
Advanced Manufacturing Systems; Springer, 1992; pp 189−199.
(50) Environmental Management-Life Cycle Assessment: Principles and
Framework; International Standards Organization: Geneva, 2006.
(51) Environmental Management-Life Cycle Assessment: Requirements
and Guidelines; International Standards Organisation: Geneva, 2006.
(52) Lorenz, E. Life-cycle assessment in US codes and standards. PCI
J. 2014, 59.
(53) Ecoinvent Database, Ecoinvent: Zurich, Switzerland, 2016.
(54) Ayer, N. W.; Tyedmers, P. H.; Pelletier, N. L.; Sonesson, U.;
Scholz, A. Co-product allocation in life cycle assessments of seafood
production systems: review of problems and strategies. Int. J. Life Cycle
Assess. 2007, 12, 480−487.
(55) Gao, J.; You, F. Economic and Environmental Life Cycle
Optimization of Noncooperative Supply Chains and Product Systems:
Modeling Framework, Mixed-Integer Bilevel Fractional Programming
Algorithm, and Shale Gas Application. ACS Sustainable Chem. Eng.
2017, DOI: 10.1021/acssuschemeng.7b00002.
(56) Gao, J.; You, F. Shale Gas Supply Chain Design and Operations
toward Better Economic and Life Cycle Environmental Performance:
MINLP Model and Global Optimization Algorithm. ACS Sustainable
Chem. Eng. 2015, 3, 1282−1291.
(57) Allen, D. T. Methane emissions from natural gas production and
use: reconciling bottom-up and top-down measurements. Curr. Opin.
Chem. Eng. 2014, 5, 78−83.
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX