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Article
Manufacturing Ethylene from Wet Shale Gas and Biomass: Comparative
Techno-economic Analysis and Environmental Life Cycle Assessment
Minbo Yang, Xueyu Tian, and Fengqi You
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b03731 • Publication Date (Web): 12 Jan 2018
Downloaded from http://pubs.acs.org on January 12, 2018
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Page 1 of 43 Industrial & Engineering Chemistry Research
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4 1 Manufacturing Ethylene from Wet Shale Gas and Biomass:
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2 Comparative Techno-economic Analysis and Environmental Life
7 3 Cycle Assessment
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10 5 Minbo Yang, Xueyu Tian, Fengqi You*
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14 7 Robert Frederick Smith School of Chemical and Biomolecular Engineering, Cornell University,
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8 Ithaca, New York, 14853, USA
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20 10 Friday, January 12, 2018
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23 11 Submitted to Industrial & Engineering Chemistry Research for the special issue of PSE
24 12 Advances in Natural Gas Value Chain
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27 13 Abstract
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29 14 This paper presents comparative techno-economic and environmental analyses of three
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31 15 ethylene manufacturing pathways based on ethane-rich shale gas, corn stover, and corn grain.
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33 16 The shale gas-based pathway includes two processing steps, namely shale gas processing to
34 17 produce ethane and ethane steam cracking to manufacture ethylene. The two biomass-based
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36 18 pathways also contain two processing steps each, namely bioethanol production via fermentation
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38 19 and ethylene manufacturing via bioethanol dehydration. A distributed-centralized processing
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20 network that consists of distributed ethane/bioethanol production and centralized ethylene
41 21 manufacturing is employed for each of the three pathways. Detailed process simulation models
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43 22 are developed for major processing steps, and the three pathways are then modeled on five
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45 23 different ethylene production scales. Based on the detailed mass and energy balances and life
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24 cycle inventory results, we conduct techno-economic and life cycle analyses to systematically
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48 25 compare the economic and environmental performances of the three ethylene manufacturing
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50 26 pathways. The results indicate that the shale gas-based pathway is the most attractive due to the
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52 27 lowest breakeven ethylene prices ($0.32/kg~$1.67/kg); however, it leads to the highest
53 28 greenhouse gas emissions of about 1.4 kg CO2-eq/kg ethylene. On the contrary, the corn stover-
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56 *
Corresponding author. Phone: (607) 255-1162; Fax: (607) 255-9166; E-mail: fengqi.you@cornell.edu
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Industrial & Engineering Chemistry Research Page 2 of 43
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3 1 based pathway results in the lowest greenhouse gas emissions of around −1.0 kg CO2-eq/kg
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5 2 ethylene but the highest breakeven ethylene prices ($2.0/kg~$4.1/kg). Sensitivity analyses are
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7 3 performed to systematically investigate the influences of parameter deviations on the economic
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4 and environmental performances of the three ethylene manufacturing pathways.
10 5 Key words: shale gas, corn stover, corn grain, breakeven ethylene price, greenhouse gas
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12 6 emissions.
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15 7 1. Introduction
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17 8 Ethylene is the most important building block for the chemical industry.1 As a typical
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9 chemical feedstock, ethylene is widely used to produce polyethylene, glycol, vinyls, etc. Steam
20 10 cracking of hydrocarbons plays the most important role in the U.S. ethylene production. Among
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22 11 these hydrocarbons, ethane contributes about 67% of the total U.S. ethylene production in 2014.2
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24 12 In recent decades, advancements of hydraulic fracturing and horizontal drilling have resulted in a
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13 boom of the U.S. shale gas production,3-5 which provides a tremendous increase in the yield of
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27 14 ethane for ethylene production.6-7 Taking into account the non-renewability of fossil fuel-based
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29 15 feedstocks for ethylene production, dehydration of bioethanol derived from renewable biomass
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31 16 demonstrates significant potential for ethylene production.8-12 In the U.S., corn grain serves as
32 17 the leading feedstock for bioethanol production.13-14 Besides, producing bioethanol from
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34 18 cellulosic biomass, such as corn stover, is of increasing interest, as corn stover not only is an
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36 19 abundant agricultural residue but also can avoid controversy on food versus energy.15-16 Based on
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20 the aforementioned feedstocks (ethane-rich shale gas, corn stover, and corn grain),
39 21 manufacturing ethylene may result in different economic performances and environmental
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41 22 impacts. For judicious selection of feedstocks for ethylene production, it is necessary to
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43 23 systematically compare ethylene manufacturing from these feedstocks under the same conditions
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24 from economic and environmental perspectives.
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46 25 Shale gas has been of great research interest in recent years. Several contributions address
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48 26 the process design and synthesis of ethylene production from shale gas. Three process designs
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50 27 integrating shale gas processing and ethane steam cracking were proposed to increase the overall
51 28 energy efficiency and profitability.17 Salkuyeh and Adams proposed a polygeneration process to
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53 29 co-produce ethylene and electricity from shale gas via methane oxidative coupling.18 Towards
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55 30 more cost-effective and greener ethylene production, an integrated process design considering
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3 1 methane oxidative coupling, stream cracking of ethane and propane, and bioethanol dehydration
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5 2 was developed.19 Besides, costs and environmental impacts of mega-scale shale gas-based
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7 3 ethylene production in the U.S. major shale plays were studied,20 and a comparative techno-
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4 economic and environmental analysis was performed for manufacturing ethylene and propylene
10 5 from shale gas and naphtha.21 In addition to producing ethylene, shale gas also serves as the
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12 6 feedstock for the production of syngas,22 methanol,23-25 hydrogen, liquid fuels,26 and other light
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14 7 olefins.27 Optimization models associated with shale gas supply chain were proposed for water
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8 management,28-29 uncertainty handling,30 and optimal supply chain design,31-32 Moreover, several
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17 9 life cycle analysis (LCA) studies were performed for shale gas regarding greenhouse gas (GHG)
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19 10 emissions,33-34 water consumption,35 and energy consumption.36
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21 11 There are some publications related to ethylene manufacturing via dehydration of ethanol
22 12 derived from biomass. McAloon et al. performed techno-economic analyses to evaluate and
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24 13 compare costs for producing bioethanol from corn stover and corn grain.37 Later, Wallace et al.
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26 14 studied the co-location and integration of bioethanol production from corn grain and corn
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15 stover.38 A detailed process design for manufacturing bioethanol from corn stover was presented,
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29 16 and the economics of bioethanol production was evaluated.39 Recently, Mohsenzadeh et al.
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31 17 investigated the economic performance of manufacturing ethylene from bioethanol.40 However,
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33 18 the economics of manufacturing ethylene from corn stover and corn grain are not explored, since
34 19 these existing analyses are conducted under different economic conditions and do not
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36 20 simultaneously consider bioethanol production and ethylene manufacturing. Other researchers
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38 21 have examined the life cycle environmental impacts of ethylene manufacturing from biomass.
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22 Hong et al. performed a life cycle assessment to estimate the environmental impacts of corn-
41 23 based and cassava-based ethylene production in China.41 Besides, environmental impacts of
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43 24 ethylene produced from sugar cane, corn grain, corn stover, and naphtha were analyzed and
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45 25 compared.42 Existing publications cover environmental life cycle analyses of ethylene
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26 manufactured from shale gas,20-21 corn stover, and corn grain.41-42 Nevertheless, the results of
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48 27 these LCA studies suffer from lack of comparability, because these studies serve different
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50 28 purposes with distinct temporal and geographical scopes, methods, and system boundaries.43 To
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52 29 the best of our knowledge, there is no existing publication addressing the systematic comparison
53 30 of ethylene manufacturing based on ethane-rich shale gas, corn stover, and corn grain under the
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55 31 same conditions from both economic and environmental perspectives.
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3 1 In this work, we perform comparative techno-economic and environmental life cycle
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5 2 analyses of three ethylene production pathways based on ethane-rich shale gas, corn stover, and
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7 3 corn grain. In the shale gas-based pathway, raw shale gas is first processed to produce ethane,
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4 which is then cracked to manufacture ethylene. In the two biomass-based pathways, bioethanol is
10 5 produced from corn stover and corn grain by means of ethanol fermentation first. The resulting
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12 6 bioethanol is then converted to ethylene via ethanol dehydration. We consider a distributed-
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14 7 centralized processing network that combines distributed ethane/bioethanol production with
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8 centralized ethylene manufacturing for the three pathways. High-fidelity process simulation
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17 9 models are developed for processing steps including shale gas processing, ethane steam cracking
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19 10 to ethylene, and bioethanol dehydration to ethylene. The three ethylene production pathways are
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21 11 modeled considering five different ethylene production scales. Next, we conduct techno-
22 12 economic and environmental life cycle analyses for the three ethylene production pathways. The
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24 13 economic performances of the three ethylene production pathways are compared in terms of
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26 14 breakeven ethylene prices. The life cycle environmental impacts of ethylene manufactured via
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15 the three pathways are compared in terms of GHG emissions, which are of special interest in
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29 16 both academia and industry.44-46 Finally, sensitivity analyses are performed for the three ethylene
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31 17 production pathways to investigate the influences of parameter deviations.
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33 18 The rest of the paper is organized as follows. The overall description of the three pathways
34 19 and corresponding process models are presented in Section 2. Section 3 provides results of
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36 20 process simulation, economic analyses, and environmental analyses. The conclusion is given in
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38 21 Section 4.
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41 22 2. Process Description
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43 23 The three ethylene manufacturing pathways based on ethane-rich shale gas, corn stover, and
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24 corn grain are introduced in detail. Besides, we present the distributed-centralized processing
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46 25 network considered for manufacturing ethylene from ethane-rich shale gas, corn stover, and corn
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48 26 grain.
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50 27 2.1. Shale Gas-based Ethylene Production
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52 28 In this study, raw shale gas from the Marcellus shale play is analyzed for ethylene
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54 29 production, because shale gas produced in this region arouses great interest in ethylene
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30 manufacturing.47 The composition of raw shale gas considered in this study is given in Error!
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3 1 Reference source not found. in the supporting information. Figure 1 shows the block flow
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5 2 diagram of the shale gas-based ethylene production pathway, which consists of two processing
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7 3 steps, namely, shale gas processing to produce ethane and ethane steam cracking to manufacture
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4 ethylene.
10 5 In the shale gas processing step, raw shale gas is first pressurized to satisfy the downstream
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12 6 operating conditions and maximize the recovery of natural gas liquids (NGLs).48 The pressurized
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14 7 shale gas is then introduced into an acid gas removal unit to remove acid components. In the
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8 following dehydration unit, the water content in shale gas is reduced to prevent hydrate
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17 9 formation. Next, the obtained dry gas is sent to a cryogenic separation unit to recover NGLs. The
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19 10 resulting methane-rich gas is compressed and sent out as pipeline gas. The recovered mixture of
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21 11 NGLs is fractionated into ethane, propane, butanes, and natural gasoline in an NGLs
22 12 fractionation unit.
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24 13 In the ethylene production step, ethane derived from shale gas is cracked in cracking
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26 14 furnaces first. The cracking gas from furnaces is then quenched and pressurized. Finally, in an
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15 ethylene purification unit, the cracking gas is separated into ethylene, ethane, and other
29 16 byproducts. Details of each unit are introduced in the rest of this subsection.
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54 18 Figure 1. Block flow diagram for manufacturing ethylene from ethane-rich shale gas.
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3 1 The process flowsheets for the processing of raw shale gas are shown in Figure 2. As
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5 2 depicted in Figure 2(a), raw shale gas is first pressurized to meet downstream operating
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7 3 conditions by compressors (K-101 and K-102) with coolers (E-101 and E-102) to control the
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4 temperature. As given in Error! Reference source not found., the raw shale gas contains some
10 5 carbon dioxide, which may cause solids formation and device corrosion for the shale gas
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12 6 processing system.49 Thus, a monoethanolamine (MEA)-based absorption unit is employed for
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14 7 acid gas removal, because MEA has the advantage of a high solution capacity at moderate
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8 concentrations,48 as shown in Figure 2(b). The compressed shale gas is fed into an absorber (T-
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17 9 201) from the bottom and contacts with a lean MEA solution from the top. After being
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19 10 depressurized, flashed, and preheated, the rich MEA solution from the bottom of absorber T-201
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21 11 is sent into a stripper (T-202), where carbon dioxide in the rich MEA solution is stripped off.
22 12 Along with makeup water and MEA, the regenerated MEA solution is pumped back to absorber
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24 13 T-201 after being cooled down. Since amine treating is used for acid gas removal, the resulting
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26 14 sweet gas is water-saturated.48 Water in the sweet gas must be reduced to avoid undesired
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15 hydrate formation in the following cryogenic separation process. As demonstrated in Figure 2(c),
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29 16 a triethylene glycol (TEG)-based dehydration unit is adopted for water removal. The sweet gas
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31 17 enters the bottom of a glycol contactor (T-301), where it contacts with lean glycol and leaves as
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33 18 dry gas. The rich glycol from the contactor bottom flows through a valve and a flash tank to
34 19 release dissolved gas. After being preheated, the rich glycol is introduced into a TEG regenerator
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36 20 (T-302). The lean glycol from the bottom of regenerator T-302 is further purified in a stripper
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38 21 (T-303), which uses a small portion of dry gas from contactor T-301 as stripping gas. Mixed with
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22 makeup TEG, the regenerated TEG is finally pumped back to contactor T-301 after being cooled
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43 24 After dehydration, a cryogenic separation unit is used to recover NGLs from shale gas, as
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45 25 exhibited in Figure 2(d). The dry shale gas is cooled in a series of heat exchangers (E-401 to E-
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26 406) and pre-separated in two-phase separators (V-401, V-402, and V-403), before entering a
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48 27 demethanizer (T-401). The gas product from separator V-403 flows through an expander (EX-
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50 28 401) to reduce its temperature to lower than −90ºC. In the demethanizer (T-401), NGLs are
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52 29 recovered from shale gas and a methane-rich gas product is obtained from the top. The methane-
53 30 rich gas serves as a coolant in heat exchangers E-406, E-404, and E-401, and it is subsequently
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55 31 compressed and piped out as sales gas, as shown in Figure 2(e). Note that in the NGLs recovery
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3 1 unit, a compression refrigeration system using propylene as refrigerant is employed to provide
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5 2 cold utility at −40ºC to heat exchanger E-403. The liquid product from the bottom of
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7 3 demethanizer T-401 is a mixture of NGLs, and this stream is fed into an NGLs fractionation unit,
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4 which contains three distillation columns, namely, a deethanizer (T-603), a depropanizer (T-601),
10 5 and a debutanizer (T-602), as depicted in Figure 2(f). Leveraging these distillation columns, the
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12 6 mixture of NGLs is finally separated into ethane, propane, butanes, and natural gasoline. Note
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14 7 that the propylene refrigerant also serves as coolants at −40ºC and 0ºC in condensers of the
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44 2 Figure 2. Process flowsheets of shale gas processing. (a) inlet compression; (b) acid gas removal;
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47 4 Figure 3 shows the process flowsheets for the production of ethylene via ethane steam
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49 5 cracking. In the ethane steam cracking unit depicted in Figure 3(a), ethane produced from shale
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51 6 gas is fed to cracking furnaces with dilution steam at a mass-based ratio of 1:0.4.50 In the
52 7 convection section of a cracking furnace, ethane and dilution steam are preheated to about
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54 8 680ºC.50 Next, ethane enters the radiant section of the cracking furnace, where it is thermally
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56 9 cracked into small molecules, including ethylene, hydrogen, methane, etc. In this work, a
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3 1 cracking furnace is modeled as a plug flow reactor combined with heaters.19, 51 The kinetic model
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5 2 for ethane steam cracking is given in Error! Reference source not found. in the supporting
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7 3 information. The cracking gas from a cracking furnace enters a transfer-line exchanger (E-701)
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4 to generate high pressure (HP) steam at 12 MPa,37 which is then super-heated in the convection
10 5 section of the cracking furnace. After further heat recovery in a heat exchanger (E-702), the
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12 6 cracking gas is sent to a quench water tower (T-701) to finally reduce its temperature to 40°C, as
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14 7 demonstrated in Figure 3(b). In the next step, the cracking gas is pressurized to 3.7 MPa by a
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8 five-stage compressor with intercoolers to control the temperature of cracking gas lower than
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17 9 100°C.1 Acid components in the cracking gas are removed by sodium hydroxide in a caustic
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19 10 tower before the fourth stage compression, and water content in the cracking gas is reduced in a
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21 11 molecular sieve dryer.
22 12 After dehydration, the cracking gas is introduced into an ethylene purification unit, as
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24 13 depicted in Figure 3(c). The cracking gas is precooled in heat exchangers (E-801 to E-808) and
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26 14 pre-separated in separators (V-801 to V-804). The gas product from separator V-804 mainly
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15 containing methane and hydrogen is further cooled in a heat exchanger (E-809) and then
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29 16 separated in a separator (V-805). All liquid products from separators V-801, V-802, V-803, and
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31 17 V-804 are fed to a demethanizer (T-801), where methane in those liquid products is removed.
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33 18 The methane-rich products from the top of column T-801 and the bottom of separator V-805, as
34 19 well as the hydrogen-rich product from the top of separator V-805, serve as coolants to cool
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36 20 down the cracking gas. With the help of a deethanizer (T-802) and a depropanizer (T-803), the
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38 21 methane-free liquid product from the bottom of column T-801 is separated into a C2 mixture, a
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22 C3 mixture, and a C4 mixture. The C2 mixture is fed to a C2 splitter (T-804) after acetylene is
41 23 hydrogenated in a reactor (R-801). Polymer-grade ethylene (99.9% purity) is drawn from the
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43 24 ninth tray of splitter T-804. An ethylene-rich stream is obtained from the top of splitter T-804,
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45 25 and it enters a cooler (E-813) to reduce the amount of gas to be recompressed. After heat
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26 recovery, the unreacted ethane from the bottom of splitter T-804 is fed to cracking furnaces. The
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48 27 C3 mixture is introduced into a C3 splitter (T-805), where heavy impurities are removed from the
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50 28 bottom and polymer-grade propylene (99.5% purity) is obtained from the top. Note that the
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52 29 bottom product of splitter T-805 and the methane-rich products from column T-801 and
53 30 separator V-805 are consumed as fuel for cracking furnaces. In the ethylene purification unit,
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55 31 three compression refrigeration systems using propylene, ethylene, and methane, respectively, as
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3 1 refrigerants are employed to provide cold utilities at different temperatures depending on the
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5 2 process requirements.1, 52 Power for all compressors are provided by steam turbines driven by the
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49 5 Figure 3. Process flowsheets for manufacturing ethylene via the steam cracking of ethane. (a)
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52 7 2.2. Corn Stover-based Ethylene Production
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54 8 The block flow diagram for manufacturing ethylene from corn stover is depicted in Figure 4.
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56 9 This process consists of two processing steps: bioethanol production from corn stover and
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3 1 ethylene production from bioethanol.
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5 2 In the bioethanol production step, corn stover is first delivered to a feed handling unit
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7 3 consisting of weighing and uploading stations, queuing storage, and conveyors. In the following
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4 pretreatment and conditioning unit, corn stover is pretreated with dilute sulfuric acid to liberate
10 5 hemicellulose sugars and break down biomass, and ammonia is then added to the pretreated
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12 6 slurry to adjust its acidity to be suitable for enzymatic hydrolysis. Next, the resulting hydrolysate
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14 7 is sent to an enzymatic hydrolysis and fermentation unit, where a cellulase enzyme is used for
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8 enzymatic hydrolysis. The hydrolyzed slurry is then fermented to convert cellulose and xylose
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17 9 into bioethanol. The required cellulase enzyme is produced on-site in an enzyme production unit
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19 10 using glucose as the primary carbon source. In a production recovery section, the resulting beer
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21 11 is separated into bioethanol, water, and residual solids via distillation and solid-liquid separation.
22 12 Wastewater streams generated during bioethanol production are gathered and treated by
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24 13 anaerobic and aerobic digestion in a wastewater treatment unit. Solids and biogas from product
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26 14 recovery unit and wastewater treatment unit are combusted to produce HP steam, which is used
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15 to generate electricity and satisfy the process heat demand. Detailed process flowsheets for the
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29 16 production of bioethanol from corn stover are available in the literature.39
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31 17 In the ethylene production step, bioethanol derived from corn stover is first dehydrated into
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33 18 ethylene, water, and other byproducts. Next, the dehydration reactor effluent is quenched and
34 19 pressurized. Finally, the effluent is sent to an ethylene purification unit, where it is separated into
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36 20 ethylene, water, and others. Details of each unit in the ethylene production step are presented
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38 21 below.
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4 Figure 5 illustrates the process flowsheets of bioethanol dehydration to ethylene. Firstly,
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39 5 bioethanol is pumped to 1.2 MPa and preheated in a heat exchanger (E-902), as shown in Figure
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41 6 5(a). Afterwards, bioethanol is diluted with steam at a mass-based ratio of 1:1. The resulting
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43 7 mixture is heated to 450°C in a fired heater (FH-901) and then enters an adiabatic reactor (R-
44 8 901). The reaction scheme for bioethanol dehydration is given in Error! Reference source not
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46 9 found. in the supporting information. Since the ethanol dehydration reaction is endothermic,
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48 10 only a limited proportion of bioethanol can be converted into ethylene and water under an
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11 adiabatic condition.40 To achieve a high bioethanol conversion, the bioethanol dehydration unit
51 12 employs four adiabatic reactors.53 After recovering heat in heat exchangers (E-901 and E-902),
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53 13 the effluent from reactor R-904 is introduced into a quench water column (T-1001) to finally
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55 14 reduce its temperature to 40°C, as demonstrated in Figure 5(b). Most of the water in the reactor
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3 1 effluent is condensed and recovered from the bottom of column T-1001. The gas product from
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5 2 the top of column T-1001 is then pressurized to 2.7 MPa via a three-stage compressor.
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7 3 Subsequently, carbon dioxide and the remaining water in the gas product are removed by sodium
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4 hydroxide in a caustic tower and a molecular sieve dryer, respectively.
10 5 After removing water, the resulting gas product is introduced in an ethylene purification unit,
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12 6 as depicted in Figure 5(c). The gas product is first cooled to −20°C via two heat exchangers (E-
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14 7 1101 and E-1102), and its temperature is further reduced by expansion. Next, impurities in
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8 ethylene are removed by two distillation columns (T-1101 and T-1102). Heavy impurities in
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17 9 ethylene are removed from the bottom of column T-1101, and light impurities in ethylene are
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19 10 removed from the top of column T-1102. These two streams are used as fuel in fired heaters to
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21 11 reduce the demand of external fuel. Finally, polymer-grade ethylene is obtained from the bottom
22 12 of column T-1102. In the ethylene purification unit, a compression refrigeration system using
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24 13 propylene as refrigerant is employed to provide cold utilities at 5°C, −25°C and −40°C to satisfy
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26 14 the process demands.
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53 16 Figure 5. Process flowsheets for manufacturing ethylene via bioethanol dehydration. (a)
54 17 bioethanol dehydration; (b) quench and compression; (c) ethylene purification.
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1 2.3. Corn Grain-based Ethylene Production
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5 2 Figure 6 shows the block flow diagram of corn grain-based ethylene production consisting
6
7 3 of two processing steps, i.e., bioethanol production from corn grain and ethylene production
8
9 4 from bioethanol.
10 5 In the bioethanol production step, corn is first conveyed to grain-cleaning equipment and
11
12 6 then milled to fine meal by hammer mills. Next, the corn meal is sent to a liquefaction unit,
13
14 7 where it is mixed with water and alpha-amylase. Also, caustic and lime are added to provide
15
16
8 suitable acidity and calcium for the alpha-amylase, and urea is consumed to supply nitrogen for
17 9 the downstream yeast fermentation. Maltose and higher oligomers are produced from corn starch
18
19 10 using the alpha-amylase enzyme in the liquefaction unit. The resulting mash is introduced into a
20
21 11 saccharification unit and mixed with gluco-amylase and sulfuric acid to create sugars. After
22
12 saccharification, the mash is cooled and then fed to four continuous cascade fermenters with
23
24 13 yeast added. Bioethanol and carbon dioxide are produced during the yeast fermentation. In a
25
26 14 product recovery unit, bioethanol is obtained from the whole beer by distillation, scrub, and
27
28 15 dehydration. The conserved stillage is partially evaporated and then fed to a centrifugation unit.
29 16 A part of the thin stillage from the centrifugation unit is recycled as backset to the liquefaction
30
31 17 unit, and the rest is concentrated to syrup in the following evaporation unit. Finally, the wet
32
33 18 grains from the centrifugation unit and the syrup from the evaporation unit are dried and sent out
34
35
19 as distiller’s dried grains with solubles (DDGS). Detailed information for the production of
36 20 bioethanol from corn grain can be found from the literature.38, 54 The ethylene production step in
37
38 21 the corn grain-based pathway is the same as that in the corn stover-based pathway described in
39
40 22 the previous subsection.55-57
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
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59 14
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33 1
34 2 Figure 6. Block flow diagram for manufacturing ethylene from corn grain.
35
36
37 3 2.4. Distributed-centralized Processing Network for Ethylene Production
38
4 Shale gas reserves and corn farms are usually geographically distributed.58-59 Typically,
39
40 5 shale gas processing and bioethanol production from corn stover and corn grain take place at
41
42 6 plants located in the corresponding feedstock production regions.59-61 Besides, to accommodate
43
44 7 the ethane/bioethanol demand for ethylene production on commercial scales, an ethylene plant is
45 8 often supplied with feedstock from several suppliers (shale gas processing plants or bioethanol
46
47 9 plants).20, 62 Therefore, we consider a distributed-centralized processing network that combines
48
49 10 distributed ethane/bioethanol production with centralized ethylene manufacturing for the three
50
51
11 pathways,63-64 as shown in Figure 7. Error! Reference source not found. in the supporting
52 12 information provides data associated with the production of raw shale gas, corn stover, and corn
53
54 13 grain.
55
56 14 In the distributed-centralized processing network for manufacturing ethylene from shale gas,
57
58
59 15
1
2
3 1 we assume that ethane is first produced at several distributed shale gas processing plants and
4
5 2 transported to a centralized ethane cracking plant by trucks, as depicted in Figure 7(a). In the
6
7 3 typical shale gas production process, multiple shale gas wells are drilled at a well pad.65 Raw
8
9
4 shale gas extracted from shale gas wells is gathered at a well pad and transported to a nearby gas
10 5 processing plant by pipelines. To estimate the raw shale gas transportation distance, we assume
11
12 6 that a shale gas processing plant is located at the center of a large square area and each well pad
13
14 7 is located at the center of a smaller square area making up the large square area,13 as shown in
15
8 Figure 7(a). The minimum number of well pads in the square area can be determined based on
16
17 9 the estimated ultimate recovery (EUR) of a well and raw shale gas required by a gas processing
18
19 10 plant. The side length of the square area can be estimated based on the well spacing and the
20
21 11 number of well pads in the square area. In the square area, the shale gas transportation distance
22
23
12 from a well pad p with location of ( x p , y p ) to a shale gas processing plant with location of
24
25 13 (xplant , yplant ) can be estimated by Equation (1). The average distance for transporting ethane to the
26
27 14 centralized ethane cracking plant is assumed to be 100 km in this study.41
28
29
(x − x plant ) + ( y p − y plant )
2 2
30 15 Lp, plant = τ ⋅ p (1)
31
32 16 where Lp,plant is the distance between the well pad p and the central plant, and τ is the tortuosity
33
34
17 factor assumed to be 1.2 on average.20
35 18 The distributed-centralized processing network is also employed for manufacturing ethylene
36
37 19 from corn stover and corn grain. Bioethanol is first produced at several distributed ethanol plants,
38
39 20 and then transported to a centralized ethylene plant by trucks, as shown in Figure 7(b). A square
40
21 area is assumed around a bioethanol plant, which consumes biomass produced in the square area.
41
42 22 The average biomass transportation distance to a bioethanol plant is estimated as the average
43
44 23 distance from a random point in the square area to the center of the square area, as given by
45
46 24 Equation (2).66 Similarly, the average bioethanol transportation distance to the centralized
47 25 ethylene plant is assumed to be 100 km as well.41
48
49
50
51
26
1
Lbiomass , plant = τ ⋅
6
F
Y
⋅ ( 2 + ln(1 + 2) ) (2)
52
53 27 where Lbiomass,plant is the average biomass transportation distance, F is the annual biomass input of
54 28 a bioethanol plant, and Y is the annual biomass yield per square mile.
55
56
57
58
59 16
1
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5
6
7
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22 1
23
24 2 Figure 7. Distributed-centralized processing networks for manufacturing ethylene from ethane-
25 3 rich shale gas, corn stover, and corn grain.
26
27 4
28
29 5 In summary, three ethylene manufacturing pathways are considered in this study. The shale
30
31
6 gas-based pathway includes two processing steps: shale gas processing and ethylene
32 7 manufacturing. Each of the two biomass-based pathways also contains two processing steps:
33
34 8 bioethanol production and ethylene manufacturing. We consider a distributed-centralized
35
36 9 processing network that combines distributed shale gas processing/bioethanol production with
37
10 centralized ethylene manufacturing for each of the three pathways. On this basis, techno-
38
39 11 economic and environmental analyses are conducted for ethylene manufacturing via the three
40
41 12 pathways to systematically evaluate and compare the economic and environmental performances
42
43 13 of different pathways.
44
45
46 14 3. Techno-economic and Life Cycle Analyses Results
47
48
15 For systematic comparisons, we consider five different ethylene production scales for each
49 16 pathway, namely, 1,000 kt/yr, 800 kt/yr, 600 kt/yr, 400 kt/yr, and 200 kt/yr, according to
50
51 17 commercial capacities of ethylene plants.43, 47
In terms of the distributed ethane/bioethanol
52
53 18 production, on each ethylene production scale, three cases are analyzed considering different
54 19 numbers of distributed shale gas processing/bioethanol plants, i.e. 5, 10, and 15. Therefore, 45
55
56 20 ethylene production cases are investigated in this work. We assume the distributed shale gas
57
58
59 17
1
2
3 1 processing plants and the bioethanol plants have the same capacity, which is determined by
4
5 2 dividing the total ethane/bioethanol demand of the centralized plant by the total number of the
6
7 3 distributed plants. The main objective of this work is to compare the three ethylene production
8
9
4 pathways from the economic and environmental perspectives. Social issues related to the use of
10 5 corn for food or fuels production are considered beyond the scope of the current study.
11
12
13
6 3.1. Mass and Energy Balances
14 7 The process designs for shale gas processing, ethylene production via ethane steam cracking,
15
16 8 and ethylene production via bioethanol dehydration are modeled in Aspen HYSYS. Detailed
17
18 9 operating parameters of important distillation columns can be found in the supporting
19
20
10 information. The corresponding mass and energy balance information of each unit is determined
21 11 by HYSYS simulation. As for bioethanol production from corn stover and corn grain, the mass
22
23 12 and energy balances are extracted from existing literature.38-39, 67 We assume that the mass and
24
25 13 energy balances are directly proportional to the ethylene production scale, as in the existing
26
14 literature.38 The plant-level mass and energy balances for manufacturing ethylene via the three
27
28 15 pathways on the ethylene production scale of 1,000 kt/yr are summarized in Table 1. Note that
29
30 16 the operating time is assumed to be 8,000 hours per year.
31
32 17 For manufacturing ethylene from ethane-rich shale gas, 835.5 MMSCFD (million standard
33 18 cubic feet per day) of raw shale gas is consumed to accommodate the ethylene production of
34
35 19 1,000 kt/yr. The shale gas processing step generates multiple products, including sales gas,
36
37 20 ethane, propane, butanes, and natural gasoline. Among these products, sales gas is the main
38
21 product and occupies approximately 61.1% of the total energy output, while ethane only takes
39
40 22 about 17.5% of the total energy output. At the ethylene production step, ethylene is the major
41
42 23 product in terms of mass flows. The ethane steam cracking results in an ethylene yield of 78.1 wt%
43
44 24 of the ethane input.
45 25 The corn stover-based pathway consumes 816.2 t/h of corn stover to meet the ethylene
46
47 26 production scale of 1,000 kt/yr. At the bioethanol production step, bioethanol and electricity are
48
49 27 co-produced. The bioethanol production step results in a bioethanol yield of 26.2 wt% of the
50
51
28 corn stover input and generates 164 kWh of electricity based on 1 tonne of corn stover
52 29 consumption. At the ethylene production step, the bioethanol dehydration results in an ethylene
53
54 30 yield of 58.4 wt% of the bioethanol input.
55
56 31 When it comes to ethylene manufacturing from corn grain, 669.9 t/h of corn grain is
57
58
59 18
1
2
3 1 consumed to reach the ethylene production rate of 1,000 kt/yr. The bioethanol production step
4
5 2 shows a bioethanol yield of 31.9 wt% of the corn grain input. Besides, DDGS are co-produced
6
7 3 with a slightly higher mass flow rate than bioethanol. The ethylene production step in the corn
8
9
4 grain-based pathway is the same as that in the corn stover-based pathway.
10 5 Comparing the ethylene production steps in the three ethylene production pathways, more
11
12 6 bioethanol is consumed than ethane in terms of mass flows to meet the ethylene production scale
13
14 7 of 1,000 kt/yr. This is because ethane stream cracking could result in higher ethylene yields
15
8 compared with bioethanol dehydration. However, we find that producing ethylene via ethane
16
17 9 stream cracking leads to higher fuel consumption than via bioethanol dehydration. This is
18
19 10 because the reaction condition of ethane steam cracking is much tougher than that of ethanol
20
21 11 dehydration in terms of operating temperatures and energy consumption.1 Compared with the
22 12 separation of hydrogen and hydrocarbons from the cracking gas, the removal of water from the
23
24 13 ethanol dehydration reactor effluent is much easier. Therefore, producing ethylene via bioethanol
25
26 14 dehydration consumes less power than via ethane stream cracking for gas compression and
27
15 refrigerant generation, as shown in Table 1.
28
29
30
31
32
33
34
35
36
37
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59 19
1
2
3 1 Table 1. Plant-level mass and energy balances of manufacturing ethylene from ethane-rich shale
4
2 gas, corn stover, and corn grain. MP and LP are short for medium pressure and low pressure.
5
6
7 Shale gas-based pathway Corn stover-based pathway Corn grain-based pathway
8 Shale gas processing Bioethanol production Bioethanol production
9 Input Input Input
10 Raw shale gas (MMSCFD) 835.5 Corn stover (t/h) 816.2 Corn grain (t/h) 669.9
11 MEA (kg/h) 35.4 Sulfuric acid, 93% (t/h) 19.4 NaOH (kg/h) 3,340.5
12 TEG (kg/h) 5.9 Ammonia (t/h) 11.4 Alpha-amylase (kg/h) 466.0
13 Output Corn steep liquor (t/h) 13.0 Gluco-amylase (kg/h) 673.1
14 Sales gas (MMBTU/h) 27,513.4 Diammonium phosph (t/h) 1.4 Sulfuric acid (kg/h) 1,329.0
15 (t/h) 160.0 Glucose (t/h) 23.7 Lime (kg/h) 794.1
16 Ethane
(MMBTU/h) 7884.9 Host nutrients (kg/h) 659.7 Urea (kg/h) 1,329.0
17 Propane (MMBTU/h) 4,559.5 Sulfur dioxide (kg/h) 160.8 Yeast (kg/h) 125.6
18
Butanes (MMBTU/h) 2,463.2 NaOH (t/h) 22.1 Output
19
Natural gasoline (MMBTU/h) 2,576.5 Boiler chemicals (kg/h) 2.4 Ethanol (t/h) 214.0
20
CO2 emissions (kg/h) 2,732.7 Lime (t/h) 8.8 DDGS (t/h) 221.1
21
Utilities Cooling tower chemicals (kg/h) 23.4 Utilities
22
23 Power (MW) 146.5 Output Power (MW) 57.2
24 HP steam (GJ/h) 4.4 Ethanol (t/h) 214.0 Natural gas (MMBTU/h) 2,297.9
25 MP steam (GJ/h) 255.4 Electricity (MW) 133.9 Makeup water (t/h) 1,422.1
26 LP steam (GJ/h) 256.6 Utilities Cooling water (t/h) 6,173.3
27 Makeup water (t/h)
188.7
Makeup water (t/h)
1,441.
28 2
29 Cooling water (GJ/h) 1,032.6
30 Ethylene production Ethylene production Ethylene production
31 Input Input Input
32 Ethane (t/h) 160.0 Ethanol (t/h) 214.0 Ethanol (t/h) 214.0
33 NaOH (kg/h) 56.1 NaOH (kg/h) 562.5 NaOH (kg/h) 562.5
34 Output Output Output
35 Ethylene (t/h) 125.0 Ethylene (t/h) 125.0 Ethylene (kt/h) 125.0
36 Propylene (t/h) 1.3 CO2 emissions (t/h) 37.6 CO2 emissions (t/h) 37.6
37 Crude C4 (t/h) 12.3 Utilities Utilities
38
Hydrogen (t/h) 11.9 Natural gas (MMBTU/h) a 693.6 Natural gas (MMBTU/h) a 693.6
39
CO2 emissions (t/h) 117.0 Power (MW) 28.8 Power (MW) 28.8
40
Utilities Makeup water (t/h) 407.0 Makeup water (t/h) 407.0
41
42 Natural gas (MMBTU/h) a 2,254.1 Cooling water (GJ/h) 462.2 Cooling water (GJ/h) 462.2
43 Power (on-site) (MW) 85.8
44 Makeup water (t/h) 1,249.3
45 Cooling water (GJ/h) 1,367.5
a
46 3 Natural gas consumed in the three ethylene production stages is assumed bought from suppliers
47
48 4 from the U.S. market for a fair comparison.
49
50 5 3.2. Economic Analysis
51
52 6 The techno-economic analyses are conducted for the 45 case studies to evaluate and
53
54 7 compare the economic performances of the three ethylene production pathways. Input
55 8 parameters and assumptions for the techno-economic analyses are listed in Error! Reference
56
57
58
59 20
1
2
3 1 source not found. in the supporting information.
4
5 2 3.2.1. Capital Investment
6
7 3 Aspen Process Economic Analyzer is employed to estimate the capital investments
8
9 4 associated with shale gas processing, ethylene production via ethane steam cracking, and
10
5 ethylene production via bioethanol dehydration on different scales. Besides, the capital
11
12 6 investments for bioethanol production from corn stover and corn grain are estimated based on
13
14 7 literature.38-39, 67 The bare-module cost of each equipment unit can be estimated according to
15
16 8 Equation (3).68-69 The total bare-module investment is the sum of the bare-module costs of all
17 9 equipment units, as given by Equation (4).
18
β
19  Capacityi   CEPCI 
20 10 C BM ,i = C base
BM ,i ⋅ base 
⋅ base 
(3)
21  Capacityi   CEPCI 
22
23 11 CTBM = ∑ CBM ,i (4)
24 i
25 base
26 12 where CBM,i is the bare-module cost of the equipment unit i, CBM ,i is the bare-module cost of the
27
28 13 equipment unit i in the base case, Capacityi is the capacity of the equipment unit i, Capacityibase is
29
30 14 the capacity of the equipment unit i in the base case, β is the cost scale factor, CEPCI is the
31
32 15 current cost index, CEPCIbase is the cost index in the base case, and CTBM is the total bare-module
33
16 investment.
34
35 17 The total depreciable capital CTDC can be evaluated as a percentage of the total bare-module
36
37 18 investment, as shown in Equation (5),68 where tdcc is the total depreciable capital coefficient.
38
39 19 CTDC = tdcc ⋅ CTBM (5)
40
41 20 Based on the total depreciable capital, the total permanent investment CTPI is estimated by
42
43
21 Equation (6), where tpic is the total permanent investment coefficient.
44 CTPI = tpic ⋅ CTDC
22 (6)
45
46
23 The total capital investment CTCI is estimated as the sum of the total permanent investment
47
48 24 and working capital, as shown in Equation (7), where wcc is the working capital coefficient.
49
50 25 CTCI = CTPI + wcc ⋅ CTPI (7)
51
52 26 The total capital investments for manufacturing ethylene via the three pathways are
53
54 27 evaluated and compared in Figure 8. For manufacturing ethylene from ethane-rich shale gas,
55
28 capital investments associated with shale gas transportation, shale gas processing, and ethylene
56
57
58
59 21
1
2
3 1 production via ethane steam cracking are estimated. As aforementioned, on each scale of
4
5 2 ethylene production, three cases based on 5, 10, and 15 distributed shale gas processing plants
6
7 3 are considered to meet the given ethylene production rate. Note that on each ethylene production
8
9
4 scale, more distributed shale gas processing plants imply a smaller capacity of each plant. As
10 5 shown in Figure 8, the capital investment in shale gas transportation decreases as the number of
11
12 6 distributed shale gas processing plants increases. This is because shale gas processing plants with
13
14 7 smaller capacities result in shorter distances for shale gas transportation. Nevertheless, due to the
15
8 economy of scale, more distributed shale gas processing plants lead to higher capital investments
16
17 9 in shale gas processing, as well as higher total capital investments. Additionally, we find that the
18
19 10 contribution of distributed shale gas processing plants to the total capital investments becomes
20
21 11 significant as the ethylene production scale decreases and the number of distributed shale gas
22 12 processing plants increases.
23
24 13 The total capital investment for manufacturing ethylene from corn stover is determined by
25
26 14 bioethanol production and ethylene production via bioethanol dehydration. As demonstrated in
27
15 Figure 8, the capital investment in bioethanol production increases notably as the number of
28
29 16 distributed bioethanol plants increases. The total capital investments on all the considered
30
31 17 ethylene production scales are dominated by bioethanol production from corn stover, and the
32
33 18 centralized ethylene plant contributes less than 5% of the total capital investments.
34 19 For manufacturing ethylene from corn grain, the total capital investment is also determined
35
36 20 by bioethanol production and ethylene production via bioethanol dehydration. We find that more
37
38 21 distributed bioethanol plants result in higher total capital investments. Also, bioethanol
39
40
22 production from corn grain dominates the total capital investments on all the considered ethylene
41 23 production scales, contributing over 84% of the total capital investments.
42
43 24 Compared with manufacturing ethylene from ethane-rich shale gas, manufacturing ethylene
44
45 25 from corn stover results in much higher total capital investments by 83%~186%, because of the
46
26 considerable high capital investments in bioethanol production. Besides, producing bioethanol
47
48 27 from corn stover requires much higher capital investments than from corn grain, because of the
49
50 28 high investments in the feedstock handling section, pretreatment and neutralization section,
51
52 29 enzymatic hydrolysis and fermentation section, wastewater treatment section, and enzyme
53 30 production section. As a result, manufacturing ethylene from corn stover leads to higher total
54
55 31 capital investments than from corn grain by 207%~224%. As the ethylene production scale
56
57
58
59 22
1
2
3 1 decreases, the differences between total capital investments costs for the corn stover-based
4
5 2 pathway and the other two pathways reduce, because the total capital investments are nonlinearly
6
7 3 related to plant capacities.
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 4
31 5 Figure 8. Breakdowns of the total capital investments for manufacturing ethylene from ethane-
33
34
35
7 3.2.2. Total Annual Production Cost
36 8 The total annual production cost is evaluated as the sum of direct manufacturing costs
37
38 9 (feedstocks, utilities, labor-related operations, and maintenance), operating overhead, fixed costs
39
40 10 (property taxes, insurance, and depreciation), and general expenses.68
41
11 The total annual costs of feedstocks and utilities can be calculated using Equations (8) and
42
43 12 (9), respectively.
44
45 13 FC = ∑ fprj ⋅ fcq j (8)
46 j
47
48 14 UC = ∑ uprk ⋅ ucqk (9)
49 k
50
51
15 where FC is the total annual cost of feedstocks, fprj is the price of feedstock j, fcqj is the annual
52 16 consumption quantity of feedstock j, UC is the total annual cost of utilities, uprk is the price of
53
54 17 utility k, and ucqk is the annual consumption quantity of utility k.
55
56 18 The annual cost associated with labor-related operations LOC can be evaluated by Equations
57
58
59 23
1
2
3 1 (10), where no is the number of operators for a plant that is estimated based on the guideline of
4
5 2 the direct operating labor requirements and the plant capacity,68 so is the annual salary per
6
7 3 operator, dsbc is the coefficient to evaluate the direct salaries and benefits for supervisory and
8
9
4 engineering personnel, ossc is the coefficient for operating supplies and services cost, nota is the
10 5 number of operators for technical assistance, sota is the annual salary per operator for technical
11
12 6 assistance, nocl is the number of operators for control laboratory, and socl is the annual salary
13
14 7 per operator for control laboratory.
15
16 8 LOC = no ⋅ so ⋅ (1 + dsbc + ossc ) + nota ⋅ sota + nocl ⋅ socl (10)
17
18 9 The annual maintenance cost MC is estimated as a fraction of the total depreciable capital,
19
10 as shown in Equation (11),68 where mwbc, msbc, mmsc, and mo are the coefficients for
20
21 11 maintenance wages and benefits, maintenance salaries and benefits, maintenance materials and
22
23 12 services, and maintenance overhead, respectively.
24
25 13 MC = mwbc ⋅ CTDC ⋅ (1 + msbc + mmsc + mo ) (11)
26
27 14 The annual operating overhead cost OOC can be estimated as a fraction of the combined
28
29 15 salary, wages, and benefits for maintenance and labor-related operations, as given by Equation
30
16 (12),68 where oocc is the coefficient for the operating overhead cost.
31
32 17 OOC = oocc ⋅  no ⋅ so ⋅ (1 + dsbc ) + mwbc ⋅ CTDC ⋅ (1 + msbc )  (12)
33
34
35
18 The total annual cost for property tax and insurance PTIC can be estimated as a percentage
36 19 of the total depreciable cost, as shown in Equation (13), where pticc is the coefficient for the
37
38 20 property tax and insurance.
39
40 21 PTIC = pticc ⋅ CTDC (13)
41
42 22 Depreciation DP can be estimated as a constant percentage of the total depreciable capital
43
44 23 using the straight-line method over the plant life, pl, as given in Equation (14).
45 CTDC
46 24 DP = (14)
47 pl
48
49
25 The total annual general expenses GE can be estimated as a percentage of the total sales
50 26 revenue SR, as shown in Equations (15) and (16).
51
52 27 SR = ∑ pprl ⋅ ppql (15)
53 l
54
55 28 GE = SR ⋅ gec (16)
56
57
58
59 24
1
2
3 1 where pprl is the selling price of product l, ppql is the annual production quantity of product l,
4
5 2 and gec is the general expenses coefficient.
6
7 3 The total annual production cost TAPC can be calculated by Equation (17).
8
9
4 TAPC = FC + UC + LOC + MC + OOC + PTIC + DP + GE (17)
10 5 Figure 9 shows the breakdowns of the total annual production costs for manufacturing
11
12 6 ethylene from ethane-rich shale gas, corn stover, and corn grain. For manufacturing ethylene
13
14 7 from ethane-rich shale gas, raw shale gas is the largest contributor for the total annual production
15
8 costs on all considered ethylene production scales, occupying 35%~51% of the total annual
16
17 9 production costs. The other notable contributions come from utilities, maintenance, and general
18
19 10 expenses, as shown in Figure 9. In terms of each ethylene production scale, more distributed
20
21 11 shale gas processing plants result in higher total annual production costs. The main reason is that
22 12 more distributed shale gas processing plants lead to higher costs associated with maintenance,
23
24 13 operating overhead, property taxes and insurance, and depreciation. We also find that the total
25
26 14 annual production cost decreases nonlinearly as the ethylene production scale decreases and a
27
28
15 smaller ethylene production scale could lead to a higher production cost of 1 tonne of ethylene.
29 16 For manufacturing ethylene from corn stover, the costs contributed by corn stover take up
30
31 17 only 15%~28% of the total annual production costs. As shown in Figure 9, maintenance and
32
33 18 depreciation result in the largest proportions (32%~47%) of the total annual production costs.
34
19 This is because manufacturing ethylene from corn stover requires high total capital investments
35
36 20 (see Figure 8). The other notable contributions come from the consumption of other feedstocks,
37
38 21 including glucose, sodium hydroxide, lime, corn steep liquor, etc. Additionally, we find that
39
40 22 smaller ethylene production scales and more distributed bioethanol plants could result in higher
41 23 production costs of 1 tonne of ethylene.
42
43 24 The total annual production costs for manufacturing ethylene from corn grain are highly
44
45 25 dependent on the corn grain costs, which could take up 41%~57% of the total annual production
46
47
26 costs. The utilities, maintenance, and general expenses are other considerable contributors for the
48 27 total annual production costs. In terms of each ethylene production scale, the total annual
49
50 28 production cost increases as the number of distributed bioethanol plants increases. We also find
51
52 29 that a smaller ethylene production scale leads to a higher production cost of 1 tonne of ethylene.
53 30 Comparing the three ethylene production pathways, the corn grain-based pathway results in
54
55 31 the lowest total annual production costs on each ethylene production scale considering the same
56
57
58
59 25
1
2
3 1 number of distributed shale gas processing/bioethanol plants. With a further insight into Figure 9,
4
5 2 we find that the total annual production costs for manufacturing ethylene from corn stover are
6
7 3 more sensitive to the number of distributed plants than that for manufacturing ethylene from both
8
9
4 ethane-rich shale gas and corn grain. For example, on the ethylene production scale of 1,000
10 5 kt/yr, the total annual production cost for manufacturing ethylene from corn stover is lower than
11
12 6 that for manufacturing ethylene from ethane-rich shale gas, when 5 distributed shale gas
13
14 7 processing/bioethanol plants are considered. However, this trend is altered as the number of
15
8 distributed shale gas processing/bioethanol plants changes to 10 and 15.
16
17 9
18
19
20
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22
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24
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36
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40 10
41
11 Figure 9. Breakdowns of total annual production costs for manufacturing ethylene from ethane-
42
44
45 13 3.2.3. Net Present Value and Breakeven Ethylene Price
46
47 14 The net present value (NPV) is a principal measure of process economics involving the time
48 15 value of money in terms of discounted cash flows. The NPV of a project is evaluated as the sum
49
50 16 of all the discounted cash flows, as given by Equations (18) and (19).68
51
52 17 CFt = (1 − tax) ⋅ (SRt − TAPCt ) + DPt (18)
53
54 pl
CFt
55 18 NPV = ∑ − CTCI (19)
(1 + r )
t
t =1
56
57
58
59 26
1
2
3 1 where CFt is the cash flow in year t, tax is the tax rate, NPV is the net present value, and r is the
4
5 2 interest rate.
6
7 3 Figure 10 shows the NPVs for manufacturing ethylene from ethane-rich shale gas, corn
8
9
4 stover, and corn grain. In terms of the shale gas-based pathway, 11 of the 15 investigated cases
10 5 result in positive NPVs. On each ethylene production scale, more distributed shale gas
11
12 6 processing plants result in lower NPVs. Besides, the NPV of manufacturing ethylene from
13
14 7 ethane-rich shale gas decreases as the ethylene production scale decreases. It means that
15
8 manufacturing ethylene from ethane-rich shale gas on larger scales is more economically
16
17 9 attractive.
18
19 10 For manufacturing ethylene from corn stover, all the 15 cases lead to significantly negative
20
21 11 NPVs, indicating that manufacturing ethylene from corn stover is unprofitable. On each ethylene
22 12 production scale, the NPV of manufacturing ethylene from corn stover increases as the number
23
24 13 of distributed bioethanol plant decreases. Additionally, we find that a smaller ethylene
25
26 14 production scale could result in a higher NPV.
27
15 Manufacturing ethylene from corn grain also leads to negative NPVs regarding the 15 cases,
28
29 16 meaning that it is unprofitable to make ethylene from corn grain. Similar to manufacturing
30
31 17 ethylene from both ethane-rich shale gas and corn stover, more distributed bioethanol plants lead
32
33 18 to lower NPVs on each ethylene production scale. Besides, it can be found that manufacturing
34 19 ethylene from corn grain on smaller scales results in higher NPVs. Such a trend is the same as
35
36 20 that for manufacturing ethylene from corn stover.
37
38 21 As shown in Figure 10, on each ethylene production scale, the NPVs of manufacturing
39
40
22 ethylene from ethane-rich shale gas are always higher than those of manufacturing ethylene from
41 23 both corn stover and corn grain. This indicates that the shale gas-based pathway is more
42
43 24 attractive than corn stover-based pathway and corn grain-based pathway for ethylene production.
44
45 25 Besides, the corn grain-based pathway could show a better economic performance than the corn
46
26 stover-based pathway, although both of the two pathways lead to negative NPVs. It is
47
48 27 noteworthy that the difference among NPVs of manufacturing ethylene from ethane-rich shale
49
50 28 gas, corn stover, and corn grain becomes greater as the ethylene production scale increases.
51
52
53
54
55
56
57
58
59 27
1
2
3
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5
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7
8
9
10
11
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17
18
19
20
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22
23
24
1
25
26 2 Figure 10. Net present values of manufacturing ethylene from ethane-rich shale gas, corn stover,
27 3 and corn grain.
28
29 4
30
31 5 The breakeven ethylene price can be defined as a price at which the net present value of a
32
33 6 pathway is equal to zero. The breakeven ethylene prices for the three ethylene production
34
35
7 pathways are estimated by adjusting the selling price of ethylene until the corresponding NPV
36 8 equals to zero. The breakeven prices of ethylene manufactured via the shale gas-based pathway,
37
38 9 corn stover-based pathway, and corn grain-based pathway are evaluated and compared in Figure
39
40 10 11. For each of the three ethylene production pathways, the breakeven ethylene price increases as
41
11 the ethylene production scale decreases and the number of distributed shale gas
42
43 12 processing/bioethanol plants increases. On each ethylene production scale, the shale gas-based
44
45 13 pathway results in the lowest breakeven ethylene prices. The breakeven prices of ethylene
46
47 14 produced via the corn grain-based pathway are notably higher than that of ethylene produced via
48 15 the shale gas-based pathway by 21%~284%. The corn stover-based pathway leads to the highest
49
50 16 breakeven ethylene prices, which are 2.4~6.3 times of the breakeven prices of ethylene produced
51
52 17 via the shale gas-based pathway. Also, we find that the breakeven ethylene prices of ethylene
53
54
18 manufactured via both the corn stover-based pathway and the corn grain-based pathway are
55 19 higher than the market ethylene price. This means that the corn stover-based pathway and the
56
57
58
59 28
1
2
3 1 corn gran-based pathway have no economic advantage for ethylene production currently. On
4
5 2 large ethylene production scales, the shale gas-based pathway could result in lower breakeven
6
7 3 ethylene prices than the market ethylene price. Such results indicate that manufacturing ethylene
8
9
4 from ethane-rich shale gas on large scales is cost-effective. In summary, the shale gas-based
10 5 pathway is more competitive than from both the corn stover-based pathway and the corn grain-
11
12 6 based pathway regarding the breakeven ethylene prices.
13
14 7
15
16
17
18
19
20
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22
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24
25
26
27
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29
30
31
32
33
34
35
36
37
8
38 9 Figure 11. Breakeven prices of ethylene manufactured from ethane-rich shale gas, corn stover,
40
41
42
11 3.3. Environmental Analysis
43 12 The environmental impacts of manufacturing ethylene from ethane-rich shale gas, corn
44
45 13 stover, and corn grain are systematically analyzed following the LCA approach. The objective of
46
47 14 this LCA study is to evaluate and compare the life cycle environmental impacts of ethylene
48
15 manufactured via the shale gas-based pathway, corn stover-based pathway, and corn grain-based
49
50 16 pathway. The functional unit of this LCA study is defined as 1 kg of ethylene manufactured at
51
52 17 the plant gate. The impact category to assess the life cycle environmental performance of
53
54 18 manufacturing ethylene via the three pathways is dedicated to GHG emissions, which arouse
55 19 special interest in both academia and industry.70-72 Most LCA studies related to shale gas and
56
57
58
59 29
1
2
3 1 biomass focus on GHG emissions.72-83 A cradle-to-gate LCA is considered in this study, as the
4
5 2 use and end-of-life phases of the ethylene products could vary significantly.84 The system
6
7 3 boundaries of the three ethylene production pathways are demonstrated in Figure 12. As for
8
9
4 manufacturing ethylene from ethane-rich shale gas, this LCA encompasses the environmental
10 5 impacts during shale gas production, shale gas transportation, shale gas processing, ethane
11
12 6 transportation, and ethylene production. In terms of manufacturing ethylene from corn stover and
13
14 7 corn grain, this LCA considers the environmental impacts at the stages of corn stover/corn grain
15
8 production, corn stover/corn grain transportation, bioethanol production, bioethanol
16
17 9 transportation, and ethylene production. The process designs for shale gas processing, ethylene
18
19 10 production via ethane steam cracking, and ethylene production via bioethanol dehydration are
20
21 11 modeled in Aspen HYSYS. The corresponding mass and energy balance information of each unit
22 12 is determined by HYSYS simulation. As for bioethanol production from corn stover and corn
23
24 13 grain, the mass and energy balances are extracted from existing literature.38-39, 67 Data used to
25
26 14 model the GHG emissions during the production of feedstocks and utilities and the transportation
27
15 of feedstocks, ethane, and bioethanol are collected from the Ecoinvent database,85 GREET
28
29 16 Model,86 and existing publications.73, 87 As shown in Figure 12, the steps of shale gas processing,
30
31 17 bioethanol production, and ethylene production produce more than one product. The
32
33 18 corresponding mass and energy flows as well as the associated environmental burdens must be
34 19 allocated to each of the products to accurately reflect their individual contributions to the
35
36 20 environmental impacts of the studied system.88 The economic value-based and the mass-based
37
38 21 allocation methods are used most frequently.88 In this study, electricity is generated at the step of
39
40
22 bioethanol production from corn stover, which implies that the mass-based allocation method is
41 23 not suitable. Therefore, the environmental burdens are allocated using the economic value-based
42
43 24 allocation method.
44
45
46
47
48
49
50
51
52
53
54
55
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59 30
1
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34
35
36 1
37
38 2 Figure 12. System boundaries of manufacturing ethylene from ethane-rich shale gas, corn stover,
40
41 4
42
43 5 Figure 13 shows the breakdowns of the life cycle GHG emissions of ethylene produced from
44
45 6 ethane-rich shale gas, corn stover, and corn grain. Note that the GHG emissions do not account
46 7 for the construction of shale gas pipeline systems, shale gas processing plants, bioethanol plants,
47
48 8 and ethylene plants. In terms of the GHG emissions of ethylene produced via the shale gas-based
49
50 9 pathway, the ethylene production step is the major contributor, which contributes over 66% of
51
52
10 the total GHG emissions. The production of shale gas also leads to considerable GHG emissions
53 11 that occupy about 25% of the total GHG emissions, while the processing of shale gas results in
54
55 12 approximately 7% of the total values. Compared with these contributors, shale gas transportation
56
57
58
59 31
1
2
3 1 and ethane transportation lead to much less GHG emissions, taking up about 1% of the total
4
5 2 GHG emissions.
6
7 3 Different from manufacturing ethylene from ethane-rich shale gas, manufacturing ethylene
8
9
4 from corn stover and corn grain could sequester renewable carbon due to the biorenewable
10 5 feedstocks. As 1 mole of bio-ethylene sequesters 2 moles of renewable carbon, in terms of 1 kg
11
12 6 of ethylene, the amount of sequestered renewable carbon equals to 3.1 kg CO2-eq
13
14 2 mol×44 kg CO 2 -eq/kmol 43
7 ( ≈ 3.1 kg CO 2 -eq/kg ). For manufacturing ethylene via the corn
15 1 mol × 28 kg/kmol
16
17 8 stover-based pathway, the corn stover production, bioethanol production, and ethylene
18
19 9 production stages contribute about 27%, 47%, and 23% of the total GHG emissions excluding
20 10 the sequestered renewable carbon, respectively. In comparison with these major contributors, the
21
22 11 corn stover transportation and bioethanol transportation stages result in much less GHG
23
24 12 emissions, occupying less than 3% of the total values. The GHG emissions of ethylene produced
25
26
13 from corn grain are dominated by the stages of corn grain production, bioethanol production, and
27 14 ethylene production, which lead to approximately 37%, 43% and 18% of the total GHG
28
29 15 emissions excluding the sequestered renewable carbon, respectively. The corn grain
30
31 16 transportation and bioethanol transportation stages cause less significant GHG emissions
32
17 compared with those major contributors.
33
34 18 Regarding each of the three pathways, differences among the net GHG emissions of
35
36 19 ethylene produced on different scales are insignificant, as illustrated in Figure 13. This is because
37
38 20 the GHG emissions contributed by feedstock transportation are negligible compared with the
39 21 total GHG emissions across the product life cycle. The net GHG emissions of ethylene produced
40
41 22 via the shale gas-based pathway are positive. In comparison, the corn stover-based pathway and
42
43 23 the corn grain-based pathway could result in negative net GHG emissions of ethylene, due to the
44
45
24 sequestration of renewable carbon. Such results indicate that the corn stover-based pathway and
46 25 the corn grain-based pathway are more advantageous over the shale gas-based pathway for
47
48 26 ethylene production in terms of the net GHG emissions.
49
50
51
52
53
54
55
56
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59 32
1
2
3
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7
8
9
10
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13
14
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16
17
18
19
20
21
22
23
24
1
25
26 2 Figure 13. Life cycle greenhouse gas emissions of ethylene manufactured from shale gas, corn
27 3 stover, and corn grain.
28
29
4 3.4. Sensitivity Analysis
30
31 5 As economic parameters, such as prices, are volatile in most circumstances, it is worth
32
33 6 investigating how these parameters could affect the economic and environmental performances
34
35 7 of the three ethylene production pathways. Therefore, sensitivity analyses are conducted to
36 8 examine the influences of altering economic parameters on the economic and environmental
37
38 9 performances of the three ethylene production pathways.
39
40 10 Figure 14 presents how the breakeven ethylene prices change when the prices of feedstocks
41
42
11 and products and the total bare-module investments of shale gas processing plants, bioethanol
43 12 plants, and ethylene plants deviate by 10% and 20% from their current values. Note that this
44
45 13 sensitivity analysis is conducted for the case of ethylene production on the scale of 1,000 kt/yr
46
47 14 with 5 shale gas processing/bioethanol plants. For the shale-gas based pathway, the raw shale gas
48
15 price is the most important factor for the breakeven ethylene price, as shown in Figure 14(a). The
49
50 16 influence of the sales gas price ranks second. Besides, all other investigated factors have notable
51
52 17 impacts on the breakeven ethylene price. In terms of the corn stover-based pathway, the total
53
54 18 bare-module investment of bioethanol plants causes the largest change in the breakeven ethylene
55 19 price, as can be seen from Figure 14(b). Besides, the corn stover price leads to greater influence
56
57
58
59 33
1
2
3 1 on the breakeven ethylene price than the other investigated factors. For the corn grain-based
4
5 2 pathway, the corn grain price has the greatest influence on the breakeven ethylene price, as
6
7 3 depicted in Figure 14(c). In addition, both the total bare-module investment of bioethanol plant
8
9
4 and the price of DDGS cause notable changes in the breakeven ethylene price. If the bare-
10 5 module investment of the bioethanol plant could be reduced significantly, the corn stover-based
11
12 6 pathway may be more competitive than the corn grain-based pathway. It is noteworthy that the
13
14 7 shale gas-based pathway always shows better economic performances than the other two
15
8 ethylene production pathways under any changes investigated in Figure 14.
16
17 9
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40 10
41
11 Figure 14. Sensitivity analysis results for the breakeven prices of ethylene produced via the three
42
43 12 pathways on the production scale of 1,000 kt/yr with 5 shale gas processing/bioethanol plants.
44
45 13
46
47 14 Figure 15 illustrates the sensitivity analysis results for the breakeven prices of ethylene
48 15 produced via the three pathways based on the case of ethylene production on the scale of 200
49
50 16 kt/yr with 5 shale gas processing/bioethanol plants. As shown in Figure 15(a), the raw shale gas
51
52 17 price causes the largest change in the breakeven ethylene price. However, we find that the total
53
54
18 bare-module investment of ethylene plant and the sales gas price are of similar influence level
55 19 for the breakeven ethylene price, which is different from the result shown in Figure 14(a). As for
56
57
58
59 34
1
2
3 1 the corn stover-based pathway, the total bare-module investment of bioethanol plants results in
4
5 2 obviously greater influence on the breakeven ethylene price than the other investigated factors.
6
7 3 Such a result is the same as that presented in Figure 14(b). The corn grain price is the most
8
9
4 predominant factor for the breakeven price of ethylene manufactured via the corn grain-based
10 5 pathway, as shown in Figure 15(c). For the three ethylene production pathways, the prices of
11
12 6 feedstocks and the total bare-module investments of plants are in a positive correlation with the
13
14 7 breakeven ethylene price, while the prices of products are in a negative correlation with the
15
8 breakeven ethylene price, as can be seen from Figure 14 and Figure 15.
16
17 9
18
19
20
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22
23
24
25
26
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29
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31
32
33
34
35
36
37
38
39
40
41
42
43 10
44
45 11 Figure 15. Sensitivity analysis results for the breakeven prices of ethylene produced via the three
46 12 pathways on the production scale of 200 kt/yr with 5 shale gas processing/bioethanol plants.
47
48 13
49
50 14 The economic parameters could affect the net GHG emissions of ethylene, since the
51
52
15 allocation of environmental impacts is conducted based on the economic values of products in
53 16 this study. Figure 16 shows how the net GHG emissions of ethylene change when prices of
54
55 17 products deviate by 10% and 20% from their current values, based on the case of ethylene
56
57
58
59 35
1
2
3 1 production on the scale of 1,000 kt/yr with 5 shale gas processing/bioethanol plants. In terms of
4
5 2 the shale gas-based pathway, the prices of ethane and ethylene are two main factors that affect
6
7 3 the net GHG emissions of ethylene, as shown in Figure 16(a). Besides, we find that the prices of
8
9
4 ethane and ethylene are in a positive correlation with the net GHG emissions of ethylene, while
10 5 the prices of other products are in a negative correlation with the net GHG emissions of ethylene.
11
12 6 As can be seen from Figure 16(b), the net GHG emissions of ethylene produced via the corn
13
14 7 stover-based pathway increases as the ethanol price increases or the electricity price decreases.
15
8 As for the corn grain-based pathway, the increase in the ethanol price or the decrease in the
16
17 9 DDGS price could increase the net GHG emissions of ethylene, as illustrated in Figure 16(c).
18
19 10 From the viewpoint of GHG emissions of ethylene, we find that the corn stover-based pathway
20
21 11 and the corn grain-based pathway are more environmentally sustainable than the shale gas-based
22 12 pathway under any investigated changes in prices of products.
23
24 13
25
26
27
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29
30
31
32
33
34
35
36
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43
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45
46
47 14
48 15 Figure 16. Sensitivity analysis results for the net GHG emissions of ethylene produced via the
49
16 three pathways on the production scale of 1,000 kt/yr with 5 shale gas processing/bioethanol
50
51 17 plants.
52
53 18 4. Conclusion
54
55 19 In this work, manufacturing ethylene from ethane-rich shale gas, corn stover, and corn grain
56
57
58
59 36
1
2
3 1 were systematically compared from both economic and environmental perspectives. For the
4
5 2 purpose of systematic comparisons, the ethylene production cases on five different scales were
6
7 3 investigated. The techno-economic and life cycle analyses were conducted for the three ethylene
8
9
4 production pathways based on the same conditions. From the viewpoint of economic
10 5 performance, the shale gas-based pathway resulted in the lowest breakeven ethylene prices. The
11
12 6 breakeven prices of ethylene produced via the corn stover-based pathway and the corn grain-
13
14 7 based pathway were 2.4~6.3 and 1.2~3.8 times of the breakeven prices of ethylene produced via
15
8 the shale gas-based pathway, respectively. Besides, we also found that manufacturing ethylene
16
17 9 via the three pathways on large scales was attractive because of low breakeven ethylene prices.
18
19 10 As for the environmental impacts, the life cycle GHG emissions of ethylene produced via the
20
21 11 three pathways were assessed. The net GHG emissions of ethylene produced via the shale gas-
22 12 based pathway were about 1.4 kg CO2-eq/kg ethylene. This value was much higher than the net
23
24 13 GHG emissions of ethylene produced via the corn stover-based pathway (−1.0 kg CO2-eq/kg
25
26 14 ethylene) and the corn grain-based pathway (−0.5 kg CO2-eq/kg ethylene). The obtained results
27
15 indicated that each of the three ethylene production pathways had pros and cons. The shale gas-
28
29 16 based pathway showed the best economic performance, but it led to the highest net GHG
30
31 17 emissions of ethylene. In comparison, the corn stover-base pathway was more competitive than
32
33 18 the other two pathways in terms of the net GHG emissions of ethylene, although this pathway
34 19 resulted in the highest breakeven ethylene prices. It was interesting to find that the corn grain-
35
36 20 based pathway was pinched between the other two pathways regarding both the breakeven
37
38 21 ethylene prices and the net GHG emissions of ethylene.
39
40
41 22 Acknowledgement
42
43 23 The authors acknowledge financial support from National Science Foundation (NSF)
44
24 CAREER Award (CBET-1643244).
45
46
47
48
25 Supporting information
49 26 Input data, reaction kinetics, and model parameters. This information is available free of
50
51 27 charge via the Internet at http://pubs.acs.org/.
52
53 28
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59 37
1
2
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18 4 Manufacturing Ethylene from Wet Shale Gas and Biomass: Comparative Techno-economic
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