Acs Energyfuels 6b00619

Article
pubs.acs.org/EF
Biomass-Based Production of Benzene, Toluene, and Xylenes via

Methanol: Process Synthesis and Deterministic Global Optimization
Alexander M. Niziolek,§,†,‡ Onur Onel,§,†,‡ Yannis A. Guzman,§,†,‡ and Christodoulos A. Floudas*,†,‡
†
Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, United States
‡
Texas A&M Energy Institute, 3372 Texas A&M University, 302D Williams Administration Building, College Station, Texas 77843,
United States
§
Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, United States
*
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ABSTRACT: The pursuit toward an environmentally sustainable energy landscape requires the development of economically
competitive renewable processes. Efficient utilization of renewable resources is an important first step toward meeting this goal.
To this extent, we introduce a systematic deterministic global optimization-based process synthesis framework that determines
the most profitable processes to produce benzene, toluene, and/or xylenes from biomass via methanol. Our framework incor-
porates several novel, competing, and/or commercial technologies. We quantify the effect that biomass type has on the overall
profit of a refinery by investigating forest residues, agricultural residues, and perennial crops as potential feedstocks. A thorough
economic analysis, together with material, energy, carbon, and greenhouse gas balances, are provided for every proposed process
design. The capability of our proposed approach is illustrated through several case studies that produce varying ratios of p-, o-,
and m-xylene across several refinery scales. The most profitable aromatics refineries consistently produce p-xylene, while o-xylene
refineries consistently have the lowest required investment costs. The net present values for the biomass to aromatics, BTA,
refineries producing 2000 t per day of product are as high as $1200 MM dollars with payback periods less than 10 years.
1. INTRODUCTION investigating the technical feasibility of producing one billion

The conversion of biomass into more valuable products, such as tons of biomass in the United States,60,61 and by numerous
liquid transportation fuels or electricity, has received significant studies in the literature focusing on the supply chain aspects of
interest from several United States government agencies, biorefineries.62−92 It is remarkable, however, that very few studies
industries, and academia over the past decade. As highlighted have investigated the economic and technical feasibility of
in a recent perspective article by Floudas et al., renewable energy producing high-value aromatics from biomass.93−95 Aromatics
research areas, and in particular, biomass based processes, have constitute a large portion (one-third) of the market for
greatly benefited from multiscale systems engineering compo- commodity petrochemicals,96 and a significant portion (approx-
nents, which include modeling, design, synthesis, simulation, imately 70%) of the world’s benzene, toluene, and xylenes supply
and optimization.1 Two recent reviews have highlighted comes from petroleum naphtha.97 Biomass-based aromatics
key contributions in the production of liquid transportation production additionally offsets import requirements for petro-
fuels and the supply chain optimization of hybrid energy pro- chemicals, crude oil, or naphtha, and thus aids in energy inde-
cesses.2,3 A recent perspective article outlined the state of the pendence objectives set by the U.S. government. A stand-alone
art approaches and major challenges toward integrated bio- biomass to aromatics plant has the potential to penetrate the
mass and fossil-fuel systems that can simultaneously provide chemical market if it is shown to be profitable. To address this,
economical and environmental benefits.4 Biomass has several we propose a process synthesis superstructure composed of
advantages over the other two feedstocks, natural gas and coal, several existing or novel process technologies for the thermo-
considered as alternatives to petroleum. Namely, it is a renewable chemical conversion of biomass into aromatics. The most
resource that has the ability to absorb atmospheric CO2 during profitable, optimal process topology is determined using a novel
photosynthesis,5−7 thus reducing net life-cycle greenhouse gas branch-and-bound global optimization framework.
emissions. The U.S. Energy Information Administration projects The world demand for benzene, p-xylene, o-xylene, and
that most of the growth in primary energy consumption until m-xylene was approximately 40, 26, 6, and 0.4 million metric tons
2040 will occur with an increase in the consumption of natural per year, respectively, between 2005 and 2008.98 Aromatics serve
gas and renewable energy.8 However, in order for biomass to as midproducts in petroleum refining and have a variety of end
penetrate the large energy market, the processes utilizing it uses across several industries.97,99−102 Benzene, for example, is
should be profitable and efficient, and it should be harvested used as a precursor for styrene, phenol, nylon, and aniline
sustainably. The former concern has been and is currently being production. In 2008, the United States used 5.6 million metric
addressed by several studies in the literature that have mainly
focused on the production of liquid fuels from biomass via Received: March 15, 2016
thermochemical, catalytic, or biological routes.9−59 The latter Revised: April 30, 2016
concern has been assessed by the Department of Energy Published: May 2, 2016
© 2016 American Chemical Society 4970 DOI: 10.1021/acs.energyfuels.6b00619

Energy Fuels 2016, 30, 4970−4998
Energy & Fuels Article
tons of benzene as a chemical feedstock.101 Toluene is typically proper operation. Several novel, commercial, and/or competing
blended into unleaded gasoline but is also converted into technologies are modeled within the framework, including
benzene and xylenes and is used in solvent applications.101 methanol-to-aromatics, toluene alkylation with methanol,
o-Xylene applications include the production of phthalic selective toluene disproportionation, toluene disproportionation
anhydride, while m-xylene is converted into isophthalic acid. and transalkylation of toluene with C9+ aromatics, p-xylene
p-Xylene is converted into terephthalic acid and dimethyl separation via adsorptive separation or crystallization, isomer-
terephthalate, which are ultimately used to produce polyethylene ization of xylenes, dehydrocyclodimerization of liquefied
terephthalate (PET) fibers, resins, and films.97,103 petroleum gas, and separation via conventional distillation, to
Despite the fact that aromatics represent a significant portion name a few. The optimal process topology, economic and
of the world market for commodity petrochemicals, few studies environmental trade-offs, and life-cycle emissions analysis are
have considered stand-alone production of aromatics from determined and discussed for several case studies.
alternative sources. Lin et al. investigated the production of The process synthesis framework for the BTA process will
p-xylene from lignocellulosic biomass and analyzed the economics include (i) biomass gasification with/without recycle light gas,
and life cycle emissions for their proposed processes in a series of (ii) synthesis gas treatment, (iii) synthesis gas conversion via
papers.93,94,104 Ashraf et al. simulated and developed a process for methanol synthesis, (iv) methanol conversion via methanol-
the methylation of toluene to produce p-xylene using Aspen to-aromatics or methylation of toluene, (v) hydrocarbon upgrading,
Plus.105 Several other studies considered the coproduction of (vi) aromatization over a Ga/H-ZSM-5 based catalyst, and
liquid transportation fuels and aromatics. Wang et al. used (vii) separation and production of additional high-value chemicals
ChemCad to investigate the coproduction of ethanol with via an aromatics complex. The major products will be benzene,
aromatics, olefins, and synthetic gasoline and diesel.106 In our toluene, p-xylene, m-xylene, and/or o-xylene. Gasoline, LPG, and/
previous work, we investigated the coproduction of C6−C8 or electricity are allowable byproducts. A description of the major
aromatics and liquid fuels from biomass and natural gas using an
sections of the refinery is included in the following section.
optimization-based process synthesis framework and calculated
high net present values for these refineries.95 We also recently
proposed a stand-alone chemicals facility for the conversion of 2. BTA PROCESS SUPERSTRUCTURE: CONCEPTUAL
natural gas into aromatics (GTA).107 Additionally, we have DESIGN AND MATHEMATICAL MODELING
investigated the coproduction of olefins and liquid fuels from The following subsections will describe the major components of
biomass and natural gas, as well as stand-alone production of the BTA refinery. In each of the figures illustrated throughout
olefins from natural gas.108,109 this section, input and output units are colored light green, units
In order to rigorously compare existing and novel process represented with a binary variable are dark blue, all other units are
designs, we include several technologies within a process light blue, variable process streams are blue, and existing process
synthesis superstructure. The methanol-to-aromatics (MTA) streams are gray. The complete mathematical model of the
reaction has been identified as one promising alternative for the process synthesis superstructure is included in Appendix B.
production of aromatics. Several studies investigated this 2.1. Biomass Handling and Gasification. Three different
reaction over ZSM-5 and H-ZSM-5 catalysts impregnated with categories of biomass are investigated to determine the effect of
metals, such as Zn-,110−112 La/Zn-,113 Cu-,111,114 Zn/Sn-,115 biomass type on the overall profit of the refinery. The types
Ag-,114,116 as well as others.111,114,117 Recently, a pilot plant investigated include agricultural residues (corn stover), perennial
which utilized this technology and produced 10 ktpa (kiloton crops (switchgrass), and forest residues (hardwood). The refinery
per annum) of aromatics was successfully operated by Huadian
will input only one type of biomass to increase uniformity and
Coal Industry Group Company in China. Coal was used as the
decrease complexity in the preprocessing steps. Forest residues are
feedstock in this pilot plant because of the lack of oil and natural
delivered as woodchips to the refinery and screened to direct any
gas in China, and the company has plans to build a 1 million
sizes larger than 2 in. to a grinder before entering the gasifier.
metric tons per year commercial scale coal to aromatics plant
in the upcoming years.118 Additionally, toluene methylation Agricultural residues and perennial crops are delivered as bales and
has been identified as an attractive alternative for xylenes pro- grinded before being sent to the gasifier. The proximate and
duction119−125 since the amount of toluene used as a chemical ultimate analyses for the biomass types are shown in Table 1.134
feedstock pales in comparison to its global production.101 In this
study, we focus on the economic and environmental trade-offs of Table 1. Feedstock Proximate and Ultimate Analysis for
producing benzene, toluene, and/or the xylenes from biomass via Biomass Species134
methanol, since it is a versatile product that can be converted heating values
from biomass via the synthesis gas route. We propose the proximate analysis (db, weight %) (kJ/kg)
f irst quantitative f ramework capable of systematically comparing feed type moist. (ar) ash VMa FCb HHVc LHVd
several novel and commercial technologies to determine the agricultural 6.1 5.1 80.9 14 18101 16849
optimal process topology for the production of aromatics from perennial 8.2 4.6 79.2 16.2 18636 17360
biomass. forest 45 2.14 N/A N/A 19130 17842
The process synthesis superstructure proposed in this paper ultimate analysis (db, weight %)
constitutes a large-scale, mixed-integer, nonlinear, nonconvex
feed type C H N Cl S O
optimization model that is solved to global optimality using a
branch-and-bound global optimization framework. Simultaneous agricultural 46.8 5.74 0.66 0.266 0.11 41.4
heat, power, and water integration is included within the perennial 46.9 5.85 0.58 0.501 0.11 41.5
framework to minimize the intake of freshwater into the refinery forest 50.19 5.9 0.32 0 0.03 41.42
and convert waste heat into electricity.126−133 Each unit within a
VM = volatile matters. bFC = fixed carbon. cHHV = higher heating
the process superstructure is rigorously modeled to ensure value. dLHV = lower heating value.
4971 DOI: 10.1021/acs.energyfuels.6b00619

Energy Fuels 2016, 30, 4970−4998
Figure 1. Biomass gasification flow sheet.
The biomass gasification flow sheet is shown in Figure 1. one presented by the National Renewable Energy Laboratory.135
The biomass drier is modeled using a binary variable and is activated A circulating catalyst between the tar reformer and the catalyst
if the biomass moisture content is greater than 20 wt % in order to regenerator supplies a portion of the heat necessary for tar
reduce the moisture down to this threshold. Otherwise, the biomass conversion.137 Additional combustion gases are sent to the
bypasses this unit. Flue gas generated within the refinery supplies regenerator to provide the balance of heat for the endothermic
the heat necessary for drying. The flue gas exits the drier at 110 °C tar reforming reactions.137 After exiting the tar cracker, the
and 1.05 bar and is passed through an air cyclone and baghouse filter biomass syngas is directed to the syngas cleaning section.
so that any particulates may be removed.135 The biomass is 2.2. Synthesis Gas Cleaning. The synthesis gas cleaning
lockhopped using compressed CO2 (10 wt %) and is transferred to section for the BTA refinery is shown in Figure 2. The biomass
the gasifier. synthesis gas can either be split to a dedicated sour water−
The biomass gasifier operates at 30 bar and at a temperature of gas-shift reactor or can bypass this unit. The sour water−gas-shift
either 900 °C, 1000 °C, or 1100 °C. The input into the gasifier reactor operates at a pressure of 26 bar and at a temperature of
will either be solid biomass or a mixture of solid biomass and either 300 °C, 400 °C, 500 °C, or 600 °C. This unit can either be
recycle light gases and is modeled using the stoichiometry-based used as a forward or reverse WGS reactor. Any CO2 generated
model proposed by Baliban et al.128,136 The composition of the within the refinery can be consumed via the reverse water−
effluent is a function of the biomass gasifier temperature, oxidizer gas-shift reaction. Hydrogen produced within the refinery will
flow rate, and biomass composition. The gasifier effluent will help facilitate the consumption of CO2. Heat necessary for the
contain a mixture of synthesis gas (H2, CO, CO2, H2O), C1 and reverse water−gas-shift reaction will be provided by combusting
C2 hydrocarbons, ash, tar, char, NH3, and acid gases such as a portion of the synthesis gas species via oxygen input into the
H2S.128,136 The solid ash and char are separated from the vapor reactor. The forward water−gas-shift reaction provides a means
phase effluent using two biomass cyclones and are recycled back of increasing the H2/CO ratio of the syngas at the expense of
to the gasifier. This ensures that effectively 100% of the carbon producing CO2. Since the forward water−gas-shift reaction is
present in the biomass feedstock is converted. The ash is ulti- exothermic, low pressure steam will be generated. Reformed
mately output as slag. gases from the autothermal reformer are also allowed to enter the
Steam input into the biomass gasifier will reform the C1−C2 water−gas-shift reactor. The existence of the dedicated WGS
hydrocarbons and the tar species, as well as gasify the feed. The reactor depends on the H2/(CO + CO2) ratio needed for syngas
heat necessary for the reforming reactions will be provided by conversion, the amount of H2 that can be economically produced
high-purity oxygen, which additionally serves to facilitate the using the PSA, the economics surrounding H2 production from
cracking of the tar species. Since the biomass gasifier operates at electrolysis, the investment costs associated with the WGS
high temperatures, the syngas species will approach the water− reactor, and the specified life cycle greenhouse gas emissions of
gas-shift (WGS) equilibrium. Hydrocarbons, however, will be the refinery. If the WGS reactor is included in the optimal
above their equilibrium values. Additional CO2 produced within topology, the syngas effluent will be cooled down to 185 °C and
the refinery can be recycled back to the biomass gasifiers. will be directed to the scrubbing section. Otherwise, the synthesis
However, this will require generation of H2 from either pressure- gas exiting the tar cracker is cooled down to 185 °C before being
swing adsorption or electrolysis of water to aid in the conversion sent to the scrubbing section.
of CO2 via the reverse water−gas-shift reaction. The scrubbing section removes residual tar, particulates, and
The effluent exiting the biomass ash cyclones is sent to a catalytic NH3 that is contained within the raw synthesis gas. The waste-
tar cracker operating at 825 °C. The tar cracker is modeled after water stream from this section is directed to the wastewater
Energy Fuels 2016, 30, 4970−4998
Figure 2. Biomass syngas cleaning flow sheet.
Figure 3. Methanol synthesis and conversion flow sheet.
treatment section. The scrubbed synthesis gas is directed to a within the refinery to methanol via the water−gas-shift reaction
Rectisol unit that removes the acid gases from the synthesis gas. and the methanol synthesis reaction, shown in eqs 1 and 2,
This unit is necessary within the refinery to prevent contami- respectively. The process flow diagram is shown in Figure 3.
nation in the downstream hydrocarbon production and upgrading
CO + H 2O ↔ CO2 + H 2 (1)
sections. The effluent from the Rectisol unit contains a sulfur-rich
stream that is directed to the Claus recovery system to convert CO + 2·H 2 ↔ CH3OH (2)
95% of the H2S and SO2 into solid sulfur.138 The tail gas from the
Claus system is hydrogenated to H2S, thus effectively achieving The effluent from the methanol synthesis reactor is cooled
100% recovery of the sulfur in the refinery. The carbon dioxide and flashed to remove the majority (96 mol %) of the methanol.
from the acid gas recovery units can either be (i) compressed to The vapor effluent is split so that the majority (96 mol %) is
31 bar and recycled within the refinery, (ii) compressed to 150 bar recycled back to the methanol synthesis reactor, while the rest
for sequestration, or (iii) vented to the atmosphere. (4 mol %) is used as fuel gas within the refinery. The liquid
2.3. Hydrocarbon Production & Upgrading. 2.3.1. Meth- effluent is heated to 371 °C to form a vapor and expanded in a
anol Synthesis. The methanol synthesis reactor operates at turbine to generate electricity. The turbine effluent is cooled
250 °C and 45 bar and converts the synthesis gas generated down and sent to a degasser distillation column. The degasser
Energy Fuels 2016, 30, 4970−4998
removes the entrained gases from the methanol/water mixture. assumed to be formed, and it is assumed that the distribution
The light gases are recycled back to the refinery as fuel gas. between the m- and o-xylene isomers is 68 wt % meta to 32 wt %
The methanol/water mixture is split to either the methanol- ortho.141 Wastewater produced within the process is directed to
to-aromatics reactor or the GTC GT-TolAlk toluene methyl- the wastewater treatment section, the aromatics produced are
ation reactor. sent for further processing in the aromatics complex, and the
2.3.2. Methanol Conversion. The methanol/water mixture light gases are recycled within the BTA refinery.
exiting the methanol degasser can be processed in one of two 2.3.3. LPG-Aromatics Separation. The LPG-aromatics
options, the methanol-to-aromatics (MTA) reactor or the toluene separation section inputs the raw hydrocarbon product produced
methylation reactor. Prior to entering the MTA reactor, the in the methanol-to-aromatics reactor. Light gases are initially
degasser effluent is heated up to 425 °C. Several metal-promoted knocked out from the hydrocarbon mixture, which is then
ZSM-5 catalysts, such as Zn/ZSM-5, Ga/ZSM-5, and Ag/ZSM-5, directed to a deethanizer distillation column that separates any
are known to increase overall selectivity of methanol to residual light hydrocarbons. The bottoms from the deethanizer
aromatics.112,114,116 The methanol enters the MTA reactor and distillation column are directed to the stabilizer column to remove
is converted into an aromatic-rich hydrocarbon stream over the C3/C4 gases from the heavier hydrocarbons. The C3/C4 gases
a Ag-ZSM-5 catalyst. The overall reaction is shown in eq 3. are directed to a HF alkylation reactor which converts the
The reactor operates at 425 °C, and the methanol is completely isobutane and butene into isooctane.135 The effluent from the HF
converted into 56 wt % water and 44 wt % hydrocarbons.116 alkylation reactor is directed to the LPG/Alkylate splitter, which
The MTA reactor is modeled using an atom balance assuming that separates out the byproduct LPG. The bottoms from the stabilizer
the hydrocarbon product is distributed according to Table 1 and column is directed to a splitter column, which provides lean oil for
Table 2 of Inoue et al. at 700 K.116 For convenience, the data use in the absorber column. The effluent from the splitter column
is directed to the aromatics complex since it contains a mixture of
Table 2. Product Distribution (in C%) for the Methanol to heavier aliphatics and aromatics.
Aromatics Reaction Using a Ag/ZSM-5 Catalyst116 The tops from the deethanizer column is directed to an
absorber column which uses the lean oil to remove any C3+
temperature (°C) 425
species.135 The light gases are ultimately recycled back into the
product distribution in C% refinery, while the lean oil and absorbed hydrocarbons are
CH4 1.3 refluxed back to the deethanizer column. The LPG-aromatics
C2H6 0.4 flow diagram is shown in Figure 4 and is based off one presented
C3H8 3.5 by the National Renewable Energy Laboratory.135
C4H10 4.0 2.4. LPG Processing. The LPG processing section is shown
C2H4 8.1 in Figure 5. LPG generated within the refinery can either be
C3H6 6.2 output as byproduct, recycled back in the refinery and utilized, or
C4H8 2.5 can undergo dehydrocyclodimerization over a metal promoted
C5+ aliphatics 1.5 H-ZSM-5 catalyst to produce high-value aromatics, as is the
C6H6 1.6675 case in the Cyclar process.97,144 The Cyclar process utilizes a
C7H8 7.6125 Ga/H-ZSM-5 catalyst to convert LPG into aromatics via
e-C8H10 0.5075 dehydrogenation and subsequent aromatization.97,144 Devel-
m,p-C8H10 23.9975 oped by BP and UOP, the first commercial scale Cyclar process
o-C8H10 7.105 was commissioned by BP in 1990. Along with high-value
C9H12 aromatics 25.955 aromatics, a valuable coproduct, hydrogen, is also produced.
other aromatics 5.655 The decision of whether to include the Cyclar process within the
BTA refinery depends on the total cost associated with this
from Inoue et al. is shown in Table 2.116 Other aromatics unit, as well as the relative selling prices of LPG and aromatics.
are modeled as C10H14 aromatic compounds. As eq 3 illustrates, The branch-and-bound global optimization framework will
0.22 mol of H2 will be produced for every mole of methanol determine the optimal split fraction to send to the Cyclar
converted. The MTA effluent is upgraded and separated in the process. The hydrogen and fuel gas are recycled back within the
LPG-Aromatics Separation section, which is modeled after the refinery, while the aromatics are directed to the aromatics
scheme presented by the National Renewable Energy Laboratory complex.
and is described later in the text.135 The LPG-Aromatics separation 2.5. Aromatics Complex. Several commercial and compet-
section separates the light gases, LPG, and higher hydrocarbons; ing technologies are included within the aromatics complex to
ultimately, a portion of the higher nonaromatic hydrocarbons are determine the optimal configuration for the upgrading and
sent to the gasoline pool. separation of high-value C6−C8 chemicals. The following
CH3OH → CH1.56 + 0.22·H 2 + H 2O subsections will describe these technologies. The process flow
(3)
diagram for the aromatics complex is shown in Figure 6.
Alternatively, a portion of the methanol may be split to a 2.5.1. Sulfolane Unit. The UOP Sulfolane process recovers
toluene methylation reactor that uses a proprietary zeolite aromatics from reformate, pyrolysis gasoline, and coke-oven light
catalyst developed by GTC Technology Corporation.139−142 oil using a combination of liquid−liquid extraction and extractive
The methanol is mixed with toluene produced within the refinery distillation. The solvent commonly used is tetrahydrothiophene
and is reacted over a ZSM-5 based catalyst to produce fuel gas, 1,1-dioxide, or sulfolane.97,145 The process recovers 99.9% of
mixed xylenes, C9 aromatics, and process water that are separated the benzene, 99.8% of the toluene, and 99% of the C8 aromatics
downstream.139 The weight ratio of toluene to methanol input from the incoming stream. The MTA effluent will contain some
into the reactor is 4:1.89.139,142,143 Xylenes are produced with paraffins that are separated and directed to the gasoline blender.
a selectivity of 85 wt % to p-xylene.139,142,143 No ethyl-benzene is Before being directed downstream for further fractionation,
Energy Fuels 2016, 30, 4970−4998
Figure 4. LPG-aromatics separation flow sheet. Reprinted from ref 107 with permission. Copyright 2016 Wiley.
Figure 5. LPG processing flow sheet.
the aromatic-rich effluent is clay treated to remove any impu- The toluene depleted bottom is mixed with any other C8+-rich
rities.100 The Sulfolane process was developed by UOP in the aromatic stream in the refinery and is then directed to either
1960s. The aromatic-rich stream from the UOP Sulfolane one of two xylene distillation columns, described below.
process is mixed with any other aromatic-rich streams within 2.5.4. Xylene Column 1. The first xylene distillation column
the refinery and directed to the benzene distillation column. allows for the production of o-xylene within the BTA refinery.
2.5.2. Benzene Distillation Column. As shown in Figure 6, the Since the boiling point of o-xylene is higher than those of the
benzene distillation column inputs a stream of C6+ aromatics other C8 isomers, as shown in Table 3, separation of o-xylene
and separates high-purity (99.8 wt %) benzene in the distillate. from these compounds via distillation is possible.146 Xylene
The distillation column recovers 99.9% of the incoming benzene column 1 recovers p-xylene, m-xylene, and ethylbenzene (all with
in the distillate, which is then cooled to 40 °C before being greater than 99.9% recovery) in the distillate stream. The distillate
output as benzene product. The benzene depleted bottom is is directed to a splitter that determines the optimal ratio of C8
aromatics to be directed to the UOP Parex process. The bottom
directed to the toluene distillation column.
stream contains o-xylene and heavier aromatics that are directed to
2.5.3. Toluene Distillation Column. The toluene distillation
the ortho-distillation column. The production of o-xylene within
column recovers high-purity (99.8 wt %) toluene in the distillate,
the refinery must proceed through this route.
which also contains any leftover benzene and a small portion of
2.5.5. Ortho-Xylene Distillation Column. The bottom from
C8 aromatics. The toluene distillate can then be split among xylene column 1 is directed to the o-xylene distillation column,
five different processing options. The toluene distillate can be which recovers high purity (99.5%) o-xylene in the distillate
(1) output as toluene product, (2) directed to the UOP Tatoray stream. The o-xylene distillation column recovers 99.9% of the
reactor, (3) directed to the UOP TAC9 reactor, (4) directed incoming o-xylene. The bottom from the o-xylene distillation
to the UOP PX-Plus XP process, or (5) directed to the GTC column contains mostly C9+ aromatics and is either split to the
GT-TolAlk reactor. The optimal split fraction to each of these gasoline pool or to the C9 distillation column.
alternatives depends on the selling price of toluene, the invest- 2.5.6. Xylene Column 2. Alternatively, the C8+-rich aromatic
ment and operating costs of the alternatives, and the composition stream can be directed to xylene column 2, which recovers over
of the products formed. This decision will be determined by the 99.4% of the p-xylene, o-xylene, m-xylene, and ethylbenzene from
deterministic global optimization branch-and-bound framework. the incoming feed in the distillate. The distillate is mixed with any
Energy Fuels 2016, 30, 4970−4998
Figure 6. C6−C8 aromatics upgrading and separation flow sheet.
Table 3. Boiling Points (°C) of C8 Aromatics146 cooled down to 40 °C before being output as product. The p-xylene
depleted effluent is split to either the UOP MX Sorbex process to
C8 isomer boiling point
selectively recover m-xylene or to the UOP Isomer process, both of
ethylbenzene 136.19 which are described below.
m-xylene 139.10
2.5.8. UOP MX Sorbex. m-Xylene is recovered from the other
o-xylene 144.41
C8 isomers using the UOP MX Sorbex process, a continuous
p-xylene 138.35
adsorptive separation system which recovers 95% of the incoming
m-xylene.149 The m-xylene effluent has a mass purity of at least
other C8-rich aromatic stream and is sent to a splitter, which 99.5% and is cooled down to 40 °C before being output as
determines the optimal ratio of C8 aromatics to be directed to the
product. The m-xylene depleted stream is sent to the UOP Isomar
UOP Parex process. The bottom from this distillation column is
to reestablish an equilibrium mixture of xylene isomers.
split to either the C9 distillation column or directed to the gasoline
2.5.9. UOP Isomar. The UOP Isomar process uses an I-400
blender. Xylene column 1 and xylene column 2 are modeled with
binary variables such that only one of the columns is allowed to EB isomerization catalyst to reestablish an equilibrium mixture of
exist within the refinery. xylene isomers and convert any ethylbenzene within the feed
2.5.7. UOP Parex. p-Xylene may be selectively recovered from to mixed xylenes with 30% wt per pass conversion.97,100
a mixture of C8 isomers using an adsorptive separation system An alternative catalyst, the I-300 EB dealkylation catalyst, exists
(also known as a simulated moving bed technology), as is the and converts ethylbenzene to benzene with greater than 70% wt
case in the UOP Parex process.147,148 Since the boiling point per pass conversion.97,100 However, it is not modeled within the
of p-xylene is close to the boiling points of the other isomers, BTA process superstructure. The UOP Isomar allows for the
separation of p-xylene using conventional distillation is not practical exclusive production of either p-xylene, m-xylene, and o-xylene,
and typically occurs through either fractional crystallization or an important consideration that will be depicted within the case
adsorption. The Parex process consists of two adsorption chambers studies later in the paper. The effluent from the UOP Isomar
with 12 beds each and utilizes a solid zeolitic adsorbent to selec- process is sent to a deheptanizer distillation column that purges
tively separate para-xylene.97 The process operates at a temperature the C7 light ends. The C8-rich aromatic mixture is then mixed
of 180 °C and 1.2 bar and recovers 99% of the incoming para- with the bottoms from the toluene distillation column and
xylene with a mass purity of at least 99.5%. The p-xylene effluent is directed to one of the two xylene distillation columns.
Energy Fuels 2016, 30, 4970−4998
2.5.10. C9 Distillation Column. The BTA process super- other C8 isomers. The first alternative, the UOP Parex process,
structure currently contains three processing options for the was described above. Before the introduction of the Parex
heavy aromatics produced within the refinery. The heavy system, the only method of separating p-xylene from the other C8
aromatics exiting the bottom of the o-xylene distillation column aromatic isomers was via fractional crystallization. However, the
and xylene column 2 can either be split to the C9 distillation effective separation of p-xylene using crystallization is impaired
column or output as gasoline. The distillate from the C9 because of a eutectic composition limit that only allows for
distillation column contains 99% of the incoming C9 aromatics 65% per pass recovery of p-xylene.97 This is mediated, however,
and a small portion of the incoming C10 aromatics. The distillate when the feed into the crystallization system contains over 70%
is split between the UOP Tatoray process and the UOP TAC9 p-xylene.156 Because of this, the crystallization process is coupled
process, which are described in the subsequent subsections. The with the UOP PX-Plus process. The single-stage crystallization
bottoms product, which predominantly contains a C10+-rich process recovers high-purity p-xylene (99.9%).
aromatic stream, is directed to the gasoline blender to be output The effluent from the PX-Plus is directed to an upgrading
as gasoline. process that separates out benzene and heavier aromatics. Light
2.5.11. UOP Tatoray. Any toluene produced within the gases exiting the PX-Plus are recycled in the refinery, and the C9
refinery can be reacted with C9 aromatics via transalkylation (eq 5) aromatics are split and either output as gasoline or directed to
within the Tatoray reactor to produce mixed xylenes. Additionally, the UOP Tatoray or UOP TAC9 processes. The Badger/Niro
the disproportionation of toluene (shown in eq 4) to produce mixed crystallization process outputs high-purity para-xylene, while the
xylenes and benzene also takes place.97,150 The UOP Tatoray mother liquor (a mixture of C8 aromatic isomers) is directed to
process utilizes a fixed bed reactor that operates at a temperature the UOP Parex process. The effluent exiting the PX-Plus reactor
of 430 °C and 35 bar.97,151 A 50−50 wt % ratio of toluene and C9 is composed of 7.5 wt % light gases, 43.4 wt % benzene, 35.6 wt %
aromatics is input along with a small amount of makeup hydrogen. p-xylene, 11.4 wt % mixed xylenes, and 2.1 wt % C9 aromatics.156
The UOP Tatoray process is modeled using an atom balance and The mixed xylenes are decomposed according to Table 3 of an
the information provided in Table 1 of U.S. Patent 7,109,389 B2.151 excellent review by Tsai et al. and the information in the PX-Plus
The effluent from the Tatoray process is mixed with the effluent packet provided by UOP.102,156 Ernst also provides a typical
from the UOP TAC9 process and the UOP Sulfolane process and is product distribution for the PX-Plus reactor.142
sent to be fractionated, as shown in Figure 6. 2.6. Light Gas Handling. Light gas that is generated within
2·C7H8 ↔ C6H6 + C8H10 the BTA refinery can be recycled back within the process in order
(4)
to increase overall conversion, produce heat for process units, or
C7H8 + C9H12 ↔ 2·C8H10 generate electricity. An internal or external gas loop config-
(5)
uration is designed in order to handle the light gases produced
2.5.12. UOP TAC9. Alternatively, the distillate from the C9 within the BTA refinery. The internal gas loop configuration will
distillation column can be split to the UOP TAC9 process, where recycle light gases produced via methanol synthesis back to the
the conversion of heavy aromatics into xylenes via transalkylation reactor to increase the overall conversion. A portion of these light
takes place in a fixed bed reactor. A mixture of C9−C10 aromatics gases must be purged to prevent buildup of inert species within
can be input into the TAC9 process to be converted into mixed the refinery. The light gases purged from methanol synthesis,
xylenes.152,153 The maximum amount of C9+ aromatics that the along with any other light gases generated within the refinery, will
TAC9 process is able to handle is 70%;154 therefore, a 2.5:1 molar be handled via the external gas loop configuration. The external
ratio of C9 aromatics and toluene is input. The reactor operates at gas loop configuration will direct the light gases to either the fuel
a temperature of 300 °C, a pressure of 1.2 bar, and the per-pass combustor to provide heat for process units, the gas turbine to
conversion of toluene and C9 aromatics is roughly 40% and 45%, generate electricity, or an autothermal reformer to reform the
respectively.155 The composition of the TAC9 effluent is derived light gases into syngas components that can be recycled back
from Table 3 of a study by Krejči ́ et al.155 and is modeled using an in the refinery. The effluent from the fuel combustor and the
atomic balance. The aromatic effluent exiting the reactor is mixed gas turbine can either be vented or cooled down to 35 °C, passed
with the effluent from the UOP Sulfolane process and the UOP through a water knockout unit, and sent to a CO2 capture unit.
Tatoray process and is directed to the fractionation columns. The reformed gases from the autothermal reformer can be
The global optimization branch-and-bound framework will deter- recycled to several process units within the BTA refinery,
mine whether the UOP Tatoray process, the UOP TAC9 process, including the water−gas-shift reactor and the biomass gasifier,
or both will exist within the BTA refinery. This decision depends among others. The external gas loop configuration is shown in
on the relative amounts of C9+ aromatics and toluene exiting the Figure 7.
hydrocarbon production section, the investment and operating 2.7. Hydrogen/Oxygen Production. Several process units
costs of these processes, and their respective effluent compositions. within the BTA superstructure require hydrogen and oxygen. In
2.5.13. UOP PX-Plus XP Process. The UOP PX-Plus XP is the order to satisfy this requirement, high purity hydrogen will be
final alternative for the conversion of toluene within the biomass provided via electrolysis of water or pressure-swing adsorption.
to aromatics process synthesis superstructure. The UOP PX-Plus An air separation unit or an electrolyzer will provide the neces-
XP process is a combination of the PX-Plus process, which sary oxygen. The process flow diagram is shown in Appendix A
selectively disproportionates toluene into p-xylene, and the (Supporting Information).
Badger/Niro p-Xylene crystallization process, which recovers 2.8. Wastewater Treatment. A comprehensive wastewater
p-xylene from a stream of C8 isomers.142,156 The selectivity to the treatment section is included within the BTA superstructure to
p-xylene isomer is close to 90%.142 Additionally, a small amount treat process wastewater.129 The process wastewater treatment
of H2 is input into the process. The PX-Plus process also section includes a biological digestor and sour stripper that
produces a benzene coproduct. inputs sour water and acid-rich wastewater from process units
The Badger/Niro p-Xylene crystallization process represents within the refinery. The utility wastewater treatment section
the second alternative for the separation of p-xylene from the outputs process water for electrolysis and steam to process units.
Energy Fuels 2016, 30, 4970−4998
Figure 7. Light gas recycle flow sheet.
The process flow diagrams are shown in Appendix A (Supporting 4.5% of the total plant costs and the refinery is assumed to
Information). operate for 330 days/yr (CAP). These values are used to convert
2.9. Unit Costs. The total direct costs (TDC) of each unit in the total cost of a unit into its levelized unit cost, (costU), as
the BTA refinery are rigorously calculated using eq 6: shown in eq 8:
Sr sf ⎛ LCCR· IDCF OM ⎞ ⎛ TPCu ⎞
TDC = (1 + BOP)Co( ) cos t Uu = ⎜ + ⎟·⎜ ⎟
So (6) ⎝ CAP 365 ⎠ ⎝ Prod ⎠ (8)
where BOP represents the balance of plant (site preparation, civil where Prod levelizes the cost based on the total energy of
works, etc.) percentage (20% of the total installed cost), Co is the products produced.
base component cost, So is the base component size (capacity), Sr 2.10. Utility Requirements. Several units within the BTA
is the actual component size (capacity), and sf is the scaling refinery have utility requirements that are already known, and
factor. In order to accurately estimate the total cost of each thus are modeled with known energy balances and require-
unit, several literature sources16,32,97,135,138,139,152,156−159 are used ments. The utility requirements for these units are shown in
to the determine the parameters used in eq 6. The Chemical Appendix A.1 (Supporting Information). The remaining units
Engineering Plant Cost Index is used to convert all costs in (e.g., heat exchangers, compressors, and others) are calculated
2015 dollars.160 The cost parameters are shown in Table 4. using the conservation of energy and total heat balance equations
Engineering, contingency, startup, royalties, fees, and spare shown in Appendix B (Supporting Information). The process
parts are included within the indirect costs of the refinery.32 synthesis framework determines the total minimum utility cost
The indirect costs are assumed to be 32% of the total direct costs for the process.
in the BTA refinery. The total plant costs (TPC), also referred to 2.11. Objective Function. Equation 9 illustrates the
as the fixed capital investment (FCI), are calculated as the sum of objective function for the MINLP model described in the previous
the total direct costs and the total indirect costs. To levelize the sections:
total plant costs to a yearly cost, the levelized capital charge rate
(LCCR) and the interest during construction factor (IDCF) MIN ∑ cos t f + cos tEl + cos tSeq + ∑ cos tUu
f ∈ Feed u ∈ UInv
are used in eq 7 to calculate the capital charges:
CC = LCCR· IDCF· TPC (7) − ∑ cos t p
p ∈ Products (9)
The values of LCCR (14.38%/yr) and IDCF (7.16%/yr) are
taken from Kreutz et al.32 The overall multiplier, 15.41%/yr, The summation represents the total negative profit and includes
converts the total plant costs into total yearly capital charges. contributions from the feedstock costs, costf, the electricity
The operating and maintenance (OM) costs are assumed to be costs/profit, costEl, the CO2 sequestration cost, costSeq, the
Energy Fuels 2016, 30, 4970−4998
Table 4. BTA Refinery Upgrading Unit Reference Capacities, Costs (2015 $), and Scaling Factors
description Co (MM$) So SMax units scale basis sf ref
Biomass Conversion
biomass handling (forest) $4.55 17.90 33.30 kg/s as received biomass 0.77 Kreutz et al., 200832
biomass handling (nonforest) $14.11 17.90 33.30 kg/s as received biomass 0.77 Kreutz et al., 200832
biomass gasification $54.04 17.90 33.30 kg/s dry biomass 0.77 Larson et al., 200916
Synthesis Gas Handling/Clean-Up
water-gas-shift unit $3.67 150.00 250.00 kg/s feed 0.67 NREL, 2011135
rectisol unit $31.42 2.51 8.78 kmol/s feed 0.63 Kreutz et al., 200832
Hydrocarbon Production
methanol synthesis and degasser $8.05 35.65 kg/s feed 0.65 NREL, 2011135
methanol-to-aromatics unit $8.67 10.63 42.50 kg/s feed 0.65 NREL, 2011135
GTC toluene alkylation $42.42 13.89 200.00 kg/s toluene feed 0.67 GTC, 2014139
Hydrocarbon Upgrading
deethanizer $0.57 5.13 kg/s feed 0.68 NREL, 2011;135 Mobil R&D, 1978157
absorber column $0.89 0.96 kg/s feed 0.68 NREL, 2011;135 Mobil R&D, 1978157
stabilizer column $1.01 4.57 kg/s feed 0.68 NREL, 2011;135 Mobil R&D, 1978157
splitter column $0.99 3.96 kg/s feed 0.68 NREL, 2011;135Mobil R&D, 1978157
HF alkylation unit $8.79 0.61 kg/s feed 0.65 NREL, 2011;135 Mobil R&D, 1978157
LPG/alkylate splitter $1.04 0.61 kg/s feed 0.68 NREL, 2011;135 Mobil R&D, 1978157
autothermal reformer $21.50 12.20 35.00 kg/s feed 0.67 NETL, 2013158
Aromatics Production Complex
UOP sulfolane $21.15 15.14 100.00 kg/s feed 0.67 Meyers, 200497
UOP isomar $45.91 1555.50 200.00 kg/s feed 0.67 Meyers, 200497
UOP Tatoray $22.25 24.82 200.00 kg/s feed 0.67 Meyers, 200497
UOP Parex $153.54 106.20 200.00 kg/s feed 0.67 Meyers, 200497
UOP MX Sorbex $96.54 5.58 200.00 kg/s feed 0.67 Meyers, 200497
benzene distillation $0.56 10.83 200.00 kg/s feed 0.52 Aspen Plus PEA
toluene distillation $1.16 10.04 200.00 kg/s feed 0.72 Aspen Plus PEA
xylene1 column $5.00 12.11 200.00 kg/s feed 0.49 Aspen Plus PEA
xylene2 column $2.19 11.72 200.00 kg/s feed 0.77 Aspen Plus PEA
ortho-xylene distillation $0.99 12.14 200.00 kg/s feed 0.66 Aspen Plus PEA
C9 distillation $0.93 15.31 200.00 kg/s feed 0.53 Aspen Plus PEA
PXPLUS XP $65.38 19.38 200.00 kg/s toluene feed 0.67 UOP, 2006156
UOP TAC9 $16.06 13.19 200.00 kg/s feed 0.67 Hydrocarbon Processing, 2010152
cyclar process $112.67 16.42 200.00 kg/s feed 0.67 Meyers, 200497
Hydrogen/Oxygen Production
pressure-swing adsorption $7.79 0.29 kmol/s purge gas 0.65 Larson et al., 200916
air separation unit $243.50 145.00 41.70 kg/s O2 feed 0.50 NETL, 2013158
air compressor $5.90 10.00 30.00 MW electricity 0.67 Larson et al., 200916
electrolyzer $0.49 1.00 MW electricity 0.90 Larson et al., 200916
Heat and Power Integration
gas turbine $79.84 266.00 334.00 MW electricity 0.75 Larson et al., 200916
steam turbine $64.87 136.00 500.00 MW electricity 0.67 Larson et al., 200916
Wastewater Treatment
sour stripper $3.91 11.52 kg/s feed 0.53 NETL, 2010138
biological digestor $4.65 115.74 kg/s feed 0.71 Balmer, 1994159
reverse osmosis $0.31 4.63 kg/s feed 0.85 Balmer, 1994159
cooling tower $61.04 1.75 gW heating deficit 0.65 NETL, 2010138
levelized investment cost, costU, and the profits from selling the variables, 23 463 constraints, and 528 nonconvex terms. The
products, costp. The feedstock costs include contributions from nonconvex terms consist of 468 bilinear terms, 1 trilinear term,
biomass and freshwater, while the product profits include 3 quadrilinear terms, and 56 concave power functions. In order to
contributions from benzene, toluene, p-xylene, m-xylene, o-xylene, solve the model, a novel branch-and-bound161 algorithm is used
gasoline, and LPG. Each term is normalized with respect to and refined to generate satisfactory initial starting points that are
the total energy of products (aromatics/liquid fuels) produced. used to find upper bound solutions. Any nonlinearity within
The objective function is minimized, which is equivalent to the model is underestimated with its linear relaxation, and the
maximizing the total profit of the BTA refineries. resulting mixed-integer linear optimization (MILP) model is
2.12. Deterministic Global Optimization. The process solved using CPLEX162 to generate the lower bound of the
synthesis superstructure described in the preceding sections is overall MINLP model. Bilinear terms are underestimated using
modeled mathematically as a large-scale, nonconvex, mixed- piece-wise McCormick underestimators, where the number of
integer, nonlinear optimization (MINLP) model. The resulting pieces used depends logarithmically on the number of binary
MINLP model contains 19 303 continuous variables, 28 binary variables. Concave power functions used to represent the
Energy Fuels 2016, 30, 4970−4998
investment cost of each individual unit are underestimated using Table 5. Cost Parameters for the BTA Refinery
piece-wise linear relaxations where each piece is represented
commodity nominal prices
using a binary variable. The solution of the lower bound (MILP
model) generates several initial starting points. The binary agricultural (corn stover) $120/dry metric ton
variables are fixed at the starting points, and the resulting non- perennial (switchgrass) $100/dry metric ton
linear optimization model (NLP) is solved using CONOPT163 forest (hardwood) $70/dry metric ton
freshwater $0.50/metric ton
to generate upper bound solutions. An optimality-based bounds
electricity $0.07/kWhr
tightening (OBBT) routine is formulated at the root node to
CO2 TS&Ma $5/metric ton
tighten all variables associated with the total molar flow rates and
propane $0.99/gal
nonlinear investment cost. After the completion of the OBBT
gasoline $2.86/gal
route, a feasibility-based bounds tightening (FBBT) routine is
p-xylene $1.602/kg
started to additionally tighten all species molar flow rates. Each m-xylene $1.405/kg
node in the branch-and-bound tree branches to form two children o-xylene $1.367/kg
nodes, and an OBBT routine is again completed on selected benzene $1.431/kg
variables before the start of each node. The upper bound is toluene $1.294/kg
updated if the solution of the NLP is lower than the current upper a
TS&M - transportation, storage, and monitoring.
bound. Nodes with a lower bound greater than the current upper
bound are eliminated. For a detailed explanation of deterministic The minimum number of heat exchanger matches is calculated using the
global optimization theory and algorithm, the reader is directed to above information as previously described.127−129,164,168 A super-
textbooks by Floudas.164,165 structure approach is then utilized to determine the minimum
investment cost of the heat exchanger network.127,129,164,168 The min-
imum cost of the heat exchanger network is then added to the overall
3. COMPUTATIONAL STUDIES BTA refinery investment cost.
The process synthesis model described above (see Appendix B 3.1. Optimal Process Topologies. Table 6 shows the optimal
(Supporting Information) for its full description) is used to examine process topologies selected for the biomass to aromatics refineries using
45 distinct case studies across three sets of feedstocks: corn stover, nominal prices. Table 6 illustrates (i) the type of gasifier selected, (ii) the
switchgrass, and hardwood biomass. Three sets of aromatics products operating temperature of the biomass gasifier, (iii) the existence and
are considered that (a) place no restriction on the type of xylenes operating temperature of the forward/reverse water−gas-shift reactor,
produced, (b) limit xylenes output to only the o-xylene isomer, and (iv) the selection of the methanol conversion units, (v) the existence of
(c) limit xylenes output to only the m-xylene isomer. These case studies the ortho-xylene distillation column, (vi) the existence of the UOP Parex
reflect the capability of our superstructure-based approach to produce process, (vii) the existence of the UOP Tatoray process, (viii) the
any ratio of the p-, o-, and m-xylene isomers. The effect of refinery existence of the UOP TAC 9 process, (ix) the existence of the UOP
capacity is investigated by constraining the total output from the refinery PXPLUS XP process, (x) the existence of the UOP Cyclar process,
to be 100, 200, 500, 1000, or 2000 t per day of xylene equivalent (based (xi) the selection of a CO2 sequestration system, and (xii) the existence
on its lower heating value) chemicals. The refinery capacities were of a gas turbine.
selected such that a feasible amount of biomass could be economically As explained earlier, the input into the biomass gasifier can either be
transported to the plant gate every day. Allowable byproducts include solid biomass or a mixture of solid biomass and recycle gases.
gasoline, LPG, and electricity. A 75% minimum mass threshold for Additionally, the biomass gasifier can operate at a temperature of either
aromatics output was imposed in each of the case studies to enforce 900 °C, 1000 °C, or 1100 °C. In each of the corn stover and switchgrass
the stand-alone chemicals concept. The case studies will be denoted as BTA refineries, the input included a mixture of solid biomass and recycle
N−C, where N represents the aromatics composition in the unrestricted gases. The only refineries that input solid biomass into the gasifier are
(U), o-xylene (O), and m-xylene (M) refineries, and C represents the the hardwood M-200 and O-500 refineries. In each of the refineries
capacity in metric tons per day. Throughout the text, descriptions such investigated, the optimal operating temperature of the gasifier was
as F−N−C may be used to differentiate between the corn stover (CS), selected to be 900 °C. At lower operating temperatures, the gasifier
switchgrass (SG), and hardwood (HW) refineries. requires less oxygen for combustion and produces less waste heat for
The MINLP model includes a constraint that imposes at least a 50% steam generation. Additionally, the equilibrium constant of the forward
reduction in life cycle greenhouse gas emissions from the biomass-based water−gas-shift reaction is higher at lower temperatures, thus resulting
aromatics facility. This reduction is based on typical petroleum-based in less favorable conditions for CO2 consumption. Since the synthesis
refineries (91.6 kg CO2eq/GJLHV),166 a high-value chemicals (HVC) gas produced from biomass has a H2/CO ratio that is less than ideal for
production plant (1.7 kg CO2eq/kg of HVC),167 and a natural gas methanol production, it needs to pass through a forward water−gas-shift
combined cycle plant (101.3 kg CO2eq/GJ) that produces electricity.138 reactor operating at 300 °C.
If electricity is input (output) into the refinery, the GHG emissions are All of the methanol exiting the methanol synthesis reactor was
added (subtracted) to the life-cycle emissions of the BTA refinery. directed to the MTA (methanol-to-aromatics) reactor. The decision to
Nominal cost parameters used in the process synthesis model are exclude the GTC-TolAlk process was dependent on the operating and
illustrated in Table 5. Feedstock costs include costs associated with capital costs of the process and the composition of the effluent leaving
delivery to the plant gate. Product costs do not include costs associated the reactor.
with transportation of the products from the plant gate. The costs The types of aromatics to produce and the relative ratios of these
associated with the capture and compression of CO2 are included in the chemicals is an important topological decision. In all of the case studies
investment costs of the BTA refinery, shown in Table 4. The costs investigated, benzene was always produced as it is a major product in the
shown in Table 5 include the transportation, storage, and monitoring methanol-to-aromatics reaction and currently no benzene conversion
costs of CO2. reactors exist within the superstructure.
The global optimization algorithm was allowed to run for 100 CPU In all of the unrestricted case studies, the only C8 aromatic produced
hours or until all nodes in the branch-and-bound tree were processed. was para-xylene. The CS-U-100 and CS-U-1000 case studies also
After completion of the global optimization branch-and-bound produced a toluene product.
algorithm, the optimal BTA process topology will yield (i) the operating In the o-xylene case studies, only the CS-O-1000 and CS-O-2000
conditions of the heat engines, (ii) the amount of electricity produced produced a toluene product. All of the m-xylene refineries inputting corn
by the heat engines, (iii) the amount of cooling water necessary, and stover and switchgrass produced toluene. The only hardwood m-xylene
(iv) the locations of all pinch points in the heat exchanger network. refineries that produced toluene were the M-500 and M-1000.

Energy Fuels 2016, 30, 4970−4998
Table 6. Topological Information for the Optimal Solutions for Each of the Case Studies Is Displayed Belowa
Corn Stover
U-100 U-200 U-500 U-1000 U-2000 O-100 O-200 O-500 O-1000 O-2000 M-100 M-200 M-500 M-1000 M-2000
biomass conv. S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V
Energy & Fuels
BGS Temp. 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00
WGS/RGS Temp. 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00
MTA usage Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
GTC-tolAlk Usage
ortho distillation Y Y Y Y Y
UOP MX Sorbex Y Y Y Y Y
UOP Parex Y Y Y Y Y
UOP Tatoray Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
UOP Tac9 Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
UOP PXPLUS XP
UOP Cyclar Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
CO2SEQ usage
GT usage
Hardwood
biomass conv S/V S/V S/V S/V S/V S/V S/V S S/V S/V S/V S S/V S/V S/V
BGS temp 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00
WGS/RGS temp 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00
4981
MTA usage Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
GTC-TolAlk usage
UOP Parex Y Y Y Y Y
UOP Tac9 Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
UOP PXPLUS XP
UOP Cyclar Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
CO2SEQ Usage
GT Usage
Switchgrass
Biomass Conv. S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V S/V
BGS Temp. 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00 900.00
WGS/RGS Temp. 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00 300.00
MTA Usage Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
GTC-TolAlk usage
UOP Parex Y Y Y Y Y
Article
DOI: 10.1021/acs.energyfuels.6b00619
Energy Fuels 2016, 30, 4970−4998
Toluene and heavy aromatics produced within the refinery were
Biomass conversion (Biomass Conv.) can proceed through either gasification of the solid biomass (S) or a mixture of solid biomass and recycle gases (S/V). Temperature of the biomass gasifier
Tatoray, the UOP TAC9, or the UOP PX-Plus XP processes will be denoted using yes (Y) or no (−). The existence of the Cyclar unit to convert LPG into additional aromatics will be denoted using yes
xylene using the UOP MX Sorbex reactor will be denoted using yes (Y) or no (−). Separation of p-xylene using the UOP Parex process will be denoted using yes (Y) or no (−). The existence of the UOP
aromatics (MTA) process or toluene methylation technologies (GTC-TolAlk) will be denoted using yes (Y) or no (−). Production of o-xylene using an o-xylene distillation column or production of m-
(BGS temp; °C), along with the operating temperature of the forward/reverse water−gas-shift reactor (WGS/RGS temp; °C), is shown. The conversion of methanol using either the methanol-to-
M-2000
always split to both the UOP Tatoray and UOP TAC9 reactors.
The UOP Tatoray reactor produces mixed xylenes and benzene, while
Y
the UOP TAC9 process produces xylenes. The UOP PX-Plus XP
process was never selected.
M-1000
The LPG produced within the MTA reactor was always sent to the
Cyclar process to produce additional aromatics, despite the added
Y
Y
investment cost associated with this unit. All of the aromatics refineries
were able to meet the environmental constraint (at least a 50% reduction
in GHG emissions) imposed within the model without the additional
M-500
investment and operating costs associated with a CO2 sequestration

Y
system. This is to be expected, since it is well-known that the utilization

of biomass has significant environmental benefits. Finally, none of the
case studies utilized a gas turbine.
M-200
3.1.1. Detailed Discussion on the Optimal Topology for the HW-U-

2000 Refinery. The process flow diagram for the HW-U-2000 case study
Y
is shown in Figure 8 as an illustrative example. Figure 9 shows the

process flow diagram of the HW-U-2000 aromatics complex with
M-100
corresponding stream flow rates shown in Table 7 for several relevant

units. In both figures, the key topological decisions are shown. Note that
Y
(Y) or no (−). Likewise, the utilization of a gas turbine (GT) or a CO2 sequestration system (CO2SEQ) is denoted using yes (Y) or no (−).
several process units such as heat exchangers, compressors, and turbines

are not shown.
O-2000
All of the methanol exiting the methanol synthesis reactor is split to

the MTA reactor. The input into the toluene alkylation process requires
Y
toluene and methanol in a weight ratio of approximately 4:1.89.

The global optimization branch-and-bound framework determined that
O-1000
it is more profitable to split the toluene (produced from the MTA

reactor and processed in the aromatics complex) to the UOP Tatoray
Y
process and the UOP TAC9 process rather than include an additional
expensive hydrocarbon production unit. Additionally, the selection of
O-500
the UOP Tatoray process and UOP TAC9 process in the optimal
topology allows for the conversion of heavy aromatics into more
Y
valuable mixed xylenes and benzene. The UOP PXPLUS-XP process is

not selected in the optimal topology because of the input into the
Switchgrass
process and required investment cost. Although the PXPLUS process

O-200
also produces mixed xylenes and benzene (43.4 wt % benzene, 35.6%

Y
p-xylene, 11.4 wt % mixed xylenes), it does not allow for the conversion
of C9 aromatics within the refinery, which would then have to be
directed to the gasoline pool if all toluene were split to the PXPLUS
O-100
process. Additionally, the UOP Tatoray and the UOP TAC9 processes
Y
are both less expensive than the UOP PXPLUS-XP process. Even if
the UOP PXPLUS-XP process were selected in the optimal topology,
the UOP Parex process would still be required to separate p-xylene
U-2000
because the C8 aromatic streams within the refinery do not contain a

Y
large amount of p-xylene (i.e., > 70%). As Figure 9 and Table 7 show,
72.2% of the toluene distillate is split (from SPTOL to MXTATORAY) to the
UOP Tatoray process, while the balance (27.8% - from SPTOL to
U-1000
MXTAC9) is directed to the UOP TAC9 process. 44.4% of the C9

Y
distillate is split (from SPC9A to MXTATORAY) to the UOP Tatoray

process, while the balance (55.6% - from SPC9A to MXTAC9) is directed to
the UOP TAC9 process. The effluents from the UOP Tatoray and UOP
U-500
TAC9 processes are mixed with the other aromatic-rich effluents from
the refinery and directed to the benzene distillation column.
Y
Note that the H2 balance exiting the UOP Tatoray process (Table 7)
is used to close the atom balances around the process and is not recycled
U-200
back within the process.151 Also note that the values of the output
streams in Figure 9 and Table 7 correspond exactly to the material
Y
balances shown in Table 11.

The gasoline blend produced within the refinery contains mostly
U-100
paraffins and heavy aromatics, along with some benzene, toluene, and
xylenes. To meet all physical property specifications of gasoline, the
Y
aromatic-rich gasoline from the BTA refinery must be blended.135,169,170

Table 6. continued
The energy content for gasoline, which is used in Table 12, is based on a
generic lower heating value of 5505.2 GJ per thousand barrels and a
UOP PXPLUS XP
CO2SEQ Usage
density of 747 kg/m3.

3.2. Overall Profit of Aromatics Production. The overall profit
UOP Cyclar
UOP Tac9
GT Usage
for each of the biomass to aromatics refineries is shown in Table 8.

The overall profit is presented as the difference between the costs
associated with the production of the aromatics/byproducts and the
revenue from selling these products. Thus, the more negative the value
a

Energy Fuels 2016, 30, 4970−4998
Figure 8. Process flow diagram for the HW-U-2000 refinery.
Figure 9. Aromatics complex process flow diagram with stream information for the HW-U-2000 refinery.

Energy Fuels 2016, 30, 4970−4998
Table 7. Stream Flow Rates (in mol/s) for the Aromatics Complex for the HW-U-2000 Refinery, As Shown in Figure 9
Stream Number
component 1 2 3 4 5 6 7 8 9 10 11 12
C6H6 8.68695 23.18395 23.16076 0.02318 0.02318 0 0 0 0 0 0 0
Energy & Fuels
C7H8 27.69430 85.45948 0.00299 85.45648 85.37103 0.08546 0.08546 0.08546 0 0.08546 0.08546 0.08546
o-C8H10 18.93431 33.67842 0 33.67842 0.00002 33.67839 145.49042 144.74609 0 144.74609 111.81203 0
m-C8H10 42.96353 75.52819 0 75.52819 0.00073 75.52746 309.35804 309.23739 0 309.23739 233.83058 0
p-C8H10 20.99561 36.32567 0 36.32567 0.00052 36.32515 150.43594 150.38915 148.88526 1.50389 114.11079 0
e-C8H10 1.32341 4.36836 0 4.36836 0.00022 4.36814 14.32221 14.32035 0.10024 14.22010 9.95407 0
C9H12 60.87253 107.61650 0 107.61650 0 107.61650 107.62726 0.01076 0 0.01076 0.01076 0
C10H14 12.18034 24.47819 0 24.47819 0 24.47819 24.47819 0 0 0 0 0
C11H16 0 0.31388 0 0.31388 0 0.31388 0.31388 0 0 0 0 0
Stream Number
component 13 14 15 16 17 18 19 20 21 22 23 24
C6H6 0 0 0 0 0.01675 0.00644 0 0 0 0 14.13290 0.36409
C7H8 0 0 0 0 61.66383 23.70720 0 0 0 0 43.34339 14.42179
o-C8H10 111.81203 0.74433 0 0.74433 0.33027 0.41408 0 0 0 0 8.37864 6.36546
m-C8H10 233.83058 0.12065 0 0.12065 0.05406 0.06732 0 0 0 0 18.32223 14.24242
p-C8H10 114.11079 0.04679 0 0.04679 0.02114 0.02617 0 0 0 0 8.37864 6.95141
e-C8H10 9.95407 0.00186 0 0.00186 0.00099 0.00110 0 0 0 0 3.04385 0.00110
C9H12 0.01076 107.61650 1.07724 106.53926 47.27126 59.26799 0 0 0 0 14.83991 31.90405
0 24.47819 24.47574 0.00245 0.00109 0.00136 0 0 0 0 3.37039 8.92746
4984
C10H14
C11H16 0 0.31388 0.31388 0 0 0 0 0 0 0 0 0.31388
H2 0 0 0 0 0 0 0.27340 0.20873 0 0.20873 0 0
H2 balance 0 0 0 0 0 0 0 0 13.62514 0 0 0
Article
Energy Fuels 2016, 30, 4970−4998
Table 8. Overall Cost Results (in $/GJ) for the Case Studies Are Showna
Corn Stover
biomass 9.68 9.84 9.83 9.68 9.69 9.00 8.87 9.35 9.38 9.45 9.21 9.21 10.07 10.19 10.23
Energy & Fuels
water 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.02
investment 22.19 17.42 12.68 10.03 8.40 20.09 15.73 11.73 9.35 7.82 27.17 21.34 16.21 12.90 10.69
CO2 TS&M 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
O&M 5.86 4.60 3.35 2.65 2.22 5.30 4.15 3.10 2.47 2.06 7.17 5.63 4.28 3.41 2.82
electricity 2.57 2.57 2.56 2.56 2.57 2.59 2.61 1.79 1.57 1.48 2.58 2.57 1.16 0.99 0.91
gasoline −5.45 −5.23 −5.23 −5.45 −5.45 −5.33 −5.24 −5.24 −5.45 −5.45 −5.45 −5.45 −5.45 −5.45 −5.45
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene −2.37 −2.71 −2.71 −2.37 −2.37 −2.88 −2.68 −2.68 −2.36 −2.36 −2.36 −2.36 −2.36 −2.36 −2.36
toluene −0.19 0.00 0.00 −0.19 0.00 0.00 0.00 0.00 −0.19 −0.19 −0.19 −0.19 −0.19 −0.19 −0.19
p-xylene −26.25 −26.50 −26.50 −26.25 −26.48 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 −22.31 −22.63 −22.63 −22.41 −22.41 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 −23.03 −23.03 −23.03 −23.03 −23.03
total ($/GJ) 6.05 0.00 −6.01 −9.34 −11.42 6.47 0.82 −4.57 −7.63 −9.59 15.12 7.75 0.69 −3.54 −6.36
lower bound ($/GJ) 4.79 −1.04 −6.83 −9.94 −12.05 4.95 −0.31 −5.53 −8.42 −10.28 13.24 6.14 −0.62 −4.60 −7.31
absolute difference 1.27 1.04 0.82 0.60 0.63 1.52 1.14 0.96 0.79 0.69 1.88 1.61 1.31 1.06 0.95
Hardwood
biomass 5.51 5.51 5.50 5.73 5.73 5.03 5.39 8.07 5.39 5.39 5.42 8.06 5.78 5.77 5.87
4985
water 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.03 0.01 0.01 0.01 0.03 0.01 0.01 0.01
investment 22.00 17.17 12.40 10.17 8.40 19.75 16.39 12.49 9.11 7.53 26.70 22.71 16.08 12.72 10.49
CO2 TS&M 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
O&M 5.81 4.53 3.27 2.68 2.22 5.21 4.33 3.30 2.41 1.99 7.05 6.00 4.25 3.36 2.77
electricity 2.65 2.65 2.64 2.05 2.05 2.64 1.50 −1.98 1.50 1.50 2.63 −1.61 0.93 0.92 0.91
gasoline −5.23 −5.23 −5.23 −5.23 −5.23 −5.32 −5.24 −5.24 −5.24 −5.24 −5.45 −5.45 −5.45 −5.45 −5.24
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene −2.71 −2.71 −2.71 −2.71 −2.71 −2.86 −2.68 −2.68 −2.68 −2.68 −3.25 −3.22 −2.36 −2.36 −2.69
toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 −0.19 −0.19 0.00
p-xylene −26.50 −26.50 −26.50 −26.50 −26.50 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 −22.35 −22.63 −22.63 −22.63 −22.63 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 −22.38 −22.41 −23.03 −23.03 −23.25
total ($/GJ) 1.54 −4.58 −10.61 −13.82 −16.04 2.12 −2.92 −8.64 −12.13 −14.13 10.73 4.10 −3.99 −8.26 −11.12
lower bound ($/GJ) 0.01 −5.57 −11.50 −14.48 −16.62 0.60 −4.08 −9.31 −12.68 −14.60 8.41 2.41 −5.07 −9.02 −11.72
absolute difference 1.52 0.99 0.89 0.66 0.58 1.52 1.16 0.67 0.54 0.47 2.32 1.69 1.08 0.76 0.60
Switchgrass
biomass 8.12 8.12 8.13 8.13 8.44 7.46 7.33 7.91 7.90 7.91 7.61 7.61 8.49 8.49 8.49
water 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02
investment 22.28 17.45 12.69 10.06 8.66 20.04 15.69 11.88 9.38 7.86 27.16 21.34 16.33 12.96 10.72
CO2 TS&M 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Article
O&M 5.88 4.61 3.35 2.66 2.29 5.29 4.14 3.14 2.48 2.07 7.17 5.63 4.31 3.42 2.83
Energy Fuels 2016, 30, 4970−4998
shown, the more profitable the refinery is. The value shown in Table 8
more negative this value is the more profitable a refinery becomes. The overall profit can be determined by taking the negative of the “total ($/GJ)” value. The lower bound values are reported along with
Contributions to the total costs (in $/GJ) of the BTA refineries come from biomass, water, CO2 transportation/storage/monitoring, investment, input electricity, and operating and maintenance. The
M-2000
0.83
−5.45
0.00
−2.36
−0.19
0.00
0.00
−23.03
−8.14
−8.89
0.75
takes the (i) feedstock costs, (ii) CO2 sequestration costs, (iii) investment
costs, (iv) operating and maintenance (O&M) costs, (v) electricity costs
or revenue, (vi) revenue from selling LPG, (vii) revenue from liquid
products, and (viii) revenue from aromatics into account. The values
M-1000
0.83
−5.45
0.00
−2.36
−0.19
0.00
0.00
−23.03
−5.31
−6.25
0.93
shown in Table 8 are normalized with respect to the total energy (in GJ)
of products produced. The absolute difference between the lower bound
and the upper bound of the solutions obtained is shown; this difference
represents how close the solutions obtained are to the mathematically best
possible solution.
0.83
−5.45
0.00
−2.36
−0.19
0.00
0.00
−23.03
−1.06
−2.26
1.20
M-500
Across all three feedstock types, the unrestricted refineries are the
most profitable. They are followed by the o-xylene refineries and the
m-xylene refineries, respectively. The unrestricted refineries mainly
produce p-xylene, with smaller amounts of benzene and gasoline also
2.52
−5.45
0.00
−2.36
−0.19
0.00
0.00
−23.03
6.08
4.37
1.71
M-200
produced. Gasoline byproduct is inevitable in each of the case studies

since the methanol-to-aromatics reaction produces some C6+ paraffinic
components. The Cyclar process is utilized to convert all low-quality
LPG into high-value aromatics; therefore, no LPG is output from
2.52
−5.45
0.00
−2.36
−0.19
0.00
0.00
−23.03
13.45
11.15
2.30
M-100
the refineries. Electricity is input into every BTA refinery except for the
HW-O-500 and HW-M-200 refineries, for which output electricity is
sold to the grid. The m-xylene refineries are the least profitable refineries
because of the increased investment cost with the UOP MX Sorbex
O-2000
1.44
−5.24
0.00
−2.68
0.00
0.00
−22.63
0.00
−11.25
−11.85
0.60
process.
The hardwood aromatics refineries are the most profitable refineries
across all case studies. The switchgrass refineries are the second most
profitable refineries, with the corn stover refineries being the least
O-1000
1.44
−5.24
0.00
−2.68
0.00
0.00
−22.63
0.00
−9.34
−10.03
0.69
profitable. This trend follows the costs of the individual feedstocks: with
hardwood ($70/dry metric ton) being the least expensive, followed by
switchgrass ($100/dry metric ton), and finally corn stover ($120/dry
metric ton). The refineries at small scales (≤500 MT/day) represent
1.44
−5.24
0.00
−2.68
0.00
0.00
−22.63
0.00
−6.16
−6.98
0.82
O-500
pilot plant scale refineries. All of the 100 t per day case studies are
unprofitable. This is in addition to the CS-U-200, CS-O-200, CS-M-200,
CS-M-500, HW-M-200, and SG-M-200 refineries, which are also
unprofitable.
Switchgrass
As Table 8 illustrates, the investment cost represents the largest

2.55
−5.25
0.00
−2.68
0.00
0.00
−22.62
0.00
−0.82
−2.08
1.26
O-200
expenditure associated with each of the hardwood aromatics refineries.

As Table 8 shows and is made more explicit in Table 9, the o-xylene
refineries always have the lowest required investment cost across similar
capacity BTA plants. This is also clear from comparing the values across
2.53
−5.35
0.00
−2.94
0.00
0.00
−22.22
0.00
4.81
3.31
1.50
O-100
similar capacity plants in the Investment row in Table 8. However,

despite the increased investment costs associated with the unrestricted
refineries, they are still more profitable than the o-xylene refineries
because of the higher value of p-xylene compared to o-xylene. As an
U-2000
1.93
−5.23
0.00
−2.71
0.00
−26.50
0.00
0.00
−13.11
−13.72
0.61
example, Table 8 shows that the investment cost for the HW-O-2000
refinery ($7.53/GJ) is $0.87/GJ less expensive than the HW-U-2000
the absolute difference between the upper bound and the lower bound.
refinery ($8.40/GJ). However, the revenue from selling p-xylene in the

HW-U-2000 refinery ($26.50/GJ) is $3.87/GJ higher than from selling
U-1000
2.51
−5.23
0.00
−2.71
0.00
−26.50
0.00
0.00
−11.07
−11.76
0.69
o-xylene in the HW-O-2000 refinery ($22.63/GJ). This relative

difference in the selling prices of the two C8 isomers is the main driver
in determining the relative profitability in the unrestricted and o-xylene
refineries.
2.51
−5.23
0.00
−2.71
0.00
−26.50
0.00
0.00
−7.75
−8.60
0.84
U-500
The HW-U-2000 case study has an overall profit of $16.04/GJ,

the SG-U-2000 refinery has an overall profit of $13.11/GJ, and the
CS-U-2000 case study has an overall profit of $11.42/GJ.
3.3. Investment Costs. The total capital investment cost, or the
fixed capital investment (FCI), is shown in Table 9 for each case study.
2.51
−5.23
0.00
−2.71
0.00
−26.50
0.00
0.00
−1.74
−2.79
1.05
U-200
The breakdown for each section of the BTA refinery is also shown;
it consists of the syngas generation, syngas cleaning, hydrocarbon
production, hydrocarbon upgrading, chemicals production, hydrogen
2.52
−5.23
0.00
−2.71
0.00
−26.50
0.00
0.00
4.37
2.91
1.46
and oxygen production, heat and power integration, and wastewater

U-100
treatment sections.
In the unrestricted corn stover case studies, the largest contributor to
Table 8. continued
the investment cost is the syngas generation section. This section

lower bound ($/GJ)
constitutes between 23 and 29% of the total investment cost across these
absolute difference
case studies. Likewise, the syngas generation section is also the largest
contributor to the investment cost in all of the unrestricted switchgrass
total ($/GJ)
refineries. This section constitutes between 24 and 30% of the total

electricity
m-xylene
p-xylene
benzene
o-xylene
gasoline
toluene
investment cost across the case studies. The largest contributor to the
LPG
total investment cost for the unrestricted hardwood case studies is the
chemicals production section at scales less than or equal to 500 t per day.
a

Energy Fuels 2016, 30, 4970−4998
Table 9. Investment Costs of the Syngas Generation, Syngas Cleaning, Hydrocarbon Production, Hydrocarbon Upgrading, Chemicals Production, Hydrogen/Oxygen Production,
Heat and Power Integration, and Wastewater Treatment Sections of the BTA Refinery Are Showna
Corn Stover
Energy & Fuels
syngas generation 45.74 74.96 143.12 237.75 432.51 45.00 73.17 141.05 234.39 428.01 45.18 73.61 144.06 243.58 445.70
syngas cleanup 33.82 52.94 95.57 149.30 234.98 33.71 52.66 95.12 148.92 234.34 33.69 52.60 95.77 150.23 236.83
HC production 16.99 26.16 46.38 71.63 127.64 17.63 27.67 46.86 71.87 128.43 17.27 26.59 46.27 71.44 126.70
HC upgrading 24.54 38.55 69.92 109.59 193.08 24.56 38.53 69.91 109.61 193.27 24.54 38.50 69.86 109.61 193.29
chemicals production 44.07 70.63 130.81 207.38 334.25 24.06 37.83 67.87 105.72 165.27 87.40 139.12 257.22 409.51 652.07
H2/O2 production 23.06 32.37 51.72 74.77 106.70 24.71 35.63 54.29 77.02 109.30 24.14 34.37 50.31 70.81 101.42
H&P integration 2.01 3.13 5.79 9.38 14.84 2.28 3.71 26.87 53.08 82.85 2.17 3.45 35.93 58.20 92.12
wastewater treatment 6.00 9.42 17.23 26.91 42.21 5.74 8.97 16.75 26.26 41.83 5.94 9.29 17.24 27.32 43.43
total (MM$) 196.24 308.15 560.54 886.71 1486.20 177.67 278.18 518.71 826.87 1383.29 240.33 377.53 716.64 1140.70 1891.56
Hardwood
syngas cleanup 31.96 49.50 88.30 137.47 214.62 31.72 49.39 93.49 136.57 212.54 31.89 52.35 88.81 137.51 215.57
HC production 16.31 25.09 44.48 68.82 120.56 16.58 25.04 48.56 68.51 119.46 16.28 27.48 44.68 68.79 121.23
HC upgrading 24.57 38.56 69.93 109.75 193.67 24.56 38.55 70.05 109.73 193.63 24.57 38.60 69.88 109.65 193.68
H2/O2 production 27.62 39.23 62.62 87.25 125.14 28.89 39.65 45.58 90.40 129.18 27.80 28.55 60.99 86.63 123.57
H&P integration 1.94 3.04 5.64 39.29 57.91 2.22 22.36 71.41 54.46 80.82 1.97 36.63 41.05 63.54 99.70
4987
total (MM$) 194.58 303.69 548.54 899.04 1485.35 174.67 289.99 552.54 805.71 1331.42 236.12 401.70 711.23 1124.72 1855.81
Switchgrass
syngas cleanup 33.70 52.56 94.89 148.62 234.94 33.44 52.23 94.61 148.16 232.68 33.44 52.20 95.35 149.35 234.93
HC production 16.52 25.27 44.82 69.21 121.34 16.87 26.52 44.88 69.28 121.33 16.61 25.60 44.80 69.18 121.20
HC upgrading 24.56 38.54 69.90 109.68 193.52 24.55 38.53 69.90 109.67 193.51 24.53 38.49 69.84 109.59 193.26
H2/O2 production 22.68 32.51 51.86 73.95 101.42 24.68 35.69 53.25 76.00 108.49 24.21 34.46 49.37 70.36 100.49
H&P integration 1.92 2.99 5.53 8.80 50.18 2.18 3.57 33.27 52.73 86.04 2.09 3.32 39.51 61.11 95.83
total (MM$) 197.02 308.61 561.05 889.97 1532.13 177.21 277.62 525.46 829.35 1389.73 240.24 377.43 722.19 1146.49 1896.86
a
All values are shown in MM$.
Article
Energy Fuels 2016, 30, 4970−4998
At scales larger than 500 t per day, the syngas generation section is the is included in Appendix A.2 (Supporting Information). For more
largest contributor to the investment for the unrestricted hardwood case information on net present value calculations, the reader is directed to
studies. In all of the o-xylene case studies, the largest contributor to the following textbook.171
the investment cost is the syngas generation section. This is because the The net present values for the corn stover, hardwood, and switchgrass
chemicals production section does not include any expensive adsorptive refineries are shown in Figures 10, 11, and 12, respectively. Since the
technologies. The chemicals production section is the largest contributor BTA refineries at small scales (≤500 MT/day) represent pilot plants,
in the m-xylene case studies because of the high capital costs associated they just barely break-even or do not return the initial investment.
with m-xylene separation. The hardwood case studies have the highest net present values, followed
The investment costs across feedstock types are relatively similar for by the switchgrass case studies and finally the corn stover refineries.
each individual refinery scale and product type. The value of the The HW-U-2000 refinery has a net present value of over $1200 MM, the
investment costs ranges from $174 to $240 MM for the 100 MT/day
SG-U-2000 refinery has a NPV of over $750 MM, and the CS-U-2000
plants, $277 to $402 MM for the 200 MT/day plants, $518 to $722 MM
refinery has a NPV of over $550 MM dollars.
for the 500 MT/day plants, $806 to $1147 MM for the 1000 MT/day
Table 10 illustrates the amount of time it takes to pay back the initial
plants, and $1331 to $1896 MM for the 2000 MT/day plants. The
o-xylene case studies are consistently the least expensive refineries investment of the plants. The most profitable biomass to aromatics
because of the absence of adsorptive technologies. The m-xylene case refineries take roughly 9 years to pay back at the largest scales.
studies are consistently the most expensive refineries because of the 3.5. Material and Energy Balances. Table 11 shows the material
large cost associated with the MX Sorbex unit. balances for the BTA refineries, while the energy balances are shown in
3.4. Discounted Cash Flow Analysis. A discounted cash flow Table 12. The amount of biomass input into the refinery is shown in dry
analysis is carried out for all case studies investigated. Our previous tons per hour, while the freshwater input is shown in thousand barrels
studies have described the main parameters and methodology used in per day. The amount of LPG and gasoline output are also shown in
this analysis in detail.95,108 We use the same methodology in this paper thousand barrels per day, the amount of aromatics output is shown is
to calculate the net present value (NPV) for each biomass to aromatics metric tons per day, and the amount of vented and sequestered CO2 is
refinery. The main parameters, as well as a description of our methodology, shown in metric tons per hour.
Figure 10. Net present values for the corn stover case studies.
Figure 11. Net present values for the hardwood case studies.

Energy Fuels 2016, 30, 4970−4998
Figure 12. Net present values for the switchgrass case studies.
Table 10. Payback Period in Years for Each Case Study

corn stover 26 13 15
hardwood 29 13 9 13 9 17
switchgrass 18 11 21 12
Across all feedstock types, the unrestricted 2000 MT/day refineries to photosynthesis or soil storage. The amount of atmospheric CO2 that
produce roughly 450 thousand metric tons of p-xylene per year. is captured during photosynthesis in part (e) is based on the carbon
These case studies also produce benzene and byproduct gasoline. The content of the biomass.9 Perennial crops are assumed to store 0.3 g of
CS-U-2000 case study requires 278 dt/h of corn stover, the HW-U-2000 carbon in degraded lands per gram of as-received biomass over the
case study requires 282 dt/h of hardwood, and the SG-U-2000 case lifetime of the crop.9 Using information on the emissions avoided from
study requires roughly 291 dt/h of switchgrass. None of the case studies chemicals (GHGAC), liquid fuels (GHGAF), and electricity (GHGAE)
sequestered CO2 produced within the refinery. The reader is referred
that was described earlier, the relative life cycle emissions to typical fossil
to Table 11 for the amounts of biomass required for the o-xylene and
m-xylene case studies as well as the corresponding product outputs. fuel based process are compared. The greenhouse gas index (GHGI) is
The contributions to the overall energy balance for all case studies is calculated by dividing the life cycle greenhouse gas emissions (LGHG)
illustrated in Table 12. The energy inputs include electricity and by the summation of the GHGAC, GHGAF, and GHGAE. A GHGI of
biomass, while the energy outputs include the aromatics, LPG, gasoline, less than 1 has superior life cycle emissions compared to fossil fuel based
and electricity. If electricity is input into (output from) the refinery, it is processes, while a GHGI that is negative indicates processes that absorb
shown as a positive (negative) value. The overall energy efficiency is also more CO2 than is released by the refinery.
calculated. The unrestricted corn stover refineries have energy As Table 14 indicates, all biomass to aromatics refineries achieve
efficiencies between 66 and 67%, the unrestricted hardwood refineries significant reduction in GHG emissions compared to fossil fuel based
have energy efficiencies between 63 and 65%, and the unrestricted processes. For corn stover and hardwood refineries, this reduction in life
switchgrass refineries have energy efficiencies between 63 and 65%. cycle GHG emissions is between 89 and 90% and 80−85%, respectively.
3.6. Carbon and Greenhouse Gas Balances. Table 13 shows the However, the most environmentally beneficial biomass aromatics use
carbon balances for each of the case studies. The only carbon input into
perennial crops, which have GHGI’s between −0.8 and −0.73. These are
the BTA refineries is biomass; the carbon outputs include the aromatics,
gasoline, LPG, vented CO2, and sequestered CO2. The amount of net-negative processes due to the additional CO2 captured and stored in
carbon input into the refineries by air is considered negligible and is the soil.
therefore not shown in Table 13. Carbon conversion is calculated for all 3.7. Parametric Analysis. The impact of higher or lower feedstock
refineries by summing the carbon output as products and dividing it by costs on the overall profitability of the unrestricted 2000 MT/day
the carbon input into the refinery. The unrestricted corn stover aromatics refineries is examined. The net present values illustrated
refineries have carbon conversions of approximately 55−56%, the in Figures 10, 11, and 12 are based on corn stover, hardwood, and
unrestricted hardwood refineries have carbon conversions between switchgrass prices of $120, $70, and $100 per dry metric ton, respec-
51 and 54%, and the unrestricted switchgrass refineries have carbon tively. The net present value is recalculated for corn stover prices of $100
conversions between 53 and 56%. and $140 per dry metric ton, hardwood prices of $60 and $80 per dry
Table 14 shows the total greenhouse gas emissions (in kg CO2 metric ton, and switchgrass prices of $80 and $120 per dry metric ton.
equivalent/s) for the inputs and outputs of the BTA refineries. As The values are then compared with the nominal results presented in
mentioned previously, an environmental constraint imposed in the Figures 10, 11, and 12. This comparison is explicitly shown in Table 15.
process synthesis model forces the BTA refineries to have at least 50%
For a hardwood price of $60 the NPV of the U-2000 aromatics
reduction in life cycle greenhouse gas emissions from current fossil-fuel
based processes. The life cycle GHG emissions (GHG) are calculated by refinery is $1340 MM. The NPV of the HW-U-2000 refinery decreases
summing the respective emissions rates from each stage of production, to $1102 MM when the hardwood price increases to $80. Similarly, the
which include (a) the acquisition and transportation of the biomass feed, NPVs of the corn stover U-2000 refineries decrease from $786 MM
(b) the transportation and use of the aromatics, gasoline, and LPG to $310 MM when the price increases from $100 to $140 per dry
(c) venting of CO2, (d) the transportation and sequestration of CO2, metric ton. The switchgrass refineries have NPVs between $532 and
and (e) atmospheric sequestration of CO2 during growth of biomass due $1023 MM when the switchgrass price ranges from $80 to $120.

Energy Fuels 2016, 30, 4970−4998
Table 11. Overall Material Balances for the Case Studies Are Showna
Corn Stover
biomass (dt/h) 13.89 28.22 70.50 138.75 277.79 12.90 25.44 67.01 134.53 270.98 13.21 26.43 72.21 146.09 293.29
Energy & Fuels
LPG (kBD) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
gasoline (kBD) 0.19 0.36 0.90 1.88 3.75 0.18 0.36 0.90 1.88 3.75 0.19 0.38 0.94 1.88 3.75
benzene [MT/day] 6.83 15.63 39.08 68.32 136.94 8.32 15.46 38.64 68.05 136.11 6.82 13.64 34.09 68.17 136.35
toluene [MT/day] 0.62 0.00 0.00 6.19 0.00 0.00 0.00 0.00 5.94 11.88 0.60 1.21 3.01 6.02 12.05
p-xylene [MT/day] 67.66 136.66 341.65 676.62 1365.22 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene [MT/day] 0.00 0.00 0.00 0.00 0.00 67.40 136.72 341.80 677.12 1354.24 0.00 0.00 0.00 0.00 0.00
m-xylene [MT/day] 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 67.69 135.38 338.46 676.92 1353.84
water (kBD) 0.76 1.54 3.78 7.42 14.87 0.62 1.22 3.35 7.04 14.21 0.70 1.41 4.03 8.35 16.72
seq CO2 (MT/h) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
vented CO2 (MT/h) 10.42 21.57 53.83 103.99 208.50 8.71 16.79 47.83 96.75 196.79 9.26 18.53 56.87 116.60 235.10
Hardwood
biomass (dt/h) 13.55 27.07 67.65 140.75 281.96 12.35 26.51 99.16 132.53 265.16 13.33 39.65 71.08 141.93 288.85
LPG (kBD) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
gasoline (kBD) 0.18 0.36 0.90 1.80 3.60 0.18 0.36 0.90 1.80 3.61 0.19 0.38 0.94 1.88 3.60
benzene [MT/day] 7.82 15.63 39.08 78.17 156.33 8.25 15.46 38.64 77.29 154.58 9.37 18.57 34.09 68.17 155.25
toluene [MT/day] 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 3.01 6.02 0.00
p-xylene [MT/day] 68.33 136.66 341.65 683.30 1366.59 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
4990
o-xylene [MT/day] 0.00 0.00 0.00 0.00 0.00 67.51 136.72 341.80 683.60 1367.20 0.00 0.00 0.00 0.00 0.00
m-xylene [MT/day] 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 65.78 131.72 338.46 676.92 1366.93
water (kBD) 0.41 0.83 2.06 4.65 9.35 0.29 0.78 7.15 3.87 7.78 0.39 2.61 2.47 4.94 10.12
seq CO2 (MT/h) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
vented CO2 (MT/h) 11.60 23.16 57.87 125.83 252.50 9.40 22.14 116.16 110.64 221.46 11.21 46.45 64.33 128.22 265.27
Switchgrass
biomass (dt/h) 13.98 27.96 69.95 139.88 290.63 12.84 25.23 68.08 136.01 272.38 13.10 26.20 73.04 146.10 292.32
LPG (kBD) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
gasoline (kBD) 0.18 0.36 0.90 1.80 3.60 0.18 0.36 0.90 1.80 3.61 0.19 0.38 0.94 1.88 3.75
benzene [MT/day] 7.82 15.63 39.08 78.17 156.33 8.47 15.48 38.64 77.29 154.58 6.82 13.64 34.09 68.17 136.35
toluene [MT/day] 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.60 1.21 3.01 6.02 12.05
p-xylene [MT/day] 68.33 136.66 341.65 683.30 1366.59 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene [MT/day] 0.00 0.00 0.00 0.00 0.00 67.14 136.68 341.80 683.60 1367.20 0.00 0.00 0.00 0.00 0.00
m-xylene [MT/day] 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 67.69 135.38 338.46 676.92 1353.84
water (kBD) 0.70 1.38 3.49 6.98 15.07 0.56 1.09 3.31 6.51 13.30 0.64 1.27 3.88 7.84 15.74
seq CO2 (MT/h) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
vented CO2 (MT/h) 10.61 21.24 53.18 106.34 231.40 8.66 16.54 49.97 99.70 200.01 9.13 18.25 58.61 117.26 234.72
a
The inputs to the BTA refinery are biomass and water, while the outputs include gasoline, LPG, benzene, toluene, p-xylene, o-xylene, m-xylene, sequestered CO2, and vented CO2.
Article
Energy Fuels 2016, 30, 4970−4998
Table 12. Overall Energy Balances (in MW) for the Case Studies Are Showna
Corn Stover
biomass 65.00 132.09 329.96 649.39 1300.13 60.37 119.05 313.62 629.66 1268.25 61.84 123.68 337.98 683.75 1372.68
Energy & Fuels
gasoline 11.95 22.92 57.31 119.50 239.00 11.67 22.98 57.44 119.50 239.00 11.95 23.90 59.75 119.50 239.00
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 3.21 7.36 18.39 32.14 64.43 3.91 7.27 18.18 32.02 64.04 3.21 6.42 16.04 32.08 64.15
toluene 0.29 0.00 0.00 2.94 0.00 0.00 0.00 0.00 2.82 5.64 0.29 0.57 1.43 2.86 5.71
p-xylene 32.34 65.32 163.31 323.43 652.59 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 32.22 65.35 163.38 323.67 647.34 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 32.36 64.71 161.79 323.57 647.15
electricity 6.31 12.62 31.52 62.96 126.12 6.36 12.83 22.02 38.62 72.60 6.33 12.66 14.23 24.33 44.96
efficiency (%) 67.04 66.07 66.12 67.10 67.03 71.63 72.49 71.21 71.53 71.30 70.11 70.12 67.86 67.51 67.44
Hardwood
biomass 67.13 134.15 335.27 697.56 1397.40 61.22 131.41 491.45 656.84 1314.15 66.07 196.50 352.29 703.42 1431.57
gasoline 11.46 22.92 57.31 114.61 229.22 11.65 22.98 57.44 114.88 229.76 11.95 23.90 59.75 119.50 229.57
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 3.68 7.36 18.39 36.78 73.55 3.88 7.27 18.18 36.36 72.73 4.41 8.74 16.04 32.08 73.04
toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.43 2.86 0.00
p-xylene 32.66 65.32 163.31 326.62 653.24 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 32.27 65.35 163.38 326.77 653.53 0.00 0.00 0.00 0.00 0.00
4991
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 31.44 62.96 161.79 323.57 653.40
electricity 6.53 13.01 32.49 50.28 100.79 6.50 7.38 −24.35 36.91 73.85 6.47 −7.93 11.38 22.63 44.98
efficiency (%) 64.89 64.96 64.99 63.92 63.81 70.58 68.88 53.59 68.90 68.88 65.89 52.69 65.72 65.84 64.75
Switchgrass
biomass 67.40 134.84 337.30 674.53 1401.48 61.90 121.64 328.27 655.89 1313.48 63.18 126.35 352.21 704.52 1409.63
gasoline 11.46 22.92 57.31 114.61 229.22 11.72 22.98 57.44 114.88 229.76 11.95 23.90 59.75 119.50 239.00
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 3.68 7.36 18.39 36.78 73.55 3.99 7.28 18.18 36.36 72.73 3.21 6.42 16.04 32.08 64.15
toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.29 0.57 1.43 2.86 5.71
p-xylene 32.66 65.32 163.31 326.62 653.24 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 32.09 65.33 163.38 326.77 653.53 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 32.36 64.71 161.79 323.57 647.15
electricity 6.20 12.36 30.87 61.71 94.93 6.21 12.53 17.71 35.49 70.89 6.20 12.39 10.19 20.41 40.81
efficiency (%) 64.95 64.95 64.92 64.93 63.89 70.18 71.25 69.08 69.14 69.06 68.90 68.91 65.95 65.94 65.91
a
The energy inputs come from biomass or electricity, while the energy outputs are the aromatics, gasoline, LPG, or electricity. Electricity is denoted as a positive value if it is input into the system and as a
negative value if it is output from the system. The overall efficiency (in percent) of the refineries is calculated by dividing the energy outputs by the energy inputs.
Article
Energy Fuels 2016, 30, 4970−4998
Table 13. Carbon Accounting (in kg/s) Is Shown for the Case Studiesa
Corn Stover
biomass 1.80 3.67 9.16 18.02 36.08 1.68 3.30 8.70 17.48 35.20 1.72 3.43 9.38 18.98 38.10
gasoline 0.23 0.43 1.09 2.27 4.53 0.22 0.44 1.09 2.27 4.53 0.23 0.45 1.13 2.27 4.53
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 0.07 0.17 0.42 0.73 1.46 0.09 0.17 0.41 0.73 1.45 0.07 0.15 0.36 0.73 1.46
toluene 0.01 0.00 0.00 0.07 0.00 0.00 0.00 0.00 0.06 0.13 0.01 0.01 0.03 0.06 0.13
p-xylene 0.71 1.43 3.58 7.09 14.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 0.71 1.43 3.58 7.09 14.19 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.71 1.42 3.55 7.09 14.18
vented CO2 0.79 1.64 4.08 7.88 15.81 0.66 1.27 3.63 7.33 14.92 0.70 1.40 4.31 8.84 17.82
seq CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
conversion 56.25 55.44 55.49 56.30 56.24 60.63 61.51 58.37 58.07 57.66 59.12 59.12 54.09 53.47 53.27
(%)
Hardwood
biomass 1.89 3.77 9.43 19.62 39.31 1.72 3.70 13.83 18.48 36.97 1.86 5.53 9.91 19.79 40.27
gasoline 0.22 0.43 1.09 2.17 4.34 0.22 0.44 1.09 2.18 4.35 0.23 0.45 1.13 2.27 4.35
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 0.08 0.17 0.42 0.83 1.67 0.09 0.17 0.41 0.83 1.65 0.10 0.20 0.36 0.73 1.66
toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.06 0.00
p-xylene 0.72 1.43 3.58 7.16 14.32 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 0.71 1.43 3.58 7.16 14.32 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.69 1.38 3.55 7.09 14.32
vented CO2 0.88 1.76 4.39 9.54 19.14 0.71 1.68 8.81 8.39 16.79 0.85 3.52 4.88 9.72 20.11
seq CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
conversion 53.81 53.86 53.88 51.79 51.71 58.99 54.98 36.75 55.00 54.98 54.65 36.75 51.20 51.28 50.47
(%)
Switchgrass
biomass 1.82 3.64 9.11 18.22 37.85 1.67 3.29 8.87 17.71 35.47 1.71 3.41 9.51 19.03 38.07
gasoline 0.22 0.43 1.09 2.17 4.34 0.22 0.44 1.09 2.18 4.35 0.23 0.45 1.13 2.27 4.53
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 0.08 0.17 0.42 0.83 1.67 0.09 0.17 0.41 0.83 1.65 0.07 0.15 0.36 0.73 1.46
toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01 0.03 0.06 0.13
p-xylene 0.72 1.43 3.58 7.16 14.32 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 0.70 1.43 3.58 7.16 14.32 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.71 1.42 3.55 7.09 14.18
vented CO2 0.80 1.61 4.03 8.06 17.54 0.66 1.25 3.79 7.56 15.16 0.69 1.38 4.44 8.89 17.79
seq CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
conversion 55.84 55.82 55.78 55.79 53.70 60.77 61.87 57.31 57.37 57.30 59.47 59.48 53.34 53.33 53.31
(%)
a
Biomass is the carbon input, while the carbon outputs are the aromatics, the liquid products, the LPG byproduct, vented CO2, or sequestered (Seq.)
CO2. Carbon conversion for each case study is calculated by dividing the total carbon exiting as either aromatics, liquid product, LPG by the total
carbon input into the refinery.
4. CONCLUSIONS The most profitable BTA refineries had net present values
greater than $1200 MM dollars with payback periods less than
This paper proposes novel methods of producing aromatics from
10 years. The required investment cost for a plant producing
biomass. A deterministic global optimization-based process
approximately half a million metric tons of aromatics per year was
synthesis framework was proposed to determine the most prof-
as low as $1331 MM dollars. The most profitable BTA refineries
itable process topology of a biomass to aromatics refinery. Several input hardwood, followed by switchgrass, and finally corn stover.
commercial, novel, and competing technologies were designed A hardwood biorefinery that produces 2000 MT/day has a net
and described to convert biomass into aromatics via methanol. present value of over $1200 MM. A similar scale switchgrass
Three types of biomass (agricultural residues, perennial crops, and biorefinery has an NPV of over $750 MM, while a biorefinery
forest residues) were investigated to determine the effect that the inputting corn stover with a similar capacity has a NPV of over
type of biomass has on the overall profit of the refinery. Three sets $550 MM dollars. The process synthesis framework described
of product compositions across five refinery scales were high- has the ability to produce any combination of xylene isomers and
lighted. Plant profitability, net present value, material and energy three sets of aromatics products were considered that placed no
balances, and carbon and greenhouse gas balances were illustrated restriction on the type of xylenes produced, limited xylenes
for all case studies investigated. output to only the ortho-xylene isomer, and limited xylenes
Energy Fuels 2016, 30, 4970−4998
Table 14. Greenhouse Gas (GHG) Balances for the Case Studies Are Showna
Corn Stover
biomass −6.05 −12.30 −30.72 −60.45 −121.03 −5.62 −11.08 −29.19 −58.62 −118.06 −5.76 −11.51 −31.46 −63.65 −127.78
Energy & Fuels
gasoline 0.80 1.54 3.85 8.02 16.05 0.78 1.54 3.86 8.02 16.05 0.80 1.60 4.01 8.02 16.05
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 0.27 0.61 1.53 2.67 5.36 0.33 0.60 1.51 2.66 5.33 0.27 0.53 1.33 2.67 5.33
toluene 0.02 0.00 0.00 0.24 0.00 0.00 0.00 0.00 0.23 0.46 0.02 0.05 0.12 0.23 0.47
p-xylene 2.60 5.25 13.11 25.97 52.40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 2.59 5.25 13.12 25.99 51.98 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.60 5.20 12.99 25.98 51.96
vented CO2 2.89 5.99 14.95 28.89 57.92 2.42 4.66 13.29 26.88 54.66 2.57 5.15 15.80 32.39 65.31
seq CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
LGHG 0.53 1.09 2.73 5.34 10.69 0.49 0.98 2.58 5.17 10.41 0.51 1.01 2.79 5.64 11.34
GHGAF 1.09 2.10 5.25 10.95 21.89 1.07 2.10 5.26 10.95 21.89 1.09 2.19 5.47 10.95 21.89
GHGAE −0.64 −1.28 −3.19 −6.38 −12.78 −0.64 −1.30 −2.23 −3.91 −7.35 −0.64 −1.28 −1.44 −2.47 −4.55
GHGAC 4.37 8.85 22.13 43.66 87.32 4.40 8.85 22.12 43.66 87.32 4.37 8.73 21.83 43.66 87.32
GHGI 0.11 0.11 0.11 0.11 0.11 0.10 0.10 0.10 0.10 0.10 0.11 0.11 0.11 0.11 0.11
Hardwood
biomass −6.14 −12.26 −30.64 −63.75 −127.72 −5.60 −12.01 −44.92 −60.03 −120.11 −6.04 −17.96 −32.20 −64.29 −130.84
gasoline 0.77 1.54 3.85 7.70 15.39 0.78 1.54 3.86 7.71 15.43 0.80 1.60 4.01 8.02 15.41
4993
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 0.31 0.61 1.53 3.06 6.12 0.32 0.60 1.51 3.02 6.05 0.37 0.73 1.33 2.67 6.07
toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.12 0.23 0.00
p-xylene 2.62 5.25 13.11 26.23 52.45 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
o-xylene 0.00 0.00 0.00 0.00 0.00 2.59 5.25 13.12 26.24 52.48 0.00 0.00 0.00 0.00 0.00
m-xylene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 2.52 5.06 12.99 25.98 52.47
vented CO2 3.22 6.43 16.07 34.95 70.14 2.61 6.15 32.27 30.73 61.52 3.12 12.90 17.87 35.62 73.69
seq CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
LGHG 0.79 1.57 3.92 8.18 16.38 0.71 1.54 5.84 7.68 15.36 0.77 2.33 4.12 8.23 16.80
GHGAF 1.05 2.10 5.25 10.50 21.00 1.07 2.10 5.26 10.52 21.05 1.09 2.19 5.47 10.95 21.03
GHGAE −0.66 −1.32 −3.29 −5.09 −10.21 −0.66 −0.75 2.47 −3.74 −7.48 −0.66 0.80 −1.15 −2.29 −4.56
GHGAC 4.43 8.85 22.13 44.27 88.54 4.40 8.85 22.12 44.23 88.47 4.37 8.74 21.83 43.66 88.49
GHGI 0.16 0.16 0.16 0.16 0.16 0.15 0.15 0.20 0.15 0.15 0.16 0.20 0.16 0.16 0.16
Switchgrass
biomass −10.55 −21.10 −52.78 −105.55 −219.30 −9.69 −19.03 −51.37 −102.63 −205.53 −9.89 −19.77 −55.11 −110.24 −220.58
gasoline 0.77 1.54 3.85 7.70 15.39 0.79 1.54 3.86 7.71 15.43 0.80 1.60 4.01 8.02 16.05
LPG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
benzene 0.31 0.61 1.53 3.06 6.12 0.33 0.61 1.51 3.02 6.05 0.27 0.53 1.33 2.67 5.33
toluene 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.02 0.05 0.12 0.23 0.47
p-xylene 2.62 5.25 13.11 26.23 52.45 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Article
o-xylene 0.00 0.00 0.00 0.00 0.00 2.58 5.25 13.12 26.24 52.48 0.00 0.00 0.00 0.00 0.00
Energy Fuels 2016, 30, 4970−4998
Table 15. NPVs for the Unrestricted 2000 MT/day Aromatics
The total GHG emissions (in CO2 equivalents - kg CO2 eq/s), as well as the GHG emissions avoided from liquids production (GHGAF), emissions due to electricity usage (GHGAE), GHG emissions
51.96
65.20
0.00
−81.56
21.89
−4.13
87.32
−0.78
M-2000
Refineries
Cornstover U-2000
price ($/dry metric ton) 100 120 140
NPV (MM $) 786 552 310
0.00
−2.07
−0.78
25.98
32.57
−40.77
10.95
43.66
M-1000
Hardwood U-2000
NPV (MM $) 1340 1221 1102
Switchgrass U-2000
12.99
16.28
0.00
−20.38
5.47
−1.03
21.83
−0.78
M-500

NPV (MM $) 1023 778 532
5.20
5.07
0.00
−7.32
2.19
−1.25
8.73
−0.76
M-200
output to only the meta-xylene isomer. The BTA refineries had

superior life cycle greenhouse gas emissions compared to fossil-
fuel based processes.
■
M-100
2.60
2.54
0.00
−3.66
1.09
−0.63
4.37
−0.76
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the ACS
0.00
55.56
0.00
−76.02
21.05
−7.18
88.47
−0.74
O-2000
Publications website at DOI: 10.1021/acs.energyfuels.6b00619.

Appendix A and B (PDF)
■
0.00
27.69
0.00
−37.96
10.52
−3.59
44.23
−0.74
O-1000
AUTHOR INFORMATION
Corresponding Author
*Tel: (979) 458-0253. E-mail: floudas@tamu.edu.
Notes
0.00
13.88
0.00
−19.00
5.26
−1.79
22.12
−0.74
O-500
The authors declare no competing financial interest.
■
avoided from chemicals production (GHGAC), and overall GHG emissions (LGHG), are also illustrated.
Switchgrass
ACKNOWLEDGMENTS
The authors acknowledge partial financial support from the
0.00
4.59
0.00
−7.05
2.11
−1.27
8.85
−0.73
O-200
National Science Foundation (NSF EFRI-0937706 and NSF

CBET-1158849).
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O-100
0.00
2.40
0.00
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1.07
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4.40
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Article

Biomass-Based Production of Benzene, Toluene, and Xylenes via

1. INTRODUCTION investigating the technical feasibility of producing one billion

© 2016 American Chemical Society 4970 DOI: 10.1021/acs.energyfuels.6b00619

4971 DOI: 10.1021/acs.energyfuels.6b00619

Figure 1. Biomass gasiﬁcation ﬂow sheet.

Figure 2. Biomass syngas cleaning ﬂow sheet.

Figure 3. Methanol synthesis and conversion ﬂow sheet.

Figure 5. LPG processing ﬂow sheet.

Figure 6. C6−C8 aromatics upgrading and separation ﬂow sheet.

Figure 7. Light gas recycle ﬂow sheet.

4980 DOI: 10.1021/acs.energyfuels.6b00619

Toluene and heavy aromatics produced within the reﬁnery were

investment and operating costs associated with a CO2 sequestration

system. This is to be expected, since it is well-known that the utilization

3.1.1. Detailed Discussion on the Optimal Topology for the HW-U-

is shown in Figure 8 as an illustrative example. Figure 9 shows the

corresponding stream ﬂow rates shown in Table 7 for several relevant

several process units such as heat exchangers, compressors, and turbines

All of the methanol exiting the methanol synthesis reactor is split to

toluene and methanol in a weight ratio of approximately 4:1.89.

it is more proﬁtable to split the toluene (produced from the MTA

valuable mixed xylenes and benzene. The UOP PXPLUS-XP process is

process and required investment cost. Although the PXPLUS process

also produces mixed xylenes and benzene (43.4 wt % benzene, 35.6%

because the C8 aromatic streams within the reﬁnery do not contain a

MXTAC9) is directed to the UOP TAC9 process. 44.4% of the C9

distillate is split (from SPC9A to MXTATORAY) to the UOP Tatoray

balances shown in Table 11.

aromatic-rich gasoline from the BTA reﬁnery must be blended.135,169,170

density of 747 kg/m3.

for each of the biomass to aromatics reﬁneries is shown in Table 8.

4982 DOI: 10.1021/acs.energyfuels.6b00619

Figure 8. Process ﬂow diagram for the HW-U-2000 reﬁnery.

4983 DOI: 10.1021/acs.energyfuels.6b00619

produced. Gasoline byproduct is inevitable in each of the case studies

As Table 8 illustrates, the investment cost represents the largest

expenditure associated with each of the hardwood aromatics reﬁneries.

similar capacity plants in the Investment row in Table 8. However,

reﬁnery ($8.40/GJ). However, the revenue from selling p-xylene in the

o-xylene in the HW-O-2000 reﬁnery ($22.63/GJ). This relative

The HW-U-2000 case study has an overall proﬁt of $16.04/GJ,

and oxygen production, heat and power integration, and wastewater

the investment cost is the syngas generation section. This section

reﬁneries. This section constitutes between 24 and 30% of the total

4986 DOI: 10.1021/acs.energyfuels.6b00619

4988 DOI: 10.1021/acs.energyfuels.6b00619

Table 10. Payback Period in Years for Each Case Study

4989 DOI: 10.1021/acs.energyfuels.6b00619

Table 15. NPVs for the Unrestricted 2000 MT/day Aromatics

price ($/dry metric ton) 80 100 120

output to only the meta-xylene isomer. The BTA reﬁneries had

Publications website at DOI: 10.1021/acs.energyfuels.6b00619.

The authors declare no competing ﬁnancial interest.

National Science Foundation (NSF EFRI-0937706 and NSF

(1) Floudas, C. A.; Niziolek, A. M.; Onel, O.; Matthews, L. R. Multi-

(2) Floudas, C. A.; Elia, J. A.; Baliban, R. C. Hybrid and Single

(6) National Research Council, Water Implications of Biofuels

Engineering and National Research Council, Liquid Transportation

(9) Baliban, R. C.; Elia, J. A.; Floudas, C. A. Biomass to Liquid

4994 DOI: 10.1021/acs.energyfuels.6b00619

4995 DOI: 10.1021/acs.energyfuels.6b00619

4996 DOI: 10.1021/acs.energyfuels.6b00619