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Fuel Processing Technology 106 (2013) 577–586

Contents lists available at SciVerse ScienceDirect

Fuel Processing Technology


journal homepage: www.elsevier.com/locate/fuproc

Comprehensive techno-economic assessment of dimethyl ether (DME) synthesis


and Fischer–Tropsch synthesis as alternative process steps within
biomass-to-liquid production
Frederik Trippe a,⁎, Magnus Fröhling a, Frank Schultmann a, Ralph Stahl b, Edmund Henrich b, Ajay Dalai c
a
Karlsruhe Institute of Technology (KIT), Institute for Industrial Production (IIP), Hertzstr. 16, D-76187 Karlsruhe, Germany
b
Karlsruhe Institute of Technology (KIT), Institute of Catalysis Research and Technology (IKFT), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany
c
University of Saskatchewan, Department of Chemical and Biological Engineering, Catalysis & Chemical Reaction Engineering Laboratories, 57 Campus Drive, Saskatoon SK, Canada S7N5C5

a r t i c l e i n f o a b s t r a c t

Article history: The conversion of lignocellulosic biomass, such as residual wood or straw, to synthetic fuels and chemicals is
Received 13 June 2012 currently being developed within the bioliq® concept. The aim of this study is to model and assess two
Received in revised form 5 September 2012 different biomass-to-liquid (BtL) concepts for the production of gasoline via dimethyl ether (DME) synthesis
Accepted 5 September 2012
as well as gasoline and diesel via Fischer–Tropsch (FT) synthesis. The techno-economic assessment concludes
Available online 3 October 2012
that total energy efficiencies from biomass to final products range between 38 and 39%. The resulting produc-
Keywords:
tion costs of gasoline via DME synthesis are about 1.15 €/L (0.82 US$/L). Gasoline and diesel via FT synthesis
Dimethyl ether (DME) synthesis can be produced at costs of about 1.23 €/L (0.88 US$/L). The production costs for biomass-derived fuels are 76
Fischer–Tropsch (FT) synthesis to 93% higher than current market prices. However, the considered technologies are close to becoming com-
Biomass-to-liquid petitive to conventional refineries since the production costs are only 7 to 18% higher than current market
Techno-economic assessment prices when coal is used as main feedstock. Further, the implications of negative CO2 emissions, mineral oil
Process simulation tax reduction and the combination of both kinds of subsidies in order to compensate high biomass feedstock
2nd generation biomass utilization costs as well as the sensitivity of production costs to biomass feedstock costs are evaluated in this study.
© 2012 Elsevier B.V. All rights reserved.

1. Background plants to liquefy the biomass collected from a radius of about 30 km


around each pyrolysis plant. The slurry, a mixture of pyrolysis oil and
Political efforts are made all over the world to enforce a shift towards char, offers a tenfold increased volumetric energy density and allows
renewable energy sources. Especially biomass is believed to reduce fossil more economical transportation over long distances to the centralized
CO2-emissions, to replace non-renewable carbon resources in numerous large scale gasification and synthesis plant [5]. The capacity of the
applications, to enhance energy security by reducing import dependen- gasification and synthesis plant should be as large as possible in order
cies and to promote development in rural areas [1]. Hence the European to produce more efficiently and cost-effectively by means of economies
Union enforces the use of biomass derived transportation fuels by setting of scale [6]. After cleaning and conditioning, the syngas can be used to
a share of 10% biofuels for 2020 [2]. In North America, the US government synthesize fuels or chemicals by different pathways. In earlier studies,
also aims for a production of 136 billion liters of biofuels per year by 2022 the authors assessed the pyrolysis step [7], the production of syngas
by implementing the Energy Independence and Security Act (EISA) [3]. by entrained flow gasification [8] as well as the production of gasoline
The production of synthetic gasoline and diesel from biomass via gasifi- and olefins via DME synthesis [9]. This study is based on the results of
cation is one of the most promising technologies as it can be used in reg- the previous conversion steps.
ular internal combustion engines without modifications. The aim of this study is to model and assess two different process
BtL fuel and chemical production concepts such as the bioliq® concepts for the production of synthetic transportation fuels from
concept, which is currently being developed at the Karlsruhe Institute biomass-derived syngas. The considered concepts are the gasoline pro-
of Technology (KIT) [4], allow conversion of low-grade lignocellulosic duction via DME synthesis and the gasoline and diesel production via
biomass, such as residual wood or straw, to synthetic fuels and other FT synthesis. Similar studies have been conducted for the production of
organic chemicals, as presented in Fig. 1. The bioliq® concept offers a transportation fuels from coal-derived syngas by [10] and also for
two-stage approach to cope with the comparably low energy density biomass-derived synthetic gasoline by [11–16]. Within the techno-
of biomass. The first stage consists of multiple decentralized pyrolysis economic assessment of this study, the considered concepts are com-
pared in terms of energetic efficiency, capital requirement and produc-
⁎ Corresponding author. Tel.: +49 721 60844444; fax: +49 721 60844682. tion costs. The economic assumptions are based on a near future
E-mail address: frederik.trippe@kit.edu (F. Trippe). realization of the bioliq® concept in Germany. The resulting production

0378-3820/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fuproc.2012.09.029
578 F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586

Gasification and synthesis plant

Entrained
Biomass Gas
Slurry flow Raw syngas Syngas Synthesis Fuel & chemicals
cleaning
gasification

System boundaries

Multiple
decentralized
pyrolysis plants

Fig. 1. Overview of the bioliq® concept and system boundaries of this study.

costs are compared to current market prices and possibilities to foster the monoxide (H2:CO) ratio for the subsequent synthesis reactor. The
competitiveness of biomass-derived transportation fuels are assessed. adjusted wet syngas is then cleaned of most of the impurities and
Within the system boundaries of this study, two concepts for gaso- cooled down to about 300 K in a scrubber and a gas cooler. By cooling
line production via dimethyl ether (DME) synthesis as well as gasoline down the adjusted syngas, most of the contained water is removed
and diesel production via Fischer–Tropsch (FT) synthesis are assessed. from the product gas stream as well. In order to guarantee a high syn-
The clean and conditioned syngas feed in the DME synthesis concept gas quality for either DME or FT synthesis, the syngas is treated in a
is first converted into DME and further converted to hydrocarbons in acid gas removal unit similar to the commercially available Rectisol®
a gasoline synthesis reactor. Due to the comparably narrow product dis- process. The syngas input is assumed to be free from water, CO2 and
tribution, the main product is gasoline. Lighter hydrocarbons are used other impurities and has a H2:CO ratio about 1:1 and 2:1 for the
as fuel gas to generate electricity in both concepts. In the FT synthesis DME and FT synthesis, respectively.
concept, syngas is directly converted to a broad range of hydrocarbons,
i.e. light gases, naphta, distillate and wax fractions, which require fur- 2.2. Gasoline via DME synthesis
ther processing in order to meet commercial gasoline specifications.
For both concepts, three syngas feedstock options, i.e. 4 MPa, 8 MPa The production of gasoline via DME synthesis considered in this
and 8 MPa (Coal), are assessed, which leads to six different cases con- study is a two-step conversion of syngas. In the first step, syngas is
sidered in this study. converted to DME and in the second step, gasoline is synthesized from
First, the technology involved in converting syngas into gasoline and DME. Commercial processes for the production of DME from syngas
diesel, as well as the respective process designs, are presented. Follow- are proven technology by companies like Haldor Topsøe A/S, Toyo Engi-
ing, the methodology for the process modeling and techno-economic neering Ltd., Air Liquide, S.A. or JFE Holding Inc. These processes are
assessment is provided. The results of mass and energy balances, invest- applicable for syngas from various feedstocks, i.e. biomass, coal or natu-
ment and production costs estimations are outlined for each concept. ral gas. Gasoline production from methanol was developed in the 1980s
Implications of negative CO2 emissions and mineral oil tax reductions in response to the oil crisis. Several facilities were constructed but most
on the competiveness to fossil gasoline and diesel are discussed. Finally, of them were shut down when oil prices made the process unprofitable
a sensitivity analysis for the economic results is conducted and conclu- [17]. Those processes could also use DME or mixtures of DME and meth-
sions of this study are drawn. anol as feedstock [18].
The reaction pattern for the single step DME synthesis is presented
2. Process description in Eqs. (1) to (4) [19] in Table 1. The reactions involved in single step
DME synthesis (Eq. (4)) are the formation of methanol (Eq. (1)), the de-
Producing fuels and chemicals from resources other than fossil hydration of methanol resulting in DME and water (Eq. (2)) and the
crude oil has been subject of syngas conversion research and develop- water-gas shift reaction (Eq. (3)). The advantage of the single step
ment since the early 1930s. The conversion of syngas offers a large DME reactor is that syngas with an H2:CO ratio of 1 is required, which
number of routes to fuels and chemicals.This section provides the def- is close to the natural composition of biomass-derived syngas. A meth-
inition of the input to the system boundaries in this study, a summary anol synthesis reactor on the other hand requires an H2:CO ratio of 2
of the technology involved in the main conversion steps and the pro- and therefore more extensive syngas conditioning.
cess design for the considered concepts. An important parameter in order to describe the DME synthesis
reactor as well as the FT synthesis reactor is the conversion. The con-
2.1. Syngas feed version of synthesis reactors most commonly refers to the conversion
of CO and is defined as the total molar flow of CO consumed during
The input for the concepts investigated in this study is syngas pro-
duced in a pressurized entrained flow gasifier with a capacity of 1
Table 1
GWth input. Different process configurations for the syngas produc-
Reactions in syngas to DME conversion.
tion have already been assessed by the authors in a previous study
[8]. The assessment of the gasification process included the quench 2CO þ 4H2 ↔2CH3 OH ð1Þ
cooling of the raw syngas by injecting water which removes part of 2CH3 OH↔CH3 OCH3 þ H2 O ð2Þ
CO þ H2 O↔H2 þ CO2 ð3Þ
the particle loading. The wet raw syngas is then partly led through a
3CO þ 3H2 ↔CH3 OCH3 þ CO2 ð4Þ
sour water-gas shift reactor in order to adjust the hydrogen to carbon
F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586 579

the reaction divided by the total molar input flow of CO into the reac- Table 3
tor as illustrated in Eq. (5). Process conditions and product distribution of the gasoline synthesis reactor (adapted
from [23,24]).
molar input f low of CO−molar output f low of CO Temperature in K 653
CO conversionð% Þ ⋅100
molar input f low of CO Pressure in MPa 3.3
ð5Þ DME conversion 1.0
Inert compounds in % CO2, CO, H2, H2O 66.5
(volume fraction)
The process conditions and product distribution assumed for the sin- Hydrocarbon product Light gases 21.9
gle step DME synthesis in this study are summarized in Table 2. Data for distribution in % Light gasoline 66.3
process conditions of the DME synthesis reactor are taken from [20–22]. (mass fractions) Heavy gasoline 11.8
The considered experimental data stem from processes that use copper-
based catalysts for the methanol formation as well as the water-gas shift
reaction and zeolite catalysts for the dehydration of methanol. the light gasoline in a fractionation column. The heavy gasoline enters
DME or a mixture of DME and methanol produced in the single step an isomerization reactor where durene is converted to a compound
DME synthesis reactor is converted into hydrocarbons in the downstream with lower melting point. The outlet stream is cooled and led to a gas–
gasoline synthesis reactor. The basic reaction is shown in Eq. (6), where liquid-separator, where hydrogen and light hydrocarbons are recovered.
-CH2- monomers represent the building blocks for gasoline. This and other fuel gas streams, shown in Fig. 2, are fed to the gas turbine
of the combined cycle. The waste heat of the gas turbine is used for high
CH3 OCH3 ↔2  CH2  þH2 O ð6Þ
pressure steam generation. This is used in the steam turbine together
Kinetics for the methanol and/or DME to gasoline conversion is with the steam generated by the gasoline synthesis reactor. The steam
described by Chang and Silvestri [23] who found the dehydration of generated in the DME synthesis reactor serves for the thermal integra-
methanol to be the only difference between methanol and DME con- tion of the fractionation columns. The process configuration in the
version without effect on the hydrocarbon distribution. The DME to 8 MPa (Coal) case is the same but the syngas input is lower.
hydrocarbon conversion is a complex reaction pattern of methylation,
oligomerization, hydrocarbon formation and cracking using zeolites
2.3. Gasoline and diesel via FT synthesis
as catalyst [24].
The data for the process conditions of the gasoline synthesis reactor,
Currently, Sasol is one of the most important producers of industrial
shown in Table 3, are adapted from [11,14,23,25–28]. The conversion of
FT fuels and chemicals. Sasol is operating commercial FT plants since
DME into gasoline results in about 22% light gases, 66% hydrocarbons in
1955 [29]. There are mainly two technologies applied. On the one
the light gasoline range and 12% on mass basis in the heavy gasoline
hand, there is a high temperature FT synthesis process which is operat-
range. The most prominent compound of the heavy gasoline fraction
ed at temperatures between 603 and 623 K and designed for the pro-
is durene (1,2,4,5-tetramethyl-benzene), which needs to be further
duction of gasoline and light hydrocarbons based on syngas derived
processed in order to meet current gasoline specifications. The durene
from coal. On the other hand, there is a low temperature FT synthesis
is isomerized to compounds with lower melting points in a fixed bed re-
process operated at temperatures between 493 and 523 K which is
actor in presence of hydrogen at 3.2 MPa and 493 K [11]. The upgraded
designed to produce diesel and wax. The low temperature processes
heavy gasoline is blended with the light gasoline fraction to give total
are designed to handle both coal and natural gas derived syngas. The
production of commercial grade gasoline.
Sasol Slurry Phase Distillate reactor is designed for the low temperature
The process flowchart of the gasoline via DME synthesis concept is
synthesis processes and assumed in this study [30,31].
illustrated in Fig. 2. In the 8 MPa case, the syngas is first expanded to
The formation of hydrocarbons during FT synthesis is a complex
meet the DME synthesis pressure of 3.5 MPa. This brings an additional
network of numerous reactions. The most important mechanism is
possibility in the 8 MPa cases to generate electricity which is not avail-
the formation of the monomer \CH2\ which sets the starting point
able in the 4 MPa case. Downstream of this point, the 4 and 8 MPa
for the polymerization reactions. The \CH2\ monomers then polymer-
cases are identical. The syngas is led through the DME synthesis reactor
ize to longer paraffins, olefins and oxygenated hydrocarbons [32]. The
and the whole outlet stream is heated up to 573 K and sent to the gaso-
stoichiometry of all reactions involved in FT synthesis is best represent-
line synthesis reactor. The DME and gasoline synthesis reactors allow the
ed by using the following two basic reaction equations [31]:
generation of steam which is used for heat and power integration in the
gasification and synthesis plant. The product stream of the gasoline syn- nCO þ ð2n þ 1ÞH2 ↔Cn H2nþ2 þ nH2 O ð7Þ
thesis reactor is degasified to remove unconverted syngas and CO2,
which make up about molar 60%. The required amount of hydrogen for
the downstream isomerization reactor is recovered from the distillate
nCO þ 2nH2 ↔Cn H2 þ nH2 O ð8Þ
stream in a pressure swing adsorption unit. The bottom stream is led
to a decanter where water is removed from liquid hydrocarbons. The Eqs. (7) and (8) describe the formation of paraffins and olefins from
recovered water is led to waste water treatment. Raw gasoline is split syngas, respectively. Both of the reactions are highly exothermic. The
up into light and heavy fractions. Dissolved gases are removed from reaction enthalpies average between 160 and 170 kJ/mol [29]. Another
important reaction that takes place during FT synthesis is the water-gas
shift reaction. This undesired reaction pathway can be reduced to a
minimum when using cobalt catalysts. The decomposition of CO to
Table 2
Process conditions and product distribution of the DME synthesis reactor (adapted elementary carbon and carbon dioxide, the so-called Boudouard reac-
from [20–22]). tion, as well as the formation of methane, are further undesirable reac-
tion pathways that have to be reduced by adapting the process
Temperature in K 523
Pressure in MPa 3.5
conditions of the FT synthesis. The operating pressure of FT reactors
CO conversion 0.85 can be varied between 0.1 and 4 MPa [32]. With increasing pressure,
Product distribution in % DME 49.3 the average chain length also increases and the methane production de-
(mass fractions) MeOH 1.4 creases [31]. In order to produce as much liquid FT products as possible,
CO2 48.8
the FT synthesis process should be designed for relatively low temper-
H2O 0.5
atures, high operating pressures and H2:CO ratios slightly around 2.
580 F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586

Synthesis

Syngas DME Gasoline


synthesis synthesis
T = 473 K reactor T = 613 K reactor T = 303 K
P = 3.5 MPa P = 3.3 MPa P = 1 MPa

Product recovery & upgrading

Fractionation Gasoline
T = 308 K column
P = 0.1 MPa

Degassing Fractionation
Decanter
column T = 303 K column Fuel gas
P = 0.2 MPa

To waste
water treatment T = 493 K Isomerization Gas-liquid-
Pressure swing Hydrogen P = 3.2 MPa reactor T = 303 K separator
adsorption P = 3.2 MPa

Fuel gas Fuel gas

Fig. 2. Process flowchart of the gasoline via DME synthesis concept.

Schulz and Flory found a statistical description of the product dis- hydrocarbon fractions. Water and heavy hydrocarbons are led to a dehy-
tribution during polymerization and oligomerization processes, dration unit to separate the water from the product stream. In the subse-
which was adapted by Anderson to the product distribution of FT syn- quent hydrocarbon fractionation, the FT products are separated into
thesis. The basic assumption for this statistical description is that the naphta, distillate and wax fractions. Hydrotreaters are saturating the ole-
rate of chain growth as well as the rate of chain termination are both fins in the naphta and distillate fractions by addition of hydrogen. The
independent of the chain length of the formed hydrocarbons. The wax fraction is further converted in a hydrocracking reactor, where
chain growth probability α, which is defined by the ratio of chain heavy hydrocarbons are cracked into naphta and diesel fractions. This die-
growth rate and the sum of chain growth and termination rate, is sel fraction and the hydrotreated distillate fraction give the final diesel
therefore constant. The chain growth probability α determines the production which is ready for use without further treatment. The naphta
product distribution and is dependent on the type of catalyst as well fractions from the hydrocracker and from the hydrotreater have to pass
as the FT process conditions [29]. The percentage distribution of FT another catalytic reformer in order to meet gasoline specifications. The
products can be calculated according to the Anderson–Schulz–Flory H2 that is needed in the hydrocracking and hydrotreatment units is recov-
equation. Eq. (9) provides the mass fraction of hydrocarbons pro- ered from the gaseous outlet stream of the degassing column, which
duced by FT synthesis. The carbon number of the produced hydrocar- mainly consist of unconverted syngas and light hydrocarbons, by pressure
bons is represented by n [12]. swing adsorption. A hydrogen rich gas stream is a by-product of the cat-
alytic reforming unit which is sent to the pressure swing adsorption
n−1 2 unit. The purge gas of the pressure swing adsorption unit is combusted
wn ¼ α ⋅ð1−α Þ ⋅n ð9Þ
in a combined cycle. In contrast to the gasoline via DME synthesis concept,
the heat of the FT synthesis cannot be used for high pressure steam gen-
The investigation in this study is based on the experimental and eration but only for thermal integration of the gasification and synthesis
literature data from cobalt catalysts [16,31–34]. Even though the spe- plant. Other than that, the combined cycles in both concepts are identical.
cific activity of cobalt catalysts is lower compared to those of iron and The 8 MPa (Coal) case again only differs from the 8 MPa case by its lower
ruthenium, cobalt-based catalysts seem to be most promising for the syngas input stream.
production of liquid FT products because of a relatively high chain
growth probability and a very low activity towards the water-gas
shift reaction [35]. Further the cobalt catalysts have a longer lifetime
and overcompensate the higher costs compared to iron catalysts.
Table 4 summarizes the process conditions and product distribu-
tion of the FT synthesis reactor. The chain growth probability α was
calculated according to the findings of [36] for cobalt catalysts. The Table 4
Process conditions and product distribution of the FT synthesis reactor (adapted from
wax fraction is converted into naphta and diesel by hydrocracking. [16,31–35]).
The naphta and distillate fractions also need further treatment in
order to meet commercial fuel requirements. Temperature in K 493
Pressure in MPa 3.5
Fig. 3 gives an overview on the gasoline and diesel via FT synthesis
CO conversion 0.8
concept. The only difference between 4 and 8 MPa cases is the possibility Chain growth probability α 0.87
for additional electricity generation in the 8 MPa case by expanding syn- Hydrocarbon product distribution Light gases 12.9
gas to the pressure of the synthesis reactor. The FT reactor converts syngas in % (mass fractions) Naphta 39.0
Distillate 25.9
into the previously mentioned mixture of different hydrocarbon species.
Wax 22.2
The FT output gas flow is cooled to condense out water and heavy
F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586 581

Synthesis Product recovery & upgrading

Syngas FT synthesis Degassing


Decanter
T = 493 K reactor T = 308 K column
P = 3.5 MPa P = 2 MPa

To waste
Hydrogen Pressure swing water treatment
adsorption

Fuel gas

Naphta Naphta
Gasoline
T = 573 K hydrotreater reformer
P = 2.5 MPa

Hydrocarbon Distillate Diesel


fractionation T = 593 K hydrotreater
P = 3 MPa

Wax
T = 613 K hydrocracker
P = 3.5 MPa

Fig. 3. Process flowchart of the gasoline and diesel via FT synthesis concept.

3. Methodology The isomerization of heavy gasoline is carried out in a stoichiometric reac-


tor (RStoic) where durene is assumed to be converted to 1,2,3,4-t
In order to conduct the techno-economic analysis for the DME etramethyl-benzene [11].
synthesis and FT synthesis concepts, the mass and energy flows with- The production of hydrocarbons in the FT synthesis with varying
in the system boundaries are analyzed at first. For this purpose, the carbon numbers of the gaseous, naphta, diesel and wax fractions,
process simulation software Aspen Plus is used. The mass and energy was modelled using a stoichiometric reactor (RStoic). The conversion
flow balancing builds up the foundation for the economic assessment. fractions of CO and H2 into the respective hydrocarbon were calculat-
Fixed capital investment estimates for the considered process config- ed in a spreadsheet according to the Anderson-Schulz-Flory distribu-
urations are derived using the determined capacities. Investment de- tion. The CO conversion rate of the FT reactor was adjusted to 80%
pendent costs together with personnel and other operating costs, as [38]. In order to model the hydrocracking of heavy hydrocarbons
well as revenues from by-products, lead to specific production costs with carbon numbers exceeding 20, a stoichiometric reactor (RStoic)
for gasoline and diesel in both concepts. A sensitivity analysis for is used. The long hydrocarbon chains are broken down into naphta
the economic results is conducted in the discussion section. and diesel. The weight fractions of naphta and diesel amount to
approximately 25 and 75%, respectively.
3.1. Process modeling Rigorous fractionation columns (RadFrac) are used to give adequate
results in the product recovery. Column design and modeling in terms
Following, the most important criteria and assumptions used to simu- of molar split fractions, optimization of utility consumption and thermal
late the considered concepts are outlined. The thermodynamic method integration of columns was performed according to [39]. Thermal inte-
used to model the high pressure processing is Soave–Redlich–Kwong gration of the considered concepts is carried out by using a minimum
(SRK). The low pressure processing is modeled using Redlich–Kwong– temperature difference of 20 K for steam heating and generation as
Soave with Boston–Mathias modifications (RKS-BM). These thermody- well as for water cooling. A minimum temperature difference of 40 K
namic methods give accurate results in modeling hydrocarbons and is imposed for gas-to-gas heat transfer. An inventory of heat demand
light gases [37]. The input streams for the DME synthesis and FT synthesis and supply is used to find the optimum thermal integration of each
considered in the Aspen Plus models consist of only CO and H2. Water, case [40,41]. The process turbine and compressors as well as the gas
CO2 and impurities are assumed to be eliminated from the FT input and steam turbines in the combined cycle were modeled by assuming
flow by syngas cleaning and conditioning. The H2:CO ratio equals values common isentropic and mechanical efficiencies [42].
of 1 and 2 for the DME synthesis and FT synthesis, respectively.
According to the experimental results of [21,22], an equilibrium reac- 3.2. Fixed capital investment estimate
tor (REquil) is used for the DME synthesis. Since the experimental results
show that the equilibrium is not achieved, a 10 K temperature approach The economic assessment aims to determine gasoline and diesel
is used in the thermodynamic modeling. The specific product yields of production costs for six cases, i.e. a 4 and an 8 MPa as well as an
the subsequent gasoline synthesis reactor (RYield) are calculated in 8 MPa (Coal) case each for the DME synthesis and FT synthesis concepts
a spreadsheet using the distribution of hydrocarbons, according to each. To achieve this goal, the fixed capital investment (FCI) for the pro-
Table 2, and fixing the remaining products to meet the atom balance. cess configurations as described in the previous chapter is estimated. All
582 F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586

Table 5 [44], as presented in Eq. (10). Table 6 shows the assumed ratio factors
Summary of investment data for main equipment components (installed). for controls, piping and further direct capital investments as well as
Description Base Unit M€ Scaling Reference the ratio factor for indirect capital investments, such as engineering
scale 2010 factor or legal expenses. The ratio factors are selected according to process
DME synthesis 2.7 kmol of total 8.7 0.65 [13] conditions, design complexity and required materials in this study.
reactor feed/s The applied ratio factor method implies uncertainties of ± 30% [44],
Gasoline synthesis 0.4 kmol of DME/s 2.9 0.65 [14] which are discussed later.
reactor
Isomerization 4.7 t of heavy 1.9 0.70 [13] !
reactor gasoline/h
X
n
Fixed capital investment ðFCIÞ ¼ I IE ⋅ 1 þ fi ð10Þ
Cryogenic system 6.8 MWth 6.4 0.70 [44]
i¼1
FT synthesis 2.7 kmol of total 13.4 0.72 [13]
reactor feed/s
Naphta 5.8 t of total feed/h 1.8 0.70 [13]
hydrotreater
Naphta reformer 8.5 t of total feed/h 7.3 0.70 [13]
IIE Investment for installed main equipment components
Distillate 3.0 t of total feed/h 2.0 0.70 [13]
hydrotreater fi Ratio factor for direct/indirect capital investment i = 1…n
Wax hydrocracker 19.7 t of total feed/h 12.0 0.70 [13]
Hydrogen recovery 0.05 kmol of 1.2 0.70 [13]
unit hydrogen/s
3.3. Production costs estimate
Hydrogen 0.4 MWe 0.3 0.67 [13]
compressor
Gas turbine 86.7 MWe 10.1 0.75 [13] The annual production costs consist of investment dependent, per-
Steam generator 201.0 MWth 12.4 1.00 [13] sonnel and consumption dependent costs as well as revenues from
Steam cycle 98.6 MWe 16.1 0.67 [13] by-products. The investment dependent costs in turn are comprised of
capital costs, maintenance, tax as well as insurance and interests on
working capital. Syngas, catalysts and cooling water make up the con-
equipment components are designed according to the results of mass sumption dependent costs. In order to calculate the production costs
and energy balancing. for gasoline and diesel, revenues from selling excess electricity are
Investment data for the main equipment components are summa- subtracted. The composition of the annual production costs is summa-
rized in Table 5. Investment data for components not listed in Table 5, rized by Eq. (9).
e.g. heat exchangers and distillation columns, are calculated according
to [43,44]. If necessary, capacity adaptations have been made using C Production ¼ FCI⋅ðpa þ pm þ pti þ pwc Þ þ C Personnel þ C Consumables
the scaling exponents which are also presented in Table 5. Since the in- þ RBy−products ð11Þ
vestment data date back to different base years for their respective cal-
culations, they are converted into € and updated to the year 2011. The
investment data are converted from US$ to € using the yearly average
exchange rate of the respective year. The exchange rates are taken FCI Fixed capital investment
from the European Commission [45]. To account for price developments pa Annuity (percentage of FCI for interests and depreciation),
of equipment components, the German price index from Kölbel/Schulze pm Percentage of FCI for maintenance,
[46] is used. The presented results in Section 4 for capital investment pti Percentage of FCI for tax and insurance,
and costs can be converted to US$ by using the average 2011 exchange pwc Interests on working capital
rate of 1.401.
Based on the investment data for the installed main equipment The personnel demand and costs estimation is based on previous
components, the total capital investment can be estimated using studies from Henrich et al. [4] and Siemens [47] for similar facilities
ratio factors for direct and indirect capital investment according to based on data for German workforce. Personnel costs vary between
40,000 and 90,000 € per employee and year, depending on the neces-
sary qualifications. The overall number of personnel needed in three
shift operation sums up to about 60 employees with average personnel
Table 6 costs per employee and year of about 55,000 €. Further economic as-
Ratio factors for direct and indirect capital investment (adapted from sumptions used for the economic assessment are presented in Table 7.
[44]).
The production costs of biomass derived syngas have been evalu-
Direct investments % ated by the authors of this study in a previous publication [8] and are
Investment for installed equipment 100 based on biomass feedstock costs of 71 € per dry ton. The biomass
Instrumentation and controls 24 feedstock costs include transportation to the pyrolysis plants. Since
Piping 46 the prices for feedstock will vary substantially during the considered
Electrical systems 8
lifetime, these prices should be regarded as average values whose
Buildings 12
Yard improvements 7 variation is investigated in the discussion section.
Service facilities 48
Total direct investment 245 4. Results

Indirect investments %
The following chapter compares the resulting mass and energy
Engineering and supervision 22 balances as well as fixed capital investment and production costs esti-
Construction expenses 28
mates for the six considered cases. They comprise three process config-
Legal expenses 3
Contractor's fee 15 urations each for gasoline production via DME synthesis as well as
Contingency 30 gasoline and diesel production via FT synthesis, respectively. The differ-
Total indirect investment 98 ent cases refer to the syngas feed. The 4 and 8 MPa cases consider
Fixed Capital Investment (FCI) 343 production of syngas in an entrained flow gasifier with 4 and 8 MPa
F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586 583

Table 7 Table 8
Summary of economic assumptions. Mass and energy balances for the considered cases.

Parameters for investment dependent costs Gasoline via Gasoline and


Capacity factor 80 % DME synthesis diesel via FT synthesis
Expected lifetime 20 years
4 MPa 8 MPa 8 MPa 4 MPa 8 MPa 8 MPa
Depreciation (no scrap value) linear -
(Coal) (Coal)
Interest rate 7.0 %
Working capital 5.0 % of FCI Input to system boundaries
Maintenance costs (average) 3.1 to 3.7 % of FCI Syngas in t/h 144 144 136 103 103 97
Insurance & taxes 2.0 % of FCI (MW HHV) (758) (758) (718) (760) (760) (719)

Prices for consumables Output from system boundaries


Syngas 4 MPa with H2:CO ratio 1 / 2 (adapted from [8]) 0.243 / 0.246 €/Nm3 Gasoline in t/h (MW 30.0 30.0 28.4 15.7 15.7 14.8
Syngas 8 MPa with H2:CO ratio 1 / 2 (adapted from [8]) 0.238 / 0.240 €/Nm3 HHV) (394) (394) (373) (206) (206) (195)
Syngas 8 MPa (Coal) with H2:CO ratio 1 / 2 0.156 / 0.157 €/Nm3 Diesel in t/h (MW HHV) – – – 15.1 15.1 14.3
(adapted from [8]) (198) (198) (187)
Cooling water [14] 0.26 €/m3 Electricity generation in 121 126 119 113 118 111
Waste water treatment [8] 0.32 €/m3 MW net (gross) (126) (132) (124) (116) (121) (114)
DME catalyst [11] 22 €/kg Total output on energy 515 520 492 517 522 493
Gasoline catalyst [11] 113 €/kg basis in MW HHV
FT catalyst [14] 24 €/kg Energy efficiency from 67.8 68.5 68.5 68.1 68.7 68.7
syngas to final products
Market prices of (by-)products (without taxes) in % (HHV basis)
Electricity (2011 average, [48]) 89.95 €/MWh Energy efficiency from 37.9 38.6 43.7 38.1 38.7 43.9
Gasoline (2011 average, [49]) 0.651 €/L biomass & coal to final
Diesel (2011 average, [49]) 0.722 €/L products in %
(HHV basis)

operating pressure, respectively. The 8 MPa (Coal) cases consider syn- is calculated according to Eq. (11) and presented in Table 8. The
gas production in an entrained flow gasifier with 8 MPa operating pres- presented efficiencies are based on wheat straw as biomass feedstock
sure as well as 10% biomass-derived and 90% coal-derived slurry on [7,8]. Because of its relatively high ash content, the efficiencies are
energy basis as gasifier feed. conservative estimates that would be higher when e.g. wood is used
as biomass feedstock.
4.1. Mass and energy balances
Energy ef f iciency
The mass and energy balances for gasoline production via DME HHV of productsðMW Þ þ net electricity generatedðMW Þ
¼
synthesis, as well as gasoline and diesel production via FT synthesis, HHV of biomass f eedðMW Þ þ HHV of optional coal f eedðMW Þ
are presented in Table 8. Considering the syngas input to the DME and ð12Þ
FT syntheses, the input is about the same on molar basis and on energy
basis for both concepts. The differences in the syngas input on mass The differences in energy efficiency in all cases between the DME
basis are due to the H2:CO ratio of 1 for the DME synthesis and 2 for synthesis and FT synthesis concepts remain constant. The difference
the FT synthesis, respectively. The syngas input in the 8 MPa (Coal) between the 4 and 8 MPa cases in both concepts also remains constant.
cases is about 6% lower on mass and energy balance for both concepts. In the 8 MPa (Coal) cases, there is a significant change since 90% of the
This is a result of higher operating temperatures in the entrained flow biomass-derived slurry feed to the gasifier is replaced by coal-derived
gasifier when coal slurry is used as co-feed. The fuel production, i.e. slurry. The coal-derived slurry is prepared in the gasification and syn-
gasoline in the DME synthesis concept and gasoline and diesel in the thesis plant by mixing with water and there are no conversion losses
FT synthesis concept, is about 3% higher in the cases of the FT synthesis as with the slurry production from biomass. Furthermore, this reduces
concept. In contrast, the amount of electricity generated in the DME the electricity consumed in the pyrolysis plants to about 10% and brings
synthesis concept is about 7% higher. On the one hand, this is caused only a slight increase of electricity consumption in the gasification and
by different product distributions of the gasoline synthesis in the DME synthesis plant. In total, about 20 MWe less are consumed in the
synthesis concept compared to the FT synthesis. The gasoline synthesis 8 MPa (Coal) cases. Due to the avoided conversion losses and electricity
in the DME synthesis concept produces comparably light hydrocarbon savings, the energy efficiency in the 8 MPa (Coal) cases is significantly
and therewith a higher amount of gaseous products, which are used as increased.
fuel gas in the power island. On the other hand, the heat of the gasoline
synthesis reactor produces additional high pressure stream available for 4.2. Fixed capital investment estimate
electricity generation in the DME synthesis concept. The amount of elec-
tricity generated in the 8 MPa cases is increased by the additional expan- The results of the fixed capital investment estimation corresponding
sion of syngas before entering the synthesis reactors. Since the energy to the system boundaries of this study are illustrated in Fig. 4. The fixed
efficiency from syngas to electricity compared to syngas to hydrocarbons capital investment in cases of the FT synthesis concept is about 24%
is lower, the energy efficiencies from syngas, as well as biomass, to final higher compared to the DME synthesis concept. This is mainly caused
products stated in Table 8 are slightly lower in the DME synthesis con- by the more complex product upgrading of the FT products. The slightly
cept. The results are calculated using the higher heating value (HHV) of more capital intensive two step synthesis of DME and subsequent
inputs and outputs. hydrocarbon leads to a narrower product distribution with less need
The electricity generation stated in Table 8 only considers the gener- for upgrading in order to meet gasoline specifications. Due to the small-
ation and consumption within the system boundaries of this study. In er amount of available fuel gas in the FT synthesis concept, the fixed
order to take the upstream electricity consumption, as well as different capital investment of the power island is about 3% lower.
biomass and coal inputs regarding the energy content, into account, the The difference between the 4 and 8 MPa cases is a result of the addi-
energy efficiency from biomass and coal, respectively, to final products tional process turbine in the 8 MPa cases which is used to lower the
584 F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586

1.580 1.534 1.601 1.557


pressure prior to the synthesis reactors. The fixed capital investment in

Production costs in €/kg


2.0
the 8 MPa (Coal) cases is decreased due to the smaller syngas input to 1.5 0.948 0.981 Electricity revenues
the syntheses. The realization of the whole bioliq® concept including
Catalysts & other costs
entrained flow gasification, gas conditioning and cleaning, as well as 1.0

about 10 decentralized pyrolysis plants with 100 MWth capacity each 0.5
Syngas costs

to meet the slurry consumption of the gasification and synthesis plant, Personnel costs
0.0
is adding 910 and 960 M€ for the 4 and 8 MPa cases, respectively, to
Maintenance, tax &
the above mentioned fixed capital investment. In case of using coal- - 0.5 insurance
4 MPa 8 Mpa 8 MPa 4 MPa 8 Mpa 8 MPa Capital costs
derived slurry, only one pyrolysis plant and a modified gasification
(Coal) (Coal)
plant with coal slurry preparation would be needed. This would lower Gasoline via DME Gasoline & diesel via FT
the additional fixed capital investment to 510 and 530 M€ for the synthesis synthesis
DME synthesis and FT synthesis concepts, respectively.
Fig. 5. Specific production costs on mass basis.

4.3. Production costs estimate


biomass-derived CO2 emissions, are required and discussed in the fol-
Fig. 5 shows the specific production costs of gasoline and diesel for lowing chapter.
both concepts. The production costs are indicated in € per kg fuel to
help the comparison of respective products. The costs for syngas feed 5. Discussion
are the largest contributor to the production costs because of the system
boundaries of this study. The syngas costs include the total upstream The economic results show that gasoline and diesel produced from
operating costs of the gasification and gas cleaning and conditioning biomass are currently not able to compete with fossil gasoline and diesel.
as well as the decentralized pyrolysis plants. The values stated for This section investigates options to foster the growth of biomass-derived
each case take the revenues from electricity generated into account. fuels, i.e. CO2 certificates for negative emissions and mineral oil tax reduc-
The higher absolute capital costs in the FT synthesis concept are com- tions, as well as the sensitivity of gasoline and diesel production costs to
pensated by the higher fuel production, so the specific production varying biomass feedstock costs.
costs of both concepts, excluding the electricity revenues, are almost
identical. The slight advantages of the DME synthesis concept cases 5.1. Implications of negative CO2 emissions and mineral oil tax reductions
are caused by higher electricity revenues. The 8 MPa cases in both con-
cepts give a 3% advantage over the 4 MPa cases because of lower syngas The following discussion only regards the 4 and 8 MPa cases
costs and higher electricity revenues. Using 90% coal-derived slurry feed where all the CO2 available for sequestration originates from biomass
in the gasifier reduces the syngas costs drastically and results in 38 and which is considered neutral in climate change regulations and the ef-
37%, respectively, lower production costs for fuels in both concepts. fect of CO2 sequestration can be interpreted as negative emissions.
Since gasoline and diesel are sold in volumetric units, Table 9 These negative emissions have not been regulated yet. For the follow-
presents the specific volumetric production costs as well as their relation ing assessment, the authors assume that there is the possibility to sell
to 2011 average German market prices without taxes [49]. Comparing these negative emissions via CO2 certificates.
the volumetric production costs of both concepts, the advantage of the The CO2 emissions due to biomass conversion in pyrolysis, gasifica-
DME synthesis concept becomes more significant, since the volumetric tion and synthesis sections are similar for all cases, as presented in
production in the FT synthesis concept is lower due to the higher density Table 10. The higher emissions in the gasoline via DME synthesis
of diesel (about 0.83 kg/L) compared to gasoline (about 0.75 kg/L). The cases result from lower hydrocarbon production. CO2 is available for se-
8 MPa (Coal) cases in both concepts demonstrate that the considered questration in the gas cleaning section in all cases and outside the sys-
technology in the bioliq® concept is close to becoming competitive to tem boundaries of this study. The H2:CO ratio of syngas in gasoline
conventional refineries. The production costs of gasoline and diesel de- and diesel via FT synthesis cases is adapted in a water-gas shift reactor
rived in this study are assumed to be the same in the FT synthesis con- to meet 2. Therefore, the amount of CO2 removed in the acid gas remov-
cept. The different values stated for the relation to market prices are a al unit and available for sequestration is almost twice as high in the FT
result of the different market prices for gasoline and diesel in Germany synthesis cases.
due to the increased demand of diesel [49]. In order to meet technical specifications for transport and sequestra-
In order to be competitive to fossil gasoline and diesel, subsidies, tion, the CO2 removed from the process has to be compressed. The
e.g. mineral oil tax reductions or selling CO2 certificates for sequestrated authors assume that a pressure of 10 MPa is sufficient for transportation
and subsequent sequestration [50]. Additional capital and operating
costs are caused by the compressors which amount to 20 and 18 €/t
of CO2, respectively. The higher CO2 mass flows in the FT synthesis
Fixed capital investment in M€2011

300
256 265
254
250 Table 9
205 215 206
200 Specific volumetric production costs and their relation to market prices without taxes.
Power island Gasoline via Gasoline & diesel
150
DME synthesis via FT synthesis
100 Product recovery &
upgrading 4 MPa 8 MPa 8 MPa 4 MPa 8 MPa 8 MPa
50 Synthesis (Coal) (Coal)
0 Gasoline in €/L 1.181 1.147 0.708 1.260 1.225 0.772
4 MPa 8 Mpa 8 MPa 4 MPa 8 Mpa 8 MPa Relation to market 181% 176% 109% 193% 188% 118%
(Coal) (Coal)
price
Gasoline via DME Gasoline & diesel via FT Diesel in €/L – – – 1.260 1.225 0.772
synthesis synthesis
Relation to – – – 174% 170% 107%
market price
Fig. 4. Fixed capital investment for the considered cases.
F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586 585

Table 10 300
Summary of CO2 emissions, sequestration and mitigation costs.

Required price for CO2 certificates (€/t)


Gasoline via Gasoline & diesel 250
DME synthesis via FT synthesis
Gasoline via DME synthesis
4 MPa 8 MPa 4 MPa 8 MPa 8 MPa (solid), 4 MPa (dashed)
200
CO2 emissions from biomass conversion 292.5 292.5 290.1 209.1
CO2 available for sequestration in t/ha 89.6 88.0 160.3 158.9
CO2 transportation costs in €/t [40] 4 150
CO2 sequestration costs in €/t [40] 14
Total CO2 mitigation costs in €/t 38 36
a 100
Outside of system boundaries in this study. Gasoline & diesel via FT synthesis
8 MPa (solid), 4 MPa (dashed)

50

concept allow savings through scaling effects. In conclusion, CO2 would


0
be sequestrated for prices of CO2 certificates higher than 38 and 36 €/t, 0% 20% 40% 60% 80% 100%
respectively. Required mineral oil tax reduction to meet gasoline & diesel
Fig. 6 compares the possibilities of subsidies for biomass-derived market prices 2011
gasoline and diesel from industry via CO2 certificates and from the pub-
lic sector via mineral oil tax reductions. Using CO2 certificates to make Fig. 6. Required subsidies through CO2 certificates versus mineral oil tax reductions.

the considered products competitive leads to 264 and 275 €/t in the
DME synthesis concept and 169 and 177 €/t in the FT synthesis concept.
The IEA considers prices of up to 200 €/t for CO2 certificates in Europe 6. Conclusions
only in 2040 [50]. There is no longer an effect of CO2 certificates prices
as soon as it drops below 38 and 36 €/t, respectively. Since the prices In this study, a comprehensive techno-economic assessment of the
for CO2 certificates are far from current market prices (on average production of synthetic gasoline via DME synthesis as well as gasoline
about 13 €/t in 2011), mineral oil tax reductions are another option to and diesel via FT synthesis in Germany is performed. The total energy
strengthen the competitiveness in the medium term. In order to meet efficiency of biomass-derived fuels ranges between 38 and 39% corre-
the current market prices for gasoline and diesel, a mineral oil tax re- sponding to the DME synthesis and FT synthesis concepts. When replac-
duction of 76 and 81% would be required in the DME synthesis concept. ing 90% of the biomass feedstock by coal, the energy efficiency in both
In the 8 MPa case in the FT synthesis concept, a 95% tax reduction would concepts is increased to 44% because of fewer conversion losses. Resulting
be required and in the 4 MPa case, even a tax reduction of 100% would production costs for biomass-derived gasoline via DME synthesis are 76
not be enough to make the biomass-derived gasoline and diesel com- and 81% higher than the current market price for the 4 and 8 MPa
petitive. This is mostly a result of lower taxes on diesel in Germany. cases. For gasoline and diesel via FT synthesis concept, the difference to
The 8 MPa cases need less subsidies for both concepts. Evaluating the the current market prices is even 88 and 93%higher because the volumet-
ranking of the considered concepts, the FT synthesis concept would be ric production of diesel is lower compared to that of gasoline. These re-
more promising in case of mineral oil tax reductions of less than 50%. sults show that the production of gasoline and diesel from biomass is
For mineral oil tax reductions of more than 60% the DME synthesis con- not competitive at current market prices. However, this is not a result of
cept would be first to become competitive. the technology involved, but of biomass feedstock costs, as scenarios
with 90% coal and 10% biomass-derived slurry on energy basis as gasifica-
tion feed show.
5.2. Sensitivity analysis The possibility to sequestrate CO2 within the considered concepts at
costs of 38 and 36 €/t allow additional revenues from negative CO2
The effect of the biomass feedstock price on production costs of gaso- emissions. In order to make biomass-derived gasoline via DME synthe-
line and diesel in the 8 MPa cases is illustrated Fig. 7. As mentioned before, sis profitable, CO2 certificate prices of 275 and 264 €/t in the 4 and
the biomass feedstock costs also include the transportation costs to the 8 MPa cases are required. For gasoline and diesel via FT-synthesis, CO2
pyrolysis plants. A doubling of biomass feedstock costs results in a 37% certificate prices of only 177 and 169 €/t are needed because of the
increase in production costs of gasoline via DME synthesis. The produc- higher amount of CO2 available for sequestration. However, these CO2
tion costs of gasoline and diesel via FT synthesis increase by 35% when certificate prices are far from the 2011 average of about 13 €/t. There-
biomass feedstock costs are doubled. In this calculation, the production fore, the reduction of mineral oil tax is also considered. To meet the
costs of gasoline and diesel via FT synthesis are assumed to be equal.
As mentioned in the methodology chapter, the fixed capital invest-
Production costs of gasoline & diesel in

ment method has an accuracy of ±30%. To evaluate the sensitivity of 2.2


production to the total fixed capital investment, the conservative devi-
2.0
ation of +30% is calculated for the DME synthesis and FT synthesis con- Gasoline & diesel via FT synthesis (8 MPa)

cepts. In order to make a fair analysis, the fixed capital investment of the 1.8
pyrolysis plants, as well as gasification and gas cleaning sections, are 1.6
€/L

also included. In the DME synthesis concept, an increase of 30% in


1.4
total fixed capital investment results in a 16% higher production costs
for the 4 and 8 MPa cases. In the FT synthesis concept, this increase 1.2
Gasoline via DME synthesis (8 MPa)
leads to 17% higher production costs. The sensitivity to changes in the 1.0
fixed capital investment in the 8 MPa (Coal) cases is slightly higher
0.8
because capital dependent costs are dominating the biomass and coal 0 20 40 60 80 100 120 140 160 180 200 220
feedstock costs. The high sensitivity to changes in the fixed capital Biomass feedstock costs in €/dry t
investment emphasizes the importance of profiting from economies of
scale as intended by the bioliq® concept. Fig. 7. Sensitivity of gasoline and diesel production costs to biomass feedstock costs.
586 F. Trippe et al. / Fuel Processing Technology 106 (2013) 577–586

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