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Applied Energy 204 (2017) 163–180

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Plant-wide modeling and analysis of the shale gas to dimethyl ether


(DME) process via direct and indirect synthesis routes
Chirag Mevawala, Yuan Jiang, Debangsu Bhattacharyya ⇑
Department of Chemical and Biomedical Engineering, West Virginia University, Morgantown, WV 26506, USA

h i g h l i g h t s

 Systems level modeling and analysis of the shale gas to DME process are undertaken.
 Both direct and indirect synthesis routes are investigated.
 A novel DME separation process is developed.
 Models of direct DME synthesis, ATR, and pre-reforming reactors are developed.
 Effects of the CO2 recycle and H2/CO ratio are evaluated.

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

Article history: A plant-wide model of the shale gas to dimethyl ether (DME) process with integrated CO2 capture via
Received 24 April 2017 direct and indirect synthesis routes has been developed in Aspen Plus V8.4Ò. In this study, models of
Received in revised form 25 June 2017 the pre-reforming reactor, autothermal reforming (ATR) reactor and DME synthesis reactors using kinetic
Accepted 28 June 2017
data have been developed. For CO2 capture, Rectisol and methyl diethanolamine (MDEA)/piperazine (PZ)
Available online 15 July 2017
technologies have been evaluated and results have been compared with the experimental data. A novel
DME separation process has been developed and evaluated for efficient separation of DME, syngas, and
Keywords:
CO2. Binary interaction parameters for the vapor-liquid equilibrium (VLE) model of the methanol-
Shale gas
Dimethyl ether
DME-CO-CO2-H2O-H2 system are regressed using the experimental data. Effects of the key parameters
Direct synthesis like CO2 recycle ratio and H2/CO ratio on the utility consumption in the syngas synthesis unit, acid gas
Indirect synthesis removal (AGR) unit, DME synthesis unit and DME separation unit are studied. It is observed that the
CO2 capture direct shale gas to DME production process operated with an optimal H2/CO ratio of 1 has a higher
DME yield and overall equivalent electrical efficiency than the indirect shale gas to DME production
process.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction excellent refrigerant [1,2]. DME can be produced from a variety


of fossil fuels, such as coal, biomass, and natural gas. Coal is the
The shale gas boom in the United States has started replacing preferred feed for producing DME for most of the Asia-Pacific coun-
coal and petroleum as the energy source. Due to the increasing tries due to its abundance in those countries. However, in the Uni-
demand of transportation fuel and the volatile crude oil market, ted States, shale gas seems to be an attractive option for producing
it is necessary to develop cleaner and more carbon efficient non- DME due to its low-cost and high availability [3].
petroleum based transportation fuels [1]. In the recent years, use Syngas composition can vary widely depending on the feed-
of dimethyl ether (DME) as an alternative liquid fuel is being stock used. The syngas derived from coal has a much lower
strongly evaluated, because of its high cetane number (55–60) H2/CO ratio (close to 1) compared to the syngas derived from nat-
and potential to replace diesel. DME has properties similar to the ural gas or shale gas (usually >2) [4,5]. So, the feedstock has a
liquefied petroleum gas (LPG) and can be used as a high quality strong impact on the process technology. Most of the papers in
household fuel [1]. Moreover, it is non-toxic, environmentally the area of DME synthesis from natural gas/coal have mainly
friendly (with about 95% less CO2 emission than diesel) and an focused on catalyst development, intrinsic kinetic studies, and on
developing reactor technologies [1,6,7]. Systems level analysis of
⇑ Corresponding author. the DME synthesis processes from both technical and economic
E-mail address: Debangsu.Bhattacharyya@mail.wvu.edu (D. Bhattacharyya). perspectives is lacking in the open literature not only for shale

http://dx.doi.org/10.1016/j.apenergy.2017.06.085
0306-2619/Ó 2017 Elsevier Ltd. All rights reserved.
164 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

gas as the feed but also for coal/natural gas as the feed. Ohno et al. place over bi-functional catalysts such as CuO/ZnO/Al2O3 and
[8] have reported on the development of a 100 t/d natural gas to c-Al2O3. The indirect route is widely used commercially, but it
DME synthesis plant. In a study by Peng et al. [5], issues related has lower DME production rate due to the thermodynamic equilib-
to the direct DME synthesis process have been discussed. Studies rium limitation of CO conversion to methanol [32]. This problem
on the DME synthesis processes from coal are also available in can be overcome by the direct synthesis route leveraging the syn-
the open literature [9,10]. Han et al. [9] and Shim et al. [10] have ergistic effect of the simultaneous conversion of methanol to DME
developed kinetic models of the direct DME synthesis reactor. Chen which, in turn, increases syngas conversion and yield of DME [32].
et al. [11] have simulated the DME synthesis reactor by minimizing In the direct synthesis route, the yield of DME is very sensitive to
the Gibbs free energy. The authors have also performed pinch anal- the H2/CO ratio and CO2 content in the feed stream. The maximum
ysis to reduce energy consumption. Both one-dimensional model syngas conversion, i.e. the syngas conversion under equilibrium, is
as well as three-dimensional CFD models of slurry and fixed bed approximately 90% at the optimal operating condition [31]. The
direct DME synthesis reactors have been reported in the literature unconverted syngas is captured and recycled to the DME reactor
[12–14]. To the best of the authors’ knowledge, systems level study along with the fresh syngas. Since the feed composition varies
on the direct DME synthesis process using shale gas as the feed is widely when recycle is considered, it is more appropriate to
lacking in the current literature. The plant-wide process model of develop a reactor model using the reaction kinetic data for the
the shale gas to DME synthesis process developed in this work direct DME synthesis reactor for rigorous techno-economic analy-
and the systems level study conducted using this process model sis of the system.
can be instrumental in studying various design options and can The H2/CO ratio in the syngas derived from coal can be easily
be leveraged for techno-economic studies. adjusted to 1 by feeding additional steam to the ATR reactor. How-
The first step in the shale gas to DME process is to produce syn- ever, when syngas is obtained from the hydrogen rich shale gas,
gas via autothermal reforming (ATR). Unlike natural gas, shale gas this is not straightforward. The CO2 recycles from the AGR unit
consists of not only CH4 but also high amount of heavy hydrocar- and the DME separation unit have to be integrated to feed extra
bons. Reaction rates of heavy hydrocarbons are typically faster CO2 to the ATR reactor to adjust the H2/CO ratio to 1. Inclusion of
than CH4. In addition, they lead to coke formation which can signif- the CO2 recycle from the AGR and DME separation units results
icantly reduce the activity of a catalyst [15,16]. This issue can be in additional complexity and more utility costs. Hence, it is impor-
avoided by integrating an adiabatic pre-reforming reactor before tant to evaluate the effect of CO2 recycle on the H2/CO ratio. Peng
the ATR reactor to convert heavier hydrocarbons into CH4 at rela- et al. [5], Ohno et al. [8], and Ogawa et al. [31] have considered the
tively lower temperatures than the ATR reactor [17–19]. In addi- effect of CO2 recycle to the ATR reactor, but a rigorous systems
tion to prevention of catalyst coking, the pre-reformer also offers level analysis is still lacking.
several advantages such as an increase in production capacity by Various approaches for DME separation have been proposed in
10–20% and a reduction in the energy consumption in the primary the existing literature. In the study of Bhatt et al. [33], chilled
reformer due to its operation at a lower steam to carbon ratio methanol is used to separate unconverted syngas from CO2. Then
[17,20]. Existing literature in the area of pre-reforming of higher a series of flash separators and distillation columns is used to pur-
hydrocarbons has mainly focused on the development of catalysts ify DME. In some pilot plants, chilled DME is used as a solvent to
and modeling of the reactor [15,21,22]. In some studies, both the capture CO2 and then physical or chemical absorption is consid-
pre-reformer and ATR reactors have been modeled as equilibrium ered to separate CO2-DME from the unconverted syngas [8]. In
reactors [23–25]. Modeling of micro-reactors for fuel cell applica- the study of Han et al. [9], deionized water is used as a solvent
tions where ATR reactions take place in presence of high steam to separate DME from the unconverted syngas and CO2 [34]. The
to carbon ratio has been presented [26,27]. Some studies have also thermodynamic models used for DME separation technologies in
focused on one-dimensional modeling of the ATR reactor for esti- the existing literature have binary interaction parameters that
mating temperature profiles of different catalysts [28,29]. Consid- are estimated using UNIFAC-RQ or UNIFAC model [9,11]. As the
ering the key roles a pre-reformer and ATR reactor play in the DME separation unit has a large impact on the overall process tech-
DME process, reactor models using kinetic data rather than the nology and economics, it is important to estimate the binary inter-
equilibrium models are desired especially when an economic anal- action parameters using the experimental VLE data that can make
ysis has to be undertaken. the thermodynamic model more accurate. This, in turn, can
Before sending the syngas produced from the ATR reactor to the increase the accuracy of the process model for DME, syngas, and
DME synthesis unit, it has to be processed through an acid gas CO2 separation system.
removal (AGR) unit for separation of impurities, mainly CO2 from To summarize, a detailed process model for the shale gas to
the syngas. The choice of AGR technology strongly depends on DME process has been developed in this study. The focus is on con-
the partial pressure of CO2 in the feed. Physical absorption is figuration, technologies, operating conditions and energy con-
favored when the partial pressure of CO2 in the feed is relatively sumption. In particular, following contributions have been made:
high, while for low CO2 partial pressure, chemical absorption such
as amine based processes are preferred [30]. Final selection of the  Development of plant-wide models for the direct and indirect
technology also depends on the impurities to be removed, capital shale gas-to-DME production processes
costs, and energy requirements. There are several candidate tech-  Regression and validation of the key kinetic parameters for the
nologies that can be evaluated. CO2 removal by the Rectisol process direct DME synthesis reactor
has been considered by Ogawa et al. [31] for a similar application.  Regression of the binary interaction parameters for the VLE
In our study, Rectisol and methyl diethanolamine (MDEA)/piper- model of the methanol-DME-CO-CO2-H2O-H2 system
azine (PZ) technologies are evaluated as the candidate physical  Development of the reactor models using the kinetic data and
and chemical absorption technologies, respectively. validation of the kinetic models for the pre-reforming reactor,
DME can be synthesized from the clean syngas using the indi- ATR reactor, methanol synthesis and methanol dehydration
rect or direct route. In the indirect synthesis route, syngas is first reactors for the indirect route
converted to methanol followed by dehydration of methanol in a  Development of a novel configuration of the DME separation
separate reactor to produce DME. In the direct synthesis route, syn- system considering the recycle system for CO2 utilization
gas is directly converted to DME in a single reactor where both  Evaluation and comparison of Rectisol and MDEA/PZ technolo-
methanol synthesis and dehydration reactions simultaneously take gies with varying H2/CO ratio and CO2 partial pressure
C. Mevawala et al. / Applied Energy 204 (2017) 163–180 165

 Systems level energy analysis of the shale gas to DME produc- that includes the pre-reforming and ATR reactors, and the AGR unit
tion process via direct and indirect synthesis routes where either the Rectisol or MDEA/PZ technology is used. Similarly,
the DME production section can be divided into the DME synthesis
2. Process design & modeling unit that includes the DME synthesis reactor and the DME separa-
tion unit.
2.1. Steady state modeling & validation In the syngas production section, shale gas is sent to the pre-
reforming reactor where heavy hydrocarbons (>C2) react with
The block flow diagram (BFD) of the shale gas-to-DME produc- steam, generating CH4 and syngas. The effluent from the pre-
tion process via direct synthesis route is shown in Fig. 1. The entire reformer is fed to the ATR reactor along with steam, recycled
plant can be divided into two main sections- the syngas production CO2, and O2 from the air separation unit (ASU) to produce syngas
section and the DME production section. The syngas production with the desired H2/CO ratio. After removing water by condensa-
section can be further divided into the syngas synthesis section tion, syngas is compressed and sent to the AGR unit for CO2

Fig. 1. BFD of the shale gas to DME production process via direct synthesis.

Fig. 2. BFD of the shale gas to DME production process via indirect synthesis.
166 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

removal. Syngas compression before the AGR unit is required only Table 2
if the Rectisol process is used as the candidate AGR technology. Reactions considered in the Kinetic Model.

Clean syngas from the AGR unit is sent to the DME production sec- No. Reaction Rate equation DH298
tion where direct synthesis of syngas to DME takes place on a (kJ/kmol)
bi-functional catalyst. The effluent from the DME synthesis reactor 1 C3 H8 þ 3H2 O ! 3CO þ 7H2 r 1 ¼ k1 C C 3H8 497,729
is sent to a flash vessel followed by a series of columns for separat- 2 C2 H6 þ 2H2 O ! 2CO þ 5H2 r 2 ¼ k2 P 0:54 0:33 0:2 347,266
C 2 H 6 P H2 O P H 2
ing DME, unconverted syngas and CO2. The unconverted syngas is !
3 CH4 þ H2 O ¼ CO þ 3H2 P CO P 3H2 206,000
recycled back to the DME synthesis reactor. A portion of the CO2 r 3 ¼ k3 P CH4 P H2 O 1 
K 3 P CH4 P H2 O
captured in the AGR and DME separation units is recycled to the  
4 CO þ H2 O ¼ CO2 þ H2 P CO2 P H2 41,000
ATR reactor to obtain the desired H2/CO ratio. r 4 ¼ k4 P CO P H2 O 1 
K 4 P CO P H2 O
Fig. 2 is the BFD of the indirect synthesis route where the syngas
production section remains the same as the direct route. After
purifying the syngas in the AGR unit, it is compressed and fed to
the DME production section. The DME production section consists Table 3
of the methanol production unit, which includes the methanol syn- Kinetic parameters and equilibrium constants.

thesis reactor and syngas separation system, and the DME produc- No. kj Ej Kj
tion unit which includes the methanol dehydration reactor and (kJ/mol)
DME purification section. The effluent from the methanol synthesis 1 2.87  1011 h1 112 –
reactor is fed to a distillation column for separating methanol from 2 1.68  105 kmol/ 76.0 –
the unconverted syngas. Methanol is then fed to the methanol kg h bar0.41
3 0.151 kmol/kg h bar2 29.0 7.26  1014 exp(31266/T) (bar2)
dehydration reactor for producing DME. The effluent from this
4 4.39  106 kmol/ 67.1 2.24  102 exp(4160/T)
reactor is processed through two distillation columns to obtain kg h bar
the final DME product.
The plant-wide model is developed in Aspen Plus V8.4Ò and
heat integration is performed in Aspen Plus Energy Analyzer
C2-C3 hydrocarbon are rare in the open literature. The kinetic
V8.4Ò. Unit operations are modeled using the appropriate Aspen
model of ethane reforming is validated with the experimental data
PlusÒ blocks and validated with the experimental or operational
of Rostrup-Nielsen [15]. Using the same feed composition and
data available in the open literature. It is assumed that the cata-
operating conditions, ethane conversion is 22.4% from our model
lysts for the reaction units are in their mid-life. Marcellus shale
in comparison to 23% reported by Rostrup-Nielsen [15]. Ethane
gas from Well 3 as described in the work of Ding [35] is considered
steam reforming reaction is also studied in presence of methana-
to be the feed in this study. Its composition is shown in Table 1.
tion and water gas shift (WGS) reaction, and similar ethane conver-
sion is achieved. Kinetic parameters for other reactions are
2.2. Syngas synthesis section obtained from the open literature as shown in Table 3 [36,37]. It
should be noted that typical industrial operating conditions
The configuration of the syngas synthesis section is shown in achieve near-complete conversion of ethane [38,39] rather than
Fig. 3. Both the pre-reforming reactor and the ATR reactor are mod- the low conversion in the work of Rostrup-Nielsen [15]. Therefore,
eled as adiabatic plug flow reactor (PFR). Redlich-Kwong-Soave the reactor operating conditions are modified to make them
equation of state (EOS) with modified Huron-Vidal mixing rules similar to the typical industrial operating conditions [38,39]. In
(RKSMHV2 in Aspen PlusÒ) is used to calculate the thermodynamic particular, the reactor is operated adiabatically at 30 bar pressure
properties. with a steam/C ratio of 0.4 and a weight hourly space velocity
(WHSV) of 1.67 h1. The catalyst loading is 84,806 kg (particle den-
2.2.1. Pre-reformer sity = 1767 kg/m3) [40] and the bed voidage is assumed to be 0.4. It
Reactions considered for modeling the pre-reformer are shown should be noted that these operating conditions result in a com-
in Table 2. Kinetic studies on pre-reforming of syngas containing plete conversion of higher hydrocarbons, while methane steam
reforming and WGS reactions reach equilibrium [38].
Table 1
Marcellus shale gas composition.
2.2.2. Autothermal reforming (ATR) reactor
Component Mol%
In the adiabatic ATR reactor, endothermic steam reforming and
Methane (CH4) 83.8 exothermic partial oxidation reactions occur simultaneously along
Ethane (C2H6) 12.0
with the mildly exothermic WGS reaction. The reaction scheme,
Propane (C3H8) 3.00
Carbon dioxide (CO2) 0.900 LHHW kinetics, and their corresponding values used in this work
Nitrogen (N2) 0.300 have been obtained from the open literature as shown in Table 4
[27].

Fig. 3. Configuration of the syngas synthesis section.


C. Mevawala et al. / Applied Energy 204 (2017) 163–180 167

Table 4 require compressor(s). Therefore, the extent of CO2 capture from


Reactions considered in this Kinetic Model. the syngas should be determined by considering these tradeoffs.
No. Reaction Rate equation DH298 In this study, both physical and chemical CO2 removal technolo-
(kJ/kmol) gies are evaluated for treating the raw syngas as the CO2 partial
5 CH4 þ 2O2 ! CO2 þ 2H2 O k5 P CH4 P 0:5 802,000 pressure changes considerably due to the consideration of different
O2
r5 ¼ 2 H2/CO ratio at the outlet of the ATR reactor. Rectisol, a physical sol-
ð1 þ K CH4 P CH4 þ K O2 P 0:5O2 Þ
! vent, is being used commercially for CO2 capture for years. This
6 CH4 þ H2 O ¼ CO þ 3H2 k6 P 3H2 P CO 1 206,000
r 6 ¼ 2:5 P CH4 P H2 O  technology, similar to other physical solvent-based technologies,
P H2 K6 A2
  d consumes relatively less utility when operated at high pressure
7 CO þ H2 O ¼ CO2 þ H2 k7 P H2 P CO2 1 41,000
r7 ¼ P CO P H2 O  [34]. Therefore it is selected as a potential technology. A recent
P H2 K7 A2
! d study by some of the authors of this paper evaluated three CO2
8 CH4 þ 2H2 O ¼ CO2 þ 4H2 k8 P 4H2 P CO2 1 165,000
2
r 8 ¼ 3:5 P CH4 P H2 O  capture technologies, namely Selexol, monoethanolamine (MEA)
PH 2
K8 A2d
and MDEA/PZ for post Fischer-Tropsch CO2 capture in an indirect
Ad ¼ 1 þ K CO P CO þ K H2 P H2 þ K CH4 P CH4 þ ðK H2 O P H2 O =P H2 Þ
coal-biomass to liquids plant [23,43]. The shale gas to DME
production process has a strong similarity to the indirect coal-
biomass to liquids plant in terms of the feed composition to the
The model is validated using the experimental data from Hoang AGR unit and its design objective. It was observed in that study
& Chan [27] as shown in Appendix A. The total inlet flow rate is that the MDEA/PZ technology with intercooling had the lowest
14.4 kg/h. The temperature of the inlet stream is 126 °C, which is overall penalty. Hence, MDEA/PZ is evaluated as a potential chem-
lower than the oxidation reaction that gets initiated at a tempera- ical absorption technology in this study. Advantages of the Rectisol
ture of about 280 °C, heating up the bed temperature to about technology over the MDEA/PZ technology are simple solvent
300 °C [27,28]. An experimental study by Scognamiglio et al. [28] regeneration, cheap solvent, and flexible process configuration.
focusing on the temperature profiles of catalytic ATR reformer Some of the disadvantages of the Rectisol process are refrigeration
shows that the oxidation reaction is initiated as the gas tempera- requirement, requirement of high partial pressure in the absorber,
ture increases beyond a threshold due to heat exchange with the higher solvent circulation rate for removing CO2, and absorption of
hot catalyst followed by the steam reforming reaction that occurs hydrocarbons in the solvent.
as the temperature exceeds a threshold due to the oxidation reac-
tions. However, in Aspen PlusÒ, the catalyst temperature is not 2.3.1. Rectisol process
available as a variable. As a workaround, heat flux between the cat- The Rectisol process uses methanol as the solvent with the
alyst and gas phase is calculated using their respective tempera- absorber operating at temperatures between 28° and 70 °C,
ture profiles reported by Hoang and Chan [27] with the and at a pressure of 30–60 bar [30]. In this study, we used the
constraint that the total heat flux should sum up to zero since rate-based absorber model available in the Aspen PlusÒ library
the reactor operates adiabatically. This calculated heat flux profile with the Perturbed-Chain Statistical Associating Fluid Theory
is passed on to the ATR reactor. Operating conditions like steam/C (PC-SAFT) thermodynamic package, model parameters of which
ratio, O2/C ratio and inlet temperature depend on the exit syngas have been regressed using experimental data [44]. There are sev-
composition and its intended application. These operating condi- eral configurations available in the open literature for the Rectisol
tions are designed to satisfy the desired H2/CO ratio, which ranged process for selective removal of H2S and CO2 [45]. However, in our
between 1 and 2 in this study. Because of the high hydrogen con- study only CO2 is present so a new process scheme is developed as
tent in the shale gas, CO2 is recycled to the ATR reactor in order to shown in Fig. 4.
achieve lower H2/CO ratio (<1.6). This aspect will be discussed in The CO2 absorber is operated at 50 bar, which is decided based
detail later in this paper. The O2/C ratio is manipulated to keep on the operating pressure of the downstream DME synthesis unit.
the outlet reactor temperature between 850 °C and 1100 °C as rec- Fresh syngas is compressed and fed to the bottom of the absorber
ommended by the industry to achieve complete conversion of while the chilled methanol (28 °C) is fed to the top. Clean syngas
hydrocarbons [39,41]. In this study, the ATR reactor is designed is obtained from the top of the absorber, while the CO2 loaded
to operate adiabatically at 21 bar pressure with a WHSV of methanol leaves the absorber bottom. The bottom stream from
7.23 h1. The steam/C and O2/C ratios are varied between 0.5–0.7 the absorber is sent to a flash vessel operating at 15 bar to flash
and 0.6–0.7, respectively. The catalyst considered for this reactor off and recycle the captured syngas. The liquid stream from the
is Ni/Al2O3 with a loading of 77,713 kg (particle density = 1870 flash vessel is heated and fed to the stripper, a tray column, oper-
kg/m3), and the bed voidage is assumed to be 0.4 [42]. ating at 10 bar to regenerate the solvent which is then recycled to
the absorber. A design specification is implemented to limit the
concentration of CO2 in the clean syngas stream to 1 mol%.
2.3. Acid gas removal (AGR) unit An ammonia refrigeration cycle is modeled with a minimum
temperature approach of 5 °C to meet the refrigeration demand
Presence of CO2 in the feed to the DME reactor is known to have a in the Rectisol process. The refrigeration cycle consists of a
negative impact on the production of DME. A study by Kabir et al. 4-stage compressor with inter-stage cooling, an expander and a
[34] on production of DME from Victorian brown coal reported a heat exchanger. Ammonia, at 35 °C and 15 bar, from the multi-
threefold increase in the DME yield when the CO2 content in the stage compressor is expanded to 33.34 °C. A design specification
feed stream was zero. However, the utility consumption in the is used to control the temperature of ammonia, after heat exchange
AGR unit can increase significantly if the partial pressure of CO2 at with methanol, to ensure that the minimum temperature approach
the inlet and outlet of the AGR unit decreases especially when a is met. The overall energy consumption of the Rectisol process is
physical solvent is used. The partial pressure of CO2 in the AGR unit calculated using the specific equivalent electric consumption
can be increased by considering a lower extent of CO2 capture in the (SEEC) shown below [46].
AGR unit and by recycling a CO2-rich stream back to the ATR reactor.
Eref þ Ecw þ Eprocess þ Efuel þ Ereboiler
It also provides flexibility in maintaining the H2/CO ratio at the out- SEEC ¼ ð1Þ
CO2 captured
let of the ATR reactor. However, recycling of CO2-rich gas would
168 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

Fig. 4. Schematic of the Rectisol process.

In Eq. (1), Eref is the electric power required in the refrigeration [49,50]. Reactions (9), (10) and (12) are chosen as the three inde-
cycle compressors; Ecw is the electric power required for cooling pendent reactions in this study. These reactions take place on a
water circulation; Eprocess is the electric power consumed by pro- bi-function catalyst, CuO/ZnO/Al2O3 and c-Al2O3, with a loading
cess pumps and compressors; Efuel is the chemical exergy of the of 201,793 kg (particle density = 1982.5 kg/m3 [51]), and a bed voi-
fuel species co-captured with CO2 and Ereboiler is the electric equiv- dage of 0.4. The reactor is designed to operate at 260 °C and 50 bar
alent of reboiler duty. Since, the loss of fuel species i.e. H2 and CO in with a WHSV of 1.35 h1 similar to the pilot plant studies [5,30].
the AGR process is very less (<0.008) Efuel is ignored in the calcula- Fugacity was calculated from the equation of state and it was
tions. The SEEC calculated using our model is compared with the close to 1. So, partial pressure is used in place of fugacity in the
study of Gatti et al. [46] in Appendix B. reaction model. The pre-exponential factor, activation energy and
adsorption constants are obtained from the open literature [52].
2.3.2. MDEA/PZ process Zhang et al. [53] have calculated the equilibrium constants for all
The advanced amine solvent with MDEA as the base amine and species using Eq. (2).
PZ as an activator has a lower regeneration energy requirement B
compared to primary and secondary amines [47]. The rate based ln K j ¼ A þ þ C ln T þ DT þ ET 2 þ FT 3 ð2Þ
T
model of the MDEA/PZ process in Aspen PlusÒ previously reported
by some of the authors of this paper [43] is used in this study with However, since only the first four terms are allowed in Aspen
some modifications in configuration as shown in Fig. 5. The elec- PlusÒ, the parameters of the truncated equation are estimated
trolyte NRTL model with Redlich-Kwong (ENRTL-RK) EOS is used using the value of the equilibrium constant from Eq. (2) and the
to calculate the thermodynamic properties. parameters reported by Zhang et al. [53] over a temperature range
The rich solvent from the bottom of the absorber is heated by the of 200–400 °C, which is the expected feasible range of operation of
hot stream from the stripper bottom and sent to the flash vessel the DME synthesis reactor. The updated coefficients for the equilib-
where 66% CO2 is removed. The liquid stream from the flash sepa- rium constants are reported in Appendix C. In order to improve
rator is sent to the stripper. The desired CO2 mole fraction in the model accuracy, the Aspen PlusÒ Regression tool is used to obtain
clean syngas is achieved by manipulating the solvent circulation the pre-exponential factor and activation energy of Reactions (9),
rate. Energy consumption in the process is 2.41 kJ/kg of CO2 cap- (10), and (12). The key difference in the data regression approach
ture, which is similar to the results reported by Tobiesen et al. [48]. between this study and Nie et al. [52] is in the formulation of the
objective function. While Nie et al. [52] only considered weighted
output data in the objective for parameter estimation, in this work
2.4. Direct DME synthesis section
variances in both input and output data are considered. The objec-
tive function that is minimized by Nie et al. [52] is shown in Eq. (3).
Clean syngas obtained from the syngas production section is !
then sent to the DME production section. First, the kinetic model X
Nexp X
N

of DME reactor is developed. This is followed by the design of f ¼ ^i ÞT w1


ðyi  y ^
i ðyi  yi Þ ð3Þ
j¼1 i¼1
the DME separation system.
In Eq. (3), wi represents the weights used for component i; yi is
2.4.1. DME synthesis unit the experimental mole fraction and ŷi is the predicted mole frac-
The DME reactor is considered to be a PFR being modeled by the tion of the component i. The objective function that is used in this
R-PFR block in Aspen PlusÒ with BWR-Lee Sterling EOS as the ther- study is given by Eq. (4):
modynamic package. The configuration of the DME synthesis unit !!
1 X Xj X
Nexp Nr Nrr j
T
is shown in Fig. 6. Four possible reactions as shown in Table 5 f¼ c j;k Þ r2 ðW j;k  W
ðW j;k  W c j;k Þ þ b j;n ÞT r2 ðY j;n  Y
ðY j;n  Y b j;n Þ
j;k j;n
2 j¼1 k¼1
are considered in the direct DME synthesis reactor. By phase rule, n¼1

there are only 3 independent reactions for this reaction system ð4Þ
C. Mevawala et al. / Applied Energy 204 (2017) 163–180 169

Fig. 5. Schematic of the MDEA/PZ-based absorption process for CO2 removal.

deviation for the variables, respectively. Nie et al. [52] considered


only three components, CO, CO2 and DME, in their objective func-
tion, while in this study, five components, namely CO, CO2, DME,
H2O and H2, are taken into account. The estimated parameters are
shown in Appendix C. Fig. 7 shows comparison between the esti-
mated mole fractions and the experimental data [52].

2.4.2. DME separation unit


There is hardly any work in the open literature on the separa-
tion of DME from CO2. Ohno et al. have used MDEA for separating
DME from CO2 [8]. Since MDEA is a chemical solvent, it has a high
Fig. 6. Configuration of the DME synthesis unit. reboiler duty. In this study, a novel configuration for DME-CO2-
syngas separation unit is proposed as shown in Fig. 8 by using
In Eq. (4), Nexp, Nr, W, Ŵ, Nrr, Y, Ŷ, r represent the number of methanol as the solvent to reduce the utility consumption. As
experiments conducted, number of input variables, measured val- the default NRTL-RK property method in Aspen PlusÒ library does
ues of the input variables, estimated values of the input variables, not have the required binary interaction parameters for the
number of measured output variables, measured values of the out- methanol-DME-CO2-CO-H2O system, binary interaction parame-
put variables, estimated values of the output variables and standard ters in the NRTL-RK EOS are regressed using the experimental data

Table 5
Rate model of the direct syngas to DME synthesis reaction [10,52].

No. Reaction Rate equation DH298 (kJ/kmol)


9 CO þ 2H2 $ CH3 OH 2
k9 f co f H2 ð1  B9 Þ 90,400
r9 ¼  3
1 þ K co f co þ K CO2 f co2 þ K H2 f H2
f CH
where B9 ¼ 3 OH
2
K 9 f co f H
2

10 CO2 þ 3H2 $ CH3 OH þ H2 O 3


k10 f co2 f H2 ð1  B10 Þ 49,400
r 10 ¼  4
1 þ K co f co þ K CO2 f co2 þ K H2 f H2
f CH3 OH f H2 O
where B10 ¼ 3
K 10 f co2 f H2
11 CO þ H2 O $ CO2 þ H2 k11 f H2 O ð1  B11 Þ 41,000
r 11 ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1 þ K co f co þ K CO2 f co2 þ K H2 f H 2
f CO2 f H2
where B11 ¼
K 11 f co f H2 O
12 2CH3 OH $ CH3 OCH3 þ H2 O k12 f CH3 OH ð1  B12 Þ 23,000
r 12 ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2
1 þ K CH3 OH f CH3 OH
f DME f H2 O
where B12 ¼ 2
K 12 f CH3 OH
170 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

Fig. 7. Comparison of the estimated mole fractions with the experimental data from Nie et al. [52]

Fig. 8. Configuration of DME separation unit.

available in the open literature [54–61]. The regressed binary nol is recycled back to the absorber for syngas separation. The
interaction parameters and the corresponding fit to the data are desired DME purity is obtained by manipulating the reflux ratio.
shown in Appendix D.
CO2 has good solubility in DME at elevated pressure and low 2.5. Indirect DME synthesis section
temperature [54]. In this study, the outlet stream from the DME
reactor is chilled to 0 °C and fed to a flash vessel operating at In this section, details of the kinetic reactor models of the
45 bar, where more than 50% CO2 remains dissolved in the liquid methanol synthesis reactor and the methanol dehydration reactor
stream that contains about 86% DME. The vapor stream from the are discussed. In addition, design of the product recovery unit is
flash vessel is fed to the bottom of the high pressure absorber, also discussed. As mentioned before, in the indirect DME synthesis
where a methanol-water mixture is used as the solvent and fed section, syngas is first converted to methanol and then methanol is
to the absorber top to separate the unconverted syngas from other converted to DME.
components. The absorber uses Glitsch Grid EF25A structured
packing [9]. It is designed for a maximum fraction capacity of 2.5.1. Methanol synthesis unit
80% flooding. The top stream from the absorber is recycled to the The methanol synthesis unit consists of the methanol synthesis
DME reactor. The flow rate of the solvent is manipulated to keep reactor and the syngas separation column. The configuration of the
the CO2 concentration in the total feed to the DME reactor to be methanol synthesis unit is shown in Fig. 9. RKSMHV2 and PC-SAFT
less than 3 mol%. The bottoms stream is fed to a distillation col- EOS are used as the property methods for the reactor and the sep-
umn. Design parameters such as the number of stages, reflux ratio aration column, respectively. Fresh syngas from the syngas produc-
and feed tray of the distillation column are manipulated to obtain tion unit is compressed to 60 bar and heated to 250 °C in a series of
the desired CO2 release from the solvent [9]. The released CO2 is heat exchangers followed by a fired heater. After pre-heating the
recycled to the ATR reactor and the bottoms stream is fed to the reactor inlet stream, the effluent from the methanol synthesis reac-
DME column. This distillation column is designed to produce tor is further cooled to 60 °C and fed to a flash vessel for methanol
DME with more than 99.8 mol% purity at the top. The bottom separation. About 85% of the vapor stream from the flash vessel is
stream from the DME column containing mainly water and metha-
C. Mevawala et al. / Applied Energy 204 (2017) 163–180 171

Fig. 9. Configuration of the methanol synthesis unit.

Table 6
Rate model of the methanol synthesis reaction.

No. Reaction Rate equation DH298 (kJ/kmol)


!
13 CO2 þ 3H2 $ CH3 OH þ H2 O P H2 O P CH3 OH 49,400
k13 P CO2 P H2 1 
K 13 P 3H2 P CO2
r 13 ¼
ABS3
 
14 CO2 þ H2 $ CO þ H2 O K 14 P H2 O P CO 41,000
k14 P CO2 1 
P H2 P CO2
r 14 ¼
ABS
 
ABS = 1 þ K H2 O;H2 P H2 O =P H2 þ K 0:5 0:5
H2 P H2 þ K H 2 O P H 2 O

recycled to the methanol synthesis reactor and the remaining is


purged to avoid CO2 buildup. The liquid stream is sent to a
distillation column operating at 12 bar for methanol purification.
The bottom stream from the distillation column containing
99.5 mol% methanol is then sent to the methanol dehydration
reactor.
The methanol synthesis reaction takes place on a commercial
Cu/ZnO/Al2O3 catalyst with a loading of 96,609 kg (particle den-
sity = 1775 kg/m3; bed voidage = 0.5). These reactions occur under
isothermal condition typically at 210–270 °C, and 50–100 bar pres-
sure [62,63]. Three possible reactions in this reactor are CO hydro-
Fig. 10. Concentration and temperature profile of the methanol synthesis reactor.
genation, CO2 hydrogenation and reverse water gas shift (RWGS).
Only two reactions out of these three reactions are independent.
In this work, the CO2 hydrogenation and RWGS reactions are con-
sidered to be the independent reactions with the kinetic models as 2.5.2. Methanol dehydration unit
shown in Table 6 [64]. The configuration of the methanol dehydration unit is shown in
The readjusted parameters for the model are obtained from Fig. 11. Methanol from the methanol synthesis unit is heated to the
Van-Dal and Bouallou [62]. Model validation is performed using desired temperature using a fired heater and fed to the methanol
the experimental data given by Vanden Bussche and Froment dehydration reactor. The reactor effluent is cooled to 60 °C and
[64]. The concentration and temperature profiles shown in fed to the DME purification column operating at about 10 bar.
Fig. 10 closely matches the experimental data of Vanden Bussche The desired DME purity is 99.8 mol% which is obtained by manip-
and Froment [64]. ulating the reflux ratio in the DME purification column. The bottom
Two key factors for optimal methanol production are module stream from the DME purification column is fed to the methanol-
(M) of the feed syngas, defined as (H2  CO2)/(CO + CO2), and the water separation column from which 98 mol% pure methanol is
CO/CO2 ratio. A module of 2 and a high CO/CO2 ratio are recom- recovered and mixed with the methanol from the methanol purifi-
mended for higher reaction rates and high single-pass syngas con- cation unit.
version. The syngas produced by the ATR reactor has a module of The methanol dehydration reactor is modeled as a PFR with
1.7–1.8. This module can be adjusted to 2 by either adding hydro- LHHW kinetics, operating at 250 °C, 10 bar with a WHSV of
gen to the ATR reactor or removing CO2 from the syngas. In this 4.05 h1 [65]. The reaction takes place on a c-Al2O3 catalyst with
study, CO2 is removed from the syngas by using the Rectisol tech- a loading of 44,140 kg (particle density = 2141 kg/m3; bed
nology as mentioned earlier. It should be noted that if the module voidage = 0.4) [66]. The DME purification column and methanol-
is adjusted by using hydrogen, then there can be a strong energy water separation column are modeled as equilibrium-based
penalty due to the hydrogen generation and purification units. models. NRTL-RK EOS with regressed binary interaction parameters
172 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

Fig. 11. Configuration of DME synthesis unit.

from Section 2.4.2 is used as the thermodynamic model for However, the results of the rate-based reactor model is also com-
this unit. pared with a Gibbs free energy minimization reactor model, as
The rate model of the methanol dehydration reaction is shown shown in Appendix E and are found to be satisfactory.
in Table 7 [67]. Kinetic parameters of the model are taken from
Mollavali et al. [67]. The equilibrium constant for this reaction,
3. Results and discussion
given by Eq. (5), is obtained from the work of Diep and Wainwright
[68].
Table 8 provides the summary of the base case (i.e. H2/CO = 1)
material balance for the direct synthesis route with the stream
2835:2
ln K eq ¼ þ 1:675 ln T  2:39  104 T  13:360 ð5Þ numbers marked in Fig. 1. Two key design variables investigated
T
in this study for the direct synthesis process are the CO2 recycle
and the H2/CO ratio in the DME production section inlet stream.
The reactor model is validated with the work of Bercic and Sensitivity analysis of the syngas synthesis and AGR units for vary-
Levec [69]. Due to the lack of experimental data in the open liter- ing CO2 feed and H2/CO ratio is presented in Section 3.1. In Sec-
ature, a more comprehensive validation could not be performed. tion 3.2, the effect of feed composition in the DME reactor and

Table 7
Rate model of the methanol dehydration reaction.

No. Reaction Rate model DH298 (kJ/kmol)


15 2CH3 OH $ CH3 OCH3 þ H2 O k15 P CH3 OH  ðk15 =K 15 ÞðP DME P H2 O =P CH3 OH Þ 23,000
r 15 ¼
K CH3 OH P CH3 OH þ ðP H2 O =K H2 O Þ þ 1

Table 8
Summary of material balance for base case (H2/CO = 1). (Note: Mole fractions that are close to zero are left blank).

Stream # 1 2 3 4 5
Temperature (°C) 40.0 532 939 35.0 25.0
Pressure (bar) 30.4 30.1 19.9 50.6 50.0
Total flow (kg/h) 5200 8412 27,645 20,106 15,925
Total flow (kmol/h) 98,047 141,821 561,990 424,302 243,021
Mole fraction
CH3OH Trace
CO2 0.009 0.048 0.154 0.209 0.010
CO Trace 0.286 0.392 0.490
N2 0.003 Trace Trace Trace Trace
H2 0.070 0.287 0.394 0.496
CH4 0.838 0.676 Trace Trace Trace
H2O 0.200 0.270 Trace
C2H6 0.120
C3H8 0.030
Stream # 6 7 8 9 10
Temperature (°C) 1.21 1.21 48.1 60.0 61.5
Pressure (bar) 45.0 45.0 45.0 20.9 15.0
Total flow (kg/h) 4235 4207 8885 10,267 2396
Total flow (kmol/h) 184,221 88,177 239,456 305,234 110,345
Mole fraction
CH3OH 0.021 0.415 0.368
CO2 0.392 0.206 0.086
CO 0.036 0.301 0.027
N2 Trace 0.017 Trace
H2 0.428
H2O 0.026 0.448 0.398
C2H6O 0.521 0.045 0.021 0.233 0.999
C. Mevawala et al. / Applied Energy 204 (2017) 163–180 173

sensitivity of methanol content on the reboiler duty in the direct gen feed to the ATR reactor and CO2 for recycle. The increase in the
syngas-to-DME production process are discussed. Various studies utility requirement is mainly due to compression of CO2 recycle.
on the indirect syngas-to-DME production process are discussed It should be noted that the O2/C and steam/C ratio are indepen-
in Section 3.3. Finally, the effect of changing H2/CO ratio on the dent variables for each case and hence are different. As mentioned
overall utility consumption for both direct and indirect routes is earlier, these two variables are manipulated to control the temper-
presented in Section 3.4. If not mentioned otherwise, results are ature and composition at the ATR reactor outlet.
shown for the direct DME synthesis route.
3.1.2. Effect of H2/CO ratio on the AGR unit
As discussed in Section 3.1.1, higher CO2 recycle is required in
3.1. Syngas synthesis and acid gas removal order to obtain a lower H2/CO ratio. As a result of utilizing more
CO2 in the ATR reactor, the partial pressure of CO2 increases in
3.1.1. Effect of CO2 recycle on the syngas synthesis unit the ATR outlet. Table 10 compares the operating costs and utility
Due to high hydrogen content in the shale gas, obtaining a low consumptions in the AGR unit due to the change in the H2/CO ratio.
H2/CO ratio (<1.6) is difficult. Recycling of CO2 from the down- For fair comparison, only 1 mol% of CO2 in the clean syngas stream
stream AGR unit and DME production unit to the ATR reactor is goes to the DME production section in all case studies. Energy con-
required in order to obtain a lower ratio, as shown in Fig. 1. Provid- sumptions in the refrigeration unit and syngas compressor are
ing more CO2 to the ATR unit results in production of more CO included in the results of the Rectisol process. Energy consumption
thereby reducing the H2/CO ratio as seen in Fig. 12. in the syngas compressor downstream of the AGR unit is included
Recycle of CO2 has advantages and disadvantages. For example, in the results of the MDEA/PZ process. Costs of electricity, cooling
to obtain H2/CO ratio of 1, 87% of the total CO2 produced is utilized water and low pressure steam (LPS) are assumed to be $ 16.8/GJ, $
in the ATR reactor. The main disadvantage of having a CO2 recycle 0.354/GJ and $ 14.05/GJ, respectively [70].
is the increase in the utility usage due to the compression of CO2 For the Rectisol process, the major utility consumption is due to
before feeding it to the ATR reactor. It also results in more utility the syngas compressor before the AGR unit and the reboiler duty
consumption in other sections of the process. Another effect of for solvent regeneration, while for the MDEA/PZ process, more
the higher recycle ratio is the increase in the equipment size, than 40% of the utility consumption is due to solvent regeneration.
which is not captured in this work. The advantage of having a As expected, for both processes the solvent circulation rate
CO2 recycle is the higher carbon yield. As seen in Table 9, CO2 decreases with the increase in the H2/CO ratio because of the
requirement reduces with the increase in the H2/CO ratio. Electric- decrease in the amount of CO2 produced in the ATR unit. However,
ity and cooling water usage shown are for the compression of oxy- it should be noted that the cost per unit amount of CO2 captured
increases as the H2/CO ratio increases as seen in Table 10. This is
due to the decrease in the CO2 partial pressure, which has strong
impact in the physical absorption process. For chemical absorption,
the increase in cost per unit amount of CO2 captured is due to the
increase in the solvent to CO2 flowrate ratio (molar) from 1.16 to
1.23 as the partial pressure of CO2 decreases from 2.1 bar to
0.52 bar, respectively. Considering the cost of CO2 capture, it is
observed that the Rectisol process is a better option for lower
H2/CO ratio cases (i.e. 1 and 1.5) in comparison to the MDEA/PZ
process. For H2/CO ratio of 2, MDEA/PZ process is preferred in
comparison to the Rectisol process.
Fig. 12. Sensitivity of H2/CO ratio to the CO2 recycle ratio.
3.2. Direct syngas-to-DME production section
Table 9
Effect of the CO2 recycle on syngas synthesis unit.
The overall utility usage by the DME production section in the
Case H2/CO = 1 H2/CO = 1.5 H2/CO = 2 base case (i.e. H2/CO = 1) is studied by evaluating two different
O2/C (molar) 0.7 0.64 0.65 CO2 capture technologies for the AGR unit as shown in Table 11.
Steam/C (molar) 0.6 0.58 0.65 It shows how the choice of the AGR technology affects the utility
CO2 recycle/fresh feed (molar) 0.44 0.19 0 usage in the DME production section. Costs of medium pressure
Electricity consumed (MW) 5 3 2
steam (MPS) and natural gas are assumed to be $ 14.83/GJ and
Cooling water required (MW) 126 96 85
$ 2.64/GJ, respectively [70,71]. It should be noted that the overall

Table 10
Effect of H2/CO ratio on CO2 removal technologies.

H2/CO = 1 H2/CO = 1.5 H2/CO = 2


AGR technology Rectisol MDEA/PZ Rectisol MDEA/PZ Rectisol MDEA/PZ
Total pressure (bar) 50 10 50 10 50 10
CO2 mole% 21.0 21.0 11.9 11.9 5.2 5.2
CO2 feed (104 kg/h) 18.5 18.5 9.62 9.62 3.88 3.89
Solvent circulation rate (105 kg/h) 11.4 5.46 8.81 2.96 6.21 1.21
CO2 captured 94% 96% 90% 93% 78% 81%
Utility requirements
Electricity (GJ/h) 196 113 168 119 147 117
Cooling water (GJ/h) 357 401 303 246 246 133
5 barg steam (GJ/h) 157 416 114 223 79 89
Cost ($/Mt of CO2 captured) 32 44 53 58 121 103
Cost ($/Mt of CO2 captured) w/o syngas compressor 19 32 24 36 53 41
174 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

Table 11 17.2
Utility consumption by DME production section when H2/CO = 1.
17

(mol/kg catalyst h)
DME Productivity
Syngas production section with AGR technology Rectisol MDEA/PZ 16.8
Refrigeration unit 16.6
Electricity (GJ/h) 47 51
16.4
Cooling water (GJ/h) 179 201
16.2
DME synthesis unit
Fired heater (GJ/h) 7 7 16
Cooling water (GJ/h) 99 168
15.8
Electricity (GJ/h) 1 1 0 0.5 1 1.5 2 2.5 3
DME separation unit CO2 (mol%)
Electricity (GJ/h) 1 1
Cooling water (GJ/h) 274 303 Fig. 14. Effect of the CO2 content on DME productivity.
MPS (GJ/h) 191 218
LPS (GJ/h) 223 234 feed. The productivity decreases by 7% when the CO2 content is
Total utility cost ($/h) 6998 7676
3 mol%, as shown in Fig. 14. This shows that the DME productivity
is highly sensitive to the CO2 content in the feed stream.
refrigeration duty shown is only for the refrigeration required in
the DME production section. The refrigeration duty required in
3.2.2. DME separation unit
the AGR unit is not taken into account here because it is not
A summary of some important streams for the base case is
considered to be part of the DME production section.
shown in Table 12, with the stream numbers marked in Fig. 8. As
As mentioned earlier, the Rectisol process uses chilled methanol
mentioned in Section 2.4.2, DME is an excellent solvent for captur-
as a solvent at 28 °C for CO2 absorption. As a result, cold process
ing CO2 at low temperature and high pressure. In this study, the
streams are available in the AGR unit which can be utilized to cool
DME reactor effluent stream is cooled to 0 °C because the low oper-
the DME rector effluent. The DME reactor effluent is chilled
ating temperature is beneficial for physical absorption. Unfortu-
because CO2 solubility in DME increases at lower temperature
nately, the authors could not find the VLE data of DME-CO2
and higher pressure. When MDEA/PZ is used in the AGR unit, there
system below 0 °C. Cooling this stream to a lower temperature
are no cold streams available. Therefore, chilling of the DME reac-
might be beneficial, but is not investigated here since extrapolation
tor effluent is accomplished only by the refrigeration unit. This
of the thermodynamic model can lead to errors.
increases utility consumption in the refrigeration unit resulting
Methanol-water mixture is used in the absorber to capture the
in the increase in the utility cost of the DME production unit when
DME from the vapor stream of the flash vessel. The design objective
MDEA/PZ is used in the AGR unit. Similar results are obtained for
is specified to limit the DME loss to 1 mol%. To satisfy this specifi-
higher H2/CO ratios as well.
cation, the methanol content in the solvent stream is adjusted. As
shown in Fig. 15, DME capture increases with the increase in the
3.2.1. Effect of feed composition on DME productivity
methanol content, while CO2 capture changes negligibly.
Composition of the fresh feed to the DME reactor has a strong
The change in the methanol content also impacts the overall
impact on DME productivity, as shown in Fig. 13. Maximum DME
duty of the CO2 and DME columns, as shown in Fig. 16. An increase
productivity of 16.7 mol/kg catalyst h is achieved when H2/CO is 1.
in the methanol content in the solvent stream of the absorber
In comparison to the H2/CO ratio of 1, the DME productivity
decreases the reboiler duty of the CO2 column. The heat of vapor-
decreases by 42% and 14% when the H2/CO ratio changes to 0.5
ization of water and methanol is 40.7 kJ/mol and 37.6 kJ/mol,
and 2, respectively. As the H2/CO ratio increases, carbon utilization
respectively. So, as the water content decreases and methanol con-
goes up, but hydrogen utilization goes down. The reduction in car-
tent increases, less energy is required in the reboiler. On the other
bon utilization in the CO-rich region is due to the insufficient sup-
hand, an increase in the methanol content in the DME column
ply of hydrogen for CO hydrogenation reaction (Reaction (9)),
increases the reboiler duty. This is because of the high solubility
while in the hydrogen-rich region carbon utilization increases
of DME in methanol thereby requiring higher reflux ratio and
resulting in higher concentration of hydrogen in the recycle loop.
reboiler duty to achieve this difficult separation.
Due to this imbalance in the H2 and CO conversion, and the recycle
of unconverted syngas to the DME reactor, the H2/CO ratio in the 3.3. Indirect syngas-to-DME process
total feed (i.e. after the recycle is mixed) to the DME reactor
increases to 1.02, 2.20 and 3.70, when the H2/CO ratio in the fresh 3.3.1. Methanol synthesis reactor
feed is 1, 1.5 and 2, respectively. Maximum DME productivity of The module of the fresh syngas, defined as (H2  CO2)/(CO + CO2),
17 mol/kg catalyst h is achieved when there is no CO2 in the fresh has a strong impact on the methanol production, as shown in Fig. 17.
Maximum methanol production is achieved when the module
of fresh syngas, containing 1 mol% CO2, is 1.83. When the module
DME Productivity C Utilization H Utilization
of the fresh syngas is 1 and 3, methanol production drops by 16%
18 95 and 10%, respectively. The decrease in methanol production for
17 85 module far away from 2 is due to the imbalance in H2 and CO com-
(mol/kg catalyst h)
DME Productivity

Utilization (%)

16 75 ponents which limits the reaction and the methanol production.


15 65
14 55 3.3.2. Effect of CO2 capture rate on energy usage
13 45 Effects of varying amount of CO2, in the fresh syngas stream to
12 35 the DME production section on the overall process energy usage
11 25 and DME produced are shown in Table 13.
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Three cases with different concentrations of CO2 in the clean
H2/CO
syngas to the DME production section are evaluated. Cases 1, 2,
Fig. 13. Effect of the H2/CO ratio on DME productivity at 260 °C, 50 bar, 1.35 h1 and 3 have 1 mol%, 3 mol% and 5.2 mol% (no CO2 capture) CO2,
WHSV. respectively, in the clean syngas. For Cases 2 and 3, when the
C. Mevawala et al. / Applied Energy 204 (2017) 163–180 175

Table 12
Material balance for DME separation unit (H2/CO = 1). (Note: Mole fractions that are close to zero are left blank).

Stream # 1 2 3 4 5
Temperature (°C) 0.000 1.207 1.207 15.4 41.9
Pressure (bar) 49.9 45.0 45.0 45.0 45.0
Total flow (kg/h) 8442 4207 4235 7686 13,120
Total flow (kmol/h) 272,397 88,177 184,221 190,448 423,677
Mole fraction
CH3OH 0.011 0.021 0.482 0.288
CO2 0.299 0.206 0.392 0.184
CO 0.168 0.301 0.036 0.030
N2 0.010 0.017 Trace Trace
H2 0.214 0.428
CH4 0.002 Trace Trace Trace
H2O 0.013 0.026 0.518 0.312
C2H6O 0.284 0.045 0.521 0.183
Stream # 6 7 8 9
Temperature (°C) 23.4 60.0 61.5 33.4
Pressure (bar) 21.0 20.9 15.0 45.0
Total flow (kg/h) 2853 10,267 2396 3008
Total flow (kmol/h) 118,443 305,234 110,345 39,168
Mole fraction
CH3OH 0.368 Trace
CO2 0.848 0.036
CO 0.139 0.339
N2 Trace 0.021
H2 0.599
H2O 0.398 Trace
C2H6O 0.233 0.999

30
Methanol Production
(mol/kg catalyst h)

29

28

27

26

25
0.90 1.40 1.90 2.40 2.90
( 2− 2)/( + 2)

Fig. 15. Effect of methanol content on DME and CO2 captured in the absorber.
Fig. 17. Effect of syngas module on methanol production at 250 °C, 60 bar and
3.24 h1 WHSV.

Table 13
Effect of CO2 capture on indirect DME production process.

Case 1 2 3
AGR technology Rectisol Rectisol –
Solvent circulation rate (kg/h) 620,738 413,344 –
CO2 mol% allowed in Syngas 1 3 5.2
DME produced (kg/h) 105,430 104,005 101,869
Electricity (GJ/h) 365 359 352
Cooling water (GJ/h) 1338 1310 1244
Fired heater (GJ/h) 148 154 0
MPS (GJ/h) 242 239 235
Fig. 16. Effect of the methanol content on reboiler duty. LPS (GJ/h) 120 95 44
HPS (GJ/h) 97 97 96
Utility Cost ($/h) 13,774 13,292 11,949
CO2 concentration is more, the DME production decreases by 1.2%
and 3.2%, respectively. Moreover, an increase in CO2 mol% in the 3.4. Overall utility and electrical efficiency
clean syngas feed reduces the overall energy usage. In Case 3, since
the AGR unit is not considered, hot streams from the syngas pro- The summary of overall utility consumption for both direct and
duction unit are utilized to heat the feed streams to the methanol indirect synthesis routes (Cases 1 and 3) is shown in Table 14. Costs
synthesis and methanol dehydration reactors eliminating the need of the AGR unit solvents and refrigerants are not included in these
for feed heaters. calculations. All the input and output utilities have been converted
176 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

Table 14
Summary of utility consumption in the entire plant.

Direct DME synthesis Indirect DME synthesis


H2/CO = 1 H2/CO = 2
AGR technology Rectisol MDEA/PZ Rectisol MDEA/PZ Rectisol No CO2 capture
DME produced (Mt/h) 110 110 89 89 105 102
Electricity equivalent input (GJ/h)
Shale gas 2921 2921 2921 2921 2921 2921
Electricity 464 387 380 354 365 352
Cooling water 16 18 12 10 14 13
Fired heater 6 7 8 9 133 0
Steam 677 806 652 669 686 649
Electricity equivalent output (GJ/h)
Dimethyl ether 1963 1963 1579 1579 1876 1814
Steam 257 257 217 217 218 112
Utility cost ($/Mt of DME produced) 150 177 138 139 131 116
Overall equivalent electrical efficiency 54.35% 53.64% 45.21% 45.32% 50.83% 48.93%

to an electricity equivalent quantity for a fair comparison. For detailed economic study of various alternatives for the direct and
example, the LHV value of shale gas and DME is first calculated indirect routes in the near future.
and then the efficiency factor of a combined cycle gas turbine is
used to calculate the equivalent electricity generated [72]. For cool- Acknowledgement
ing water, the electricity required to circulate the cooling water
required in the process is calculated in Aspen PlusÒ. The tempera- Chirag Mevawala will like to gratefully acknowledge financial
ture of the cooling water at the outlet of coolers is set to 40 °C. Elec- support from the West Virginia University through STEM Moun-
tricity equivalent of steam is calculated by using an efficiency factor tains of Excellence fellowship.
of 0.436 [73]. For fired heater, a combustion efficiency of 90.5% is
considered in calculating the electricity equivalent. Appendix A
As shown in Table 14, the DME production as well as the overall
process efficiency is higher for the direct DME synthesis route with Table A.1 shows the validation of the ATR reactor model with
H2/CO ratio of 1, and with the MDEA/PZ process as the AGR tech- the literature data.
nology in comparison to the indirect synthesis route. In case of
indirect synthesis with no CO2 capture, the major utility consump-
Table A.1
tion is due to the compression of the syngas required before the Validation of ATR model with Hoang & Chan [27].
methanol synthesis unit. The cost per unit of DME produced is cal-
Inlet mol% Outlet mol% Error%
culated as shown in Table 14. The cost per unit for direct DME syn-
thesis process with H2/CO ratio of 1 is higher compared to the Model Reported
indirect DME synthesis process with AGR unit. However, it should H2 1.30 27.0 30.0 10.0
be noted that the direct DME synthesis process produces more CO 0.400 7.00 6.50 7.70
CO2 0.100 6.30 7.00 10.0
DME compared to indirect DME synthesis process.
O2 12.0 0 0 0
H2O 24.6 23.8 22.5 5.80
CH4 16.4 0 0 0
4. Conclusion
N2 45.3 35.8 34.0 5.30
Temperature (°C) 126 794 762 3.10
The plant-wide model of the shale gas to DME process has been
developed in Aspen plus V8.4Ò. Models of the pre-reforming
reactor, ATR reactor, and DME reactor are developed using kinetic Appendix B
data. Comparison between the Rectisol process and the MDEA/PZ
process shows that the Rectisol process has a lower CO2 capture pen- Table B.1 shows the comparison of the SEEC for our model with
alty than the later mainly due to the higher CO2 partial pressure. Sen- the literature data. The SEEC calculated using our model appears
sitivity studies on the DME reactor show that the maximum DME
productivity can be obtained when H2/CO ratio is 1, and at lower Table B.1
CO2 concentration in the feed. While it is difficult to achieve this ratio Performance of the Rectisol process in comparison to Gatti et al. [46].
for shale gas derived syngas, process configurations are developed
Our Reported
by integrating CO2 recycle streams between DME and syngas pro- model
duction plant to make this possible. A novel DME separation process Reference Scheme B mixed
is also developed. Finally, it is observed that the DME production and scheme refrigerant
the overall process efficiency is higher for the direct DME synthesis Absorber temperature (°C) 28 50 50
route with H2/CO ratio of 1 in comparison to the indirect DME syn- Absorber pressure (bar) 50 60 60
thesis route. A number of options considered in this study such as CO2 mol% 21 30 30
Eref (MW) 11.4 21.1 12.1
the higher CO2 recycle would results in larger equipment sizes and
Ecw (MW) 0.9 1.5 1
therefore for thorough investigation of these options, capital cost Eprocess (MW) 3.8 15.8 18.9
must be taken into account. The models developed in this study Ereboiler (MW) 8.4 5 0.4
can be leveraged for optimization, techno-economic analysis and Overall electric consumption (MW) 24.4 43.4 32.4
life-cycle analysis, which, in turn, can be instrumental in making CO2 captured (kg/s) 48.2 65 65.3
CO2 capture (%) 93.6 97.5 98
critical decisions such as the technology selection, plant size, and SEEC (kJ/kg of CO2 captured) 507 668 496
the location of plant. The authors look forward to presenting a
C. Mevawala et al. / Applied Energy 204 (2017) 163–180 177

reasonable considering the difference in CO2 partial pressure and first three coefficients are the same as the work of Zhang et al.
extent of CO2 capture from the work of Gatti et al. [46]. [53]. Fig. C.1(a)–(c) shows the comparison between the original
and the estimated equilibrium constant for reactions (9), (10)
Appendix C and (12).
Table C.2 shows the estimated kinetic rate parameters for the
The adjusted equilibrium coefficient for the 4th term in Eq. (2) reactions occurring in direct syngas-to-DME reactor.
is shown in Table C.1. Excel solver was used to do so. Note that the

Table C.1
Estimated equilibrium constant coefficients for DME synthesis.

Reaction # A B C D
Original Original Estimated
9 22.7 8975 7.694 3.92E03 4.10E03
10 17.6 4213 5.752 1.71E03 4.16E04
12 9.39 3205 0.836 2.35E03 1.43E03

Fig. C.1. Comparison between original and estimated equilibrium constant of reaction (9) (a), reaction (10) (b) and reaction (12) (c).

Table C.2
Estimated rate parameters.

Reaction # Pre-exponential factor Activation energy (kJ/kmol)


9 1.537 mol/g s bar3 62,915
10 1.364 mol/g s bar4 59,660
12 0.301 mol/g s bar 42,765
178 C. Mevawala et al. / Applied Energy 204 (2017) 163–180

Appendix D Appendix E

The binary interaction parameters for NRTL-RK EOS were Table E.1 shows the model validation for the rate-based metha-
regressed using the experimental data as shown in Table D.1. nol dehydration reactor. As seen below, the outlet temperature and
The objective function used in estimating the binary interaction methanol conversion calculated by the model developed here are
parameters is a maximum likelihood objective function given by in good agreement with Bercic and Levec [69]. The rate based
Eq. (D.5). methanol dehydration reactor is also compared with the Gibbs free
energy minimization model, as shown in Table E.2. The purpose of
N h
X this test is to study that the rate model correctly calculates the
f ¼ ððT e;i  T m;i ÞT r2
T ðT e;i  T m;i ÞÞ þ ððP e;i  P m;i Þ rP ðP e;i  P m;i ÞÞ
T 2

i¼1
equilibrium concentration. Reaction temperature is set to 250 °C
X
M with an operating pressure of 10 bar so that the reaction reaches
þ ððxe;i;j  xm;i;j ÞT r2
x;i;j ðxe;i;j  xm;i;j ÞÞ
equilibrium. It can been seen that the outlet concentration of the
j¼1
#
X
M
þ ððye;i;j  ym;i;j ÞT r2
y;i;j ðye;i;j  ym;i;j ÞÞ ðD:5Þ
Table E.1
j¼1
Validation of methanol dehydration reactor model with Bercic & Levec [69].
Here, N, T, P, M, x, y, e, m, r represent the number of data points in Parameter Inlet Outlet
the data, temperature, pressure, number of components in the data,
Our model Reported
liquid mole fraction, vapor mole fraction, estimated data, measured
data and standard deviation of the indicated quantity respectively. Temperature (°C) 288 407 409
Pressure (bar) 2.1 – 2.099
Fig. D.1 shows the fit for the liquid and vapor mole fractions. Exper- Methanol molar conversion – 80% 81.38%
imental data are obtained from the open literature [54–61].

Table D.1
Binary interaction parameters for NRTL-RK EOS.

Component i CO2 Methanol DME CO H2 Methanol


Component j DME CO2 H2O DME DME H2
AIJ 2.17 15.90 80.00 17.22 0.49 2.53
AJI 4.86 80.00 80.00 6.20 7.27 104.06
BIJ 913.62 1221.13 2454.24 6079.49 277.29 2610.24
BJI 1703.00 2586.82 2712.79 1464.06 1876.28 10000.14
CIJ 0.30 0.30 0.30 0.30 0.37 0.30
DIJ – – – – – –
EIJ – 2.00 12.13 – – –
EJI – 12.05 12.61 – – –

Fig. D.1. Comparison of predicted data with the experimental data; 1 – Methanol CO2; 2 – DME-CO2, 3 – DME-H2O, 4 – DME-CO systems.
C. Mevawala et al. / Applied Energy 204 (2017) 163–180 179

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