You are on page 1of 12

Energy xxx (2017) 1e12

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Exergy-based evaluation of methanol production from natural gas


with CO2 utilization
Timo Blumberg*, Tatiana Morosuk, George Tsatsaronis
t Berlin, Marchstr 18, 10587 Berlin, Germany1
Institute for Energy Engineering, Technische Universita

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

Article history: Energy and exergy analyses were carried out for a medium-capacity methanol plant based on a low-
Received 22 December 2016 pressure synthesis process for natural gas. The process comprises a pretreatment of natural gas, a
Received in revised form steam-methane reforming unit for generation of synthesis gas, a methanol synthesis, a distillation of
29 May 2017
crude methanol, and an integrated steam cycle for waste heat recovery. Carbon dioxide from carbon
Accepted 23 June 2017
capture is used for gas conditioning by adjusting the syngas module for methanol synthesis through
Available online xxx
counterbalancing of the excess hydrogen. A sensitivity analysis was performed to identify favorable
operation parameters for the tubular steam reformer. The energetic and exergetic efciencies for the
Keywords:
Methanol production
overall system were found to be 35.9% and 37.7%, respectively. The specic energy requirements (energy
Energetic analysis intensities) are 19.6 GJth/tCH3OH and 0.8 GJel/tCH3OH, while the specic methane consumption was
Exergetic analysis calculated to be 0.54 ton CH4 per ton CH3OH. Compared to a stand-alone plant, the utilization of carbon
CO2 utilization dioxide increases the methanol yield by 22%. The exergy analysis shows that the highest inefciencies
occur in the reforming unit, the steam cycle, and the synthesis unit. In particular, the steam reformer, the
synthesis reactor, and several heat exchangers show a high potential for thermodynamic improvement.
2017 Elsevier Ltd. All rights reserved.

1. Introduction major contribution to global warming. Carbon capture and storage


(CCS) as well as carbon capture and utilization represent two major
Methanol is one of the most important feedstock for the strategies to reduce these emissions in the energy sector. Although
chemical, petrochemical and energy industries, with a worldwide the former technology is currently considered as a more promising
production of 83 million metric tons in 2015. The global production avoidance mechanism, carbon capture and utilization (CCU) is
is forecasted to grow annually by an average rate of 7.2% to reach more benecial, due to the reduction of carbon dioxide in
117.5 million metric tons in 2020 [1]. The industrial applications conjunction with the effective production of a valuable feedstock
range from the further processing to bulk chemicals, e.g. formal- for the chemical and petrochemical industry. In the last decade,
dehyde and acetic acid, to the production of synthetic fuels, new carbon utilization concepts were proposed for the integration
including MTBE and DME. The increasing demand will particularly of CO2 as an auxiliary feedstock or commodity into Gas-to-Liquids
be driven by energy applications, led by rened product displace- (GtL) processes [2,3]. In particular, the large-scale methanol pro-
ment, in the form of methanol to olens (MTO) and gasoline blends duction from its predominating feedstock natural gas (NG) attrac-
[1]. ted attention, due to increasing product demand and abundant gas
CO2 emissions caused by the combustion of fossil fuels have a resources. Consequently, conventional methanol production not
only constitutes a partial replacement of fossil fuels, but also can act
as a (CO2) buffer when chemical recycling is integrated into future
and retrotting manufacture concepts.
* Corresponding author.
E-mail addresses: Blumberg@tu-berlin.de (T. Blumberg), tetyana.morozyuk@tu- The conversion of natural gas to syngas and its further pro-
berlin.de (T. Morosuk), georgios.tsatsaronis@tu-berlin.de (G. Tsatsaronis). cessing to liquid fuels is the most widely used technology for the
1
URL: http://www.campus-elgouna.tu-berlin.de, http://www.ebr.tu-berlin.de, production of methanol. Accordingly, the synthesis route has been
http://www.energietechnik.tu-berlin.de

http://dx.doi.org/10.1016/j.energy.2017.06.140
0360-5442/ 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
2 T. Blumberg et al. / Energy xxx (2017) 1e12

Nomenclature Abbreviations
ASTM American society for testing and materials
E_ exergy ow rate (W) ATR autothermal reforming
e specic exergy (J/kg) CCS carbon capture and storage
H_ enthalpy ow rate (W) CCU carbon capture and utilization
h specic enthalpy (J/kg) CMR combined-methane reforming
m_ mass ow rate (kg/s) GHR gas-heated reforming
p pressure (pa) DME dimethylether
T temperature ( C) GTL gas to liquid
HER heat exchanger in the reforming unit
Greek symbols HHV higher heating value
exergetic efciency (%) HRSG heat-recovery steam generator
h energetic efciency; isentropic efciency of a IGCC integrated gasication combined cycle
compressor, pump, or expander (%) LHHW Langmuir-Hishlewood-Houston-Watson
LHV lower heating value
Superscripts LP low pressure
D exergy destruction MTBE methyl-tert-butylether
F exergy of fuel Mtpd metric tons per day
L exergy loss MTO methanol to olens
k k-th component NG natural gas
P exergy of product NIST national institute of standard and technology
tot overall system RKS Redlich Kwong Soave
SMR steam-methane reforming
Subscripts WGS water-gas shift reactor
CH chemical
PH physical

intensively investigated in Refs. [4,5]. The focus of recent studies is Gasication combined-cycle power plant (IGCC) with carbon cap-
on two major carbon utilization strategies, which refer to the hy- ture [11]) at the inlet of the synthesis reactor for hydrogenation. A
drogenation of CO2 and the reforming of natural gas by CO2. In highly-integrated heat concept serves for electricity generation and
Ref. [6] six different utilization concepts deriving from four heat distribution within the units of the synthesis route. Before
reforming technologies that are integrated with an existing sensitivity analyses are performed, an overview of the conventional
660MWe coal-red power plant have been analyzed. The com- technology for methanol production from natural gas is given, to
parison of the scenarios revealed signicant differences based on nd favorable operation parameters for the steam reformer and the
methane and CO2 feed, and energy intensity. In Ref. [7] the inte- methanol reactor. The ndings are evaluated from an energetic
gration of CO2 (obtained from a power plant with carbon capture) point of view before an exergy analysis is conducted to reveal the
into an NG-based methanol synthesis plant has been investigated sources of inefciencies and to identify improvement potentials for
from an energetic point of view. The study shows that the inte- several subsystems and their key components.
gration reduces the methane uptake by 25.6%, while the CO2-
emissions are reduced by 21.9% at an overall energy efciency of
59%. The two concepts of carbon dioxide integration into a meth- 2. Fundamentals of the synthesis route
anol plant, including a mixed CO2/steam reforming of natural gas
and a hydrogenation of CO2 in the synthesis are reported in Ref. [8]. A variety of synthesis routes are commercially applied for the
In both cases, the utilization of CO2 improved the energetic ef- production of methanol through chemical conversion of the major
ciency, whereas the emissions were signicantly reduced. More- feedstock natural gas. The synthesis routes are highly efcient, but
over, the same authors [9] conducted a techno-economic analysis capital intensive mainly due to the heat transfer in the reformers,
on these two concepts for a production capacity in the range of reactors and the heat recovery units [12]. The decision for one
2500e20,000 Mtpd. Their studies revealed that methanol pro- specic process depends primarily on the feedstock composition,
duction from steam-reforming of natural gas is economically the availability of auxiliary materials, the production capacity, and
feasible for a capacity of 2500e5000 Mtpd. The authors of [10] the desired product quality. In general, the process units of each of
conducted an energy and exergy analysis on a commercially these synthesis routes can be assigned to ve sub-systems: A pre-
available low-pressure synthesis process without syngas adjust- treatment unit for the removal of sulfur impurities (subsystem I), a
ment and reported an overall exergetic efciency of 39%. reforming unit serving for the production of synthesis gas in
This paper presents a state-of-the-art of an NG-based low- conjunction with product conditioning (subsystem II), a synthesis
pressure synthesis process for the generation of methanol with (a) unit for the conversion of syngas to methanol (subsystem III), a
CO2 utilization, and (b) a grade AA specication for chemical pro- purication section for rening the crude methanol (subsystem IV),
cessing. The synthesis gas (syngas), as the rst step of the entire and a steam cycle for balancing the overall heat supply and demand
process, is produced by steam reforming of methane, before it is of the process units (subsystem V). Fig. 1 shows the ve subsystems
blended with a CO2-stream that is provided by an Integrated and the possible synthesis routes for the processing of natural gas
to methanol. The specic process units are illustrated by grey boxes,

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
T. Blumberg et al. / Energy xxx (2017) 1e12 3

Fig. 1. Overview of the process routes for conventional methanol production.

while the chosen process path is highlighted by red color. The syngas used in methanol synthesis should have a balanced
In this study, a NG-based state-of-the-art methanol plant with composition of CO, CO2, and H2, which is expressed by the stoi-
steam-methane reforming (SMR) and synthesis gas adjustment by chiometric number S or the stoichiometric ratio R (often referred to
carbon dioxide integration is investigated. The proposed synthesis as the module M) dened in Eqs. (1) and (2), respectively [2,4]:
route is equipped with a commercially available reactor and a
three-column distillation unit for the production of grade AA nH2  nCO2
S 2 (1)
methanol. A detailed owsheet of the entire process is shown in nCO nCO2
Fig. 5.
The process units of subsystem I are indispensable, since natural nH2
gas contains several organic sulfur compounds, which belong to the R 1 (2)
2nCO 3nCO2
potent poisons of the catalysts used in a methanol plant. The cat-
alysts that are used in the reforming unit and the methanol syn- where n denotes the total number of moles of syngas components.
thesis reactor are very sensitive to sulfur compounds and become According to the mechanism for methanol synthesis in chemical
deactivated in their presence. An upper sulfur level of 0.002 ppmv reactions Eqs. (3) and (4), a stoichiometric syngas has a value for S
for the processing of natural gas in reformers is recommended in equal to 2 and an R value close to unity.
Ref. [13]. The organic sulfur components, especially carbonyl sul- In autothermal reforming, oxygen or oxygen enriched air is
de, are hydrogenated to hydrogen sulde (H2S) at a temperature deployed together with steam to partially oxidize the methane
range of 250e400  C, and a pressure range of 25e40 bar [14]. The intake. The ATR reactor has a compact design, including a burner, a
removal of this type of impurities is generally performed by ab- combustion chamber and a catalytic bed, located in a refractory
sorption processes. In this paper, H2S is absorbed by a zinc oxide lined pressure vessel. The composition of the syngas is determined
bed to produce zinc sulphide ZnS. by the equilibrium pressure and temperature, which in turn can be
The reforming of natural gas has been investigated thoroughly calculated for an adiabatic reactor from the energy balance based
in the literature and has been commercially applied to many on the composition and ows of feed. Typically, the product
important branches of chemical industry [4,5]. From an economic composition from the autothermal reforming of methane is char-
point of view, the highest sensitivity of the overall cost of a acterized by a hydrogen deciency (S 1.7e1.9), which requires
methanol plant is related to the reforming section, accounting for measures for the adjustment of the syngas downstream. Mature
at least 60% of the capital investment. The variety of reforming conditioning technologies include the application of a water gas
technologies differs in construction, in supply of oxygen agents shift unit (WGS), which is a costly option, or the introduction of H2
and operation parameters. Accordingly, the reaction turnover and from an external source (water electrolysis). Another possibility of
consequently also the syngas composition vary widely. In princi- meeting the right stoichiometry of syngas for methanol production
ple, the commercially available technologies can be reduced to refers to the addition of carbon dioxide and steam as reforming
three major technologies: autothermal reforming (ATR), steam- agents [20]. The exothermicity of the reaction mechanism avoids
methane reforming (SMR), and a combination of those two, the need for heat supply, which is the most important benet over
named combined methane reforming (CMR). Additionally, each of the SMR technology. The savings in terms of fuel are offset by the
these units can be combined with an adiabatic pre-reformer, supply of oxygen, which requires an additional air separation unit.
which serves for the conversion of long chain hydrocarbons to Concerning the operation parameters, the ATR is operated within a
methane. The dry reforming of methane by CO2 (DMR) is a newer temperature range of 950  Ce1050  C, a pressure range of
technology for carbon utilization, which was recently applied for 23 bare28 bar and at a steam-to-carbon ratio (S/C-ratio) of 0.6e1.4
the rst time on a large scale in Shiraz, Iran [15]. The choice of [12].
technology for the production of synthesis gas depends on the In steam-methane reforming, the feedstock is catalytically
desired product capacity. Methanol production based on SMR cracked with steam in the absence of oxygen. One-step reforming
(tubular reforming) is the cheapest and predominating technol- consists of an adiabatic pre-reformer and a red tubular reformer
ogy for capacities below 2700 Mtpd, whereas ATR is favored at (steam reformer). The pre-reformer permits the use of higher
single train large scale capacities between 6000 and 10,000 Mtpd hydrocarbons, which contributes to a more stoichiometric syngas
[16e18]. The capacity demarcation is caused by the economies of due to a higher carbon-to-hydrogen ratio. Higher hydrocarbons
scale being different for the tubular reformer and the oxygen react with steam that is preheated to temperatures between 500
plant, required for the ATR. For the intermediate range a combi- and 600  C at a S/C-ratio of 2.5e5.0. The reactions occur adia-
nation of a tubular reformer and oxygen blown secondary batically and all C2 molecules are converted to methane.
reformer is the favored solution [19]. In this work, the analyzed Therefore, the pre-reforming step reduces the load and heat duty
plant is equipped with a one-step steam-methane reforming of the tubular reformer for higher throughput and improved
system. efciency.

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
4 T. Blumberg et al. / Energy xxx (2017) 1e12

In SMR, methane reacts in a highly endothermic reaction with


steam over a catalyst, typically based on nickel, at temperatures
between 800 and 1000  C and pressures of 20e30 bar [4,14,20].
The tubular reformer is encapsulated by a furnace, which is
equipped with burners for combustion of NG with air to cover
the heat demand required by the endothermic character of the
reaction mechanism. The composition of the syngas largely de-
pends on the reaction temperature and pressure as well as on the
S/C-ratio. Besides the steam-methane reforming as the main re-
action, the water-gas shift reaction causes an undesired increase
of the hydrogen yield. The synthesis gas typically contains a
Fig. 3. Concepts of methanol synthesis reactors: (a) Quench reactor, (b) adiabatic
surplus of hydrogen by about 40%. The stoichiometric number S
reactor with intercooling, and (c) isothermal reactor.
obtained by steam reforming of methane is close to 3, which is
far away from the desired value of 2. Accordingly, typical R-
values are in the range 1.4e1.5 due to the H/C ratio of methane
[4]. The surplus in hydrogen is carried out unreacted from a carried out in the secondary reformer, exposing the SMR to milder
methanol synthesis unit. An addition of CO2 downstream of the operation conditions due to a lower heat ux. This concept is used
reformer permits an optimization of the syngas composition by for capacities of up to 5000 Mtpd. Other concepts for improving the
correcting the S-value to maximize the conversion within the performance refer to a combination of the conventional technolo-
methanol synthesis. gies with heat-exchange reforming (HER). The application of SMR
Fig. 2 demonstrates the results of a sensitivity analysis, which has the constraint, that only 50% of the supplied heat can be inte-
was conducted for the SMR used in the investigated methanol grated into the process, while the remainder is recovered in a waste
plant. The inuence of the temperature, the pressure and the S/C heat section. This value can be increased to about 80% in a com-
ratio on the CH4 conversion and on the S value is shown. The bination with a heat exchange reformer or a gas heated reformer
operation conditions of the steam reformer are indicated by the red (GHR) [14,15]. Here, the ue gas or the product gas is cooled by heat
line. A preferable composition of S 2 is obtained for lower tem- transfer to the process gas owing within the tubes in a counter
peratures of 400  Ce500  C and S/C ratios of 1e2, but the conver- current arrangement. HER can also be arranged in series or in
sion rates are far below 10%, which would cause enormous mass parallel with ATR or a secondary reformer, where the heat source is
ows in the synthesis unit, due to an agglomeration of inert sub- the exiting gas.
stances (mainly CH4) in the recycle loop. Therefore, the operation The synthesis gas leaving subsystem II is converted to crude
point is selected for high conversion rates to the detriment of an methanol in a synthesis reactor. The reactions to methanol via CO2
unsuitable composition with excess H2. A positive side-effect (3) and CO (4) are exothermic, favoring the conversion at low
associated with the operation conditions refers to the avoidance temperatures and high pressures [17].
of carbon formation [21].
Combined methane reforming (CMR) includes a variety of
CO2 3H2 /CH3 OH H2 O DH298K;50bar 41:2kJ=mol (3)
reforming concepts, which all have the purpose of increasing the
syngas yield with an improved control of varying the syngas CO 2H2 /CH3 OH DH298K;50bar 90:7kJ=mol (4)
composition in certain ranges at an increased process efciency and
capacity. The conventional combination of SMR (primary reformer) The high-pressure methanol synthesis developed in the 1920s
and ATR (secondary reformer, also entitled as oxygen-red or used a chrome-oxide/zinc-oxide catalyst which favored conversion
oxygen-enhanced adiabatic reforming) is commercially sold as a at temperatures between 320  C and 450  C, and a pressure be-
two-step combined reforming by several suppliers [15e17]. The tween 250 bar and 350 bar [22e24]. Advances in catalyst tech-
serial or parallel conguration allows adjusting the syngas nology and the switch from coal to natural gas as predominant
composition to an S-value of 2. The secondary reformer requires the feedstock led to the development of the low-pressure methanol
primary reformer to be operated with a signicant leakage in synthesis during the 1960s. Today, the worldwide methanol pro-
methane (methane slip). In general, 55e65% of the conversion is duction is based on the low-pressure methanol process, which al-
lows a conversion of syngas at 25e100 bar and temperatures of

Fig. 2. Sensitivity analysis of the module factor (a), and CH4-conversion (b) for the steam-methane reformer at 30 bar.

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
T. Blumberg et al. / Energy xxx (2017) 1e12 5

200e300  C [2,5,24]. A lower temperature limit is dened by the adiabatic reactors are similar. Methanol yields of 6e7% per pass
maintenance of a sufcient activity of the copper/zinc/aluminum have been reported in Ref. [23], resulting in high recycle ratios in
oxide (Cu-Zn-Al2O3) catalyst [24], while the upper constraint con- the range of 4:1 to 5:1.
siders the sintering of the material. To match this temperature With respect to the plant layout presented in Fig. 5, an
window, heat removal is necessary. The operating pressure results isothermal reactor is chosen for the methanol synthesis in sub-
from the trade-off between the supplied energy (fuel cost) and the system III. The xed bed reactor is designed as a tube and shell
conversion rate (investment cost). The low-pressure synthesis converter, where the catalyst is loaded inside the tubes while the
consumes far less energy, while the equipment size grows due to cooling water ows on the shell side. The Lurgi pseudo- isothermal
low fractions of conversion during each pass. Therefore, most converter with boiling water on the shell side ensures a tight
common processes use a recycle loop to achieve adequate yields, temperature and ow control for high conversion rates. The oper-
with a vent of tail gas to remove impurities and inert components ation conditions in the range of 50e100 bar and 230e265  C allow
that would otherwise build up over time. The variety of industrial for conversion rates of 8% and consequently lower recycle ratios
applied reactors can be ascribed to three different concepts e [20]. Another benet refers to the catalyst volume being signicant
quench cooled reactors, adiabatic reactors with intercooling, and lower than for the other two concepts.
isothermal reactors. The selected quasi-isothermal reactor and the corresponding
Fig. 3 shows the concepts of the main reactor used for the equilibrium diagram at the operation pressure of 50 bar, which is
synthesis of methanol from synthesis gas. The congurations based on the simulation data, are shown in Fig. 4. The inlet
associated with the respective reactor type differ in terms of composition includes a methanol fraction of 2.5 mol-%, while the
capacity, cooling, energy consumption, stability, and reliability. outlet contains a fraction of 7 mol-%. The lines of constant re-
Quench converters accommodate multiple catalyst beds (up to action rate indicate the restrictions, given by the activation
ve) in one vessel, which are physically separated by support temperature for the catalysis and the equilibrium line. For higher
plates carrying the bed material. A portion of synthesis gas is fed pressures, the equilibrium conversion will shift to higher meth-
to the rst stage, where the catalytic reaction heats up the anol yields according to the reduction of number of moles in Eqs.
mixture of methanol and unconverted syngas. Downstream, the (3) and (4).
product is cooled by injection of a second portion of cold feed More detailed information on reactor designs and concepts can
shifting the reactant of the second stage away from equilibrium. be found in Ref. [24]. In the last process section (subsystem IV), the
This procedure can be repeated several times, until the entire crude methanol is puried in a three-column distillation unit to
feed has passed a catalyst bed. The reliability of the quench produce methanol with chemical grade (grade AA) specication.
converters has been proven in many plants. They are character- The specications for grade AA methanol can be found in
ized by a simple design and can be used in plants with a capacity Refs. [5,24]. The simulations showed that a two-column distillation
of up to 3000 Mtpd. The main drawback refers to a poor distri- is not sufcient to produce methanol of the required purity
bution of the synthesis gas due to bed voidage, which results in (99.8 mol-%).
hot and cold catalyst bed zones and consequently in an increased
rate of catalyst deactivation and disturbances of the conversion
3. System design
[23]. Instead of using direct cooling, the adiabatic reactor concept
uses an indirect intercooling by heat transfer to water for me-
The commercial methanol plant analyzed in this study has a
dium to high-pressure steam generation. The catalyst beds can
capacity of 2700 Mtpd. The parameters considered for the plant
either be accommodated in one vessel, as shown in Fig. 3b, or be
conguration are mainly derived from data obtained from manu-
arranged as a series of xed bed reactors with external in-
facturers and other studies. The overall system design is depicted in
tercoolers. This concept can be capital intensive due to the
Fig. 5. The thermodynamic properties for selected material streams
increased number of reactor vessels and the requirement for heat
are given in Table 1. The major data and assumptions used for the
exchangers. The conversion rates for quench converters and
simulation are presented in Table 2.

Fig. 4. Equilibrium diagram for the simulated isothermal Lurgi methanol reactor [28].

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
6 T. Blumberg et al. / Energy xxx (2017) 1e12

Fig. 5. Flowsheet of the simulated methanol plant.

The plant consists of ve major subsystems. First, NG with 884  C. Approximately 30% of the heat is transferred into the
10 bar is desulphurized by hydrogenation of carbonyl sulde process, whereas the remaining 70% of the heat duty is used in
(COS) and absorption of the reactant hydrogen sulde (H2S). The the waste heat section for steam generation. The synthesis gas is
sweet gas is saturated with steam at an S/C-ratio of 1.25 and fed then compressed to 50 bar in a multistage syngas compressor
to the pre-reformer, where higher hydrocarbons are converted to with intermediate cooling, where steam is deducted as water. The
methane to reduce the load and the heat duty of the steam compressed gas contains a surplus of hydrogen, which is repre-
reformer. The product gas exits the adiabatic reactor with a sented by an R value of 1.4 and a stoichiometric number S of 3.
temperature of 510  C and a pressure of 27 bar. Downstream, the Before entering the tubular reactor, the fresh syngas (stream 6)
efuent (stream 4) at an S/C-ratio of 3.5 is mixed with steam is blended with three recycle streams of unconverted syngas. In
before entering a regenerative heat exchanger. The plant is order to avoid production of excessive water in the synthesis unit, a
equipped with a side-red tubular steam reformer, where the captured CO2 stream is also added to adjust the composition to the
heat for the endothermic steam reforming reaction is provided by stoichiometric claim of the synthesis. In this study, CO2 is provided
the combustion of 29.3 kg/s natural gas with air (stream 7 and 8). by an Integrated Gasication Combined Cycle (IGCC) power plant
The heat of the syngas leaving the tubes with a temperature of with carbon capture. Subsequently, the syngas is preheated to
885  C and a pressure of 25 bar is transferred to the inlet stream 250  C by recuperation of the thermal energy of methanol synthesis
of the SMR. Exiting the furnace, the ue gas enters the HRSG at product. The use of this component is indispensable, since a tem-
perature above 200  C is required for the activation of the reaction
mechanism. Approximately 7% of the gas mixture is catalytically
Table 1
Thermodynamic properties for selected material streams. converted to methanol, which exits the synthesis unit through two
ash stages to separate it from unconverted syngas. Centrifugal
No. Fluid Subsystem T [ C] p [bar] h [kJ/kg] e [MJ/kg]
compressors are used to recycle the unconverted syngas to the
1 natural gas (reactant) I 15 10.0 4529 49.66 reactor inlet. The inert components, mainly nitrogen and methane,
2 natural gas 125 30.0 4287 49.86
build-up in the cycle and are removed partially from the system.
3 steam II 550 29.5 12403 1.49
4 syngas 510 26.7 3751 0.12
The tail gas is recycled and mixed with natural gas at the inlet of the
5 ue gas 884 6.5 168 0.73 SMR furnace to reduce the fuel consumption.
6 syngas 117 50.0 4746 25.07 Containing 77 mol-% methanol (CH3OH), the crude product still
7 natural gas (fuel) 15 10.0 4529 49.66 contains a considerable amount of impurities and water, which are
8 air 15 1.0 10 0.00
removed in a three-column distillation unit. The rst distillation
9 carbon dioxide III 45 50.0 8974 0.65
10 syngas 250 50.0 6438 18.65 column (topping column) serves to remove the light ends and any
11 syngas/methanol 98 49.3 6439 18.40 dissolved gases, including hydrogen, methane, carbon monoxide,
12 syngas 38 48.5 6361 18.31 and nitrogen. The top product is recycled to the reactor inlet, while
13 syngas 38 2.0 8600 3.10
the bottom product is further puried in the pressure column and
14 crude methanol IV 38 2.0 8659 19.20
15 AA methanol 71 1.0 7394 22.42
the atmospheric column, where methanol is mainly separated from
16 off-gas V 100 4.3 1074 0.17 water and higher alcohols. The product has a purity of 99.9 mol-%

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
T. Blumberg et al. / Energy xxx (2017) 1e12 7

and can be further processed for storage and transport. The LHV and RPLUG tubular reactor model. The stoichiometry of the methanol
HHV for the rened methanol are 19.8 MJ/kg and 22.6 MJ/kg, conversion includes the reaction of both carbon monoxide and
respectively. The steam cycle is highly integrated into the subsystems carbon dioxide with hydrogen, as shown in Equations (3) and (4).
I to IV. The waste heat from the SMR is recovered as steam on two The reaction kinetics inputs to the RPLUG model are based on a
pressure levels within the heat recovery steam generator (HRSG). study by van den Bussche et al. [30], in which a Cu/ZnO/Al2O3
The live steam parameters are 350  C/80 bar for the high-pressure catalyst is used for methanol conversion. The kinetics is described
(HP) level and 230  C/20 bar for the low-pressure (LP) level. Super- by the LHHW-type equations (Langmuir-Hishlewood-Houston-
heated HP steam is provided for the hydrogenation of COS, and as Watson). The data given in Ref. [30] is transformed by Emmanuel
reactant for the conversion process within the pre-reformer and the Lejeune from Aspen to obtain the information in the form as
steam reformer. Furthermore, high-temperature thermal energy is required by the software. The kinetic and adsorption parameters
used to preheat the natural gas before entering the reformer unit. entered into the Aspen LHHW reactor model are provided in
The steam cycle also includes heat-transfer units outside the HRSG Ref. [29] and their implementation is described in detail in Ref. [31].
for the integration of the cooling water of the synthesis reactor and Parameters for the distillation columns in the purication section
the connection of the reboilers of distillation columns. unit are adopted from Refs. [32e34]. The rened product meets the
requirements for grade AA methanol (Grade AA covers methanol
with the highest purication for chemical applications) dened by
4. Methodology, assumptions, simulation the American Society for Testing and Materials (ASTM) [35]. The
major data and assumptions for the simulation are given in Table 2.
The process simulation of the methanol plant was conducted The applied methodology is based on a conventional exergy
using the software Aspen Plus V8.8 (Aspen) [26]. The Redlich- analysis, which is a powerful and convenient tool to identify and
Kwong-Soave (RKS) property model was applied to all units of evaluate the thermodynamic inefciencies within energy and
the process. To manage all parameters, 14 calculators and six design chemical conversion processes [36]. The analysis is also performed
specications are used together with the software. The material in Aspen Plus by user build-in subroutines. The thermodynamic
properties derive from the NIST databank and the fuel is natural gas properties of the material streams are summarized in Table 1. The
(H-Gas) with a composition (mole-%) of 94.9% CH4, 2.5% C2H6, 0.2% results of the exergy analysis are shown in Fig. 6a for the respective
C3H8, 0.06% C4H10, 0.02% C5H12 1.6% N2, 0.7% CO2, 0.02% COS [27]. subsystems and in Fig. 6b on a more detailed unit base. Table 5 lists
The lower heating value (LHV) of natural gas is 48.8 MJ/kg, while the components with the highest thermodynamic inefciencies
the higher heating value (HHV) is 54.1 MJ/kg. The hydrolysis reactor within the overall system.
for the removal of carbonyl sulde is designed as a RSTOIC-model Concerning the exergetic analysis, the exergy rate E_ j m_ j ej of
based on the parameters given in Refs. [13] and [14]. For the pre- the j th stream of matter includes the sum of the chemical and
reforming, the operation parameters result from the use of a physical exergy for each material stream. The model of Szargut [39]
RSTOIC-reactor and a set of 12 equations implemented into the is applied to determine specic chemical exergies. The effects of
model. The operation conditions within the steam reformer are kinetic and potential exergies are neglected.
determined by minimizing the Gibbs free energy using the RGIBBS-
model with an implemented temperature approach to equilibrium.  
CH PH
With respect to the methanol synthesis, a rigorous simulation of E_ j E_ j E_ j m_ j eCH PH
j ej (5)
the Lurgi steam raising reactor [28] is performed with the imple-
mentation of process parameters from Luyben et al. [29] in a kinetic For few components, the physical exergy is split into mechanical

Table 2
Major data and assumptions for the simulation.

Component/System Unit Value Component/System Unit Value

General Purication (subsystem IV)



ambient temperature C 15 topping column
ambient pressure bar 1.013 condenser pressure [32] bar 1.24
mechanical efciency % 99 reboiler pressure [32] bar 1.64
Pretreatment (subsystem I) number of stages [29] [32] e 42
hydrogenolysis feed stage [29] [32] e 27
conversion rate of COS [37] % 99.5 reux ratio e 0.6
zinc Oxide Guard Bed distillate to feed mole ratio e 0.3
H2S absorpt. coefcient [37] % 99.9 pressure column
Reforming unit (subsystem II) condenser pressure [32] bar 1.86
pre-reformer reboiler pressure [32] bar 2.8
steam-to-carbon ratio e 1.25 number of stages [32] e 81

reactor pressure C 28 feed stage [32] e 26
reactor temperature bar 510 reux ratio e 0.75
steam reformer distillate to feed mole ratio e 0.9
steam-to-carbon ratio e 3.5 atmospheric column
reactor pressure [19] bar 25 condenser pressure bar 1

reactor temperature [19] C 885 reboiler pressure bar 1
Methanol synthesis unit (subsystem III) number of stages e 56

reactor temperature [29] C 267 feed stage e 23
reactor pressure [29] bar 50 reux ratio e 0.9
number of tubes e 10,000 distillate to feed mole ratio e 0.77
length of tubes [31] m 18 Steam Cycle (subsystem V)
diameter of tubes [29] m 0.037 steam turbine isen.eff. [38] % 92
purge ratio [29] % 5 condenser pressure bar 0.05

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
8 T. Blumberg et al. / Energy xxx (2017) 1e12

and thermal parts in order to obtain more accurate results for the gas leaving the subsystem V. The exergy of product of the overall
exergies of fuel and product. The ambient conditions were assumed system E_ P;tot consists of the nal product methanol (stream 15) and
to be 15  C and 1.013 bar. An exergy balance for the overall system is the net electricity W _ NET that is generated from recovering the waste
written as [40] heat within the steam cycle. Natural gas as a fuel for combustion
within the SMR (stream 7) and as a reactant for chemical conver-
X sion (stream 1) is taken into account for the exergy of fuel E_ F;tot of
E_ F;tot E_ P;tot E_ D;k E_ L (6) the overall system. Additional entering streams are considered in
k
the exergy of fuel, e.g., puried CO2 (stream 9). The exergy
With reference to the analyzed system shown in the owsheet destruction rate for the k th component of the system can be
in Fig. 2, the exergy losses E_ L are mainly related to the steam of off- calculated from

Table 3
Denitions of the exergy of fuel and product for selected components (own representation based on [40]).

Component/Assumption E_ F;k E_ P;k


a PH PH PH
Combustion Chamber CH
E_ 1
CH
E_ 2 
CH
E_ 3 E_ 3  E_ 1  E_ 2

Steam reformera E_ 4 E_ 5  E_ 6 E_ 3  E_ 1  E_ 2

Distillation columna E_ 4  E_ 5 CH CH CH
E_ 2 E_ 3  E_ 1 m_ 2 ePH PH _ PH PH
2  e1 m2 e3  e1
2 > e1 e3 > e1 e2 > e1 e3 > e1
eCH CH CH CH PH PH PH PH

Synthesis reactora E_ 1 PH PH
E_ 2 E_ 4  E_ 3

Compressora W_ E_ 2  E_ 1
CM
T1  T0

Turbinea E_ 1  E_ 2 _ EXP
W
T2  T0

Heat Exchangera E_ 3  E_ 4 E_ 2  E_ 1
T1  T0

a
The stream numbers do not correspond to the numbers of the material streams in Table 1.

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
T. Blumberg et al. / Energy xxx (2017) 1e12 9

Table 4 Table 5
Comparison of performance indicators. Results of the exergy analysis for the components with the highest exergy
destruction (E_ F;tot 2361:3 MW).
Performance indicator Unit This study Other studies
No. Component E_ D;k [MW] yD;k [%] k [%]
Overall efciency % 35.9 (68.3*) 60 [4], 67e72 [5],
63 [41] 1 Steam reformer 478.5 20.27 31.9
Feed to recycle ratio e 4.2 3.4 [31] 2 HP Evaporator 145.4 6.17 72.0
Conversion per-pass CO2 % 9.9 17 [31] 3 SMR Recuperator 66.3 2.81 70.4
Conversion per-pass CO % 19.6 64 [31] 4 HP Economizer 56.9 2.41 28.8
Conversion per-pass H2 % 12.8 25 [31] 5 Synthesis reactor 56.4 2.39 94.4
Methane intensity t CH4/t CH3OH 0.54 0.44e0.59 [7], 0.62 [4] 6 HP Steam turbine 37.9 1.61 90.5
Thermal intensity GJth/t CH3OH 45.7 33.2 [4], 33.45 [7] 7 Atmospheric Column 30.7 1.30 24.1
Electric intensity GJel/t CH3OH 0.8 0.64 [7], 1.34 [42] 8 Topping Column 27.9 1.18 14.4
CO2 feed intensity t CO2/t CH3OH 0.42 0.35 [7], 0.15e0.45 [8] 9 Air Compressor 23.3 0.98 88.9
10 HP Superheater 21.7 0.93 76.2

E_ D;k E_ F;k  E_ P;k (7) cycle. Only 30% of heat is transferred to the process gas, while the
remainder is recovered as steam in the HRSG. On the basis of the
The equations dening the terms E_ P;k and E_ F;k are listed in LHV of natural gas, a high thermal intensity of 45.7 GJ/tCH3OH re-
Table 3 for selected components. The ratio of the exergy destruction sults. In Refs. [4] and [7], a thermal intensity of approximately 33GJ/
rate of the k th component and the exergy rate of fuel of the overall tCH3OH is reported for a stand-alone NG-based methanol plant of
system E_ F;tot is referred to as exergy destruction ratio yD;k , while the the same capacity without electricity generation. In this work, a
y*D;k refers E_ D;k to the entire exergy destruction rate within the part of the fuel to the furnace is recovered as steam for electricity
overall system. generation in a steam cycle, so that the thermal intensity refers to a
cogeneration. Due to design complexity, a clear assignment of the
E_ D;k thermal effort to the products is not possible using energy-based
yD;k (8)
E_ F;tot tools. This, however, can be obtained by applying exergoeconomic
approaches [36]. The steam turbine output of 420 MW is sufcient
E_ D;k to cover the internal consumption of various subsystems. The cor-
y*D;k (9) responding electric intensity is found to be 0.8 GJ/tCH3OH, which is
_
E D;tot close to the results reported in Ref. [7], i.e., an electric intensity of
The exergetic efciency of the overall system is dened by 0.64. The electricity consumption mainly considers the air-, the
syngas- and the recycle compressors. The difference to the values of
E_ P;tot W_ NET E_
15
the electric intensity given in Refs. [7] and [42] is caused by a
tot (10) different steam-to-carbon ratio, which determines the amount of
_
E F;tot E_ 7 E_ 1
syngas that needs to be compressed in the syngas compression
unit. Furthermore, the conversion rates in the synthesis reactor
directly inuence the electric consumption of the recycle com-
pressors. The demand of the air separation unit amounts to
5. Results and discussions
200 MW, whereas the electricity demand of the multistage syngas
compressor is low, because the pressure ratio between subsystem II
5.1. Plant performance analysis
and subsystem III is small for the low-pressure methanol synthesis
process. The same applies for the recycle loop, where the main
A performance analysis is conducted to validate the model by
compressor has to compensate a pressure drop of only 2 bar.
considering similar studies, and to evaluate it from an energetic
In regard to the captured CO2, a retrot of the IGCC with the
point of view. Based on the LHV of natural gas and methanol, the
analyzed methanol plant would reduce the emitted amount by
overall plant efciency is 35.9%, which is far below the efciency
13%e19%, depending on the operation mode. In total, 13.5 kg/s
range documented in other studies [5], [7], [41]. The deviation of
carbon dioxide can be integrated into the plant, resulting in a CO2
the efciency can be explained by the inclusion of a full heat
feed intensity of 0.42 ton of CO2 per ton of methanol, which is above
integration concept within the system boundaries. Here, however,
the values found in other studies [7]. Compared to a stand-alone
and contrary to the reference studies, all thermodynamic in-
NG-based plant, the methanol production capacity is increased by
efciencies within the combustion process, the heat recovery units,
22%. The performance of the quasi eisothermal methanol reactor is
and the steam cycle are taken into consideration. Furthermore, a
investigated in detail and the results are validated in
large mass ow of ue gas (stream 16) is released to the environ-
Refs. [29,31,34]. The authors implemented the same reaction ki-
ment. The energy losses associated with the release of streams to
netics in an Aspen RPLUG model with a slightly different design
the environment decrease the overall efciency. With congruent
(Table 2). The values of the conversion per-pass in Table 3 deviate
system borders including only the duties along the synthesis route,
from the values given in Refs. [31,34], since not only the geometric
an overall plant energetic efciency of 68.3% is obtained.
design, but also the composition of the inlet gas is different. The
Based on several performance indicators, the results of the
sensitivity of the methanol yield to the inlet composition was
methanol plant are validated by comparing them to the results
analyzed. The results showed low conversion rates of CO, CO2, and
from other studies, Table 4. A stream of 16.9 kg/s of natural gas is
H2 for CO2 mole fractions above 7-8 mol-%. At higher concentration,
fed to the plant to produce 31.3 kg/s of methanol. These values
CO2 reduces the catalyst activity by inhibition of the methanol
result in a ratio of 0.54 tCH4/tCH3OH and correspond to the data re-
synthesis [43]. According to the lower conversions, the feed to
ported in Ref. [6]. A large amount (29.3 kg/s) of natural gas is
recycle ratio (FTRR) is calculated to be 4.2, which is comparatively
supplied to the furnace to cover primarily the energy demand of the
high with respect to a FTRR of 3.4 in Ref. [31]. The recycle ratio
steam reformer. The endothermic character of the reforming unit
results from a trade-off between the compression work, the fuel
requires heat at a temperature level above 900  C, while the waste
consumption, the conversion rate, and the amount of CO2 utilized
heat on a lower temperature level is supplied to HRSG of the steam

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
10 T. Blumberg et al. / Energy xxx (2017) 1e12

for hydrogenation. A high ratio results in an increased work for the thermodynamic improvement potentials. First an analysis was
recycle compressors. To lower the ratio, the amount of tail gas conducted for the ve aggregated subsystems in Fig. 6a to quantify
recycled to the furnace of the steam reformer could be increased to the inefciencies and to identify the most important units. For
reduce the fuel consumption. Simultaneously, the feed to the syn- more accurate information, the exergy destructions are assigned to
thesis reactor would decrease and consequently also the methanol smaller component units in Fig. 6b. Based on these results, a
production capacity. In addition, the CO2 feed intensity would detailed exergy analysis is presented in Table 5 for the components
decline due to a reduction in the hydrogen concentration at the with the highest exergy destruction E_ D;k . Furthermore, the table
inlet of the synthesis reactor. contains the values of the exergetic efciency k and the exergy
destruction ratio yD;k .The exergetic efciency of the overall process
5.2. Exergy analysis considered here is 37.7%, which is close to the reported exergetic
efciency of 39% for a commercial low-pressure
A conventional exergetic analysis is performed to pinpoint the methanol process [10].
real inefciencies within the process and to identify the

Steam Cycle
305.09 MW

Pretreatment
9.63 MW

Purification
77.68 MW

Synthesis Unit
Reforming Unit 142.82 MW
616.09 MW

(a)
Low pressure steam
cycle
High pressure steam
Fuel preparation unit 34.39 MW
cycle
40.29 MW
270.71 MW
Prestreatment
9.63 MW
Topping Column
27.85 MW
Atmospheric Column
30.65 MW
Pressure Column
19.18 MW

Syngas Compressor
65.53 MW
Synthesis Reactor
73.12 MW
Recycle Unit
Steam Reformerunit 4.18 MW
547.80 MW
Prereformer unit Preheating unit
8.00 MW 20.01 MW
(b)
Fig. 6. Exergy destruction (a) for the subsystems, and (b) for the main units.

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
T. Blumberg et al. / Energy xxx (2017) 1e12 11

Subsystem II is associated with the highest irreversibilities, in Fig. 6b, the synthesis unit is associated with the highest exergy
causing 54% of the exergy destruction of the overall plant. The pie destruction. An interesting observation can be made for the
chart in Fig. 6b shows the four main units of subsystem II, where methanol reactor at position number 5, which has an outstanding
the steam reformer unit has a large contribution to the in- exergetic efciency of 94.4%. In general, chemical reactions would
efciencies. The unit comprises the tubular reformer, the regener- suggest a lower exergetic efciency, due to the high degree of
ative heat exchanger and a unit for the mixing of steam with associated irreversibilities. This high value can be explained by the
process gas. On a component level, the steam reformer has the chemical equilibrium of low-pressure synthesis, which restricts the
highest irreversibilities. This signicant role results from the high chemical conversion rate to only 7% per pass, as illustrated in Fig. 4.
conversion rates in irreversible reactions taking place in the tubes In addition, the inuence of the heat transfer on the exergy
of the reformer vessel and more from the highly irreversible destruction is insignicant, because the maximum temperature
combustion in the furnace. Irreversibilities, associated with the difference of 100 K at the inlet is quickly reduced over the length of
transfer of high-temperature heat though the tubes, also signi- the tubes. Even if the value of exergy destruction is comparatively
cantly contribute to the exergy destruction. The combustion gases high in Table 5, it is small in comparison to the exergy of fuel and
within the furnace have a temperature of 1000  C, while the pro- product, whose values result from large mass ows caused by the
cess gas enters the tubes with 835  C. In consequence, the corre- high recycle ratio. In addition to the irreversibilities within the
sponding exergetic efciency is low for the steam reformer. The tubular synthesis reactor, also the mixing of recirculation streams,
recuperator is rated to position number three. The irreversibilities fresh syngas and CO2 has a contribution to the exergy destruction.
mainly result from the high temperature difference of 400  C be- The potential for an improvement of the recuperator is small, since
tween the hot efuent of the steam reformer and the cold reformer the heat exchanger operates with an exergetic efciency of above
inlet stream. The fuel preparation unit comprises the air 90%. The exergy destruction of the multi-stage syngas compressor
compressor and two units for the mixing of the tail gas with fuel shown in Fig. 6b includes the pre-cooler, which is the main source
and air. The inefciencies within the air compressor, which is rated of inefciencies within this unit. The component also serves as the
to position number eight, are related to friction of a large process HP economizer, but was taken into account for the exergy calcu-
stream. An operation with low pressure ratio and the assumption of lations of subsystem III. The high exergy destruction is caused by
a high polytropic efciency restricts the inefciencies for this the large temperature spread between the hot process gas leaving
component. The remaining exergy destruction is caused by mixing the SMR and the feedwater. The relatively low exergy destruction
of streams with different compositions and different temperatures. within the syngas compressors is due to the small pressure differ-
The exergy destruction within the pre-reformer is low, since the ence between subsystems II and III.
mole fraction of C2 molecules to be converted is small. The pre- As shown in Fig. 6a, the exergy destruction for the purication
heating of the fuel and the process gas only has a minor impact on unit (subsystem IV) is relative low, having a share of 7% in the
the overall exergy destruction. exergy destruction of the overall plant. The subsystem consists of
High irreversibilities also occur within the components of Sub- three distillation columns, whereby the rst two distillation steps
system V, which has a share of 26% in the exergy destruction of the appear at position seven and eight in Table 5. The exergy destruc-
overall plant. The inefciencies are caused by friction within the tion within a column is caused on one hand by the heat transfer
turbomachinery of the steam cycle and by the heat transfer within within the reboiler and the condenser and on the other hand by the
elements of the heat recovery steam generator. The superheated temperature spread between the top and the bottom stage. The
steam temperatures are 230  C and 350  C, while the ue gas enters exergy loss related to the purication is attributed to the bottom
the HRSG with a temperature of 880  C. Moreover, the main exergy products leaving the pressure column and the atmospheric column.
loss associated with the overall plant is represented by the off-gas With respect to the pre-treatment unit in subsystem I, the ir-
leaving the HRSG with a temperature of 100  C. reversibilities have a small inuence on the exergy destruction of
In Fig. 6b the steam cycle is disaggregated into the low-pressure the overall system. Here, the hydrogenation reaction of sulphur is
and high-pressure cycles. The quantitative difference in the exergy the main source for inefciencies. The results obtained from the
destruction results from different loads, whereby the circulated exergy analysis suggest that the high exergy destructions of sub-
mass ow within the high-pressure level is approximately ve systems II, III and V have the highest potential for an improvement
times higher than for the low-pressure cycle. Correspondingly, the from a thermodynamic point of view. In particular, the steam
components of the HP HRSG can be found in Table 5 at positions reformer and several heat exchangers should be subject to a design
two, four and ten. The HP economizer is integrated into the syngas optimization.
cooling section and therefore is taken into account for subsystem
III. The most inefcient component within the steam cycle is the HP 6. Conclusions
evaporator, since a large amount of heat transfer is required for the
phase change of the water mass ow at 300  C. The heat transfer In the present studies, a state-of-the-art NG-based methanol
not only is conducted at an unfavorable low temperature level, but synthesis process with of CO2 utilization has been investigated.
also under a high temperature difference between the hot ue gas Sensitivity analyses were performed to determine favorable oper-
and the cold-water stream. However, the exergetic efciency is ation parameters for the steam reformer. Based on several perfor-
high due to high values of the exergy of product and the exergy of mance indicators, the plant design was validated by comparing the
fuel. With respect to the steam turbines the exergy destruction is results to those of other studies. It was found that the integration of
mainly caused by friction on the turbine blades. Due to the CO2 into the methanol plant increases the production capacity by
assumption of a high isentropic efciency of 92% the exergy 23%, while the CO2 emissions of the IGCC decrease by up to 19%. The
destruction is relatively low. The HP steam turbine is rated to po- overall plant efciency is 35.9% with an energy intensities of 19.6
sition number six, having an exergetic efciency of 91%. GJth/tCH3OH and 0.8 GJel/tCH3OH. The calculated methane intensity of
The third highest share of 12% in total exergy destruction occurs 0.54 tCH4/tCH3OH is within the range of reported values. Moreover,
within the methanol synthesis unit (subsystem III), which com- the energy analysis identies the streams of energy supply, the
prises the syngas compression, the three recycle compressors, and energy associated with the chemical feedstock and products as well
the synthesis unit. The synthesis unit in turn consists of a mixing as internal producers and consumers. The combustion of natural
unit, the reactor and the recuperator. Among the three units shown gas within the steam reformer furnace is the main heat source,

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140
12 T. Blumberg et al. / Energy xxx (2017) 1e12

whereby only 30% of the heat can be fed to the process gas. The 2001. p.441e46.
[16] Aasberg-Petersen K, Stub Nielsen K, Dybkjr I, Perregaard J. Large scale
remaining heat is recovered as steam on two pressure levels for
methanol production from natural gas. Appl Catal A General 2001;221:
electricity generation. The power of the turbomachinery not only 379e87.
covers the internal consumption, but is sufcient to supply [17] Naqvi S. Synthesis gas production from natural gas reforming. IHS Chemical
200 MW of excess electricity to the grid. The air compressor is Process Economics Program, Report 148B. 2013.
[18] Hiroaki O, Junichi H, Hashizume K, Masutani J. High efciency Mitsubishi
identied as the main electricity consumer with a share of above centrifugal compressors and steam turbines for large methanol and DME
90% in the overall consumption. Within the low-pressure methanol plants. Mitsubishi Heavy Industries, Ltd.; 2004. p. 41. Technical Review.
synthesis, the consumption of the syngas compressor and the [19] Holm-Larsen H. Selection of technology for large methanol plants. In: Pro-
ceedings of the 1994 world methanol conference; 1994 Nov 30e Dec 1.
recycle compressors is low, since the pressure differences to over- Geneva, Switzerland: Crocco & Associates; 1994.
come are small. The results of the exergy analysis show an exergetic [20] Rostrup-Nielsen JR, Rostrup-Nielsen T. Large-scale hydrogen production. In:
efciency of 37.7% for the investigated process. The majority of 6th world congress of chemical engineering; 2001.
[21] Annesini MC, Piemonte V, Turchetti L. Carbon formation in the steam
exergy losses can be attributed to the off-gas leaving the HRSG. The reforming process: a thermodynamic analysis based on the elemental
high values of exergy destruction, particularly for the subsystems of composition. Chem Eng Trans 2007;11:21e6.
the reforming unit, the methanol synthesis, and the steam cycle iz A. Kinetic study and process simulation.
[22] De Mara R, Daz I, Rodrguez M, Sa
Int J Chem React Eng 2013;11(1):469e77.
indicate a high potential for improvement. The thermodynamic [23] Hawkins GB. Methanol converter types. GBH Enterprises Ltd; June 2013.
inefciencies can be reduced by optimizing the heat integration in [24] Tijm P, Waller F, Brown D. Methanol technology developments for the new
the overall plant, especially in the HRSG. Conducting an advanced millennium. Appl Catal 2001;221:275e82.
[26] Aspen Plus. http://www.aspentech.com.
exergy analysis would allow for a consideration of the avoidable
[27] Union Gas. Chemical composition of natural gas. 2016. https://www.uniongas.
irreversibilities and the interdependencies among them. com/about-us/about-natural-gas/Chemical-Composition-of-Natural-Gas
[Accessed 5 December 2016].
References [28] Wurzel T. Lurgi MegaMethanol Technology. In: DGMK-conference; 2006 Oct
4e6; Dresden, Germany.
[29] Luyben WL. Design and Control of a methanol reactor/column process. Ind
[1] Methanol and Derivates Analysis (MDA). 11th volume. Singapore: Methanol Eng Chem Res 2010;49:6150e63.
Market Services Asia (MMSA); 2016. [30] Vanden Bussche KM, Froment GF. A steady-state kinetic model for methanol
[2] Olah G, Goeppert A, Prakash GKS. Beyond oil and gas: the methanol economy. synthesis and the water-gas shift reaction on a commercial Cu/ZnO/Al2O3
2nd ed. Los Angeles: Wiley VCH Verlag GmbH & Co. KGaA; 2009. catalyst. J Catal 1996;161:1e10.
[3] Zhang C, Jun K, Ha K, Lee Y, Kang S. Efcient utilization of greenhouse gases in [31] Luyben WL. Chemical Reactor Design and Control. New Jersey: John Wiley &
a gas-to-liquids process combined with CO2/steam-mixed reforming and fe- Sons, Inc; 2006.
based scher-tropsch synthesis. Environ. Sci. Technol 2014;48(14):8251e7. [32] Hawkins G. Methanol plant, theory of distillation; GBH Enterprises Ltd..
[4] Cheng WH, Kung H. Methanol production and use. In: Chemical industries. [33] Ross T, Kooijman H, Walker B. Modelling Luyben's chemical processes with
CRC Press; 1994. COCO Chempsep. In: AIChE meeting october- distillation honors session
rg O, Gronemann V, Pontzen F, Fiedler E, Grossmann G, Kersebohm DB,
[5] Jo william Luyben; 2011.
Weiss G, Witte C. Methanol. In: Ullmann's encyclopedia of industrial chem- [34] Luyben WL. Distillation design and control using aspen simulation. New Jer-
istry. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA; 2012. sey: John Wiley & Sons, Inc.; 2006.
[6] Luu M, Milani D, Bahadori A, Abbas A. A comparative study of CO2 utilization [35] ASTM D-1152/06(2012). Specication for methanol. American Society for
in methanol synthesis with various syngas production technologies. J CO2 Util Testing and Materials; 2012.
2015;12:62e76. [36] Bejan A, Tsatsaronis G, Moran M. Thermal design & optimization. John Wiley
[7] Milani D, Khalilpur R, Zahedi G, Abbas A.;10: 12e22. & Sons, Inc; 1996.
[8] Zhang C, Jun K, Gao R, Kwak G, Park H. Efcient utilization of carbon dioxide in [37] Cost and performance baseline for fossil energy plants e volume 2: coal to
a gas-to methanol process combined with CO2/Steam-mixed reforming. J CO2 synthetic natural gas and ammonia. National Energy Laboratory; U.S.
Util 2016;16:1e7. Department of Energy; July 2011. Final Report. Report No.: DOE/NETL-2010/
[9] Zhang C, Jun K, Gao R, Kwak G, Park H. Carbon dioxide utilization in a gas-to- 1402. Contract No. DE-FE0004001.
methanol process combined with CO2/steam-mixed reforming: techno- [38] Deckers M. CFX aids design of world's most efcient steam turbine. Germany.
economic analysis. Fuel 2017;190:303e11. 2003.
[10] Rosen A, Scott D. Energy and exergy analyses of a production process for [39] Szargut J, Morris DR, Steward FR. Exergy analysis of thermal, chemical, and
methanol from natural gas. Int J Hydrogen Energy 1988;13(10):617e23. metallurgical processes. New York: Hemisphere; 1988.
[11] Blumberg T, Sorgenfrei M, Tsatsaronis G. Design and assessment of an IGCC [40] Tsatsaronis G, Cziesla F. Thermoeconomics, enyclopedia of physical science
concept with CO2 capture for the co-generation of electricity and substitute and technology. 3rd ed., 16. Academic Press; 2002. p. 659e80.
natural gas. Sustainability 2015;7(12):16213e25. [41] Allard M. CO2 emissions from methanol production. Technical Report.
[12] Lange JP. Prospectives for manufacturing methanol at fuel value. Ind Eng Washington DC: American Methanol Institute; 1999.
Chem Res 1997;36(10):4282e90. [42] Machando C, Medeiros J, Arajo O, Alves R. A comparative analysis of meth-
[13] Antoniak K, Kowalik P, Narowski R, Konkol M, Ryczkowski J. Investigations on anol production routes: synthesis gas vs. CO2 hydrogenation. In: Proceedings
hydrogenation of selected organic sulfur compounds on the Ni-Mo/Al2O3 of the 2014 international conference on industrial engineering and operations
catalyst in terms of natural gas desulfurization. Ann Univ mariae curie-sklo- management. Indonesia; 2014 Jan 7 e 9. Bali.
dowska 2011;64:107e16. [43] Spath PL, Dayton DC. Preliminary screening dtechnical and economic
[14] Molburg J, Doctor R. Hydrogen from steam-methane reforming with CO2- assessment of synthesis gas to fuels and chemicals with emphasis on the
capture. Pittsburgh: 20th annual international Pittsburgh coal conference; potential for biomass-derived syngas. National Renewable Energy Laboratory;
2003. December 2003. Technical Report NREL/TP-510e34929.
[15] Holm-Larsen H. CO2-reforming for large scale methanol plants e an actual
case. In: Studies in surface science an catalysis. Denmark: Elsevier Science B.V;

Please cite this article in press as: Blumberg T, et al., Exergy-based evaluation of methanol production from natural gas with CO2 utilization,
Energy (2017), http://dx.doi.org/10.1016/j.energy.2017.06.140

You might also like