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org/IECR Article

Renewable Methanol Synthesis through Single Step Bi-reforming of

Biogas
Nazanin Entesari, Alain Goeppert, and G. K. Surya Prakash*
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ABSTRACT: Biogas is considered a renewable source of carbon for methanol

production. For this, biogas, containing mainly CH4 and CO2, is first reformed into
syngas (a CO/H2 mixture) followed by conversion to methanol. Conventional
reformers, however, require additional upgrading steps to adjust the H2:CO ratio
in syngas to 2:1; ideal for methanol synthesis. We formerly introduced the concept
Downloaded via UPPSALA UNIV on May 20, 2020 at 19:09:12 (UTC).

of bi-reforming that provides the ideal H2:CO ratio by combining dry and steam
reforming in one stage without the need for additional syngas ratio adjustments.
Based on these experimental bi-reforming findings, we have now developed a
thermodynamic model to determine the optimal conditions for the highest
possible carbon conversion and minimum coke formation. The proposed process
based on bi-reforming was found to be an efficient alternative, delivering the ideal H2:CO ratio of 2 for methanol synthesis with no
coke formation (a common challenge in conventional reformers) and complete carbon conversion at atmospheric pressure and
temperatures of around 900 °C.

1. INTRODUCTION supply is a core component of any green process employing

According to the “Global Energy and CO2 Emission Status
Report”, world energy demand rose by 2.3% in 2018, the
highest rate in the past decade.1 Fossil fuels, including coal,
petroleum oil, and natural gas, remain our primary sources of
energy, particularly for heat and electricity generation and in
the transportation sector.2 On the other hand, the same report
indicated that the higher energy consumption led to a 1.7%
increase in energy-related CO2 emissions, to a total of 33.1 Gt
per year, pointing out the enormity of the problem that we are
facing. To address these issues, humanity clearly needs to
rapidly shift to renewable energy sources and sustainable
processes with lower or, better yet, no carbon emissions.1
To address concerns of anthropogenic CO2 emissions and
their associated consequences, including global warming, ocean
acidification, and sea-level rise, many researchers have been
proposing possible solutions. A number of approaches have
been explored such as carbon capture and storage (CCS) or
CO2 utilization (CCU) to produce value-added products like
methanol, dimethyl ether, plastics, and a variety of other
hydrocarbons.3−9 However, CCS and CCU by themselves will
not be able to solve our fossil fuel addiction problem. For that,
we need to rapidly wean ourselves off these forms of fossilized
sunshine and replace them with alternative energy resources
such as wind, solar, geothermal, hydro, and biogas.10,11 One of
the issues with the most scalable renewable energy sources,
solar and wind, is their intermittence and fluctuation on a
minute, hourly, daily, and seasonal basis. A steady supply of
energy over time is a crucial yet challenging matter when it
comes to renewable resources. Therefore, efficient storage and
transportation of surplus energy to address fluctuations in
renewable energies.12
The Methanol Economy concept, as suggested by Olah et
al.,9,13,14 offers a feasible approach to store surplus renewable
energy while at the same time closing the carbon cycle. The
concept is based on the conversion of carbon-containing
sources to methanol and derived hydrocarbons such as
dimethyl ether (DME). Methanol is a safe and easy-to-handle
liquid and is considered as one of the most promising green
energy carriers. Methanol has a high octane number of greater
than 100 and an energy density of 15.8 MJ·L−1. This soot-free
combustion fuel with low NOx emissions is blendable with
other hydrocarbons and has the potential for replacing gasoline
and diesel fuels in many applications. Methanol, produced on
an annual 100 million metric ton scale, is already a major
chemical feedstock for a wide range of valuable products such
as formaldehyde, DME, olefins, and polypropylene.15−17
Methanol is also an excellent hydrogen carrier and fuel for
direct methanol fuel cells (DMFCs). More importantly, a
mismatch between supply from renewables and demand can be
well managed by storing the energy in the form of methanol:
easy to store and transport liquid with high energy density. As
a result, considerable attention has been given to the
Received: February 13, 2020
Revised: May 4, 2020
Accepted: May 5, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.iecr.0c00755

A Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
development of efficient reaction routes and processes with
low carbon footprint to convert carbon oxides into
methanol.7,9
Methanol is synthesized through direct hydrogenation of
CO and CO2, as shown in reactions (R1) and (R2).18,19 The
hydrogenation is an exothermic and equilibrium-limited
reaction. Therefore, higher pressures and lower temperatures
thermodynamically favor methanol production.20 Concurrent
to methanol synthesis, CO2 and H2 can also undergo the
reverse water gas shift reaction (R3) (RWGSR), a reversible
reaction that produces CO and H2O. In contrast to
hydrogenation, RWGSR is endothermic and has a weak
dependency on pressure. Yield of methanol synthesis is
strongly dependent on the extent of the competing RWGSR.
Currently, Cu/ZnO/Al2O3-based heterogeneous catalysts are
used for the commercial production of methanol.9 These
catalysts deliver a 25−70% conversion and more than 99%
selectivity per pass at a pressure of 50−100 bar and elevated
temperatures of 220−300 °C.21,22 Designing a more effective
catalyst, either heterogeneous or homogeneous, for methanol
synthesis that would require lower temperature, pressure, or
have higher yields is still the focus of many research
programs.20,23
CO + 2H 2 F CH3OH, ΔH298K = − 91 kJ·mol−1
(R1)
CO2 + 3H 2 F CH3OH + H 2O, ΔH298K = − 50 kJ· mol−1
(R2)
CO2 + H 2 F CO + H 2O, ΔH298K = + 41 kJ·mol−1
(R3)
Synthesis gas (syngas) is a mixture of CO and H2 and serves
as the main feed stream for methanol reactors.24 Natural gas,
coal, and petroleum are the main resources for syngas
production.25 Biogas, a renewable energy source with high
carbon content (mainly CH4 and CO2), has received
considerable attention recently as an alternative green
feedstock for syngas generation. Conventionally, these
carbon-containing streams go through partial oxidation or
reforming to obtain syngas.
Depending on the source of carbon and the intended
application, there are three common reforming methods for
syngas production: steam reforming (SR), dry reforming
(DR), and partial oxidation (PO). Steam reforming is a widely
implemented approach to produce syngas by reaction with
water at high temperature. SR commonly uses natural gas
(mostly methane) as the carbon source (R4).26,27 Dry
reforming, on the other hand, is the oxidation of methane
with CO2 (R5).28 Partial oxidation (PO) is an alternative path
to convert CH4 and added O2 to CO and H2 (R6).29
Practically, the syngas composition or, in other words, the
H2:CO ratio defines its area of application from the production
of hydrocarbons to a wide range of chemical feedstocks,
including methanol. SR delivers a H2:CO ratio of 3:1, DR a
ratio of 1:1, and PO a ratio of 2:1. If syngas is intended to be
converted into methanol in an economic and energy-efficient
manner, a H2:CO ratio of 2:1 is desired. Among the standard
reforming processes, syngas from PO has the optimal ratio for
methanol synthesis. However, the risk of thermal runaway and
local hotspots is high in the case of PO. In most instances, the
H2:CO ratio needs to be adjusted for the intended application
after the reformer module with intermediate units such as
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pressure swing adsorption (PSA), water gas shift reactors
(WGSRs), or membrane separation units.
As an alternative to conventional reforming approaches, we
have reported in a series of publications a bi-reforming process
(RRR7) that combines steam and dry reforming of CH4 and
CO2 in a single step. Bi-reforming (BR) was carried out over
NiO/MgO at high temperatures and pressures, and the
gaseous product with a H2:CO ratio of 2:1 was obtained,
which we have called metgas, a mixture highly suitable for
methanol synthesis8,30−32
SR: CH4 + H 2O F CO + 3H 2 , ΔH298K = + 206 kJ· mol−1
(R4)
DR: CH4 + CO2 F 2CO + 2H 2 , ΔH298K = + 247 kJ ·mol−1
(R5)
1
PO: CH4 + O2 F CO + 2H 2 , ΔH298K = − 36 kJ ·mol−1
2
(R6)
BR: 3CH4 + 2H 2O + CO2 F 4CO + 8H 2 , ΔH298K = +659 kJ·mol−1
(R7)
Driven by sustainability-oriented goals, in recent years more
attention has been given to the development of green
processes for renewable energy generation and storage, several
of them centered around the synthesis of methanol from
biogas.33−36 Biogas is the product of anaerobic digestion of
organic wastes that can originate from agricultural waste,
industrial waste, or landfills, each resulting in a biogas with a
different composition. Generally, CH4 (50−80%) and CO2
(25−50%) are the main constituents of biogas streams, with
potential impurities present such as sulfides, nitrates, hydrogen,
and siloxanes.37 Biogas with its high content in both CH4 and
CO2, if released into the atmosphere, can significantly
contribute to the greenhouse effect. In the framework of the
Methanol Economy concept, however, biogas can be converted
into value-added methanol and contribute to closing the
carbon cycle. In this case, after initial purification to separate
sulfides, siloxanes, and other impurities,38−40 the carbon-rich
gaseous mixture of CO2 and CH4 can then be directed to a
reforming unit to first produce syngas, followed by the
production of methanol.41
The high CO2 content in biogas favors dry reforming for
syngas production. DR has been studied mainly over Ni-based
catalysts.42−44 In a methanol synthesis process studied by
Santos et al.,45 biogas from four different sources was
converted into syngas in a dry reformer and later to methanol
in a tubular reactor. Among the selected biogas compositions,
biogas from palm oil with the highest CH4:CO2 ratio of 1.4
resulted in the highest methanol yield. Hernández et al.46,47
focused on the optimization of a biogas-to-methanol process in
a dry reformer with two objectives: the reduction of the cost of
methanol production and the reduction of the carbon footprint
of the overall process. Economic optimization in this work
favored a DR followed by a water gas shift unit, which adjusts
the ratio of H2:CO in syngas before feeding it into the
methanol reactor.
CH4 decomposition and CO disproportionation are
common side reactions of the dry reforming process.48 The
generated carbon formed in these reactions may deposit on the
catalyst and reduce its activity through coking. Addition of
steam during reforming was shown to prevent coking to a large
extent.14 Furthermore, based on Le Chatelier’s principle, the
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
presence of steam shifts the equilibrium in the WGS reaction
in favor of more H2 production. This is particularly beneficial
in the case of a syngas intended for methanol synthesis, since
the generated H2 can then be used for the hydrogenation of
carbon oxides. Vita et al.49,50 compared thermodynamic
aspects and performance of the three main reforming processes
(DR, SR, and PO) in an attempt to use the syngas produced in
the reformer directly for methanol synthesis without any
intermediate adjustments in the syngas composition. Their
feasibility studies showed that steam reforming of biogas with a
high CH4 content (CH4:CO2 of 2.3) resulted in the highest
methane conversion (over 80%). In another study, thermody-
namics of large-scale steam reforming of biogas with a
CH4:CO2 of 1.4 to methanol with a capacity of 1.8 × 106
m3 per year was studied by Ghosh et al.51 In their proposed
process, CO2 was first separated from CH4, and the obtained
methane-rich gas was directed to a SR unit. Instead of venting
it, the separated CO2 was mixed with the syngas coming out of
the reformer. In this work by Ghosh, three scenarios were
studied: (i) the RWGS reaction and hydrogenation of CO to
methanol, (ii) the direct CO2 hydrogenation to methanol in a
single reactor, and (iii) the direct CO2 hydrogenation to
methanol with intermediate steps to remove the water
generated by the RWGS during hydrogenation. Among these
scenarios, steam reforming of biogas followed by direct
hydrogenation of CO2 in two consecutive reactors with
water removal in between resulted in the highest methanol
yield. Alternatively, the endothermic steam and dry reforming
of methane were combined with the exothermic partial
oxidation to produce syngas via tri-reforming. Hernandez et
al.52 proposed a process converting biogas to syngas in such a
manner in a tri-reformer, followed by a WGS reactor to adjust
the amount of CO in the syngas composition. An optimal
H2:CO ratio for methanol synthesis was achieved using a
biogas with a high CH4 content and by adding steam to the
WGSR unit.
The thermodynamic studies discussed above have confirmed
that biogas is indeed a viable source of carbon for green
methanol synthesis. Depending on the origin of the biowaste, a
variety of biogas compositions were considered and higher
CH4:CO ratios in biogas were shown to improve the overall
methanol yield of the process. Additionally, a cost-effective and
efficient methanol production required a H2:CO ratio of 2 in
the syngas. Commonly, the CO and H2 contents of the syngas
were adjusted with WGS reactors, pressure swing adsorptions,
or membranes placed after the reformer unit.53,54 To eliminate
these often costly and energy-intensive intermediate steps, we
propose here a process for renewable methanol synthesis
through bi-reforming of biogas in a single stage bi-reformer.
The metgas produced after the BR has the ideal H2:CO ratio
of 2 and can be used directly for methanol synthesis without
any further adjustments in its composition.
Our extensive experimental studies on bi-reforming have
shown a promising performance over NiO/MgO at pressures
of 1−42 bar and temperatures of 830−910 °C. The NiO/MgO
catalyst is shown to be stable for bi-reforming under these
conditions over a time period of 320 h.30−32 These
experimental findings served as a basis for the more detailed
thermodynamic analyses presented in this work to study the
overall process schematic for the conversion of biogas to
methanol. Here, we evaluate the impact of key parameters on
the overall performance of the process implementing BR and
compare the results with the conventional approaches.
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Ultimately, the process is optimized to improve the overall
yield of methanol production.
2. METHODS
A schematic of the proposed process based on bi-reforming of
biogas to metgas and subsequent conversion to methanol is
shown in Figure 1. The initial purification steps are not
Figure 1. Process schematic for the conversion of biogas to green
methanol with a single stage bi-reformer.
considered in this work, and it is assumed that the biogas
stream only contains CH4 and CO2. Prior to the reformer,
biogas is mixed with steam and is brought to the temperature
and pressure of the BR. The amount of CO2 in the BR is
regulated with a makeup line connected to a reservoir tank of
captured CO2, potentially separated from the air.55−58 Biogas is
converted to metgas in BR and is directed to the next section
of the process for methanol synthesis. Excess amount of steam
in the feed gas of the reactor negatively impacts the overall
methanol yield. Therefore, the current process considers a
liquid trap after the reformer to control the water content in
the metgas, if necessary. The stream leaving BR unit goes
through a membrane unit that separates the unreacted CH4
and recycles it back to the reformer. The CH4-free metgas,
composed mainly of CO and H2, is then fed into a packed bed
tubular reactor for methanol synthesis. Temperature and
pressure of the metgas entering the reactor are controlled with
heat exchanger and compressor units placed before the reactor.
A flash separation is used to separate the gas and liquid phases
after the reactor. Unreacted gases after the reaction are
recycled back into the reactor to increase the overall yield of
the system. The methanol in the collected liquid can be
separated from water by simple distillation.
A flowsheet of the proposed process for renewable methanol
synthesis from biogas was developed and simulated in Aspen
Plus, as shown in Figure 2. Soave Redlich Kwong (SRK)
equations of state for nonideal gases were chosen in the
simulation to describe the thermodynamics of the overall
process.
2.1. Biogas. The composition of the biogas is defined by its
source, being from a landfill, a waste water treatment plant, or
from other organic waste streams. When the chemical
composition in biogas from various sources is compared, on
average CH4 comprises 50−75% of the biogas, while CO2 has a
share of 25−50%.40,59 In the case of a single stage bi-reformer
and based on the stoichiometries in reaction (R7), a high
methane content in biogas is desired to assure an efficient
performance. Therefore, a biogas stream with a CH4:CO2 ratio
of 3 was selected for metgas synthesis in this study. If required,
the biogas composition was adjusted with captured CO2 from
sources such as the exhaust of power plants or by direct CO2
capture from the air.56−58
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 2. Process flowsheet for renewable methanol synthesis from biogas.

Impurities such as nitrates, sulfides, and siloxanes are
removed from biogas in pretreatment steps before the
reformer. Particular attention is given to H2S and other
sulfur-containing compounds that tend to poison the Ni-based
catalysts used in this work for bi-reforming, as well as the
downstream methanol catalyst. There are several approaches to
reduce the concentration of such compounds to the ppm range
by passing the biogas through absorption units (with NaOH),
adsorption units (on iron oxides or activated carbon), or its
biological transformation to hydrates. The remaining sulfur-
containing compounds can potentially still deactivate the
catalyst depending on the source of biogas, the type of the
sulfur-containing compound, and the operating condition in
the reformer. Studies on steam reforming of biogas on Ni-
based catalysts have shown that most of the catalyst poisoning
lower temperatures. The amount of solid carbon formed in the
reformer was monitored to assure long-term stability of the BR
operation.
In a system with N components, the total Gibbs free energy
(GT) is the sum of the chemical potential of all of the
components involved, as shown in eq 1. In this equation, i
indicates each component, n is the number of moles, and μ is
the chemical potential. Chemical potential is defined in eq 2, in
which G0f i is the standard Gibbs free energy of formation for
component i, R is the constant of gases, T is the temperature, f i
is the fugacity at an operating condition, and f 0i is the fugacity
of component i at a standard state.
N
GT = ∑ niμi
(1)

ij f yz
i=1
occurs at temperatures lower than 700 °C and that the catalyst

μi = G 0fi + RT lnjjjj i0 zzzz

jf z
can effectively be reactivated by increasing the temperature in

k i{
the reformer up to 900 °C.60,61 It was also shown in the
literature that the presence of small amounts of sulfur in a (2)
CO2-rich feed gas might be beneficial and prevent carbon For a mixture at equilibrium, eqs 3 and 4 are valid to
formation on Ni-based reforming catalysts in a process known reformulate the total Gibbs free energy as in eq 5. Here, y is the
as sulfur-passivated reforming process (SPARG).62 mole fraction in gas phase, ⌀ is the fugacity coefficient, P is the
The pretreatment units for biogas before the BR were not pressure of the system, and P0 is the standard state pressure (1
modeled in this work. Additionally, the operating temperature bar).
of the BR was optimized to be higher than 700 °C; hence, the
impact of the sulfur-containing impurities on the catalyst fi = yi ⌀iP (3)
activity was considered to be minimal.
2.2. Bi-reforming (BR). In the proposed upgrading process G 0fi = ΔG 0fi and f i0 = P 0 (4)

i i yi ⌀iP yzyzz
∑ nijjjjjΔG0fi + RT lnjjjj
of biogas, impurities were not considered in the biogas
zzz
0 z zz
N
feedstock for the single stage bi-reformer. Experimental and

k k P {{
thermodynamic studies confirmed that reformers generally GT =
operate in an equilibrium state.63 It was hence assumed that i=1 (5)
the BR in this process was at equilibrium as well and was able The total Gibbs free energy at equilibrium in BR is then
to reach the highest possible conversion at any given condition. minimized by applying the Lagrange multiplier (eq 6). In the
To have a better understanding of the BR and to perform multiplier term, αik is the number of atoms of element k in
comparative thermodynamic analysis, a dry reformer was also component i, and λk is the total mass of element k.

ji i yi ⌀iP yz zy
∑ nijjjjjΔG0fi + RT lnjjjj z+ ∑ λkαik zzzzz = 0
modeled in this work under the same conditions as BR without

0 z z
N

the added steam to the biogas inlet.
At equilibrium, Gibbs free energy of a system is at its
minimum. Therefore, minimization of Gibbs free energy64 was
applied to determine conversion and metgas composition. For
this purpose, the R-Gibbs reactor model in Aspen Plus is best
suited to describe the bi-reforming unit. In addition to the
main reactants and products of bi-reforming and WGS
reactions listed in reactions R3 and R7, DME and light
hydrocarbons were also considered in calculations to account
for the potential side reactions. Undesired coking and carbon
deposition might occur during the reforming, particularly at
D https://dx.doi.org/10.1021/acs.iecr.0c00755
kP {
k {
i=1 k (6)
2.3. MeOH Reactor. Methanol synthesis is an exothermic
and equilibrium-limited reaction; hence, the effective heat
management in the reactor has a significant impact on the
performance of the reaction. Gas-phase reactions to produce
methanol are conventionally carried out in packed bed tubular
reactors under isothermal or adiabatic conditions. There have
also been efforts to shift the equilibrium either by in situ
removal of one or more products in a membrane reactor or by
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
altering the temperature and concentration profiles over the
catalytic bed in a transient reverse flow reactor such as STAR
configuration introduced by Vanden Bussche and Fro-
ment.36,65
In the methanol synthesis section of this process, we have
focused on the technology commonly practiced industrially.
Therefore, the metgas from the BR unit is directed into a
packed bed isothermal reactor. The reactor is simulated with
the R-Plug model in Aspen Plus that is equipped with a
countercurrent cooling jacket to control the heat released
during the exothermic hydrogenation. Methanol synthesis was
carried out over the CuO/ZnO/Al2O3 catalyst. This catalyst is
the well-established commercial catalyst for large-scale
methanol production, with stability over the course of several
years. Alternatively, there are also reports of other heteroge-
neous catalysts for methanol synthesis in the presence of both
CO and CO2. The commercial catalyst in this work could be
replaced by such catalysts while the composition of the inlet
stream to the reactor is in the range of (H2 − CO2)/(CO +
CO2) ∼ 2.66 If necessary, a makeup line with the captured CO2
from the air can be used to balance the composition in this
stream.
Kinetics of CO/CO2 hydrogenations, as well as WGSR over
the CuO/ZnO/Al2O3 catalysts, is well studied in the literature.
Vanden Bussche and Froment proposed a comprehensive
study of the kinetics for these reactions based on Langmuir−
Hinshelwood−Hougen−Watson (LHHW)-type rate equa-
tions.67 Predefined models in Aspen Plus use LHHW-type
kinetics in the form of eq 7. For the original kinetics found in
the literature to be compatible with the predefined form of
LHHW in the software, equations and parameters were
transformed by Luyben68 (eqs 8 and 9) and reaction rates
were redefined in kmol·kgcat−1·s−1. In this set of equations, R
stands for the rate of reaction, P is the partial pressure, KE is
the equilibrium constant, and k is the reaction rate constant.
(driving force term)
R = (kinetic term)
(adsorption term)
ÄÅ
ÅÅ
ÅÅ1 − 1 ijj PMeOHPH3 2O yzzÑÑÑ
ÅÅ KE1 j PCO2PH2 zÑ
ÅÇ k
= (k4PCO2PH 2) Ä
ÅÅ i PH O y
ÅÅ
ÅÅ1 + k 3jjj P 2 zzz + k1 PH2 + k 2PH2OÑÑÑ
RMeOH
ÅÅÇ k H2 {
ÄÅ
ÅÅ
ÅÅ1 − 1 ijjj PCOPH2O yzzzÑÑÑ
ÅÅ KE2 PCO2 PH2 Ñ
ÅÇ k {ÑÑÖ
RRWGS = (k5PCO2) ÄÅ
ÅÅ
ÅÅ1 + k 3ijjj PH2O yzzz + k1 PH + k 2PH OÑÑÑ
ÅÅ
ÅÇ k {
PH2 2 directed to a gas chromatograph for analysis. The conditions in
2.4. Compressors and Recycle Streams. Previous
studies have shown that compressors are generally the most
costly parts of the methanol production processes.68,69 The
reforming section of this process was therefore carried out
under atmospheric pressure to reduce the total cost of the
system. Pressure of the metgas was then increased to the
reaction pressure in a polytropic compressor positioned before
the methanol reactor. More detailed economic studies on the
costs associated with the compressor will be addressed in
future studies.
pubs.acs.org/IECR Article
Both reforming of biogas and synthesis of methanol are
limited by equilibrium. Unreacted gases after each of these
units were recycled back to the individual unit with a ratio of
0.7 to improve the overall yield of each section. Under optimal
reaction conditions, the stream leaving the BR will mainly
consist of CO and H2 with minimal traces of other
components such as water and CH4. Presence of H2O and
CH4 in trace amounts in the metgas will not have a significant
impact on the methanol reaction. In this case, the metgas
leaving the BR can alternatively be sent to the methanol
reactor without going through the intermediate separation and
recycle steps (SEP 1 and SEP 2 will be eliminated), to reduce
the overall cost of the process. CH4 residuals can then be
separated from the liquid phase after the reactor to be either
recycled or burned to generate heat required for the process.
3. RESULTS
3.1. Biogas to Metgas. The equilibrium state in the bi-
reforming unit was studied at temperatures in the range of
300−1000 °C and a pressure of 1−15 bar. Key parameters for
the thermodynamic analysis of BR are listed in Table 1. Both
Table 1. Process Parameters in BR
temperature [°C] 300−1000
pressure [bar] 1−15
CH4/CO2 [−] 3/1
H2O/CO2 [−] 2/1
inlet flow rate [mL·min−1] 100
catalyst NiO/MgO
experimental and numerical preliminary studies on BR with the
model developed here showed no trace of DME, ethane,
propane, butane, and higher hydrocarbons as potential
byproducts. Therefore, this work limited the components to
the ones involved in BR and WGS reactions. Biogas conversion
(7) and metgas composition, as well as the amount of solid coke
ÉÑ
Ñ
formed in BR, were determined. A biogas stream with the same
{ÑÑÖ
composition was sent to a DR unit, and the performance of the
ÉÑ3
BR was evaluated by comparing the values obtained for biogas
ÑÑ
reforming in a dry reformer under the same conditions. Finally,
ÑÑÖ
the energy input to the BR was evaluated.
In the first step, the model was validated based on our prior
experimental studies.30−32 The experimental studies on bi-
ÉÑ
(8)
reforming were carried out in a pressurized tubular flow reactor
Ñ
at 7−42 bar and 830−910 °C. The catalyst was mixed with a
ÉÑ
tabular alumina (typically 100 mg catalyst to 900 mg alumina)
Ñ
and was placed inside an alumina tube in the center of the
2 ÑÑÑÖ
metallic tube. The reactive gases leaving the reactor were
(9)
the present model were set to mimic the ones in these
experimental studies. Figure 3 shows both the theoretical and
experimental conversions of CH4, as well as CO2, in BR in a
temperature range of 830−910 °C and a fixed pressure of 7
bar. It can be seen that the developed model and experiments
with NiO/MgO are in an acceptable range of agreement in
terms of carbon conversion. The minimal deviation between
the theoretical and experimental data is likely due to the
accuracy of the trajectory fitted into the limited experimental
data in a given temperature range. Therefore, it is valid to
consider this model as a reliable tool for more detailed
evaluation and optimization on BR.
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Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 3. Theoretical and experimental conversions of (a) CH4 and
(b) CO2 at 7 bar in BR.
Figure 4 shows the theoretical conversion of CH4 in BR
compared to that in DR at different temperatures and
pressures, as determined with the equilibrium model. Higher
temperatures favor methane reforming, and consequently CH4
conversion increases with increasing temperatures until
reaching full conversion at temperatures above 900 °C and 1
Figure 4. Conversion of CH4 for a biogas stream with a CH4:CO2
ratio of 3:1 in (a) BR and (b) DR.
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bar. The observed trend shows no significant difference
between DR and BR. However, at lower temperatures,
competing WGS reaction becomes dominant and its impact
can be detected in the form of a dip in the amount of
converted CO2 for both BR and DR, as shown in Figure 5. In
Figure 5. Conversion of CO2 for a biogas stream with a CH4:CO2
ratio of 3:1 in (a) BR and (b) DR.
the case of BR, the generated CO is more likely to react with
the available steam to form CO2. A more substantial decrease
in CO2 conversion at temperatures lower than 700 °C is
therefore observed in the thermodynamic studies of bi-
reforming. Based on Le Chatelier’s principle, lower pressures
shift the equilibrium in reforming reactions toward metgas.
The decreasing trend is confirmed by CH 4 and CO 2
conversions at higher pressures in both bi-reforming and dry
reforming of biogas.
At lower temperatures, CO can potentially convert to CO2
and solid carbon in the so-called Boudouard reaction, resulting
in coking and deactivation of the catalyst.9 Thermodynamic
studies of dry reforming of biogas in Figure 6b indicate that up
to 50% of the inlet carbon content might transform into coke
during reforming, even at higher temperatures. However, it was
stated in previous studies49,70 that the addition of steam to the
reforming reaction suppresses undesired coke formation
particularly at higher temperatures. In the case of BR, Figure
6a shows that, as the temperature reaches 600 °C, steam
reforming becomes the thermodynamically preferred route,
and consequently the potential for solid carbon formation in
BR begins to fall. Based on these findings, BR can be assumed
to be coke-free at temperatures above 900 °C.
Among reforming approaches, BR has the advantage of
delivering metgas with the optimal composition for the
subsequent methanol synthesis. The thermodynamic studies
on BR in Figure 7 confirm that, at temperatures above 800 °C,
the H2:CO ratio in metgas reaches 2 with no significant
dependency on pressure. In the case of a DR, over-
stoichiometric CH4 in the biogas (CH4:CO2 ratio of 3:1
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Figure 6. Solid carbon formed per mole of inlet carbon for a biogas
stream with a CH4:CO2 ratio of 3:1 in (a) BR and (b) DR.
Figure 7. H2:CO ratio for a biogas stream with a CH4:CO2 ratio of
3:1 in (a) metgas after BR and (b) syngas after DR.
instead of 1:1) results in a syngas leaving the reformer with a
H2:CO ratio of 3. While metgas from BR can directly be sent
into the MeOH reactor, the composition of the syngas leaving
the DR requires further adjustments in a WGS reactor or a
pressure swing adsorber before it is fed into the reactor.
One of the key factors impacting the economy of the process
is the amount of heat input to each unit. The impact of
variations in pressure and temperature on the required amount
of heat in the bi-reformer was determined in this work and is
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shown in Figure 8. From the sensitivity analysis, it can be
observed that the energy input increases at higher reforming
Figure 8. Heat duty of BR.
temperatures for this endothermic reaction. In contrast to
temperature, Figure 8 indicates that higher pressures favor the
reverse reaction and reduce the total energy intake of the BR.
Hence, operating conditions in BR need to be selected in a
manner that minimizes the energy input to the unit.
Additionally, internal heat integration strategies can potentially
be employed to provide the energy requirements of units such
as BR through the heat generated within the process.
For an efficient transformation of biogas to metgas, we
propose here a process implementing a single stage bi-reformer
with no need for intermediate upgrading steps to adjust the
composition. The base temperature of BR is set to 900 °C and
pressure to 1 bar, under which nearly full conversion of biogas
is achieved with no sign of carbon deposition. The gaseous
mixture leaving the BR under this condition has a molar
composition of H2: 65%, CO: 32%, CO2: 0.4%, CH4: 0.5%,
and less than 1% of H2O. Kinetic studies on the hydrogenation
of carbon oxides have shown that the presence of CO2 in
syngas potentially improves the performance of the methanol
synthesis.46 As a result, metgas composed of H2 and CO with a
minor share of CO2 was sent directly to the methanol reactor
with no further upgrading.
3.2. Metgas to Methanol. The temperature and pressure
of the metgas were adjusted before the methanol reactor
through a series of heat exchange and compression steps.
Kinetics of hydrogenation requires elevated temperatures, yet
this equilibrium-limited reaction is hindered thermodynami-
cally at higher temperatures. Therefore, determination of the
optimal temperature for the methanol reaction is critical in
defining the overall performance of the system. The reaction
conditions in this process were adopted from the established
Lurgi methanol plant.45,71 The pressure was set to 80 bar and
temperature to 220 °C. Methanol synthesis was carried out in a
tubular reactor over the CuO/ZnO/Al2O3 commercial catalyst.
The packed bed reactor had a diameter of 0.03 m and a length
of 1 m to mimic the high-pressure pilot setup at the Loker
Hydrocarbon Research Institute for further experimental
studies on this process.32 The main parameters used in this
work to describe the methanol synthesis reactor are listed in
Table 2. The yield of the process was improved by recycling
unreacted gases back to the reactor.
Under the selected conditions, studies show that the MeOH
reactor delivers an overall conversion of 98% with a total heat
duty of 5.1 kW for the reactor, with the geometry and flow
rates given in Tables 1 and 2. The amount of heat generated by
the exothermic hydrogenation of CO2/CO in the MeOH
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
Table 2. Modeling Parameters in MeOH Reactor
diameter [m] 0.03
length [m] 1
catalyst density [kg·m−3] 2000
catalyst bed void [%] 50
reactor can be used in the bi-reforming section to either
preheat the biogas or conduct the distillation of methanol after
the reaction. Therefore, the energy efficiency of the process can
be significantly improved by applying suitable heat integration
strategies to use this generated heat within the process.
4. CONCLUSIONS
Biogas has gained increasing attention in recent years both as a
renewable source of energy and as a potential chemical
feedstock for a variety of value-added products. In the
framework of the proposed methanol economy and in its
goal to close the anthropogenic carbon cycle, biogas can be
used as a renewable and sustainable carbon source. CH4 and
CO2 present in biogas are converted into methanol, a liquid
fuel with high energy content and raw material for a wide range
of chemicals and products. In this concept, biogas is first
reformed to a gaseous mixture of H2 and CO, which is then
directed to a methanol synthesis reactor. Ideally, a H2:CO ratio
of 2 in the syngas is desired for an efficient methanol synthesis.
Conventional reforming methods, however, require additional
separation or feeding steps to adjust the composition of syngas
exiting from the reformer.
In our prior publications,30−32 we introduced a bi-reforming
process that combines steam and dry reforming in a single step
to produce metgas with an optimal H2:CO ratio of 2 for
methanol synthesis. As a result, intermediate upgrading units
such as a water gas shift reactor or pressure swing adsorption
units were no longer required. This results in a potential
improvement in the economics and energy efficiency of the
process. Our experimental studies showed a promising
performance for bi-reforming of CH4 with CO2 and water
over NiO/MgO as the catalyst. Based on our previous
findings,8,31,55 we proposed here a process concept for
renewable methanol synthesis through bi-reforming of biogas.
A thermodynamic model was developed, and the impact of key
parameters on the methanol yield and energy demand was
evaluated. The results were compared with conventional biogas
reforming processes.
Studies on bi-reforming of biogas herein were aimed at
determining the optimal conditions in a reformer to produce a
syngas for methanol synthesis with an optimized H2:CO ratio,
highest possible carbon conversion, and minimum coke
formation. The findings suggest that intermediate syngas
upgrading units are inevitable after the simple dry reforming of
biogas. Additionally, coking can be a major drawback in dry
reformers. Employing a bi-reformer, which operates at a high
temperature of about 900 °C and atmospheric pressure,
assured a coke-free reaction with nearly complete conversion
of the carbon species in the biogas feed. The optimal H2:CO
ratio of 2 in the final metgas was confirmed under these
conditions. Additionally, the energy required for the reforming
unit can be partly provided by the heat released during the
hydrogenation of carbon oxides. Thermodynamic analysis on
the single-stage bi-reforming has shown the process to be a
feasible and effective alternative for the conversion of biogas to
a value-added liquid energy carrier such as methanol. More
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detailed economic evaluations and optimizations can further
improve the overall efficiency and energy demand of this
process.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.iecr.0c00755.
Thermal properties of the main process streams for
energy analysis (Table S1); and heat exchanger network
with integrated cooling water and heating streams
(Figure S1) (PDF)
■ AUTHOR INFORMATION
Corresponding Author
G. K. Surya Prakash − Loker Hydrocarbon Research Institute
and Department of Chemistry, University of Southern
California, University Park, Los Angeles, California 90089-
1661, United States; orcid.org/0000-0002-6350-8325;
Email: gprakash@usc.edu
Authors
Nazanin Entesari − Loker Hydrocarbon Research Institute and
Department of Chemistry, University of Southern California,
University Park, Los Angeles, California 90089-1661, United
States
Alain Goeppert − Loker Hydrocarbon Research Institute and
Department of Chemistry, University of Southern California,
University Park, Los Angeles, California 90089-1661, United
States; orcid.org/0000-0001-8667-8530
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.0c00755
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors dedicate the work to their good friend, Professor
Grzegorz Mlostoń, University of Lodz, Poland, on the occasion
of his 70th birthday. The authors gratefully acknowledge the
support of their work by the Loker Hydrocarbon Research
Institute at the University of Southern California.
■
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