Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-023-04024-z

ORIGINAL ARTICLE

Techno‑economic analysis of methanol synthesis from syngas derived

from steam reforming of crude glycerol
P. C. Kgwedi1 · N. Seedat1 · L. I. Fajimi1 · B. Patel2 · B. O. Oboirien1

Received: 27 October 2022 / Revised: 17 February 2023 / Accepted: 28 February 2023

© The Author(s) 2023

Abstract
Due to the large amount of crude glycerol produced as a by-product by the biodiesel industry, alternative technologies for
converting glycerol to value-added fuels such as syngas have been proposed. By employing four main processes, the syngas
could further be used to produce methanol. The first process is steam reforming (STR) where the crude glycerol is converted
into syngas. The next step is a three-unit pressure swing adsorption (PSA) system which is employed to condition the syngas
into the required stoichiometric ratio. The final two process are the methanol synthesis and methanol purification processes.
The effects of STR temperature, steam-to-glycerol ratio (SGR), methanol synthesis temperature and pressure were all inves-
tigated. The results obtained shows that 0.29 ­kgMeOH/kgCG can be obtained through this process at STR of 650 ℃, SGR of 9,
and methanol synthesis temperature and pressure of 250 ℃ and 80 bar respectively. In addition, a methanol production plant
capacity of 6.8 tonnes/hr of crude glycerol feed for a 20-year plant life was investigated. The result from the economic analysis
carried out shows that production of methanol from glycerol is economically feasible with net present value (NPV), return
on investment, (ROI), discounted payback period (DPBP) and net production cost (NPC) of $74.2 million, 17%, 4.59 years,
and 85₵/kgMeOH respectively. The sensitivity analysis results show that the revenue from sales of methanol and byproducts
(hydrogen and methane), the manufacturing cost, the cost of raw materials, as well as fixed capital investment (FCI) were
the most sensitive economic parameters.

Keywords  Glycerol · Methanol · Steam Reforming · Pressure Swing Adsorption · Techno-economic Analysis
Abbreviations kg Kilograms
APC Annual Production Cost KPI Key Performance Indicators
ATR​ Autothermal Reforming Kp Equilibrium Constant
CG Crude Glycerol LHV Lower Heating Value
CGtM Crude Glycerol-to-Methanol MeOH Methanol
COM Cost of Manufacturing MTO Methanol-to-Olefins
COR Carbon-Oxygen-Ratio NPC Net Production Cost
DPBP Discounted Payback Period NPV Net Present Value
FAME Fatty Acid Methyl Esters POX Partial Oxidation
FC Fixed Cost PSA Pressure Swing Adsorption
FCI Fixed Capital Investment REquil Equilibrium Reactor
GHG Greenhouse gas RGIBBS Gibbs Reactor
HEN Heat Exchanger Network ROI Return on Investment
HEX Heat Exchanger RWGS Reverse Water–Gas-Shift
SCWR​ Supercritical Water Reforming
SGR Steam-to-Glycerol Ratio
* N. Seedat SN Stoichiometric Ratio
[email protected]
StM Syngas-to-Methanol
1
Department of Chemical Engineering Technology, STR Steam Reforming
University of Johannesburg, Johannesburg, South Africa TCI Total Capital Investment
2
Department of Chemical Engineering, University of South VC Variable Cost
Africa, Johannesburg, South Africa WC Working Capital

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Vol.:(0123456789)
 Biomass Conversion and Biorefinery

WGS Water-Gas-Shift between 60–80 wt.%), its application is limited. Depending

wt. Weight on its purity, glycerol has been used as a raw element in the
manufacture of cosmetics, toiletries, medicinal formulations,
Symbols
and foodstuffs [17].
℃ Degree Celsius
The cost of refining crude glycerol is high due to the
ΔHo298K Standard Enthalpy at 298 K
high cost of the processing equipment needed to purify it
K Kelvin
[18]. Also, due to the high costs of disposal and the pres-
$ US Dollars
ence of methanol, crude glycerol is currently considered a
waste product [19]. Processing crude glycerol to produce
value-added platform chemicals could be one answer to this
1 Introduction challenge [16, 20]. Reforming glycerol to hydrogen, syn-
gas, acrolein, propylene glycol, methanol, and other valuable
Over the years, the demand for non-renewable energy compounds is an example of a possible conversion process
sources such as coal, natural gas, and oil, has skyrocketed. [16, 17]. Converting glycerol to methanol is an appealing
Non-renewable resources are generally used to expand econ- solution to the problem of excess glycerol. Methanol is a
omies because they supply the energy needed to manufacture key ingredient in the production of biodiesel and other high-
essential products that can be used to sustain human life as value compounds [21]. The 1992 Energy Policy Act also
well as convey goods and people [1]. If these resources are classified methanol as an alternative fuel since, when uti-
not utilized sustainably, future generations may be left with- lized as motor fuel, it is physically and chemically identical
out supplies. As a result, new technologies must be devel- to ethanol. Around 90% of methanol now comes from fos-
oped, or existing technologies must be improved to focus sil sources [22]. A promising and environmentally friendly
on the use of renewable and sustainable energy resources. source for renewable methanol is glycerol [22]. Thus,
These new or enhanced technologies must be ecologically researchers have recently focused on the manufacture of
beneficial and capable of replacing non-renewable resources methanol from glycerol [21]. The crude glycerol to metha-
[2, 3]. From 2008 through 2035, global energy-linked C ­ O2 nol (CGtM) process can take several alternative courses, but
emission is predicted to increase by 43% if petroleum-based the most common one involves two steps: glycerol reform-
resources are used [4]. This could lead to global warming, ing to syngas and methanol synthesis from syngas [3, 23].
which could lead to climate change. Aqueous reforming, partial oxidation, pyrolysis, supercriti-
A biorefinery is a promising approach for utilizing renew- cal water reforming, steam reforming, and dry reforming
able biomass resources in a sustainable manner [5, 6]. Sarma reactions are all glycerol reforming techniques that can be
et al. [7] defined biorefinery as a processing facility to con- utilized to obtain syngas or hydrogen gas from glycerol [24,
vert biomass into valuable biofuels (such as biomethane and 25]. Another approach for producing methanol from glycerol
biodiesel), heat, power, and other value-added compounds. without reforming it to syngas has been proposed, and this
Biomass-derived energy sources are thought to be more process may be carried out under moderate conditions but
environmentally friendly, particularly in the transportation requires the introduction of hydrogen [26].
sector [8]. Biodiesel is the fatty alkyl ester formed when a Large-scale biodiesel producers can purify crude glyc-
fatty acid is transesterified with alcohol (usually methanol erol for other industrial use, unfortunately, the process of
or ethanol) in the presence of an alkali catalyst which could purifying crude glycerol is costly for small-scale producers
either be KOH or NaOH [9, 10]. This biofuel can be used [27]. However, the varying price and the increase in pro-
to replace petroleum-based diesel, which is non-renewable. duction of glycerol indicate that it is no longer economi-
Apart from the widely known transesterification process, cally feasible to use glycerol as an end product in a situation
biodiesel could also be produced by other methods such as where supply and demand are balanced [28]. Therefore,
the microemulsion process, pyrolysis, as well as direct use transforming crude glycerol is essential to maintaining the
and blending process [11]. Before the synthesis of biodiesel biodiesel business. While crude glycerol may appear to be
is technically and economically practical, there are some a disadvantage for certain biodiesel producers, it has enor-
difficulties associated with its use that must be overcome mous potential to be used as a feedstock for value-added
first [12]. The generation of huge amounts of crude glycerol biochemicals from a biorefining standpoint [29]. Converting
is one of the issues related to the usage of biodiesel. A mole glycerol into an energy derivative product is a promising and
of crude glycerol is generated for every three moles of bio- practical strategy that can be used to boost the profit earned
diesel produced during the transesterification process [13]. by the biodiesel industry [18]. As an illustration, crude glyc-
This process accounts for about 10% of glycerol's overall erol can be used to create hydrogen and syngas, which are
output [14–16]. Since the glycerol synthesized during the frequently used as primary feedstocks for the synthesis of
biodiesel production process has a very low purity (usually valuable compounds like methanol [18, 28]. The forecast for

13
Biomass Conversion and Biorefinery

glycerol production for the year 2020 was estimated to be has a high variety of liquid soluble intermediates, making
around 41.9 billion liters (as shown in Fig. 1) with an accom- glycerol reforming more difficult than methanol-reforming.
panying market price of 80% purity costs between $0.09 and Although technically possible, most reforming methods
$0.20 per kilogram of crude glycerol [27, 30]. Also, since an for converting glycerol to methanol are not yet financially
average of 1000 kilotons of glycerol are generated globally appealing [39].
each year, there are limited market information available
for it [28]. This necessitates the development of a practical 2.2 Supercritical water reforming of glycerol
and affordable method for transforming crude glycerol into
valuable compounds. In addition, previous techno-economic Supercritical water reforming (SCWR) is the most recently
studies [31–33] investigated the minimum selling price of researched process that appears to be a favourable unconven-
synthetic methanol to be around 0.5—1.5$/kgMeOH which tional route that could be used to manufacture syngas from
is more than twice the market price of methanol. However, liquid biomass. Supercritical water is defined as water that
none of these studies considered methanol production from has been compressed and heated beyond its critical pres-
the syngas derived from crude glycerol. sure (22.1 × ­10–5 bar) and temperature (374 ℃) [18]. The
Most of the critical studies [34–38] on glycerol/crude benefits of this method are due to its distinctive thermo-
glycerol steam reforming have mainly focused on hydro- physical characteristics, which include high water reactivity
gen production. There are limited studies that investigates beyond its critical conditions, and high ability of solubiliz-
the methanol production through steam reforming of crude ing gases (such as CO, C ­ O2, ­CH4, and ­CH2), and difficulty
glycerol, hence, this study aims at the technical and eco- in solubilizing polar molecules [30]. As a result, the crude
nomic evaluation of methanol production from the syngas glycerol in the product makes it easier to separate these com-
produced from the steam reforming (STR) of crude glyc- pounds, including KCl, NaCl, and several others. Because of
erol. To achieve this, a detailed sensitivity analysis on effects the hydrothermal conditions of SCWR, organic compounds
of the key operating conditions such as STR temperature, that cannot react in water except in the presence power-
steam-to-glycerol ratio (SGR), methanol synthesis pressure, ful base or acid catalyst can easily react. This is a result of
and methanol synthesis temperature on syngas composition SCWR producing a considerable amount of ions ([H+] or
and product yield were investigated. [OH–]), which causes it to behave as an acid or base during
the process [13]. Since reactions in supercritical water can
be carried out in a single fluid phase, the SWR process has
2 Literature review been explored both with and without a catalyst. This would
imply that the process may still be carried out without the
2.1 Glycerol reforming catalyst [18]. According to Markoi et al. [40], the presence
of a catalyst allows for the reduction of SCWR operating
In order to convert glycerol to hydrogen or syngas, research- expenses as well as process conditions including temperature
ers have studied various reforming processes. Crude glycerol and energy requirements. Transition metal catalysts appear
to be the ideal catalyst to use [1].

50 2.3 Steam reforming of glycerol

41.9

40
Steam reforming (STR) is a well-established process
36
approach that may be easily run at atmospheric pressures
Production (Billion liters)

30.8 without the use of expensive advanced control equipment

30
25.9 [41]. Theoretically, in glycerol STR, steam combines with
glycerol to produce mainly ­H2, CO, and ­CO2 [24]. With
20 17.2
STR, complete glycerol conversion can be accomplished
with a high syngas and hydrogen yield [42]. Glycerol could
be used as a renewable feedstock in STR process without
10 7.8
changing the nature of the procedure or any process equip-
ment [38]. Since glycerol is a carbohydrate (and not a hydro-
0 carbon), reforming it with steam is more difficult. This is
2006 2009 2012 2015 2018 2020
Year because of the more complex reactions of the STR of glyc-
erol relative to the STR of hydrocarbons [38]. Glycerol STR
Fig. 1  The estimated global production of crude glycerol from 2006 process comprises of a combination of glycerol decomposi-
– 2020 [30] tion into H­ 2 and CO and water–gas-shift (WGS) reaction

13
 Biomass Conversion and Biorefinery

as shown in Eq. 1 and Eq. 2 respectively [27]. More H ­ 2 is 862 ℃, an SGR of 4.5, and a carbon-to-oxygen ratio (COR)
produced as a result of the process's excessive steam oxidiz- of 0.9 for completely converting glycerol and attaining a
ing CO into C­ O2 [43]. The overall representation of the STR hydrogen selectivity of 79%. Their result also revealed that
of glycerol is shown in Eq. 3. under these ideal conditions, the selectivity of undesirable
products, such as ­CH4, was inhibited to less than 2% [48].
C3 H8 O3 ↔ 3CO + 4H2 ΔH o 298K = +250kJ∕mol (1)

2.5 Comparison between SCWR, STR, and ATR

CO + H2 O ↔ CO2 + H2 ΔH o 298K = −41kJ∕mol (2)
of glycerol
C3 H8 O3 + xH2 O ↔ (3 − x)CO + xCO2 + (4 + x)H2 (3) At low temperatures, SCWR reforming has been investigated
The amount of steam required during STR is denoted by x to produce the highest target products (syngas or hydrogen)
which varies depending on the target product(s) [44]. Meth- yield, however, the process requires high pressure which
ane STR, methanation, methane dry reforming, and several would increase the production cost [46]. The SCWR pro-
other parallel reactions could take place during the STR of cess has the disadvantage that substantial hydrogen yields
glycerol depending on the type of catalyst being employed are only obtained at reaction temperatures above 600 ℃,
[41]. The following variables must be carefully regulated in whereas temperatures below 450 ℃ favoured the generation
order for the STR process to be successful: pressure, steam- of methane [49]. The STR method allows for the simultane-
to-glycerol ratio (SGR), temperature, reactants-to-inert gas ous production of additional amounts of target products from
ratio, feed gas rate, and catalyst loading [44]. Most inves- the surplus water, which increases the yield of the reaction
tigations [37, 45, 46] have employed SGR of 9:1 and 6:1. [46]. Also, given that the STR method is now the most popu-
In addition, STR temperatures between 525–725 ℃ provide lar method used to produce hydrogen and syngas globally,
high yields of hydrogen and syngas in general [46]. utilising this method for glycerol reforming is advantageous
because it is simple to modify equipment that is already
in use by the industry [46]. Although the ATR processes
2.4 Autothermal reforming of glycerol can take place at atmospheric pressure, it requires oxygen
and higher temperatures to produce effective results [46].
An efficient method of making the ideal syngas composi- In comparison to STR, coke formation is reduced in ATR.
tion for the production of methanol is autothermal reforming In oxidative conditions, coke deposition is relatively low,
(ATR). It combines the partial oxidation (POX) process with enabling prolonged operation without the catalyst becom-
the STR process [28]. ATR is the process of co-feeding glyc- ing inactive.
erol and water under POX conditions to increase the output
of hydrogen or syngas as the case may be. Equation 6, which
2.6 Methanol production from syngas derived
combines the STR equation (Eq. 4), and the POX equation
from glycerol reforming
(Eq. 5) represents the total reaction for ATR. The tempera-
ture of the process affects the stoichiometric coefficients.
Syngas produced from different materials, including bio-
C3 H8 O3 + 3H2 O ↔ 3CO2 + 7H2 ΔH o 298K = 127.67kJ∕mol mass, natural gas, and petroleum, varies in quality. Biomass-
(4) derived syngas usually has a poor hydrogen-to-carbon ratio
due to their high ­CO2 content and low H ­ 2 content [8]. The
2C3 H8 O3 + 12 O2 ↔ 2CO + CO2 + 4H2 ΔH o 298K = −31.79kJ∕mol
synthesis of methanol cannot be done with the syngas in
(5)
this state. Methanol cannot be produced when only ­H2 and
C3 H8 O3 + aO2 + bH2 O ↔ cCO + dCO2 + eH2 + f CH 4 CO are present in syngas, hence, Lücking [50] asserts that
(6) the hydrogenation of CO and catalytic hydrogenation of
This process takes place at higher temperatures ­CO2 are necessary for its production. Because of this, the
(900–1150 ℃) and a wide pressure range (1–80 bar), hence a allowable level of ­CO2 during the processing of methanol
reactor that can handle these conditions is required [47]. For typically ranges from 2—8%, with the vapor phase typically
autothermal reactors to endure the high temperatures, pres- falling between 2—4% and the liquid phase typically fall-
sure, and high partial pressure of hydrogen, refractories are ing between 4—8% [51]. When syngas containing 28 mol%,
typically used as the reactor's outer shell [47]. The start-up 70 mol%, and 2 mol% of CO, H ­ 2, and ­CO2 correspondingly
time for ATR is significantly faster than that of STR because are supplied to a reactor, methanol synthesis may typically
POX is an exothermic process that takes place on the surface occur [3]. An estimate of syngas (CO, H ­ 2, ­CO2, and C
­ H 4)
of the catalyst [42]. According to Ali [48], the best working conditions was given as 24 vol.%, 67 vol.%, 4 vol.%, and 5
conditions were determined to be a high ATR temperature of vol.% respectively in the study by Van Bennekom et al. [3].

13
Biomass Conversion and Biorefinery

The syngas-to-methanol (StM) reaction is typically con- 3 Methodology

ducted in a fixed bed reactor at temperatures between 250—
280 ℃ and pressures between 50—100 bar over a Cu–ZnO- 3.1 Crude glycerol composition, proximate,
based catalyst [52]. The optimum yield of methanol from C­ O2 and ultimate analysis
has been found to be significantly less than 40% at 200 ℃ and
50 bar, but the yield from both ­CO2 and CO under the same Table 1 shows the crude glycerol composition, proximate,
conditions is higher than 80% [38]. The hydrogenation of CO and ultimate analysis obtained from Tamošiūnas et  al.
(Eq. 7), the reverse WGS process (Eq. 8), and the hydrogena- [54]. The crude glycerol employed in the study was a
tion of ­CO2 (Eq. 9) are the three major reactions that make by-product obtained from rapeseed biodiesel production
up the synthesis of methanol [3]. Equation 7 and Eq. 8 are process.
independent processes that are adequate to determine the ratio
of reactants to products at equilibrium [3].
3.2 Process description
CO + 2H2 ↔ CH 3 OH ΔH o 298K = −90.64kJ∕mol (7)
The Aspen Plus process flowsheet for the crude glycerol-
CO2 + H2 ↔ CO + H2 O ΔH o 298K = +41.17kJ∕mol (8) to-methanol (CGtM) is shown in Fig.  2. The physico-
chemical properties of fuels were determined by using the
CO2 + 3H2 ↔ CH 3 OH + H2 O ΔH o 298K = −49.47kJ∕mol Peng-Robinson equation of state as proposed in the work
(9) of Mousavi Ehteshami & Chan [55]. The CGtM process
Chemical equilibrium is what regulates the production configuration was divided into four key sections which
of methanol from syngas, thus Eq. 10 and Eq. 11 can be include the syngas production (from STR of crude glyc-
used to obtain the equilibrium constants based on fugacity erol) section, the gas treatment section (using pressured
[50]. According to Eq. 9, the entire methanol production swing adsorption (PSA) system), and the methanol syn-
process is exothermic. The effectiveness of methanol synthe- thesis section, and finally, the crude methanol purifica-
sis is hence severely constrained by thermodynamics [17]. tion section. A comprehensive description of the method
Due to the exothermic nature of the two processes, the vol- of operation of each unit is explained in the following
ume drops when CO and ­CO2 are hydrogenated. When this subsection.
occurs, it is possible to maximize the production of methanol
by using Le Chatelier's principle to favor the two reactions
by raising the pressure and lowering the temperature. The
collision theory states that rapid particle collisions only Table 1  Crude glycerol mass composition, proximate and ultimate
occur at high temperatures, making temperature reduction analysis [54]
kinetically undesirable. Additionally, it is not a good idea Composition (wt.%)
to lower the temperature during this procedure because the   Water ( 𝐇2 𝐎) 9
catalysts required for methanol synthesis are only effective   Glycerol ( 𝐂3 𝐇8 𝐎3) 85
at temperatures above 200 ℃ [53].   Methanol ( 𝐂𝐇3 𝐎𝐇) 0.5
  Methyl Oleate (𝐂19 𝐇36 𝐎2) 1.5
5139
logKpCo = − 12.621 (10)   ­Na3PO4 (Heterogenous Catalyst) 4
T
Proximate Analysis (wt.%)
  C 20.15 ± 0.9
2073
logKpRWGS = − + 2029 (11)   H 5.64 ± 0.29
T
  N  < 0.01
where KpCo is in bar−2 and KpRWGS has no units. The most ideal   S  < 0.01 (0.002)
syngas for the synthesis of methanol has a stoichiometric   Cl 0.02 ± 0.001
number ( SN  ) of 2 (see Eq. 12), which corresponds to the   O* 65.87
stoichiometric ratio for the synthesis of methanol [2]. All the Ultimate Analysis (wt.%)
reactants react to generate methanol when SN is equal to 2,   Volatile Matter 78.98 ± 1.0
only CO and ­CO2 react when SN is higher than 2, and hydro-   Fixed Carbon  < 0.01
gen is the limiting reagent when SN is less than 2 [50, 53].   Ash 8.34 ± 0.02
  Moisture 12.49
H2 − CO2
SN = =2 (12)   LHV (MJ/kg) 14.36 ± 0.03
CO + CO2
*Obtained by difference

13
 Biomass Conversion and Biorefinery

Fig. 2  Process flowsheet for methanol production from crude glycerol

Table 2  Component recovery Component PSA-1 (Top) PSA-2 (Bottom) PSA-3 (Top) PSA-3 (Bottom)
from the three PSA units
H2 0.95 - 0.0025 0.0475
CO - 0.98 0.002 0.018
CH4 - 0.01 0.90 0.09
CO2 - 0.001 0.01 0.989
Stream Richness H2-rich CO-rich CH4-rich CO2-rich

3.3 Steam reforming of crude glycerol section of a gas treatment process (see next section) before they
could be used to synthesize methanol.
As illustrated in Fig. 2, the raw feed streams (i.e., water
and crude glycerol) were introduced at room temperature 3.4 Gas treatment (Pressure swing adsorption
(25 ℃), and a pressure of 1 bar into the system. The water system) section
stream is heated to 100 °C to make the steam required for
the STR reactor. For crude glycerol, a flow basis of 100 The syngas stream was cooled down using two coolers
kmol/hr was assumed. The SGR employed was 9 which is (E-102 and E-103) connected in series, from 650 ℃ to
in line with Hunpinyo & Narataruksa [37]. Other investi- 482.2 ℃ and from 482.2 ℃ to 35 ℃, respectively [13]. This
gations have employed SGRs of 6 as well, however, a high was carried out to condense water out of the system. Water
SGR is considered to increase ­H2 yield [46]. Nonetheless, was eliminated from the process since it would increase the
to support this assertion, the flowrate of the water required energy cost due to vaporization, and also cause the cata-
for the STR process in this investigation is varied from lyst as well as the sorbent to lose their effectiveness due
300 to 1200 kmol/hr. Aspen plus RGIBBS reactor was to clogged pores [36]. Complete condensation was accom-
employed to simulate the steam reformer because RGI- plished with a streamlined separator. A two-stage compres-
BBS can produce phase equilibrium without involving a sor with intercoolers operating at a pressure ratio of 5.4 at
chemical reaction and it also minimizes the Gibbs free 35 ℃ in each stage was used to compress the gases in stream
energy within the constraints of atom balancing [48]. The S-4. The three PSA units of the pressure swing adsorption
steam reformer was fixed at 650 ℃ because it has been (PSA) system were initiated from stream S-5. The use of
established in previous works that the methanation rate is ideal component separators operating at 35 ℃ and 30 bar
negligible at temperatures above 600 ℃ [45]. The stream resulted in the simplification of all PSA units [18]. In the
designated SYNGAS (see Fig. 2) leaves the reformer at first PSA unit, 95% pure H­ 2 was recovered using the PSA-
650 °C and 1 bar and is composed of syngas ­(H2, CO, ­CO2, 1. According to Ortiz et al. [18], some of the purified ­H2
and ­CH4), alkali, and a very small quantity of glycerol, and stream can be used to run the furnace or routed to a proton-
methanol. Because of the low CO content, the syngas ratio exchange membrane fuel cell for power production. The
was also low. The syngas ratio was increased by means second PSA unit received the re-compressed gas that the

13
Biomass Conversion and Biorefinery

PSA-1 was unable to recover. As seen in Table 2, the purity distillation (T-101) was employed. The bottom product,
of CO improved in the PSA-2, where 98% of CO would which comprises mainly methanol and water, was then
be recovered. The residual gas from the PSA-2 was treated further processed in the second column. The partial-vapor
further in the PSA-3 after exiting at the bottom. The PSA-3 condenser in the first column had reflux and boil-up ratios
was employed to raise the syngas stoichiometric ratio to of 1.1 and 0.6, respectively. In the first stage of the column,
around 2 by reducing the C ­ O2 content of the gas stream. the condenser pressure was estimated to be 1.24 bar while
The excess C ­ O2 was collected for prospective sequestration in the first stage of the second column, a total condenser
or further utilization. The syngas ratio (using Eq. 12) was was chosen. In the second column, the reflux was taken to
increased after mixing the streams of H­ 2, CO, and C
­ O2 from be 1.1 and a boil-up ratio of 0.8 was used. In line with a
the three PSA units. The conditioned syngas in stream S-8 related study [57], 30 stages were selected for both T-101
was compressed to 80 bar using a compressor (C-104). The and T-102, and the feed was introduced in the middle (stage
methanol synthesis section is where methanol is produced 15). The refined methanol was extracted from the gas dis-
after the compressed syngas has been transferred there. The tillate and collected using a component separator (S-105).
procedure for simulating the generation of methanol from The S-105 methanol was mixed with the T-102 exit stream
processed syngas is explained in the next section. in the final exit stream.

3.5 Methanol production section

The compressed gas (S-11) from the gas treatment section

4 Results and discussions
was heated to 250 ℃ in the methanol synthesis section using
a heat-exchanger (E-104) in that section. Three reactions
4.1 STR and PSA section material balance
involved in the formation of methanol are Eqs. 7–9 and Eq. 8
The material balance around the steam reforming (STR)
is the primary methanol synthesis reaction. The methanol
and pressure swing adsorption (PSA) section is presented
production was simulated in Aspen REquil reactor based on
in Table  3. At an STR temperature of 650 ℃, SGR of
previous related study by Ortiz et al. [18]. The reactor was
9, and pressure of 1 bar, the conversion of glycerol was
designed to run at a minimal pressure drop under isothermal
found to be almost 100% when Eq. 13 is used [43]. The
circumstances. The crude methanol was then condensed by
same operating conditions were used in this study since
cooling the product stream (S-13) to 45 ℃. After cooling,
these variables (temperature, SGR, and pressure) have
the exit stream was fed to a flash drum (V-101) where the gas
been identified as the most beneficial for glycerol STR by
and liquid components were separated at 45 ℃ and 38 bar,
several authors, including Ali [48] and Dang et al. [35].
respectively [56]. In order to increase the overall conversion
The SN value derived from this process is found to be 1.34
of CO to methanol, the gas was compressed further with a
using the flowrates of the syngas components (­ H2, CO, and
multi-stage compressor and then recycled. In addition, to
­CO2). It can be shown that the PSA system has improved
prevent the build-up of inert gases, mostly methane, 1% of
SN value to 2 using the stream S-8 syngas component (see
the recompressed gas stream was purged off. The stream
Table 3). The ideal syngas stoichiometric ratio for the
carrying the crude methanol (S-16) was introduced into the
synthesis of methanol is within the range of this SN value
purification stage, where it is removed from dissolved gas
[2, 18]. It is designed for a ratio of 2 to reduce the molar
and water.
proportion of water, thereby limiting its adsorption onto
the catalyst, thus, improving the efficiency of methanol
3.6 Methanol purification section
synthesis [58].
Fuel grade and AA grade methanol are the two different C3 H8 O3in − C3 H8 O3out
forms of methanol available [57]. Three distillation setups C3 H8 O3conversion = × 100% (13)
C3 H8 O3in
can be employed for grade AA methanol. Among these are
two-column distillation, which is a low-cost unit, three- Table 3 shows that glycerol, methyl oleate, and metha-
column distillation, which is utilized in low-energy sys- nol were detected in very small amounts in the output
tems, and four-column distillation, which combines the stream (SYNGAS), indicating that these substances were
three-column distillation with a recovery column. One- the main compounds involved in the glycerol STR reac-
column distillation is required for methanol of the fuel tion. The output syngas stream has flow rates of 418.6
grade. In both grades of methanol, there cannot be any kmol/hr, 40.6 kmol/hr, 155 kmol/hr and 0.7 kmol/hr
dissolved gases [57]. Dissolved gases were discovered to which is equivalent to 30.1 mol%, 2.9 mol%, 11.2 mol%,
be present in S-16, hence, the two-column distillation was and 0.05 mol% of ­H 2, CO, ­CO 2, and ­C H 4, respectively.
employed in this study. To remove dissolved gas, the first Asides from the impurities, the water exiting the STR

13
 Biomass Conversion and Biorefinery

Table 3  Balance around the STR section PSA section

STR and PSA sections
Components Input (CG) (kmol/ Output (SYNGAS) Output (S9) (kmol/hr)
hr) (kmol/hr)

Glycerol ( 𝐂3 𝐇8 𝐎3) 62.89 1.5E-28 0

Methyl oleate (𝐂19 𝐇36 𝐎2) 0.35 0 0
Alkali ( 𝐍𝐚3 𝐏𝐎4) 1.66 1.66 0.29
Water ( 𝐇2 𝐎) 34.04 773.88 0
Methanol ( 𝐂𝐇3 𝐎𝐇) 1.06 3.13E-07 5.48E-8
Carbon monoxide ( 𝐂𝐎) 0 40.57 40.56
Carbon dioxide ( 𝐂𝐎2) 0 155.01 27.13
Hydrogen ( 𝐇2) 0 418.64 162.75
Methane ( 𝐂𝐇4) 0 0.70 0.012
Total (kmol/hr) 100 1390 231
Total (kg/hr) 6814 23,028 2706
SN 1.34 2.00

Table 4  Reactant conversion per pass and product yield at higher temperatures, whilst ­CO2 hydrogenation seems
to be the main channel at lower temperatures. Therefore,
Operating Conditions
at the reactor’s designated temperature, significant CO
  Temperature (℃) 250
conversion is required. The standard operating condi-
  Pressure (bar) 80
tions for the methanol synthesis are between 220—280
Syngas Conversion Per Pass
℃ and 50.7—101.3 bar [18, 31, 59–61]. Beyond 280 ℃,
  ­H2 36%
the catalyst would be prone to sintering and fusion [18],
  CO 81%
which would permanently damage the catalyst. In contrast,
  ­CO2 25%
lowering the reaction temperature favours the right shift in
Product Yield
equilibrium even though it significantly lowers the reaction
  Methanol Produced (kg/hr) 2007
rate. Consequently, the operating temperature is a com-
  Methanol Produced (kmol/hr) 62.6
promise, hence, 250 ℃ would be employed in this study
  Yield ­(kgMeOH/kgCG) 0.29
to investigate the conversion of the syngas components.
Recycle Stream (kmol/hr)
Higher pressures result in equilibrium conversion- ben-
  Methanol Recycled 3.4
efit for methanol synthesis, however, the increase above
  ­H2 Recycled 221.5
80 bar is not significant [18, 31]. Nonetheless, the effect
  CO Recycled 8.4
of varying the synthesis temperature and pressure was also
  ­CO2 Recycled 52.3
investigated in the subsequent section.
From the result presented in Table 4, the CO to metha-
nol conversion per pass was found to be 81% while ­CO2
section was around 55.7 mol% which was condensed out to methanol was around 25%. Since methanol synthesis is
of the system before introducing the gas stream into the a reversible reaction, Ortiz et al. [18] claimed that these
PSA section. The detailed material and energy balance conversions are caused by thermodynamic constraints.
around all the sections can be found in Tables S2-S5 (see The methanol produced is around 2007 kg/hr which is
supplementary information). equivalent to 0.29 ­kgMEOH/kgCG. It can also be observed
in Table 4 that at high conversions, the recycling rate tends
4.2 Methanol reactor syngas component to be very low. Low amounts of these unreacted compo-
conversion and methanol yield nents were recycled back in the equilibrium reactor when
compared to stoichiometry reactor observed by Ortiz et al.
As earlier mentioned, Aspen Plus REquil reactor was [18] with 20% and 3% CO and ­CO2 conversions per pass
employed in simulation the methanol production pro- respectively. In addition, Lücking [50] and Leonzio [53]
cess. The conversion per pass of the participating syn- both observed from their experiments that all the reactants
gas components (­ H2, CO, and C
­ O2) were investigated and react to generate methanol when SN is equal to 2, this was
presented in Table 4. In order to produce methanol, CO also the case in this study where all the syngas components
hydrogenation was observed to be the main mechanism participated in the methanol synthesis process.

13
Biomass Conversion and Biorefinery

4.3 Sensitivity analysis results temperature from 625 °C to 725 °C leads to an insignifi-

cant reduction in the H ­ 2 composition. Adeniyi and Ighalo
Critical operational parameters can be determined with the [43] also verified that ­H2 production was favoured as the
help of sensitivity analysis. In this section, sensitivity analy- STR temperature increased up to a certain point. However,
sis was used to assess how two factors affected the reform- according to Remón et al. [34], the best temperature for pro-
ing of crude glycerol and two other variables that affected ducing ­H2 was found to be between 600—650 ℃ (the peak
the synthesis of methanol. While crude glycerol flow was operating temperature) which was also confirmed in this
maintained constant at 100 kmol/hr, the flowrate of water study. As a result, when the temperature was raised above
for the STR process varied from 300 to 1200 kmol/hr. In 650 ℃, less ­H2 was produced. The ­H2 combustion process
the STR section, the effects of SGR and STR temperatures could possibly be responsible this decline at high tempera-
syngas composition were investigated between 3—12 and tures [49]. In order to ascertain this, varying the temperature
600—725 °C respectively. The reaction temperature and was also carried on at an SGR of 9 as shown in Fig. 3b. At
pressure were the two variables employed in the methanol 650 ℃, the same scenario also occurred where H ­ 2 production
synthesis section. Investigations were done into how vary- peaked, however, it was less pronounced here. According to
ing these parameters affected the methanol synthesis and Yus et al. [62], the molar proportion of C ­ H4 drops as tem-
the conversion of the main syngas components (i.e., H ­ 2, CO, perature increases. This was also seen in this investigation.
­CO2, and ­CH4). There were insignificant C ­ H4 produced at STR temperatures
above 600 ℃. This is also confirmed by Picou [45] and Silva
4.4 Effect of Steam Reforming (STR) Temperature et al. [36], who both reported that the exothermic nature of
on syngas composition the methanation reaction makes the C ­ H4 production insig-
nificant at temperatures above 600 ℃. Thus, in order to pre-
In the STR section, the temperature was the most examined vent the creation of C
­ H4 and coke, the STR of crude glycerol
parameter, and its effect on syngas composition are deter- must be carried out at high temperatures. From both Fig. 3a
mined. This effect was investigated at two SGRs (6 and 9) & b, it can also be observed that while the composition of
that have been established in literature [37, 45, 46] as the ­CO2 declines as the STR temperature increases. Contrary
best for syngas production for methanol synthesis via steam to the C­ O2 composition, the CO composition in the syngas
reforming. However, the effect of other SGRs values is also stream increased as the STR temperature increases from 600
investigated in subsequent sections. The effect of STR tem- ℃—725 ­CO2. Ismaila et al. [38] confirmed the observation
perature is illustrated in Fig. 3. as well, the authors confirmed in their study that increas-
From Fig. 3a., it can be seen that there was slight change ing temperature resulted in low ­CO2 selectivity and high ­H2
in ­H2 composition as the temperature increases from 600 and CO selectivity. Further research by Cheng [41] revealed
℃ and 625 ℃ which is consistent with the assertions made that CO production is accelerated at high temperatures. The
by Silva et  al. [36]. An additional increase in the STR improved syngas stoichiometric ratio, brought on by the high

Fig. 3  Effect of STR temperature on the syngas composition at (a) SGR = 6 (b) SGR = 9

13
 Biomass Conversion and Biorefinery

yields of H
­ 2 and CO, may be the source of the increase in the production process, hence, ­H2 peak production STR tem-
rate of methanol synthesis. Being highly endothermic, glyc- perature (i.e., 650 ℃) was taken as the reference point. In
erol STR requires high temperatures, moderate pressures, addition, since the objective of this methanol production,
and partially high SGR in order to achieve high conversion. an SGR of 9 were adopted in this study. At SGR of 9, all
the syngas components are in moderate quantities hence,
4.5 Effect of Steam‑to‑glycerol Ratio (SGR) using this value, the cost of excess C
­ O2 cleaning is moder-
on syngas composition ate, and almost all other components were used all in the
methanol production process after recycling.
From the previous section, we observed that ­H2 production
peaked at 650 ℃, hence, the effect SGR on syngas compo- 4.6 Effect of methanol synthesis temperature
sition was determined at STR temperatures of 625 ℃ and on syngas conversion and product yield
650 ℃. According to Ali [48], high SGR glycerol STR is
required to get high conversion. Since STR is an endother- The temperature and pressure of the methanol synthesis
mic and reversible reaction, it indicates that there is little reaction, the type of catalyst employed, the type of reac-
product production since the products are changed back to tor, and many other factors can all have an impact on the
reactants after attaining equilibrium. Le Chatelier's principle production of methanol [1, 43]. This section examines
was used by Ravuru and Patel [63] in their investigation in the effect of changing the temperature of the methanol
an effort to boost the conversion of glycerol by raising the synthesis reaction while maintaining the base pressure of
concentration of one of the reactants. 80 bar and also a commonly used pressure of 75 bar for
Figure  4a and b shows the syngas component (­H 2, effective comparison. The entire process of the methanol
CO, ­CO 2, and C ­ H 4) all reduced with an increase in the production process is exothermic. Laitinen [61] asserts
SGR. However, high SGR help the methane reforming that the production of methanol takes place between
and water–gas-shift reactions progress toward the forma- 220—280 ℃. As a result, a 5 ℃ increment was used in
tion of H
­ 2 [45]. One explanation for the drop in syngas the sensitivity analysis. The conversion of C ­ O2 and CO
composition at higher SGR could be that beyond equi- as well as the production of methanol as a function of
librium, the reverse reaction was favoured (see Eq. 1 and temperature during the methanol synthesis process are
Eq. 4). Silva et al. [36] reported similar findings when shown in Fig. 5a and b.
examining how SGR affected syngas composition, noting Since the production of methanol takes place in the
a decline in the syngas composition. On the other hand, gaseous phase, it stands to reason that if the reaction tem-
lower SGRs are less problematic economically because perature is raised, the rate of reaction will also increase,
the glycerol produced from the biodiesel synthesis process leading to a high amount of products being produced.
contains a small amount of water [36]. Even though H ­ 2 is This is due to the fact that rising temperatures make gas
not the target product in this study, it is required in syngas particles more kinetically energetic, which causes them
production which ultimately participates in the methanol to travel more quickly and collide with the container's

Fig. 4  Effect of SGR on the syngas composition at (a) STR = 625 ℃ (b) STR = 650 ℃

13
Biomass Conversion and Biorefinery

Fig. 5  Effect of temperature on syngas conversion and methanol production (a) at 75 bar (b) at 80 bar

wall more frequently, producing a massive volume. favourable for the synthesis of methanol, and this is
Charles' Law can also be used to explain this, unfortu- observed at both 75 bar and 80 bar as shown in Fig. 5.
nately, this is not the case with the methanol production Chemical equilibrium can be compromised with tempera-
process. Low amounts of methanol are synthesized at ture [61]. Since lower temperatures result in a higher
high temperatures because the conversion of the syn- equilibrium yield for methanol and vice-versa, optimum
gas components (­ H 2, CO and ­CO 2) reduced. Izbassarov temperature control is essential for the proper operation
et al. [64] claimed that the trend seen can be explained of a methanol synthesis reactor due to the overall severity
by the fact that methanol synthesis is predominantly an of the temperature effect [65].
exothermic process, which implies that increasing the
temperature reduces the equilibrium and consequently 4.7 Effect of methanol synthesis pressure on syngas
methanol production drops. conversion and product yield
Generally, due to thermodynamic constraints, the effi-
ciency of methanol production is reduced at high tem- At the adopted temperature (250 ℃) and also at the widely
peratures [54]. As a result, low temperatures are more used temperature (265 ℃) in methanol production, the

Fig. 6  Effect of pressure on syngas conversion and methanol production (a) STR = 250 ℃ (b) STR = 265 ℃

13
 Biomass Conversion and Biorefinery

effect of pressure on syngas component conversion and 0.32

methanol synthesis was investigated. As shown in Fig. 6a

0.31
and b, pressure significantly affects the rate of methanol

Methanol Yield (kgMeOH/kgCG)

production as well as the conversion of the syngas com- 0.3
ponents. The pressure and syngas component conversion
have a proportionate relationship because as pressure 0.29
increased, the conversion of H ­ 2, CO and C
­ O 2 increased
as well, resulting in a higher methanol yield. A similar 0.28

result was reported by Adji et al. [66], who observed that

220 225 230
the production profile of methanol increased with an 0.27
235 240 245
increase in the reactor pressure. The hydrogenation of CO 250
265
255
270
260
275
0.26
and ­CO2 reaction continues at higher pressures, according 280

to Kiss et al. [67], which is favourable for methanol syn- 0.25

thesis. This explains the observations when the pressure 50 60 70 80 90 100 110

was varied from 50—110 bar. At 250 ℃, the conversion Pressure (Bar)

of CO goes from 62%—89% and that of ­CO2 goes from
16%—34% however, at 265 ℃ there was reduction in both Fig. 7  Effect of both temperature and pressure on methanol produc-
the CO and ­CO2 46%—81% and 13%—29% respectively tion
as shown in Fig. 6. Methanol production was more pro-
nounced at high pressure, but it should be emphasized from Tamošiūnas et al. [54], was employed. Purity B and
that these pressures also increase energy demand invest- Purity C were obtained from Odoom [69] and Remón
ment costs, and safety concerns for the reactor [35, 64]. [34] experimental studies respectively. The yield from
Samimi et al. [68] found out from their experiment that the reactors as well as overall yield of methanol for each
even though high pressures are favourable for the syn- purity of crude glycerol were computed as shown in
thesis of methanol, significant amounts of water are also Table 5. Purity C produced the highest methanol yield
produced as catalyst poisoning during the procedure [68]. with 40.1 wt.% which is equivalent to 0.34kgMeOH/kg CG.
Adji et al. [66], emphasized that the operating pressure The methanol achieved in purities A and B were found
must be kept as low as feasible to reduce capital expen- to be 34.6 wt. % and 36.4 wt.% respectively. In addition,
ditures. Hence, production of methanol at any moderate Purities A and B have the highest methanol concentra-
pressure is recommended. tion in the final products stream as shown in Table  5
with 98% and 99% respectively. However, looking at the
4.8 Methanol yield at different temperatures methanol concentration in the initial concentration of
and pressures methanol in the crude glycerol and final methanol pro-
duced, the process of steam reforming will not be viable
The effects of pressure and temperature on the synthesis for crude glycerol with high methanol concentration.
of methanol were examined in the preceding subsections.
Due to thermodynamic restrictions, it was shown that 4.10 Economic analysis
methanol production is favourable at low temperatures
and high pressures. Figure 7 shows the effect of changing An economic analysis was carried out to determine the
the temperature and pressure of the methanol synthesis profitability of the refined key product (methanol). The
reaction on methanol yield. As mentioned earlier, the water condensed out of the syngas as well as the hydro-
standard operating conditions for the methanol synthesis gen fuel produced from the PSA process were also con-
are between 220—280 ℃ and 50.7—101.3 bar [18, 31, sidered as by-products from the process. A plant capac-
59–61]. However, at temperatures above 280 ℃, the cata- ity of 6.8 tonnes/hr of crude glycerol feed for a 20-year
lyst would be prone to sintering and fusion, which would plant lifetime was investigated in this study. The overall
permanently damage the catalyst [18, 68]. economic analysis was broken down into three key areas
which include cost assessment, profitability analysis
4.9 Commercial viability using the key economic performance indicators (i.e., the
net present value (NPV), return on investment (ROI), dis-
To ascertain the viability of the process commercially, counted payback period (DPBP), and the net production
three different purities of crude glycerol from differ- cost (NPC)) and finally sensitivity analysis. The data for
ent experimental studies were employed using the same the analysis are available in the supporting documents
process condition. As the base case, Purity A obtained (see costing and economics supplementary information).

13
Biomass Conversion and Biorefinery

Table 5  Effect of different crude glycerol purities on the commercial viability of the methanol synthesis process
Purity A Purity B Purity C
CG Composition (wt.%) CG Composition (wt.%) CG Composition (wt.%)

Glycerol 85 Glycerol 45.6 Glycerol 63.2

Methanol 0.5 Methanol 11.2 Methanol 34.4
Methyl oleate 1.5 Oleic acid 3.8 Acetic acid 0
Alkali (soap) 9 Soap 29.1 Ashes 2.06
Water 4 Water 8.3 Water 1.63
Sodium chloride & potassium - Sodium chloride & potassium 2 (1% each) Sodium chloride & potassium -
chloride chloride chloride
CG Inlet (kmol/hr) 100 CG Inlet (kmol/hr) 100 CG Inlet (kmol/hr) 100
CG Inlet (kg/hr) 6814 CG Inlet (kg/hr) 6549 CG Inlet (kg/hr) 5363
R-102 inlet stream (kg/hr) 5800 R-102 inlet stream (kg/hr) 3680 R-102 inlet stream (kg/hr) 4471
Methanol produced (kg/hr) 2007 Methanol produced (kg/hr) 1340 Methanol produced (kg/hr) 1794
Reactor yield (wt.%) 34.6 Reactor yield (wt.%) 36.4 Reactor yield (wt.%) 40.1
Overall yield (­ kgMeOH/kgCG) 0.29 Overall yield ­(kgMeOH/kgCG) 0.21 Overall yield ­(kgMeOH/kgCG) 0.34
Purified Methanol Concentration 98.2 Purified Methanol Concentration 97.6 Purified Methanol Concentration 99.1
(wt.%) (wt.%) (wt.%)

4.11 Cost assessment equipment costs were adjusted for the required capacity
to estimate the present values of the equipment as shown
The equipment cost estimation as well as the raw materi- in Eq. 14.
als and product cost assessment were all carried out using
CIya Aya n
( ) ( )
Aspen Plus v11 software. The cost of the main reactors Cya = Cyb × (14)
(steam reformer and methanol synthesis reactor) were CIyb Ayb
estimated from actual commercial quotations and costs
where CI is the cost index, yb and ya are the base year (2018
present in literature [1, 70]. These costs were updated to
in this case) and current year (2022 in this case), C is the
present value using the widely used chemical engineer-
equipment cost, A is the equipment capacity, n is the cost
ing plant cost index (CEPCI) [71]. In addition, the main

Fig. 8  Fixed capital investment

breakdown
Design & Engineering 9%
Contractor’s fee 5%
Conngency 9%
Buildings, process 3%
Electrical 3%
Ancillary buildings 6%
Site development 3%
Equipment Installaon 12%
Storages 3%
Ulies 6%
Instrumentaon & Control 9%
Piping 19%
Main Equipment 29%

0% 5% 10% 15% 20% 25% 30% 35%

13
 Biomass Conversion and Biorefinery

Fig. 9  Equipment cost breakdown by (a) main equipment (b) main sections

exponent. A plant cost index of 806.3 was employed for the The main contributors to the TCI are the compressors, steam
year 2022 [72]. reforming reactor, and the methanol purification distillation
For the cost analysis, the total capital investment (TCI) columns (see Fig. 9a.). Figure 9b shows the breakdown of
and the annual production cost (APC) were all investigated. the equipment cost as a function of the sections in the metha-
The TCI is estimated by summing the fixed capital invest- nol production process. The syngas cleaning (PSA) process
ment (FCI) (see Fig. 8 for FCI breakdown) and working is the most expensive, it represents 49% of the cost of the
capital (WC) and this was computed to be $43.3 million. processes involved in the methanol production process.

Fig. 10  Annual production cost breakdown

13
Biomass Conversion and Biorefinery

Fig. 11  Effect of ± 20% variation on the KPIs

Meanwhile, the cost of methanol purification was the least 4.12 Profitability analysis using the Key Economic
expensive and it represents just 6% of the whole process. Performance Indicators (KPI)
The steam reforming as well as the methanol synthesis pro-
cesses represents 22% and 23% respectively as shown in As mentioned earlier, the KPIs considered in this study
Fig. 9b. include the ROI, NPV, DPBP, and NPC. The economic
The APC on the other hand includes the fixed cost (FC), options employed include a 28% tax rate, 6% average
the variable cost (VC), research and development, sales annual inflation rate and a 3.5% annual loan interest rate
expenses, and general overheads costs. The APC was esti- over a 20-year project life (including the construction
mated to be around $38.9 million. The estimated FC was period) using South African rates as a base scenario.
around $11 million and the breakdown include maintenance, Other economic parameters employed in this analysis can
salaries, insurance, taxes, supervision, capital charges, roy- be found in Table S19 (see supporting document). For
alties, and laboratory cost. The VC was estimated to $17.8 the process to be profitable the minimum selling price of
million while the other costs involved in the APC was esti- methanol was set at $846/ton while the hydrogen was set
mated to $10.1 million. The breakdown of the APC com- at $5000/ton. The MSP of both methanol and hydrogen
ponents is shown in Fig. 10. The cost of the raw materials produced from steam reforming process are within the
(crude glycerol and water), the assumed cost of the product observed MSP from previous related studies [31–33, 73].
(methanol) and byproducts (hydrogen and water), and the The NPV, ROI, DPBP, and NPC from the process were
hazardous and non-hazardous wastes employed in this study estimated to be $74.2 million, 17%, 4.59 years, and 85₵/
are available in the supporting document (Table S10). In kgMeOH respectively. In addition, the hydrogen produced
addition, since only a very small quantity of methane was contributed to 48% of the total revenue from the pro-
recovered from the PSA, it was considered to be used up in cess, if the revenue from hydrogen is excluded, the NPC
the reactor furnace [18]. of methanol from the process is around $2.1/kg MeOH .

13
 Biomass Conversion and Biorefinery

Considering the TCI and other economic trade-offs, the From the economic assessment carried out, the net
production of methanol from steam reforming of crude present value (NPV), the return on investment (ROI), the
glycerol is proven to be economically feasible. discounted payback period (DPBP) and the net production
cost (NPC) show that methanol produced from the syngas
4.13 Sensitivity analysis using the Key Economic derived from steam STR process combined with PSA pro-
Performance Indicators (KPI) cess is economically feasible. The sensitivity analysis shows
that the revenue is the most sensitive variable. Hence, a
Parameters such as the fixed capital investment (FCI), cost minimum selling price of 85₵ per kg of methanol was the
of manufacturing (COM), cost of raw materials, the rev- most feasible for the production of methanol from crude
enue, the working capital, the income tax rate, the interest glycerol STR process. In addition, since the production of
rate, the current inflation rate, the discount rate, operating by-products hydrogen and methane from the syngas clean-
labour cost, and finally, the utilities and heat exchanger ing process are inevitable, further investigation from the
network cost were all analyzed over a ± 20% variation in STR process should be investigated. Also, future studies
the KPIs. From the analysis, the revenue from the sales of could also consider the trade-offs between producing meth-
the product and by-products, the cost of manufacturing anol from other renewable sources.
(COM), the cost of raw materials, as well as FCI were
Supplementary Information  The online version contains supplemen-
the most sensitive variables as shown in Fig. 11. It was tary material available at https://​doi.​org/​10.​1007/​s13399-​023-​04024-z.
observed that the selling price of methanol must not go
below the estimated price (85₵/kgMeOH). From the simula- Acknowledgements  The authors would like to thank the University of
tion, prices below this will have a significant effect on the Johannesburg for its support.
profitability/economic feasibility of the project. The least Authors contribution  P.C. Kgwedi: Conceptualization, Methodology,
sensitive variables are the working capital, loan interest Investigation, Formal Analysis, Software, Writing – original draft.
rate and the discount rate. N. Seedat: Conceptualization, Supervision, Investigation, Writing –
reviewing and editing. L.I. Fajimi: Software, Validation, Economic
Analysis, Writing – final draft. B.O. Oboirien: Visualization, Writing
– reviewing and editing. B. Patel: Conceptualization, Writing – review-
5 Conclusion ing and editing.

Aspen Plus was able to simulate the production of metha- Funding  Open access funding provided by University of Johannesburg.
nol from crude glycerol, proving the technical viabil-
ity of the process. To determine the effects of the key Declarations 
operating conditions which include: STR temperature, Conflict of interest  The authors declare no conflict of interest.
steam-to-glycerol ratio (SGR), methanol synthesis pres-
sure, and methanol synthesis temperature, a sensitivity Open Access  This article is licensed under a Creative Commons
Attribution 4.0 International License, which permits use, sharing,
analysis was carried out on the reforming and methanol adaptation, distribution and reproduction in any medium or format,
synthesis section. It was observed that high methanol as long as you give appropriate credit to the original author(s) and the
yield was obtained as a result of high ­H2 and CO conver- source, provide a link to the Creative Commons licence, and indicate
sion. Despite the economic performance of the limited if changes were made. The images or other third party material in this
article are included in the article's Creative Commons licence, unless
number of commercial biorefineries as well as the global indicated otherwise in a credit line to the material. If material is not
technological developments, biorefineries still face sub- included in the article's Creative Commons licence and your intended
stantial uncertainty due to the fluctuations in market use is not permitted by statutory regulation or exceeds the permitted
prices. Another key observation from this process is that use, you will need to obtain permission directly from the copyright
holder. To view a copy of this licence, visit http://​creat​iveco​mmons.​
for every 100 kmol of crude glycerol processed through org/​licen​ses/​by/4.​0/.
STR, 0.21—0.34 ­k g MeOH /kg CG can be obtained along
with high quantity of hydrogen (48%) and a little quan-
tity of methane (1%) which could either be used to fuel
the furnace or sold to obtain further revenue. The com- References
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Biomass Conversion and Biorefinery

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