Biofuels

Microwave furfural aldol condensation with acetone to biofuel intermediates over a

potassium promoted waste red mud-derived catalyst
--Manuscript Draft--

Full Title: Microwave furfural aldol condensation with acetone to biofuel intermediates over a
potassium promoted waste red mud-derived catalyst

Manuscript Number: TBFU-2024-0319

Article Type: Original Article

Keywords: furfural; aldol condensation; fuel intermediates; red mud; waste utilization

Abstract: Extending the carbon chain length and removing oxygenated species from furfural (FU)
to make it suitable for hydrocarbon fuels is a challenging task. Aldol condensation is a
promising approach to enhance the potential of furfural into fuel intermediates. We
developed a base catalyst from industrial waste red mud (RM) by modifying its surface
through acid treatment, potassium (K) doping, and thermal treatment at 800 oC. The
resulting 15K-AWRM catalyst featured a mesoporous structure with a notable basic
site density of 0.67 mmol g-1. The increase in basic sites was attributed to the
formation of K2O species within the catalyst, confirmed by XRD and CO2-TPD
analysis. This increase in basic sites after K doping correlated positively with the
catalyst's efficiency for the aldol condensation. Using microwave heating, the 15K-
AWRM catalyst achieved 99% FU conversion, with selectivity to C8 product 4-(2-furyl)-
3-buten-2-one (FAC) and 1,4-pentadien-3-one-1,5-di-2-furanyl (FA2C) at 40% and
11%, respectively. These results were observed at a low reaction temperature and time
of 90 °C and 30 minutes, respectively, due to the rapid and uniform microwave heating
combined with the high activity of the catalyst. The catalyst demonstrated appreciable
stability, maintaining performance through up to four reuses with only minor changes in
activity.

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Microwave furfural aldol condensation with acetone to biofuel intermediates over a

potassium promoted waste red mud-derived catalyst
Abstract:

Extending the carbon chain length and removing oxygenated species from furfural (FU) to

make it suitable for hydrocarbon fuels is a challenging task. Aldol condensation is a promising

approach to enhance the potential of furfural into fuel intermediates. We developed a base

catalyst from industrial waste red mud (RM) by modifying its surface through acid treatment,

potassium (K) doping, and thermal treatment at 800 oC. The resulting 15K-AWRM catalyst

featured a mesoporous structure with a notable basic site density of 0.67 mmol g-1. The increase

in basic sites was attributed to the formation of K2O species within the catalyst, confirmed by

XRD and CO2-TPD analysis. This increase in basic sites after K doping correlated positively

with the catalyst's efficiency for the aldol condensation. Using microwave heating, the 15K-

AWRM catalyst achieved 99% FU conversion, with selectivity to C8 product 4-(2-furyl)-3-

buten-2-one (FAC) and 1,4-pentadien-3-one-1,5-di-2-furanyl (FA2C) at 40% and 11%,

respectively. These results were observed at a low reaction temperature and time of 90 °C and

30 minutes, respectively, due to the rapid and uniform microwave heating combined with the

high activity of the catalyst. The catalyst demonstrated appreciable stability, maintaining

performance through up to four reuses with only minor changes in activity.

Keywords: furfural; aldol condensation; fuel intermediates; red mud; waste utilization
1. Introduction

The dwindling supply of traditional fuels like natural gas, coal, and petroleum has encouraged

the exploration of innovative chemical processes dependent on renewable sources, primarily

biomass, and its derivatives, for fuel and chemical production [1,2]. With escalating concerns

over the high cost and security risks of fossil fuels, as well as environmental considerations,

there is a growing imperative to transition towards more efficient energy consumption and

renewable energy alternatives [3]. Generally, biomass feedstock is hydrolyzed to yield

monosaccharides, which are then selectively catalyzed and dehydrated in acidic conditions to

produce platform chemicals such as furfural and 5-hydroxymethylfurfural [4–6]. Furfural (FU)

is a biomass-derived chemical with five carbon atoms and two oxygen atoms. The high oxygen

content in furfural makes it unsuitable for direct application as a fuel/fuel intermediate,

demanding modifications in terms of removing oxygen content or increasing carbon length for

its use as fuel/fuel intermediates [7]. To maximize the furfural’s potential as a platform

chemical, researchers have investigated its aldol condensation with acetone to fuel-range

intermediate molecules such as 4-(2-furyl)-3-buten-2-one (FAC) and 1,4-pentadien-3-one-1,5-

di-2-furanyl (FA2C) (Scheme 1) [8–10]. Furfural and acetone, originating from biomass

compounds, can engage in aldol condensation reactions catalyzed by acidic or basic catalysts.

The direct asymmetric aldol reaction emerges as a pivotal method for forming crucial C-C

bonds in organic synthesis, yielding products of substantial importance in pharmaceuticals,

agrochemicals, and fine chemicals industries [11–13].

The choice of catalyst significantly influences the outcome of aldol condensation reactions,

affecting conversion rates, selectivity, and overall yield of aldol condensation products (FAC

and FA2C). Typically, these reactions employ either heterogeneous or homogeneous catalysts,

with solid catalysts offering distinct advantages such as simplified product separation, reduced

equipment corrosion, and the ability to recycle and reuse the catalyst. Various solid catalysts
including dolomite, Mg/Fe, KF/g-Al2O3, zeolites, MgO/NaY, carbon-based solids, and Al/Mg

mixed oxides have been utilized for upgrading biofuels. Generally, basic catalysts tend to yield

more favorable results compared to acidic ones. Natural dolomitic rocks have been shown to

catalyze furfural aldol condensation with acetone at 150 oC and 1 h with a 72% aldol products

yield [14]. Modified zeolites, possessing either basic or acidic properties, have also been

explored for aldol condensation. For instance, nitrogen-substituted NaY could produce almost

60% FU conversion with 100% selectivity to aldol products and demonstrated higher

selectivity to monomer aldol products compared to MgO-ZrO2 because of their smaller cage

size [15]. K2O and N-doped carbon exhibited approximately 96% FU conversion with an

exceptional selectivity of 90% to FAC at 100 °C [16]. The synergistic effect between highly

basic K2O clusters and N-modified carbon was reported to produce a high activity for the aldol

condensation process [16]. Sn-MFI and Sn-Beta zeolites exhibited excellent catalytic activity,

with Sn-MFI zeolite producing monomer aldol products exclusively [17]. However, the yield

of monomer aldol products was limited to less than 60% due to the formation of byproducts at

160 °C [17]. Despite their effectiveness, basic catalysts are prone to deactivation by coke

deposition and active sites leaching [18,19]. Moreover, high reaction temperatures and times,

and high cost of metals can negatively impact the economic feasibility of aldol condensation

processes using such catalysts [9–11]. Consequently, research focusing on optimizing solid

basic catalyst properties and exploring alternative, low-cost earth-abundant solid catalysts for

aldol condensation reactions is highly important.

In the recent past, researchers have shown high interest in utilizing various wastes for catalyst

synthesis [20–22]. Red mud (RM) is an aluminum industry’s byproduct generated during the

alumina extraction from bauxite using the Bayer process [22,23]. Worldwide, approximately

130 million tons of RM are generated annually[22]. With a high pH (12-13) and the possibility

of minute radioactive elements, RM is classified as hazardous waste [24]. However, its

composition, notably including Fe, along with Al, Ti, and Si, could actively catalyze various

chemical processes, rendering RM a promising catalyst material [22]. Despite this potential,

RM's application as a catalyst or catalytic support remains largely unexplored, particularly in

aldol condensation reactions. Given that Fe, Al, Si, and Ti elements known to act as catalysts

in aldol condensation are present in RM, it holds promise as a suitable material for facilitating

such reactions.

In this study, to utilize the potential of RM as a catalyst, we have developed an active catalyst

from it by incorporating potassium (K) onto its surface. This K-incorporated red mud catalyst

was utilized in the microwave-assisted furfural aldol condensation reaction with acetone,

resulting in the production of valuable products FAC and FA2C. Microwave heating, known

for its rapid and uniform nature, has been shown to significantly reduce reaction times in

various chemical processes and enhance overall process efficiency [25]. Notably, the K-

incorporated catalyst represents a novel advancement in aldol condensation catalysis. To

understand the catalyst's performance, we conducted thorough characterization using

techniques such as XRD, CO2-TPD, FESEM, FESEM-EDX, and BET, establishing a structure-

activity relationship. Furthermore, we extensively studied reaction parameters including

temperature, catalyst loading, and furfural to acetone molar ratio, identifying optimized process

conditions. This research marks a significant step towards advancing the circular economy of

industrial waste while simultaneously addressing the synthesis of sustainable fuels from

unconventional biomass resources.

2. Material and Methodology

2.1. Materials

Red mud was supplied by National Aluminum Company Limited, Odisha, India. It was dried

at 100 oC and ground to approximately 200 µm. Furfural (≥98%), acetone ((≥99.5%), HCl
(37%), and potassium nitrate (KNO3) were procured from Merck Millipore India. 4-(2-furyl)-

3-buten-2-one (FAC) (98%) was purchased from Fisher Scientific, India.

2.2. Catalyst synthesis

The previously dried RM was acid-washed using 3 M HCl to remove unstable impurities and

to enhance its surface area. 6 g of RM was added to 30 mL of Millipore water, followed by the

addition of 60 mL of 3M HCl solution. The whole mixture was then stirred at 90 oC for 1 h. It

followed the dropwise addition of aqueous ammonia solution to the mixture under stirring until

a pH of between 7 and 8 was reached. The resulting precipitate was centrifuged and repeatedly

washed with warm water to eliminate any excess ammonia. Subsequently, the sample was dried

overnight at 100 °C. This acid-washed RM was designated as AWRM. Potassium was

incorporated on AWRM following the wet impregnation technique. 2 g of AWRM was added

to 60 mL of Millipore water and the mixture was stirred vigorously. To that solution, a known

amount of KNO3 as a K precursor was added slowly. It followed a continuous stirring of the

mixture for 3 h at room temperature. Afterward, the temperature was raised to 65 oC to allow

the excess water from the solution to evaporate. The mixture was then dried at 110 oC in an

oven for overnight. The catalyst after drying was calcined at 800 oC for 5 h to synthesize the

K-doped AWRM (XK-AWRM) catalyst where “X” represents K loading in weight percentage.

2.3. Catalyst characterization

The prepared catalysts underwent comprehensive physicochemical analysis using a series of

characterization techniques. X-ray diffraction (XRD) analysis was conducted using a Rigaku

SmartLab diffractometer, operating at 40 kV and 112 mA, utilizing Cu Kα radiation with a

0.154 nm wavelength and a 2-theta range of 10 to 80 degrees. Morphological examination was

carried out in a Zeiss Sigma-300 field emission scanning electron microscope (FESEM), while

elemental compositions were found using a Zeiss Sigma electron microscope instrument.
N2 adsorption-desorption analysis was performed to investigate surface properties such as

surface area, pore volume, and pore size of the catalysts employing a Quantachrome Autosorb-

IQ MP apparatus. Prior to analysis, samples were degassed at 180 °C for 3 h under helium gas

flow. Basicity assessment was conducted through CO2-temperature programmed desorption

(CO2-TPD) technique using a BELCAT II MicrotracBEL chemisorption apparatus. Catalyst

pretreatment under an inert atmosphere at 180 °C for 1 h preceded the analysis. Subsequently,

CO2 (50 mL/min) adsorption occurred at 50 °C for 1 h, followed by heating at 100 °C for 1 h

under a helium gas flow (30 mL/min) to remove excess CO2 from the surface of the catalyst.

CO2 desorption analysis between the temperatures 100 oC to 700 °C with a heating rate of 10

°C/min was performed, and desorbed CO2 at varying temperatures was monitored using a

thermal conductivity detector (TCD) integrated within the apparatus.

2.4. Microwave aldol condensation process

The furfural aldol condensation with acetone was conducted using a CEM Discover microwave

reactor. Furfural, acetone, and the catalyst were combined in a 10 mL glass vessel equipped

with an integrated magnetic stirring mechanism within the reactor. The reactant mixture was

heated to the reaction temperature using 120 W microwave power and kept for 30 minutes for

the reaction to happen. Upon completion of the reaction and cooling of the reactor temperature

to ambient levels, the product mixtures from the glass vessel were subjected to centrifugation

to separate different phases (liquid/solid) from each other. A detail procedure on the reaction

product analysis and catalyst stability test are mentioned in Supplementary file.

2.5. Aldol condensation reaction product analysis

The aldol condensation products were subjected to analysis using a gas chromatograph (GC)

(PerkinElmer: Calrus580). This GC was equipped with a Flame Ionization Detector (FID) and

used an Elite-5 capillary GC column for separation. The assessment of catalyst performance
included the determination of furfural conversion and the evaluation of selectivity towards

target products such as FAC and FA2C [10].

furfural reacted (mole)

Furfural conversion (%) = × 100 (1)
furfural taken (mole)

FAC produced (mole)

FAC selectivity (%) = furfural reacted (mole) × 100 (2)

2×FA2 C produced (mole)

FA2 C selectivity (%) = × 100 (3)
furfural reacted (mole)

2.6. Catalyst stability study

The catalyst’s stability study was performed by retrieving the spent catalyst from the reaction

product mixtures through centrifugation using a REMI R-24 (REMI, India) centrifuge.

Subsequently, the recovered catalyst underwent washing with acetone followed by drying at

120 °C for 12 h. The catalyst, after drying, was utilized for successive batches of reactions.

3. Results and Discussion

3.1. Catalyst activity

The activity of various prepared catalysts was tested for FU conversion and product (FAC and

FA2C) selectivity to understand the influence of K on catalyst performance. As shown in Fig.

1, AWRM exhibited minimal catalytic activity with only 14% FU conversion. However,

doping AWRM with 10 wt.% K (10K-AWRM) significantly increased FU conversion to 90%.

The selectivity for FAC and FA2C using 10K-AWRM was 51% and 7%, respectively.

Increasing the K loading to 15% further improved FU conversion to 99%, with selectivity of

40% for FAC and 11% for FA2C. The enhanced FU conversion after K introduction on AWRM

is likely due to the increased basic sites in the catalyst, as indicated by CO2-TPD analysis (Table

1). A similar correlation on basic sites with catalytic activity was also reported in earlier studies
[17,18,26]. Further increasing the K loading to 20 wt.% and 25 wt.% did not significantly alter

FU conversion. However, there was a decrease in FAC selectivity and a slight increase in FA2C

selectivity with higher K loading. This phenomenon could be attributed to the secondary

condensation of FAC with FU with the increased basic sites in the catalyst. The mesoporous

nature of the catalyst may also promote this secondary condensation, leading to FA2C

formation. Similar observations with basic oxides and shape-selective catalysts have been

reported previously [16,17]. At a K loading of 25%, the selectivity to both FAC and FA2C

decreased, likely due to the undesired polymerization of FAC and FA2C into cross-linked

heavier materials, as observed in earlier studies [27]. The findings demonstrate that K loading

on AWRM enhanced catalytic activity by increasing FU conversion. However, excessive active

sites from higher K loadings could lead to the formation of undesired polymerized products.

This observation demonstrates that the increased activity could be due to the basic sites

enhancement in AWRM through a synergistic interaction with K2O. Additionally, the

mesoporous nature of the catalyst could lead to easy access to the active sites for the reactants

to undergo reactions, resulting in a high FU conversion.

3.2. Catalyst properties

XRD analysis (Fig. 2) of both raw red mud (RM) and acid-activated red mud (AWRM)

revealed prominent peaks at 2θ angles of 33.02°, 35.6°, 41°, 49.6°, 54.1°, and 62.73°,

corresponding to the (104), (110), (113), (024), (116), and (214) planes of hematite (Fe2O3)

[28]. This suggests a predominant Fe2O3 surface composition in RM and AWRM. However,

AWRM exhibited a relative decrease in Fe2O3 phase crystallinity due to acid treatment [28].

Additionally, peaks corresponding to Al(OH)3, SiO2, and TiO2 could be seen at 18.5° (010),

26.5° (101), and 27.3° (110), respectively [28]. The XRD profiles of the XK-AWRM with K

loading between 10 wt.% to 25 wt.% is depicted in Fig. 2. It was noted that the predominant

hematite phases observed in AWRM started to diminish at higher K loading. This could be due
to surface masking caused by impregnated potassium. K2O crystalline phases with low

intensity emerged at 2θ of 19.8°, 32.3°, and 57.4° [29]. This suggests KNO3

decomposition/phase transformation to K2O on the catalyst surface at 800 oC. The intensity of

K2O peaks, particularly at 32.3o started to increase with the increase in the K loading, indicating

a gradual enhancement in the active K2O phase on the catalyst surface.

The CO2-TPD analysis (Fig. 3) was conducted to evaluate the basic site strength and density

of both the AWRM and 15K-AWRM catalysts. In the AWRM catalyst, the CO2-TPD analysis

revealed broad and low-intensity peaks at a temperature of 230 °C, corresponding to CO2

desorption from weak base sites in AWRM. No CO2 desorption at higher temperatures between

300 oC to 700 oC was observed, suggesting the lack of medium and strong basic sites in the

AWRM catalyst. In the 15K-AWRM catalyst, three CO2 desorption peaks at 353 oC, 467 oC,

and 567 oC were observed. The sharp and intense peak at 353 oC could be attributed to the

medium-strength basic sites in the 15K-AWRM catalyst. At a higher temperature of 467 oC,

the shoulder peak could be due to CO2 desorption from the moderately strong base sites,

whereas, the small and wider peak at 567 oC could be due to the CO2 desorption from relatively

stronger base sites in 15K-AWRM. The presence of CO2 desorption peaks at higher

temperatures in 15K-AWRM suggested relatively stronger base sites in the catalyst than

AWRM. The total base site density for AWRM and 15K-AWRM evaluated were 0.116 mmol

g-1 and 0.67 mmol g-1, respectively (Table 1). This observation demonstrated an increased

number of active base sites in the 15K-AWRM catalyst than AWRM, attributed to the surface

doping of potassium.

The morphology of various catalysts obtained from FESEM analysis are shown in Fig. 4. The

raw red mud (RM) morphology reveals small, clustered particles having random sizes and

structures. Notably, distinct pores were observed between these particles in the catalyst (Fig. 4

(a). Upon HCl treatment, the particles in AWRM exhibited comparatively smaller sizes and an
amorphous nature (Fig. 4(b)). Subsequent potassium doping, followed by calcination at 800

°C, restored crystallinity in 15K-AWRM (Fig. 4(c)), resulting in the formation of relatively

compact, larger particles with fewer pores compared to acid-washed red mud (AWRM). This

phenomenon could be due to the agglomeration process occurring in 15K-AWRM at a high

calcination temperature of 800 °C. Table 2 outlines the elemental composition of the 15K-

AWRM catalyst as determined through FESEM-EDX analysis. The analysis confirms the

presence of oxygen (O), iron (Fe), potassium (K), silicon (Si), and aluminum (Al) in the 15K-

AWRM catalyst. Fe, the major component of RM was found to be present in a higher quantity

than other elements in 15K-AWRM. The presence of K from the elemental analysis (FESEM-

EDX) also confirmed the doping of the element in AWRM.

The N2 adsorption-desorption isotherm (Fig. 5) of various synthesized catalysts exhibited a

type IV isotherm. This hysteresis loop's appearance in the catalysts could be due to capillary

condensation, which is a characteristic feature of mesoporous materials [28]. RM demonstrated

a modest surface area of 10 m2 g-1 (Table 3), alongside an average pore size of 16.2 nm and

total pore volume of 0.0279 cm3 g-1. The AWRM exhibited a surface area of 261 m2 g-1,

attributed to the elimination of impurities and other unstable elements from the RM during the

acid wash, leading to a significant enhancement in porosity. Conversely, the 15K-AWRM

catalyst exhibited a surface area of 16 m2 g-1 with an average pore size of 10.3 nm, which still

falls within the mesoporous range. However, the K doping and high-temperature (800 °C)

treatment could potentially block some pores and induce particle agglomeration (as observed

in the FESEM analysis, Fig. 4), resulting in a reduction in surface area.

3.3. Catalyst’s activity measurements

Experiments using the 15K-AWRM catalyst were performed in the temperature ranging

between 80 °C and 110 °C to study the temperature's impact on the aldol condensation process,
as shown in Fig. 6(a). While temperatures between 80 °C to 110 °C had a minimal effect on

FU conversion, they significantly influenced the selectivity of the products (FAC and FA2C).

FU conversions increased from 93% at 80 oC to 99% at 90 oC and remained between 97% and

99% above 90 oC. However, higher temperatures resulted in increased selectivity for FA2C.

For example, raising the temperature from 80 °C to 90 °C increased FA2C selectivity from 6%

to 11% and decreased FAC selectivity from 44% to 40%. Further temperature increases to 100

°C and 110 °C led to FA2C selectivity rising to 13% and 16%, respectively. These findings

suggested that higher temperatures favor the second condensation of FU with FAC over the

15K-AWRM catalyst, resulting in greater selectivity for FA2C and reduced selectivity for FAC,

while FU conversion remains largely unaffected. Similar observations regarding FU aldol

condensation have been reported in previous studies [14]. Additionally, further condensation

of products (FAC and FA2C) with FU at higher temperatures could lead to the formation of

undesired higher molecular weight polymerized products, decreasing overall selectivity to

FAC and FA2C. Previous studies have also identified the formation of such undesired

polymerized products [16,17].

Fig. 6(b) illustrates the impact of 15K-AWRM loading on the efficiency of the aldol

condensation process. Increasing the loading of 15K-AWRM from 6 wt.% to 15 wt.% relative

to FU weight had minimal effect on FU conversion, which remained between 93% and 99%.

The increase in FU conversion was insignificant, rising from 93% at 6 wt.% loading to 99% at

12 wt.% loading. However, changes in catalyst loading significantly affected FAC and FA2C

selectivity. Increasing 15K-AWRM loading from 6 wt.% to 9 wt.% reduced FAC selectivity

from 50% to 45% and slightly increased FA2C selectivity from 4% to 7%. Further increases in

catalyst loading to 12% and 15% decreased FAC selectivity to 40% and 30%, respectively, and

increased FA2C selectivity to 11% and 13%. Higher catalyst loading likely provided more

active sites for reactant adsorption (FAC and FU), facilitating their condensation and driving
the reaction towards the higher carbon (C13) FA2C compound, thus reducing FAC selectivity.

Additionally, further condensation of products (FAC and FA2C) with FU at higher active site

densities could lead to the formation of undesired higher molecular weight polymerized

products, decreasing overall selectivity to FAC and FA2C. Previous studies have also identified

the formation of such undesired polymerized products [16,17].

4. Catalyst stability study

The stability of 15K-AWRM was evaluated over four cycles of the FU and acetone aldol

condensation process (Fig.7). FU conversion remained consistent through the fourth use of the

catalyst. However, product selectivity changed with repeated use. FAC selectivity increased

from 40% to 56% from the first to the fourth use. Simultaneously, a decrease in the FA2C

selectivity was observed with repeated uses from first to fourth. As previously discussed, a

higher density of basic sites promotes the second condensation of FAC with FU to form FA2C.

The observed decline in FA2C selectivity with repeated catalyst use can be attributed to a slight

loss of basic sites. FESEM-EDX analysis (Table 2) of 15K-AWRM after the fourth cycle

indicated a slight reduction in K content. The reduction in K content could lead to the reduction

in the active site density, which could in the process result in a decrease in the further

condensation of FAC with FU to FA2C. However, the catalyst up to the fourth use contained

enough active potassium sites for the aldol condensation reaction of FU to proceed due to which

the FU conversion values were unaffected. The results suggested appreciable stability of the

15K-AWRM catalyst for the aldol condensation of FU with acetone.

5. Catalyst activity comparison

Table 4 outlines the efficiencies of various metal oxide catalysts applied for the aldol

condensation reaction. Notably, the reaction temperature of 90 °C employed for the FU aldol

condensation with acetone in this work is lower than the temperature used using a few other
metal oxides [9,11,17]. Other catalysts reported (Table 4) used lower (50 oC) and a same

reaction temperature (90 oC) as used in this work, however, with a high reaction time than our

reported catalyst [8,13]. A general trend indicates that an increase in basic sites in the catalysts

enhances the catalyst activity for the aldol condensation reaction, likely by providing active

sites for reactant activation. These active sites can be introduced into the catalyst support

through doping with metals such as magnesium (Mg) [9] and potassium (K) [10]. Literature

also suggests that an increased surface area can contribute to higher catalytic activity in aldol

condensation reactions [13]. For example, Zn-Al mixed oxide catalysts prepared with varying

molar ratios of Zn and Al exhibited different surface areas in the range of 49 m2 g-1 to 167 m2

g-1, and the catalytic activity for FU conversion was highest for the highest surface area catalyst

[13]. However, in many cases, including this work, it has also been seen that surface area has

little influence on the aldol condensation activity of the catalyst. Although the surface area of

our catalyst 15K-AWRM was lower than AWRM, it showed higher activity due to the

availability of a relatively higher basic site density. Furthermore, the reaction time required for

the FU and acetone aldol condensation using the 15K-AWRM catalyst is shorter compared to

other catalysts, suggesting the benefit of reduced reaction time when using microwave

irradiation. Additionally, preparing this catalyst from waste materials not only offers effective

utilization of waste but also could be economically favorable over other costly commercial

metal catalysts used in this process.

6. Conclusion

A potassium-modified red mud catalyst was developed for the FU aldol condensation with

acetone to fuel intermediates. Introducing potassium into acid-washed red mud followed by

thermal treatment caused the formation of K2O as active sites, leading to the enhancement in

the basic site density. The quantity of these basic sites, measured by the CO 2-TPD analysis,

was correlated with the catalytic activity for the aldol condensation reaction. The 15K-AWRM
catalyst contained 0.67 mmol g-1 amount of basic sites, achieving 99% FU conversion with

40% FAC and 11% FA2C selectivity. The reaction temperature required for this reaction was

90 °C with a reaction time of 30 minutes. This reaction temperature and time are relatively

lower than that required by other metal oxide catalysts, indicating the appreciable efficiency of

the 15K-AWRM catalyst under microwave heating. The performance of the 15K-AWRM

catalyst was comparable to other reported metal oxide catalysts. The catalyst also showed

appreciable activity during reuse with almost no change in FU conversion.

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Table 1. Base site analysis of various RM derived catalysts
Catalyst Base sites density mmol g-1 (From CO2-TPD)

AWRM 0.116

15K-AWRM 0.67
Table 2. Elemental analysis of 15K-AWRM and fourth used 15K-AWRM.
Elements O Fe K Al Si

15K-AWRM 39.7 30.9 17.1 10.0 2.3

Fourth used 15K-AWRM 40.4 31.1 14.2 11.5 2.8

Table 3. BET results of various RM derived catalysts
Catalyst Surface area Avg. pore size Pore volume

(m2 g-1) (nm) (cm3 g-1)

RM 10 16.2 0.0279

AWRM 261 6.1 0.3139

15K-AWRM 16 10.3 0.0107

 Table 4. Activity comparison of 15K-AWRM with other reported catalysts.
Catalyst process Temperature Time FU FAC/FA2C Ref.

(oC) (min) conversion selectivity (%)

(%)

Isolated Zr on Furfural aldol 140 120 93.6 78.4/17 [11]

mesoporous condensation

silica with acetone

Ni/Mg-Al- Furfural aldol 170 540 - 79.23 (total) [9]

O/AC condensation

with acetone

K-Sn-MFI Furfural aldol 160 60 100 75/10 [10]

condensation

with acetone

Zn-Al mixed Furfural aldol 50 360 81 66/26 [13]

oxide condensation

with acetone

Potassium Furfural aldol 100 120 77.8 67.2/17.7 [12]

containing condensation

BEA zeolite with acetone

MgAl-NO3 Furfural aldol 90 120 99 76/18 [8]

condensation

with acetone
15K-AWRM Microwave 90 30 99 40/11 Present

Furfural aldol work

condensation

with acetone
Scheme 1.

Fig. 1.
Fig. 2.

Fig. 3.
Fig. 4.

Fig. 5.
(a) (b)

Fig. 6.

Fig. 7.
Scheme 1: Reaction pathway for the furfural aldol condensation with acetone
Fig. 1. Activity of various RM derived catalysts for the furfural aldol condensation reaction.
Reaction conditions: Temperature 90 oC, Time 30 minutes, FU: acetone 1:3, Catalyst loading
12 wt.%.

Fig. 2. XRD analysis of various RM derived catalysts

Fig. 3. CO2-TPD analysis of AWRM and 15K-AWRM catalysts
Fig. 4. FESEM analysis of (a) RM, (b) AWRM, and (c) 15K-AWRM
Fig. 5. N2 adsorption-desorption analysis of various RM derived catalysts
Fig. 6. Activity of 15K-AWRM for the FU aldol condensation with acetone: (a) effect of
temperature, (b) effect of catalyst loading

Fig. 7. Stability study of 15K-AWRM for the FU aldol condensation with acetone. Reaction
conditions: Temperature 90 oC, Time 30 minutes, FU: acetone 1:3, Catalyst loading 12 wt.%.