Biorefining of Mesua ferrea L. Biocrude into Green Transport Fuels Using TBP Distillation: A Sustainable Approach towards 2-G Biorefinery

doi:10.21203/rs.3.rs-6105050/v1

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Biorefining of Mesua ferrea L. Biocrude into Green Transport Fuels Using TBP Distillation: A Sustainable Approach towards 2-G Biorefinery

https://doi.org/10.21203/rs.3.rs-6105050/v1

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published 27 Nov, 2025

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In the present work, Mesua ferrea Linn seed oil was hydroprocessed in a 2-liter batch reactor at 350-400 ^oC and 5 bar initial H₂ pressure using biomass wasted supported Ni/Mo and commercial Pd/C catalysts for one hour. The catalysts synthesized from biomass wastes materials were characterized using XRD, SEM, TEM, EDS, TGA, and FTIR techniques and used for the hydroprocessing of MFL oil. Catalytic hydroprocessing produced about 92% biocrude, with the remaining 7% escaping as non-condensable gases and 1% water at the bottom of the reactor. The resulting biocrude was distilled using the True Boiling Point (TBP) distillation unit in accordance with ASTM D2892 and ASTM D5236 specifications as applicable to petroleum refineries. After characterizing biocrude and the distillate fractions, the green gasoline fraction in the boiling range of 35-140 ^oC was found to be 6-10%, the green kerosene/aviation fuel in the boiling range of 140-180 ^oC was 5-7%, and the green diesel fraction in the boiling range of 180-370 ^oC was 33-35% by volume. Additionally, about 7–9 vol.% of the wax in the boiling range of 370–482 ^oC may also be extracted from the biocrude using TBP distillation unit. Thus, it is possible to fractionate 61–65% of the original biocrude into the distillate products. Furthermore, the fuel properties of the green gasoline, green kerosene, and green diesel fractions obtained from the MFL biocrude were on par with or even better than those of their petroleum analogs, indicating that they might be used as an equivalent substitute for drop-in-fuels.

Biorefining

Mesua ferrea Linn

Catalytic hydroprocessing

TBP distillation

Green fuels

Biorefinery

Bimetallic Catalysts

Mesua ferrea L. oil was catalytically hydroprocessed in a batch reactor to produce quality biocrude.
Biocrude was fractionated using True Boiling Point distillation unit in accordance with ASTM D2892 and ASTM D5236 specifications.
The distillate products were obtained in the range of 61–65% from TBP distillation process.
The fuel parameters of the green transport fuels are analyzed, and indicating that they could be used as an equivalent substitute for drop-in-fuels.

Biofuels play an important role in decarbonizing transport by providing a low-carbon solution for automobile and transport industries, including the shipping and aviation sectors. They frequently require little to no modifications to be employed in engines that are already in use. The demand for biofuels grew by 6% in 2022 and peaked at 4.3 EJ (1,70,000 million liters). Furthermore, the demand for biofuel accounted for more than 3.5% of the energy required for transportation worldwide, primarily for road transportation (Fig. 1). To meet the net zero emissions (NZE) scenario by 2050 and achieve the corresponding emission reductions, however, a large increase in biofuel production is required. According to the NZE scenario, biofuel output would surpass 10 EJ by 2030, necessitating an average annual growth rate of about 11%. According to the NZE scenario, biofuels will account for a comparable portion of the fuel demand for road vehicles alone by 2030, more than doubling to 9% of transportation [1].

The capacity for transport biofuel increased by 7% worldwide, the most yearly growth in more than ten years. By 2023, global investment in renewable energy is expected to reach USD 1.7 trillion (Fig. 2). During the ongoing energy crisis, biofuels helped ensure energy security. However, they are now experiencing their own set of problems, which has led to varying policy approaches. The demand for biofuel is supported by policies in more than 80 countries overall. With 85% of the overall demand, the US, Brazil, Europe, and Indonesia continue to be the leading markets. The demand for biofuel is 40% in emerging economies and nearly 60% in developed economies. The demand for biofuel is predicted to rise by 11% by 2024, with emerging nations accounting for two-thirds of this development. In 2022, the use of biofuels increased in Argentina, India, and Indonesia. India advanced faster toward its ethanol aim, Indonesia allotted larger volumes of biodiesel for the year, and Argentina raised its goal for biodiesel blending. Brazil is increasing its biodiesel blending goal from 12% in 2023 to 15% by 2026, while Indonesia is increasing its goal from 30–35% [1].

Currently, so-called conventional feedstocks like sugar cane, corn, and soybeans are used in the great bulk of biofuel production. To ensure a minimal impact on land use, food and feed prices, and other environmental issues while tripling biofuels output in accordance with the NZE scenario, it is imperative to expand biofuel production to advanced feedstocks. About 40% of the biofuels consumed in 2030 under the NZE scenario will be made from second-generation feedstocks, such as wastes, residues, and specialized crops that do not compete with food crops. This is an increase from the predicted 9% in 2021. The usage of biofuels for transportation increases dramatically in the NZE scenario by 2030, with a far higher percentage coming from wastes, residues, non-food crops, waste cooking oil, and waste animal fats [1, 2].

It is clear from the discussion above that liquid biofuels made from non-food crops and second-generation (2-G) feedstocks are a viable solution for supplying future energy needs under the NZE scenario. According to this viewpoint, non-edible vegetable oils with comparatively low economic value and commercial applications, such as waste cooking oils from Jatropha curcas, Pongamia pinnata, Castor, used cooking oil, Mesua ferrea L. etc. could be considered as potential replacements for conventional edible food crops in the production of liquid biofuels in this precarious situation of vegetable oils. In recent years, researchers from all over the world have been working on the biorefining of 2-G feedstocks to produce biocrude, which will replace fossil-based crude oil and its derivatives. Using hydroprocessing technology, liquid biocrude, a valuable renewable resource, may be converted into environmentally friendly transportation fuels that resemble petroleum products. The end products of hydroprocessing that yield green hydrocarbons are mostly aromatics, paraffin, and naphthenes. However, due to the complexity of the liquid feedstocks obtained from biomass, the process is extremely difficult to comprehend in terms of hydroprocessing chemistry [3–7].

Probably for the first time, the hydroprocessing of 2-G liquid biomass (Mesua ferrea Linn) in an indigenous batch reactor (2l capacity) to produce a high-quality biocrude was studied using Group-6 and 10 transition metal-supported biomass and non-biomass produced bimetallic catalysts. Using the True Boiling Point (TBP) distillation unit, the resulting biocrude was fractionated into sustainable transport fuels in accordance with ASTM D2892 and ASTM D5236 protocols after being analysed in accordance with the relevant standards. Fuels such as green gasoline, green kerosene, and green diesel have distillate fractions that fall inside their boiling range. This article examined the hydrocarbon contents of biocrude and confirms the maximum possibility as the healthy feedstocks for the second generation biorefinery operations. According to ASTM guidelines, the fuel characteristics of the various liquid fractions were ascertained. This contemporary method of producing biofuel is essential to reaching the UN Sustainable Development Goal 7 on "Affordable and Clean Energy" by 2030 in the NZE scenario.

2.1. Feedstock used in the work

“Mesua ferrea Linn.” (MFL) is an evergreen tree in the family Clusiaceae and mainly grown in northeast India. MFL seeds (Fig. 3) have high oil content ranging from 75–80% by weight. MFL seed oil was extracted using petroleum ether solvent by Soxhlet extraction procedures. The fatty acid profile of MFL oil was determined from GC-FID analysis. A total thirteen numbers of fatty acids were detected out of which oleic acid (50%), linoleic acid (20%), palmitic acid (14%) and stearic acid (14%) were the major contributors in MFL. The primary fatty acid is oleic acid, which is followed by palmitic, stearic, and linoleic acids. There are approximately 71 wt.% unsaturated fatty acids, 29 wt.% saturated fatty acids, and no trans fatty acids were detected in MFL oil. Table 1 showed the fatty acid profile and physicochemical properties of MFL. Other chemicals were also purchased from commercial sources and utilized exactly as supplied, including ethanol (Merck), chloroform (Merck), hexane (Merck), nickel (II) nitrate hexahydrate (Sigma Aldrich), ammonium molybdate tetrahydrate (Sigma Aldrich), and 10%Pd/C (Sigma Aldrich).

Table 1

Fatty acids profile and physicochemical characteristics of MFL oil
S. No.	Parameter (s)	MFL Oil
A.	Fatty acids profile summary
1	Total saturated fatty acids (SFA), wt.%	29.23
	Total mono-unsaturated fatty acids (MUFA), wt.%	50.98
	Total poly-unsaturated fatty acids (PUFA), wt.%	19.79
	Trans fatty acids (t-FA), wt.%	Nil
B.	Physicochemical characteristics
	Color	Reddish-brown
	Density @ 40 ^oC, g cc^− 1	0.90
	Specific Gravity @ 20 ^oC	0.92
	Kinematic viscosity @ 40 ^oC, mm² s^− 1	34.30
	Flash point, ^oC	115.0
	Higher heating value, MJ/kg	36.0
	Iodine value, g I₂/100g	131.31
	Saponification value, mg g^− 1	210.80
	Neutralization No., mg KOH g^− 1	18.80
	Free fatty acids (in terms of oleic), %	9.40

2.2. Synthesis of Biomass and Non-biomass derived Bimetallic catalysts

Biomass based catalytic support precursors; Musa balbisiana colla underground ash (MBCUS), biomass based thermal power plant fly ash (BBTPFS) and non-biomass-based material like coal-based thermal power plant fly ash (CBTPFS) were collected from various regional resources. A total of 35.92 wt. % SiO₂, 25.05 wt. % K₂O, 10 wt. % CaO, 10 wt. % MgO and 4 wt.% Al₂O₃ make up the MBCUS. BBTPFS is mostly composed of 30.74 wt. % CaO, 27.87 wt. % SiO₂, 13.96 wt. % K₂O, 6.67 wt. % MgO and 2.83 wt. % Al₂O₃. CBTPFS, on the other hand, is mostly composed of 57.43 wt. % SiO₂, 13.16 wt. % CaCO₃ and 11.38 wt. % Al₂O₃. MBCUS, BBTPFS and CBTPFS materials were further modified in order to improve the catalytic efficacy by the sequential impregnation of Group-6 and Group-10 transition metals on the support’s materials. The sequential impregnation approach was employed to synthesize bimetallic supported heterogeneous catalysts with varied loadings of Ni and Mo as transition metals. Before being impregnated, the catalytic supports MBCUS, BBTPFS, and CBTPFS were calcined for two hours at 550 ^oC in a muffle furnace. After crushing the MBCUS, BBTPFS, and CBTPFS supports, the fraction ≤ 150 µm was utilized to prepare the catalyst. A requisite quantity of transition metal salts and carriers as mentioned in Table-2 were considered for the synthesis of bimetallic catalysts. Aqueous solutions of Ni(NO₃)₂.6H₂O and (NH₄)₆Mo₇O₂₄.4H₂O were used as the source of nickel and molybdenum, respectively. At first, the catalyst was impregnated with (NH₄)₆Mo₇O₂₄.4H₂O to contain 10 wt. % Mo on MBCUS and kept overnight at room temperature to achieve sufficient impregnation and then dried overnight at 120 ◦C. Then it was calcined in a muffle furnace at 500 ◦C for 4h (Fig. 4). Subsequently, the Mo-containing MBCUS support was impregnated with Ni(NO₃)₂.6H₂O to contain 5 wt.% of Ni and kept overnight at room temperature to further achieve sufficient impregnation and dried again for overnight at 120 ◦C. Finally, the catalyst was calcined in a muffle furnace at 500 ◦C for 4h and used in further study. The same procedures were adopted for the synthesis of Ni/Mo supported on BBTPFS and CBTPFS catalysts. The synthesized catalysts were designated as NMM, NMB and NMC respectively (Table 2 and Fig. 5).

Table-2 Transition metals (Ni/Mo) loading on MBCUS, BBTPFS and CBTPFS catalytic supports

Bimetallic Catalysts	Loading (wt.%)			Synthesized Quantity	Nomenclature
Bimetallic Catalysts	Transition Metals		Carrier	Synthesized Quantity	Nomenclature
Metals	Nickel¹	Molybdenum²	MBCUS	100 %	NMM
Composition	5 %	10 %	85 %	100 %
Quantity required	19.465 g	12.26 g	85.0 g	100 g
Metals	Nickel¹	Molybdenum²	BBTPFS	100 %	NMB
Composition	5 %	10 %	85 %	100 %
Quantity required	19.465 g	12.26 g	85.0 g	100 g
Metals	Nickel¹	Molybdenum²	CBTPFS	100 %	NMC
Composition	5 %	10 %	85 %	100 %
Quantity required	19.465 g	12.26 g	85.0 g	100 g

¹Nickel nitrate hexahydrate. ²Ammonium hepta molybdate tetrahydrate

2.3. Characterization of Biomass and Non-biomass derived Bimetallic catalysts

Powder XRD (Bruker D8 Advance) was used to extract the structural information of the synthesised catalysts from the X-ray diffractograms. A Cu Kα radiation source (λ = 0.154056 nm) was used to scan from 10 to 70° (2θ) at a rate of 0.028 s − 1 in order to detect the X-ray diffraction pattern. The catalysts' surface morphology and composition were recorded using the scanning electron microscope with energy dispersive X-ray detector (SEM-EDS) approach. A FE-SEM QUANTA 200 FEG (FEI, Netherlands) with a resolution of less than 2 nm at 30 kV was used to examine the catalyst's surface morphology. The transmission electron microscope (TEM) images study of the catalysts was performed with a TEM TECNAI G2 20 S-TWIN (FEI Netherlands) electron microscope. Furthermore, the FTIR spectrometer (Agilent, USA) was used to examine the catalysts in the 4000 − 500 cm^− 1 range. A thermo-gravimetric analyser (TGA) made by Perkin Elmer (STA 6000) for thermal and oxidative stability was also used to assess the thermal stability of the catalysts. The catalyst's weight losses were measured in the temperature range 30 − 1,000 ˚C @ heating rate 10 ˚C/min under constant nitrogen and air flow (20 ± 0.5 ml/min). The efficacy of catalysts was later assessed during the hydroprocessing of MFL seed oil in a bench scale batch reactor under variable operating parameters.

2.4. Catalytic hydroprocessing of MFL oil to biocrude oil

A 2-L-capacity down-flow high pressure-high temperature (HPHT) reactor (Amar Equipment Pvt. Limited, Mumbai, India) with a feed system, reactor system, and product collection system was used to study the catalytic hydroprocessing of MFL oil. HPHT reactor system also consists of a hydrogen gas filling line with an air pressure of 35 MPa sustaining capacity. The reactor system's working capacity was 1.8 L with an operating parameter of 90% of the intended temperature and pressures. The reactor’s dimensions were 290 mm in length and 105 mm in inner diameter. Experiments were performed under varying conditions of temperature, initial H₂ pressure, duration and catalyst loading to determine the effect of the relevant parameters on product quality and yield. In all catalytic reaction, catalyst particles smaller than 150 µm were used, and the mechanical impeller's speed was set at 105 rpm. The products (biocrude) were collected from the flush bottom valve once the reactor had cooled to room temperature following each reaction. Following filtration to separate the catalyst particles from the product, the biocrude yield was computed according to the following expression;

$$\:\text{B}\text{i}\text{o}\text{c}\text{r}\text{u}\text{d}\text{e}\:\text{y}\text{i}\text{e}\text{l}\text{d}\:\left(\text{%}\right)=\frac{\text{W}\text{e}\text{i}\text{g}\text{h}\text{t}\:\text{o}\text{f}\:\text{M}\text{F}\text{L}\:\text{b}\text{i}\text{o}\text{c}\text{r}\text{u}\text{d}\text{e}\:\left(\text{g}\right)}{\text{W}\text{e}\text{i}\text{g}\text{h}\text{t}\:\text{o}\text{f}\:\text{M}\text{F}\text{L}\:\text{o}\text{i}\text{l}\:\left(\text{g}\right)}\times\:100$$

2.5. Fractional distillation of MFL biocrude oil using True boiling point (TBP) distillation unit

MFL biocrude oil was distilled using a True Boiling Point (TBP) distillation unit (B/R Instruments Corporation, USA) in accordance with petroleum refinery specifications (ASTM D2892 and ASTM D5236 protocols). To separate different liquid transport fuel fractions, the biocrude was distilled in the boiling range of 35–140 ^oC (i.e., gasoline), 140–180 ^oC (i.e., kerosene), and 180–370 ^oC (i.e., diesel). TBP distillation system consists of 2-L-capacity stainless steel (SS) pot with temperature probe that measures the actual pot temperature during distillation. TBP system also consists of packed column (D2892) for ASTM D2892 distillation and vacuum pot still (D5236) for ASTM D5236 distillation, with 15 theoretical plates. With the aid of an Edwards-made vacuum pump, diesel range and higher hydrocarbons were distilled utilizing vacuum (100 to 0.1 mm Hg) distillation techniques. The condenser condensed the distillate fractions from the distillation, and a fraction collector assisted in their automatic accumulation in the 250-cc receiver.

2.6. Characterization of feedstock, biocrudes and liquid distillate fractions

Using standard test procedures advised by ASTM, the physicochemical and fuel characteristics of MFL biocrude and the associated fractions were ascertained. A density meter (Anton Paar, Austria) was used to measure density in accordance with ASTM D-1250-08 and DIN 51757 protocols. The oil's flash point was ascertained using a Flash Point Tester (Tanaka Scientific, Japan) in accordance with ASTM D-92 & ISO 2592 (IP36), and the kinematic viscosity was ascertained from the Kinematic Viscosity Bath (Lawler, USA) in accordance with ASTM D-445 & D-2171.

3.1. Catalysts characterization

The XRD patterns of the NMM, NMB, and NMC catalysts obtained from MBCUS, BBTPFS, and CBTPFS, respectively, are displayed in Fig. 6. High amorphousness, peak overlaps, and weak peak intensities make it difficult to identify the different phases involved in fly ash-derived NMM, NMB and NMC catalysts using XRD analysis. There are many crystalline peaks with a lower degree of crystallinity and amorphous patterns in the diffraction patterns of NMM, NMB, and NMC. The NMM catalyst showed prominent diffraction peaks (2θ) at 26.78° and 28.49° angles. Silicon dioxide (SiO₂) in its quartz phase at 2θ = 26.78∘ and 2θ = 28.49∘ is a common match in NMM. In minerals such as quartz (SiO₂) phases, the (111) plane is frequently represented by a 2θ = 28.49°. According to Bragg's Law (n.λ = 2d.Sinθ), an interplanar spacing (d) of roughly 3.11 A˚ is equivalent to a 2θ = 28.70∘. NMM revealed the presence of Ni and Mo at diffraction peaks (2θ) at angles of 50.32° and 40.66° 2θ = 26.78∘ with low intensity respectively and also confirmed by the SEM-EDX spectrum (Fig. 7 and Fig. 8). NMB catalyst exhibited strong diffraction peaks (2θ) at angles of 28.71°, 18.63° and 26.62° for silicon dioxide (SiO₂) in its quartz phase. Furthermore, as illustrated in Fig. 6, NMB also demonstrates the presence of TiO₂, CaO, MgO, Ni, and Mo at various diffraction angles. In contrast, the main crystalline phases of the NMC catalyst were identified as quartz, mullite and hematite. With a chemical composition of 3Al₂O₃.2SiO₂, mullite is an alumino silicate that shows peaks at 16.41, 25.98, and 40.82 at 2θ values. The quartz (SiO₂) exhibits peaks at 2θ values 20.82, 26.25, and 26.62, while hematite (Fe₂O₃) exhibits peaks at 33.20, 37.0, and 39.25. XRD data for the synthesised catalysts observed almost in line with the findings of other researchers [8–14]. The XRD diffraction pattern demonstrated that Ni and Mo were successfully impregnated on the supports and this was coherent with the outputs of the SEM-EDX analysis conducted (Fig. 7 and Fig. 8).

The SEM and TEM analyses of the NMM, NMB, and NMC catalysts are displayed in Fig. 7. The EDS analysis associated with the SEM results for each catalyst is displayed in Fig. 8. The existence of O (SiO₂), Mg (MgO), Si (SiO₂), Cl (KCl), K (MAD-10 Feldspar), Ca (Wollastonite), Ni (Ni) and Mo (Mo) was verified by the NMM's EDX analysis. However, the NMB's SEM–EDX examination verified the presence of C (CaCO₃), O (SiO₂), Mg (MgO), Al (Al₂O₃), Si (SiO₂), K (MAD-10 Feldspar), Ca (Wollastonite), Ni (Ni) and Mo (Mo). The existence of C (CaCO₃), O (SiO2), Al (Al₂O₃), Si (SiO₂), K (MAD-10 Feldspar), Ti (Ti), Ni (Ni), and Mo (Mo) was also verified by the NMC's SEM–EDX investigation. Table 3 shows the elemental makeup of the NMM, NMB, and NMC catalysts. As indicated in Table 3, it indicates that the elected spots have significant elements. Table 3 depicts that the EDS results are very much comparable and strengthening to the XRD data (Fig. 6) [10–18]. The NMM, NMB, and NMC catalysts have irregular shapes with nanoscale dimensions (100 nm) and voids or pores dispersed throughout the catalytic surface with micro and macro porosity, as illustrated in Fig. 7 and Fig. 8.

Table 3

Elemental composition of NMM, NMB and NMC catalysts (EDX analysis)
Catalysts	Elements	C	O	Mg	Al	Si	Cl	K	Ti	Ca	Ni	Mo
NMM	Atomic (%)	-	59.33	2.35	-	9.54	3.46	16.43	-	2.58	2.56	3.75
NMM	Weight (%)	-	35.79	2.16	-	10.10	4.62	24.23	-	3.89	5.66	13.55
NMB	Atomic (%)	12.71	59.59	2.24	1.28	5.75	-	0.65	-	10.63	2.24	4.91
NMB	Weight (%)	6.33	39.55	2.26	1.43	6.70	-	1.06	-	17.68	5.47	19.52
NMC	Atomic (%)	22.04	54.25	-	8.49	10.22	-	0.24	0.31	-	2.40	2.06
NMC	Weight (%)	13.16	43.16	-	11.38	14.27	-	0.46	0.74	-	6.99	9.83

Figure 9 shows the weight loss as a function of temperature using the TGA thermograms of the MBCUS, BBTPFS, CBTPFS, and synthetic catalysts in the temperature range of 30 to 1000 ^oC. It is evident from Fig. 9(a) that about 11 wt.% losses were seen during the thermal decomposition of the uncalcined MBCUS catalyst in N₂ medium, while 8% losses were seen in air medium in the temperature range of 100–200 ^oC. In case of uncalcined BBTPFS in N₂ medium (Fig. 9b), calcined MBCUS in both N₂ and air medium (Fig. 9a) and NMM in air medium (Fig. 9c), the weight loss observed was about 2% only in the temperature range of 100–200 ^oC. As illustrated in Fig. 9c, about 1 wt.% loss was noted in the case of NMM in N₂ medium and for NMB in both N₂ and air medium. The elimination of bound moisture and other contaminants at temperatures between 100°C and 200°C is responsible for this weight reduction. However, calcined CBTPFS, BBTPFS and NMC in both N₂ and air medium do not exhibit any appreciable weight loss from the catalytic surface as a result of the calcination process [Fig. 9 (a), (b) and (c)].

In the second phase, all the catalytic materials were found to be moderately stable as no sharp changes were observed between the temperature range of 200–400 ◦C. It can be concluded that none of the catalytic materials undergo significant chemical breakdown. This could, however, be explained by the materials' loss of water of crystallization. Thereafter, heating the catalytic materials beyond the temperature of 400 ◦C, sharp weight loss was observed up to 700 ^oC. This weight loss is ascribed to the deterioration of biomass materials and the thermal decomposition of some alkaline earth metal carbonates into CO₂ and CO and more specifically, the decomposition of alkali metal carbonates of Na, K, etc., into their respective metal oxides, in line with findings by [10, 11, 13, 19–22]. At temperatures between 30 and 1000 ^oC, uncalcined MBCUS and BBTPFS catalysts showed a total weight loss of about 21–30% in both N₂ and air environments. In the same temperature range, calcined MBCUS and BBTPFS catalysts showed a weight loss of about 10% in both N₂ and air media [Fig. 9 (a) and Fig. 9 (b)]. In contrast, the synthesized NMM, NMB and NMC catalysts were observed their total weight loss about 10%, 6% and 0.5% respectively in both N₂ and air medium in the temperature range of 30-1000 ^oC (Fig. 9c). The synthesized catalysts clearly demonstrated their thermal stability and it is expected to play a key role during catalytic hydroprocessing of MFL.

FTIR analysis of catalysts

Figure 10 (a) displays the different absorption bands for the MBCUS at 2884, 2361, 1409, 940, and 669 cm^− 1, BBTPFS at 2884, 2361, 1409, 1118, 1019, 871, 713, and 669 cm^− 1, and CBTPFS at 2884, 2361, 1409, 1063, 812, and 669 cm^− 1. The absorption bands appeared at 2884 and 2361 cm^− 1 are attributed to the presence of calcium carbonate and silicate minerals. Furthermore, the existence of K, Ca, and other metal carbonates in MBCUS, BBTPFS, and CBTPFS is indicated by the stretching and bending vibrations of the (C = O) bond of carbonate ions (CO₃²⁻ group) at 1409 cm^− 1, 871 cm^− 1 and 713 cm^− 1, respectively. In MBCUS, BBTPFS, and CBTPFS materials, the Si-O-Si bond vibrations of SiO₂ were detected at 1118, 1063, 1019, 940, and 812 cm^− 1. The absorption band appeared at 669 cm^− 1 is responsible for the existence of K₂O, CaO and other metal oxides due to the bending and stretching vibrations of metal oxides. The lack of the OH functional group in MBCUS, BBTPFS, and CBTPFS materials indicates that there is no moisture present as reported in literatures [19, 20, 23–28]. The FTIR characterization data for present catalysts confirm that the catalysts consist of metal carbonates and metal oxides specifically K₂CO₃, CaCO₃, K₂O, CaO and SiO₂.

Figure 10 (b) shows the various absorption bands observed for the NMM at 3300, 2890, 2346, 1645, 1463, 1394, 970, 822, 674 cm^− 1, NMB at 2890, 2346, 1448, 975, 876, 812, 708 cm^− 1and NMC at 2890, 2346, 1418, 1068, 950, 876, 797, 708 cm^− 1. Broad peak signals that occur in NMM at 3300 and 1645 cm^− 1 are attributed to O–H stretching vibrations, which show that moisture has been adsorbed onto the catalysts' surface. Since NMM was produced from MBCUS, which has a high capacity for moisture absorption, it appears to contain moisture. The presence of calcium carbonate and silicate minerals is responsible for the weak absorption bands that show at 2890 and 2346 cm^− 1 in all catalysts. Furthermore, the presence of metal carbonates ions is indicated by the stretching and bending vibrations of the (C = O) bond of carbonate ions (CO₃²⁻ group) at 1463, 1448, 1418, and 1394 cm^− 1. The intensity of these peaks decreases as the nickel-molybdenum content is impregnated over the biomass and non-biomass derived supports as reported by authors [19, 23]. All catalytic supports primarily contain a varying degree of SiO₂/ mesoporous silica contents. At wave numbers 674–1068 cm^− 1, all catalysts have absorption bands that are frequently observed in Ni-Mo supported mesoporous silica materials. The FTIR result shows that NiMo/SBA-15 sample retained nearly identical absorption band structures at the wavenumbers corresponding to the silica material (812, 940, 1063, 1118 and 1019 cm^− 1) as reported in literatures [19, 23, 29–34]. The inclusion of NiMo metals does not change the overall peak pattern in the FTIR spectra, indicating that the framework of MBCUS, BBTPFS, and CBTPFS support did not collapse during the catalyst synthesis procedures. The FTIR characterization data for present catalysts confirm that the catalysts consist of Ni-Mo on the catalytic supports materials which are in accordance with the analyzed XRD results (Fig. 6).

Catalytic hydroprocessing of MFL oil to produce biocrude

A 1.5 L volume of MFL oil was hydroprocessed for one hour at a constant temperature and pressure of 400 ^oC and 5 bar initial H₂ pressure using a constant 3 wt.% of NMM, NMB, and NMC catalysts with impeller speed of 105 rpm. The internal vapor pressure was raised between 10 and 28 bar during the catalytic hydroprocessing. Catalytic hydroprocessing of MFL seed oil yielded biocrude, gaseous hydrocarbons and water contents. Water was formed when the oxygen bonds of the triglyceride molecules were reduced in an H₂ environment during the catalytic hydroprocessing of MFL seed oil to produce biocrude. Under high temperature and pressure, hydrodeoxygenation, hydrodecarboxylation, and hydrodecarbonylation processes produced CO₂, CO, and perhaps C₁–C₄ gases as gaseous byproducts of the hydroprocessing as reported by researchers [35, 36].

Using a blank reaction (without a catalyst) as a reference, the catalytic activity of the NMM, NMB, and NMC in the hydroprocessing of MFL oil were examined in comparison to commercial 10% Pd/C as a hydrogenation catalyst. The effect of catalyst and reaction environment on product (biocrude) quality and yield is evident from the catalytic experiment results compiled in Table 4. In brief, the performance of the catalyst was assessed in relation to the distillate recovery in liquid range (OLF yield), higher heating value (HHV), and biocrude acidity index (AI) (Table 4 and Fig. 11). Table 4 makes it clear that while the biocrude yield did not differ much between the catalysts, the yield of OLF, HHV, viscosity, and AI of biocrude did vary significantly. These variations are linked to the various reaction networks and pathways under various catalytic conditions (Table 4 and Fig. 11).

Table 4

Effect of reaction parameters on hydroprocessing of MFL oil using different catalysts (yields and biocrude properties)
Catalyst	Blank	NMM	NMB	NMC	10%Pd/C
Temperature (oC)	400	400	400	400	350, 400
Catalyst amount (wt%)	-	3	3	3	1
Duration (h)	1	1	1	1	1
Impeller Speed (rpm)	105	105	105	105	105
Initial H₂ pressure (bar)	5	5	5	5	5
Final pressure (bar)	25	11.3	10	11.7	28
Yield (w/w %)
Gas phase	4.3	4.2	4.7	4.5	-
Water	0.4	0.7	0.8	0.5	-
Biocrude	94	92.2	92.0	92.3	-
Mass balance	98.7	97.1	97.5	97.3	-
Biocrude fuel property
Acidity index (mgKOH/g)	135.5	115.8	95.74	108.8	-
Higher heating value (MJ/Kg)	38.52	39.78	40.52	37.68	-
Iodine value (g I₂/100g)	120.6	109.5	110.5	116.5	-
Viscosity (40 °C, cSt)	13.34	9.87	8.46	9.52	-
Recovery (v/v %)
^a Organic Liquid Fractions (OLF)	51.5	61.28	65.38	62.09	0.0
^b Organic Solid Fractions (OSF)	48.5	38.72	34.62	37.91	100
^aOLF recovered by TBP distillation. ^bOSF residue in TBP distillation.

Furthermore, irrespective of catalyst type, the main components of the biocrude were hydrocarbons, oxygenated compounds and organic acids, similar to the products of catalytic cracking of vegetable oil [35, 36]. However, without a catalyst, the production of hydrocarbon was insignificant and primarily comprised of organic acids and oxygenated compounds, produced by cracking of triglyceride molecules at high temperatures and H₂ pressures (Table 4). Overall, the biocrude produced in this work had characteristics and a composition that were comparable to the cracking and catalytic cracking oils made from vegetable oils using basic catalysts (Na₂CO₃, K₂CO₃, alkali/alkaline earth oxide modified zeolites, etc.). The only discernible difference between our products and cracking products was the former's higher HHV and lower AI, which is probably related to the lower concentration of oxygenated components (fatty acids, aldehydes/ketones, etc.) and also suggests how the reaction atmosphere affects the composition of biocrude.

Based on these characteristics, NMB seems to be the best catalyst in this investigation, outperforming NMM, NMC, and Pd/C catalysts. NMB produced 63.45–64.5% product in the liquid range (OLF) in a one-hour reaction at 400 ◦C and 5 bar initial H₂ pressure (Fig. 11). The catalytic performance of NMB was observed significantly higher compared to the conventional/commercial Pd/C catalyst. In particular, Pd/C demonstrated essentially no action in hydrogenating the unsaturated components found in MFL oil. In contrast, Pd/C is predicted to promote the polymerization of MFL oil's triglyceride molecules at high temperatures and pressures, resulting in a very viscous biocrude that is almost impossible to fractionate using the TBP distillation system (Table 4). It is envisaged that synthesized catalysts and commercial catalyst showed different chemical reaction network. However, Ni and Pd are both Group 10 metals with with distinct chemical characteristics. According to the experimental results, NMB worked best, and the biocrudes produced with NMB catalyst had the best fuel characteristics, the lowest AI, the highest HHV, and the highest OLF yield (Tables 4 and Table 5). This preeminence could be be explained by the fact that NMB contains 5% Ni and 10% Mo metals along with 52% alkali metal oxides present in BBTPFS, as compared to 45% and 25% alkali metal oxides in MBCUS and CBTPFS respectively with the constant composition of Ni and Mo in NMM and NMC.

Table 5

Fuel properties of liquid distillates obtained from TBP distillation of MFL biocrude
Distillate’s Boiling Range (°C)/ Products	Catalyst Employed	Density (15 °C, g/cc)	Kinematic Viscosity (40 °C, cSt)	Flash point (°C)	Higher heating value (MJ/Kg)
Petro-gasoline		0.72–0.78	0.37–0.44	-42.0	41.80
35–140 (Green Gasoline)	NMM	0.76	0.64	-	40.45
	NMB	0.74	0.65	-	40.43
	NMC	0.75	0.64	-	40.52
Petro-kerosene		0.81–0.93	5.2	35–38	42.80
140–180 (Green Kerosene)	NMM	0.83	0.91	36.0	45.52
	NMB	0.82	0.92	38.0	45.87
	NMC	0.84	0.93	37.0	45.68
Petro-diesel		0.81–0.89	2.0–5.0	52.0	43.5
180–370 (Green Diesel)	NMM	0.83	2.81	74.0	45.25
	NMB	0.85	2.80	78.0	45.45
	NMC	0.84	2.82	80.0	45.50

Fuel property analysis of green hydrocarbons

The biocrude was distilled in the boiling range of 35–140 ^oC (gasoline range), 140–180 ^oC (kerosene range), 180–370 ^oC (diesel range), and 370–482 ^oC (petroleum wax) similar to petroleum refinery specifications. Additionally, in accordance with ASTM and EN standards, all significant fuel characteristics-such as density, kinematic viscosity, flash point, and calorific value, were ascertained and contrasted with those of traditional petroleum fuels (Table 5).

Green gasoline, green kerosene, and green diesel fractions made from the MFL biocrude employing NMM, NMB and NMC catalysts were found to have lower densities than gasoline, kerosene, and diesel fuels made from crude oil, respectively (Table 5). As anticipated, the products' lower density is caused by a higher proportion of alkanes and a lower concentration of oxygenated and aromatic components in line with the similar findings by [37–38]. Furthermore, with the exception of the gasoline fraction, kinematic viscosities of all the fractions are within the acceptable ranges for conventional fuels. With the exception of a slight variation in viscosity, the density and viscosity of green hydrocarbons satisfied the conventional standards. As the light fraction contents increased and, consequently, the reaction temperature ascended, the kerosene fuel's flash point naturally dropped. The kerosene product's flash point (36–38 ^oC) was comparable to that of petroleum-based kerosene fuel. Green diesel was shown to have a substantially higher flash point than petrodiesel. Green diesel can therefore be handled, stored, and transported more easily than conventional diesel under variable climatic conditions. In addition, the higher heating values for green kerosene and green diesel fractions were slightly higher than their counterparts that clearly indicates the higher contents of carbon and hydrogen in the green hydrocarbons. Furthermore, as seen in Table 5, the fact that all of the monitored parameters for green hydrocarbons are within the permissible ranges for petroleum distillates, if not better than their petroleum analogues and evidently indicates that green hydrocarbons can be utilized directly in place of drop in fuels.

Catalytic hydroprocessing of MFL oil showed significant improvement in products (biocrude and distillates) yield and fuel quality parameters under H₂ atmosphere, which promoted triglycerides decomposition and subsequently acids removal. Further, the presence of Ni, Mo and alkaline earth metal oxides in biomass and non-biomass fly ash derived catalysts promoted hydrodecarboxylation while also suppressing oligomerization and polymerization reactions, the net effect being the production of hydrocarbon rich biocrude. The fly as derived catalysts are also environmental benign as it has the potential to replace the expensive catalytic supports with precious metal oxides utility for catalytic processes and also minimize the waste mitigation. In this investigation, NMB performed best and produced a biocrude with 65.38% product in liquid range (OLF) in 1 h reaction at 400◦C and 5 bar initial H₂ pressure. In addition, fuel qualities of different fractions obtained from the process have been improved by the catalytic hydroprocessing of MFL oil. The fuel properties of the green gasoline, green kerosene and green diesel fractions obtained from the MFL biocrude were comparable, if not better than their petroleum analogs, confirming their potential as equivalent replacements of drop in fuels. This is an emerging area with plentiful research scope and can provide new dimensions to the biorefinery development in the forthcoming years.

Acknowledgement

The author heartily acknowledges to Sardar Swaran Singh National Institute of Bioenergy, Kapurthala (Punjab) and Indian Institute of Technology, Roorkee for providing experimental and characterization facilities.

Availability of Data and materials

The data/materials used in this article are freely available and, where applicable, cited in the reference section.

Authors ‘contributions

The article is an original draft written by the sole author.

Ethics approval and consent to participate

Ethics approval

This article does not contain any studies performed on humans or animals. It is not so applicable.

Consent for publication

The author consents to publish this research in BioEnergy Research (Springer Nature).

Competing interests

The author declares no competing interests.

International Energy Agency (IEA), https://www.iea.org/energy-system/low-emission-fuels/biofuels(assessed in 2024).
US Energy Information Administration of DOE, https://www.eia.gov/ (assessed in 2024).
Buasri A, Kamsuwan J, Dokput J, Buakaeo P, Horthong P, Loryuenyong V (2024) Green synthesis of metal oxides (CaO-K₂O) catalyst using golden apple snail shell and cultivated banana peel for production of biofuel from non-edible Jatropha Curcas oil (JCO) via a central composite design (CCD). Journal of Saudi Chemical Society 28 (3):101836.
Basumatary SF, Das B, Brahma S, Basumatary S (2025) Musa ABB (Kachkal) banana waste derived heterogeneous nanocatalyst for transesterification of binary oil mixture of Jatropha curcas and Pongamia pinnata to biodiesel. Bioresource Technology Reports 29:102018.
Asfaw MD, Yadeta AT, Yewalie BG, Negash YW (2025) Production and characterization of biodiesel from Argemone mexicana seed oil. Results in Chemistry 13:102055.
Rozina, Emmanuel O, Ahmad M, Duduyemi A, Ahmad S, Khan A, Esiaba R, Elekwachi C (2025) Valorization of waste seed oil from Cupressus macrocarpa L. for biodiesel production via green-synthesized iron oxide nanoparticles: A sustainable approach toward decarbonization. Next Energy 7:100218.
Khan MSM, Kumar P, Ansari I, Sahoo N (2025) Experimental analysis of diesel engine characteristics powered with Al₂O₃ doped mesua ferrea linn vegetable oil-diesel blend. Fuel 381:133251.
Saikia K, Das A, Sema AH, Basumatary S, Moyon NS, Mathimani T, Rokhum SL (2024) Response surface optimization, kinetics, thermodynamics, and life cycle cost analysis of biodiesel production from Jatropha curcas oil using biomass-based functional activated carbon catalyst. Renewable Energy 229:120743.
Balaji M, Niju S (2023) Ultrasound-assisted biodiesel production from Ceiba pentandra oil using Musa spp Nendran banana peduncle derived heterogeneous catalyst. Bioresource Technology Reports 21:101310.
Vanhove Y, Dossa JG, Page J, Djelal C (2025) Rheological benefits of biomass fly ash as filler replacement in cement-based materials, Case Studies in Construction Materials. 22:4133.
Luo L, Chen S, Chen N, Wang F, Liu X, Xiao J (2024) Unlocking solid waste utilization: Fly ash-supported cobalt catalyzed transformation of 5-hydroxymethylfurfural into biofuel 2,5-dimethylfuran. Molecular Catalysis 567:114467.
Chutia GP, Bora S, Phukan K (2024) Musa balbisiana colla banana flower derived magnetic heterogeneous nanocatalyst for cleaner biodiesel production from jatropha oil. Materials Today Sustainability 26:100755.
Rajak AK, Madiga H, Mahato DL, Pothu R, Periyasami G, Sarangi PK, Boddula R, Karuna MSL (2024) Exploring the peel ash of musa acuminate as a heterogeneous green catalyst for producing biodiesel from Niger oil: A sustainable and circular bio economic approach. Sustainable Chemistry and Pharmacy 39:101622.
Balaji M, Niju S (2019) A novel biobased heterogeneous catalyst derived from Musa acuminata peduncle for biodiesel production– Process optimization using central composite design. Energy Conversion and Management 189:118-131.
Daimary N, Boruah P, Eldiehy KSH, Pegu T, Bardhan P, Bora U, Mandal M, Deka D (2022) Musa acuminata peel: A bioresource for bio-oil and by-product utilization as a sustainable source of renewable green catalyst for biodiesel production. Renewable Energy 187:450-462.
Hitesha, Wattala R, Lata S (2021) Development and characterization of coal fly ash through low-energy ball milling. Materials Today: Proceedings 47:2970-2975.
Yilmaz G (2012) Structural characterization of glass–ceramics made from fly ash containing SiO2–Al2O3–Fe2O3–CaO and analysis by FT-IR–XRD–SEM methods. Journal of Molecular Structure 1019:37–42.
Bellum RR, Muniraj K, Madduru SRC (2020) Influence of activator solution on microstructural and mechanical properties of geopolymer concrete. Materialia 10:100659.
Basumatary B, Brahma S, Natha B, Basumatary SF, Das B, Basumatary S (2023) Post-harvest waste to value-added materials: Musa champa plant as renewable and highly effective base catalyst for Jatropha curcas oil-based biodiesel production. Bioresource Technology Reports 21:101338.
Chutia GP, Bora S, Phukan K (2024) Musa balbisiana colla banana flower derived magnetic heterogeneous nanocatalyst for cleaner biodiesel production from jatropha oil. Materials Today Sustainability 26:100755.
Bakar NA, Othman N, Yunus ZM, Altowayti WAH, Al‑Gheethi A, Asharuddin SM, Tahir M, Fitriani N, Mohd‑Salleh SNA (2023) Nipah (Musa Acuminata Balbisiana) banana peel as a lignocellulosic precursor for activated carbon: characterization study after carbonization process with phosphoric acid impregnated activated carbon. Biomass Conversion and Biorefinery 13:11085–11098.
Basumatary S, Deka DC (2014) Transesterification of yellow oleander (Thevetia peruviana) seed oil to fatty acid methyl esters (biodiesel) using a heterogeneous catalyst derived from rhizome of Musa balbisiana Colla. International Journal of Chem Tech Research 6(4):2377-2384.
Chukanov NV, Chervonnyi AD (2016) Infrared Spectroscopy of Minerals and Related Compounds (Springer Minerology). Springer, 2016.
Vaid U, Mittal S, Babu JN (2014) Removal of hexavalent chromium from aqueous solution using biomass derived fly ash from Waste-to-Energy power plant. Desalination and Water Treatment 52:7845–7855.
Zhao X, Xiong H, Song K, Yu L, Zhang X, Han L (2024) A systematical comparation of Cu (II) adsorption behavior and mechanism between biomass fly ash and biogas residue pyrolysis char. Bioresource Technology Reports 28:101959.
Raza A, Khan WU, Khoja AH, Khan A, Hassan M, Liaquat R, Ali M, Ud Din I, Al-Anazid A (2024) Thermokinetic investigation of Polyethylene Terephthalate (PET) plastic over biomass fly ash (BFA) catalyst using pyrolysis process through non-isothermal thermogravimetric analysis. Sustainable Chemistry and Pharmacy 42:101856.
Khalid U, Khoja AH, Daood SS, Khan WH, Ud Din I, Al-Anazi A, Petrillo A (2024) Experimental and numerical techniques to evaluate coal/biomass fly ash blend characteristics and potentials. Science of the Total Environment 912:169218.
Singh A, Abdullah MMS, Sharma T (2024) Sustainable biomass derived natural surfactant of soybean seeds in fly ash industrial waste utilization for carbon storage: Evaluation of environmental impact. Journal of Environmental Chemical Engineering 12:114530.
Wijaya K, Ramadhani S, Saviola AJ, Prasetyo N, Gea S, Hauli L, Amin AK, Saputri WD, Saputra DA, Darsono N (2024) Efficient conversion of used palm cooking oil into biogasoline over hydrothermally prepared sulfated mesoporous silica loaded with NiMo catalyst. Results in Engineering 24:103185.
Elharati MA, Lee KM, Hwang S, Hussain AM, Miura Y, Dong S, Fukuyama Y, Dale N, Saunders S, Kim T, Ha S (2022) The effect of silica oxide support on the catalytic activity of nickel-molybdenum bimetallic catalyst toward ethanol steam reforming for hydrogen production. Chemical Engineering Journal 441:135916.
Saleha TA, AL-Hammadi SA (2021) A novel catalyst of nickel-loaded graphene decorated on molybdenum alumina for the HDS of liquid fuels. Chemical Engineering Journal 406:125167.
Komurcu H, Yılmaz K, Gurdal S, Yasar M (2023) Hydrogenation reactions of kerosene on nickel based catalysts, international journal of hydrogen energy 48:22934-22941.
Lycourghiotis S, Kordouli E, Bourikas K, Kordulis C, Lycourghiotis A (2023) The role of promoters in metallic nickel catalysts used for green diesel production: A critical review. Fuel Processing Technology 244:107690.
Mbarka O, Mohammed B, Abdelkrim E, Mohammed B (2020) Synthesis and Characterization of Nickel Molybdenum Catalysts Supported on Copper Orthophosphates. IOP Conf. Series: Materials Science and Engineering 948:012023.
Melo EF, Melo DMA, Anjos WSP, Correia LA, Marques JAO, Braga RM (2025) Catalytic cracking of Pachira aquatica oil over HZSM-5 for the production of low-carbon transport fuels. Biomass and Bioenergy 194:107680.
Muñoz-Arjona A, Ayala-Cortés A, Stasi CD, Torres D, Pinilla JL, Suelves I (2025) Catalytic hydrodeoxygenation of waste cooking oil into green diesel range hydrocarbons: From batch to continuous processing. Chemical Engineering Journal 503:158303.
Negm NA, Rabie AM, Mohammed EA (2018) Molecular interaction of heterogeneous catalyst in catalytic cracking process of vegetable oils: chromatographic and biofuel performance investigation. Applied Catalysis B: Environmental 239:36-45.
Suchamalawong P, Pengnarapat S, Reubroycharoen P, Vitidsant T (2019) Biofuel preparation from waste chicken fat using coal fly ash as a catalyst: Optimization and kinetics study in a batch reactor. Journal of Environmental Chemical Engineering 7(3):103155.

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Biorefining of Mesua ferrea L. Biocrude into Green Transport Fuels Using TBP Distillation: A Sustainable Approach towards 2-G Biorefinery

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Abstract

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Highlights

1.0. Introduction

2.0. Experimental

2.1. Feedstock used in the work

2.2. Synthesis of Biomass and Non-biomass derived Bimetallic catalysts

2.3. Characterization of Biomass and Non-biomass derived Bimetallic catalysts

2.4. Catalytic hydroprocessing of MFL oil to biocrude oil

2.5. Fractional distillation of MFL biocrude oil using True boiling point (TBP) distillation unit

2.6. Characterization of feedstock, biocrudes and liquid distillate fractions

3.0. Results and discussion

3.1. Catalysts characterization

4.0. Conclusion

Declarations

References

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Journal Publication

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