Home Hydrocracking optimization of palm oil over NiMoO4/activated carbon catalyst to produce biogasoline and kerosine
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Hydrocracking optimization of palm oil over NiMoO4/activated carbon catalyst to produce biogasoline and kerosine

  • Allwar Allwar EMAIL logo , Nevi Indriyani , Rina Maulina and Feby Rahmawati
Published/Copyright: December 31, 2022

Abstract

The conversion of palm oil into biofuel is continuing interest in a green alternative fuel. Catalytic hydrocracking palm oil into biofuels was carried out by NiMoO4/activated carbon catalyst. The catalyst was first designed from nanoparticle NiO–MoO3 supported by activated carbon from palm kernel shell and characterized using X-ray crystallography, Fourier transform infrared, and scanning electron microscope with energy dispersive X-ray. The efficiency of the catalyst was evaluated for the conversion of palm oil into biogasoline and kerosene using the hydrocracking process at different temperatures (150, 250, and 350°C). The resulting catalytic hydrocracking is liquid biofuels, which is analyzed using GC–MC to determine its fractions: biogasoline (C5–C10) and kerosine (C11–C16). The optimum condition of catalytic hydrocracking was obtained at a temperature of 150°C resulting in two primary fractions classified into biogasoline (37.83%) consisting of n-nonane (C9) and 1-heptene (C7) and kerosine (61.34%) consisting of three primary fractions, n-pentadecane (C15), hexadecene (C16), and 1-undecene (C11). The result of this study proved that the NiMoO4/activated carbon catalyst plays an important role in catalytic hydrocracking and becomes a promising alternative catalyst for the preparation of biofuels.

1 Introduction

In the recent decade, researchers have selected biomass as an important alternative fuel for the requirement of energy and transportation [1]. Indonesia has abundant biomass sources available in Sumatera, Kalimantan, and Irian Jaya islands. Palm oil derivates are glycerol, fatty acid, or fatty alcohol that are potential compounds for raw materials of food products, cosmetics, perfumes, and detergents [24]. Nevertheless, these compounds have made palm oil to become a sustainable replacement for the fossil fuels. The extensive use and depletion of fossil fuel resources have increased the research level to replace fossil oil with palm oil, which is low energy, renewable resources, and environmentally friendly [5,6]. Palm oil consists of predominantly paraffin and aromatic that can be converted into biofuel. However, the characteristics, utilizations, and environmental impacts of the palm oil industry should be further investigated.

Activated carbon has been extensively studied and used as a catalyst and supporting catalyst. Previous research showed that activated carbon is widely used as catalyst for the conversion of palm oil into biodiesel due to its low-cost material, rich in functional groups, and porous material [7,8]. The application of activated carbon has been developed for supporting of the heterogeneous catalyst. Therefore, it is necessary to modify the naturally activated carbon to improve its characterization and structure such as thermal stability, porous structure, and acidity. The incorporation of the activated carbon with metallic ions and metallic oxides such as nickel, iron, cobalt, platinum, and molybdenum has been widely published [9,10]. Molybdenum nitride-zeolite was used as a catalyst and successfully prepared for the hydrocracking process [11]. Ni–Fe/HZSM-5 a catalyst was prepared for the hydrocracking of coconut oil [12,13]. Ni–Cu/bentonite was used as a catalyst to convert palm oil into gasoline production [14]. Based on the porous structure of activated carbon, the dispersion of metals and metal oxides on the surface through the physical and chemical interaction can increase the active sites and be used as a heterogeneous catalyst. Increasing the active site of catalysts such as metallic active sites and acidity may support the catalytic activity through hydrocracking, isomerization, and cyclization process [15,16]. In this research, the modification of activated carbon as a porous material doped with the bimetallic nanoparticle NiO and MoO3 is a promising material for hydrocracking catalysts. The catalyst of NiMoO4/activated carbon was prepared and will test its performance for the conversion of palm oil to produce biofuels consisting of biogasoline (C5–C10) and kerosine (C11–C16) fractions at different temperatures.

2 Materials and methods

2.1 Materials

The waste of palm kernel shell (PKS) was collected from an open area around the palm oil industry in East Kalimantan, Indonesia. The PKS was found in large quantities and used as a source of energy in the steam boiler. All chemicals and reagent such as potassium hydroxide, nitrate acid, nickel nitrate hexahydrate (Ni(NO3)2·6H2O), ammonium hepta-molybdate tetrahydrate ((NH4)6Mo7O24·4H2O), chloride acid, and sodium hydroxide were of analytical grade from Merck and used without any further purification. Hydrogen and nitrogen gas were of high purity from Samator distributor gas industry, in Indonesia.

2.2 Methods

2.2.1 Catalyst preparation

The bimetallic nickel and molybdenum oxides supported by activated carbon or NiMoO4/activated carbon catalyst was obtained by the calcination process at 400°C. The activated carbon used in this study was prepared using the previous work with the modification of a pyrolysis temperature of 700°C [17]. About 5 g of the activated carbon was impregnated with 100 mL aqueous solution of 7.2 g Ni(NO3)2·6H2O and 1.8 g (NH4)6Mo7O24·4H2O and strongly stirred for 1 h. The mixture was continuously stirred at temperature of 60–70°C for 5 h followed by gradually dripped 2 M sodium hydroxide solution to control the pH in the range of 8–9. The mixture was filtered and dried in an oven at 110°C. The dried mixture was calcinated at a temperature of 400°C for 5 h and finally reduced by gas hydrogen. The NiMo4/activated catalyst was kept for further analysis.

2.2.2 Hydrocracking process

The hydrocracking process was carried out as shown in Figure 1 [18]. Approximately, 1.0 g of NiMoO4/activated carbon was placed into the catalyst chamber and 100 g of palm oil as a feedstock was injected into the feedstock reactor. The reactor was gradually heated to the temperature of 350°C and kept for 30 min as a contact time. During the catalytic process, gas hydrogen was injected with a flow rate of 20 mL/min. The palm oil slowly evaporates as the lightest gas and passes through the catalyst chamber which was set up at a temperature of 150°C. The interaction between gas particles and catalyst occurred in the catalyst chamber as a catalytic hydrocracking process. The result is a gas product and then it was condensed to form a liquid yield which was collected into a vial as the primary product. The experiment for each hydrocracking process was continued with a similar method at different temperatures (450 and 550°C) and the temperature catalyst was set up at 250 and 350°C. The result of the hydrocracking process yields three liquid products, which were obtained at the temperatures of 150, 250, and 350°C as the main product. However, some gas products cannot be collected because of disappearance during the catalytic process.

Figure 1 
                     Diagram of hydrocracking process.
Figure 1

Diagram of hydrocracking process.

2.2.3 Characterization of the catalyst

The characterization of NiMoO4/activated carbon catalyst was carried out using Fourier transform infrared spectroscopy (FTIR, PerkinElmer Spectrum Version), X-ray crystallography (XRD, Bruker D2 Phaser Gen), and scanning electron microscope with energy dispersive X-ray analysis mapping (SEM-EDX/mapping, JEOL JED-2300). The effectivity of the catalyst was tested for the conversion of palm oil into biofuel at different temperatures. The liquid product was separated into biogasoline and kerosene. The percentage fraction and composition of biogasoline and kerosine were evaluated by the gas chromatography-mass spectrometer (GC-MS, Shimadzu QP2010 SE).

3 Results and discussion

3.1 Characterization of catalyst

The determination of functional groups on the activated carbon and the catalyst is analyzed using FTIR as shown in Figure 2. A broad peak around 3,446 cm−1 is assigned to the −OH stretching vibration of hydroxyl groups. Both peaks at 1,634 and 1,638 cm−1 are attributed to the C═O stretching vibration of carboxylate and carbonyl groups. The peak at around 1,385 cm−1 is the characteristic of C–H in the −CH2 and −CH3 deformation. The peaks at 826 and 479 cm−1 are assigned to the presence of metal–oxygen bonding in the form of Ni–O or Mo–O on the surface of activated carbon [19]. The presence of an oxygen-containing functional group leads to strong bonding between oxygen and nitrogen–molybdenum during the impregnation process. This interaction is essential for achieving and preserving high nickel and molybdenum dispersion on the surface of activated carbon. This effect on the Ni–O and Mo–O dispersion on the surface of activated carbon might increase the catalyst activity [20,21].

Figure 2 
                  FTIR spectra of (a) activated carbon and (b) NiMoO4/activated carbon.
Figure 2

FTIR spectra of (a) activated carbon and (b) NiMoO4/activated carbon.

The crystallinity of the catalyst was carried out using XRD and is shown in Figure 3. The diffraction pattern of activated carbon showed a wide peak found at 2θ = 23.58° and 44.11°, which indicates an amorphous structure with the disorderly stacked up carbon rings. Metal oxide of MoO3 was detected at 2θ = 13.01° (111), 27.84° (211), 39.28° (220), 52.23° (311), and 57.30° (113), which was confirmed with JCPDS 00-005-0506. The d-spacing of MoO3 is 0.68, 0.32, 0.23, 0.16, and 0.16 nm. The NiO shows well diffraction at 2θ = 42. 93° (211) and 62.75° (222) with the average of d-spacing of 0.21 and 0.15 nm, respectively, confirmed with JCPDS 00-004-0835. The peaks at 2θ = 16.88° (200), 29.51° (211), 32.77° (121), and 48.69° (301) are the indication of NiMoO4 with the d-spacing of 0.52, 0.30, 0.27, and 0.19 nm, based on the JCPDS 00-031-0902 [22,23]. The crystallized size of the catalyst was calculated by Scherer’s equation using D (crystallize size) and full width at half maxima (FWHM) parameters. The NiMoO4/activated carbon had a crystalized size of about 14.4 nm as the crystal of nickel–molybdenum attached to the surface activated carbon.

Figure 3 
                  XRD patterns of (a) activated carbon and (b) NiMoO4/activated carbon.
Figure 3

XRD patterns of (a) activated carbon and (b) NiMoO4/activated carbon.

Figure 4 shows the SEM image and EDX elemental mapping of NiMoO4/activated carbon. The microstructure image shows that the surface morphology catalyst is an irregular tubular structure with unsmooth surface. The elemental analysis proved that molybdenum and nickel were found at about 13.38 and 250%, respectively, and distributed on the surface of the catalyst as shown in the table in Figure 4. Figure 5(a–e) shows the EDX elemental mapping as a distribution of elements on the surface of activated carbon assigned with different colors. The incorporation of metal NiO and MoO3 on the surface of activated carbon caused an increase in the thickness of the surface through the overlap among the metal elements. The thickness of NiMoO4/activated can be shown from the scanline analysis as shown in Figure 5(f). The highest element content is oxygen presented with a green color on the top of the activated carbon surface. Metal nickel and molybdenum are attached to the surface of activated carbon.

Figure 4 
                  SEM-EDX of the catalyst of NiMoO4/activated carbon.
Figure 4

SEM-EDX of the catalyst of NiMoO4/activated carbon.

Figure 5 
                  SEM-EDX/mapping of the distribution of elements on the surface of activated carbon: (a) carbon, (b) molybdenum, (c) sodium, (d) nickel, (e) oxygen, and (f) scanline.
Figure 5

SEM-EDX/mapping of the distribution of elements on the surface of activated carbon: (a) carbon, (b) molybdenum, (c) sodium, (d) nickel, (e) oxygen, and (f) scanline.

Characterization of NiMoO4/activated carbon was determined using high-resolution transmission electron microscopy (HRTEM) as shown in Figure 6. The HRTEM image shows that the spherical feature with a bright color is indication of the surface of activated carbon and a cubical dark particle is a crystal of Ni and Mo. It is difficult to differentiate the particles of metal Ni and Mo due to their appearing in similar dark cubical particles. The distribution of nanoparticles shows a relatively uniform structure with irregular size. The particles are agglomerated to create a dark spot representing the overlap particles with more layer formations [24]. This observation reveals that the particles NiO and MoO3 are successfully immobilized on the surface of activated carbon as the catalyst of NiMoO4/activated carbon. The EDX mapping shows that the particle Mo leads the formation of metals in the catalyst.

Figure 6 
                  The HRTEM of (a) MoO3 and (b) NiO.
Figure 6

The HRTEM of (a) MoO3 and (b) NiO.

Figure 7 shows that the high-resolution TEM of the catalyst displays a crystal lattice structure of Mo–O and an agglomeration of Ni–O crystal that are immobilized on the activated carbon. The inter-planar distance of the fringes was obtained at 0.68 and 0.21 nm for the MoO3 and NiO, respectively. This result is also confirmed from the XRD data. A different d spacing is caused by the different ionic radii of metals NiO and MoO3 [25].

Figure 7 
                  TEM image of NiMoO4/activated carbon at different sizes: (a) 0.2 µm and (b) 20 nm.
Figure 7

TEM image of NiMoO4/activated carbon at different sizes: (a) 0.2 µm and (b) 20 nm.

3.2 Conversion of palm oil by catalytic reaction

The optimizing hydrocracking of palm oil to biofuel was carried out using the NiMoO4/activated carbon catalyst. The hydrocracking process was conducted at different temperatures of 150, 250, and 350°C with a hydrogen flow rate of 20 mL/min. The hydrogen gas is passed in flow over the catalyst bed at a certain temperature. The main product of the hydrocracking process is liquid and then analyzed using GC–MC to determine the hydrocarbon fuel product. The liquid product is light hydrocarbon fuel that was separated into biogasoline (C5–C10), kerosine (C11–C16), and a heavy product (>C18). The side product of the hydrocracking process is coke, residue, and gas. The determination of total percentage of the side product and liquid is written as follows:

(1) C ( wt % ) = w cat w cbt w f w r × 100 % ,

(2) R ( wt % ) = w f w r w f w r × 100 % ,

(3) L ( wt % ) = w l w f w r × 100 % ,

(4) G ( wt % ) = 100 L ( wt % ) R ( wt % ) C ( wt % ) .

Here L is the liquid conversion obtained from the catalytic process (wt%), C is the coke formation on the catalyst (wt%), R is the residue in the reactor (wt%), G is the gas conversion (wt%), w l is the weight of liquid obtained after treatment, w r is the residue weight after treatment, w f is the weight of crude palm oil, w cat is the weight of catalyst after treatment, and w cbt is the weight of catalyst before treatment.

Figure 8 shows the total percentage conversion of the coke, liquid, residue, and gas resulted from the hydrocracking process. Coke occurs due to the clumping of residual oil on the surface that can inhibit the interaction between the active site of the catalyst and oil. The percentage yield of coke was calculated according to equation (1). The amount of coke found is about 2.01 wt% as a solid compound that strongly attaches to the catalyst surface. The residue was obtained inside the reactor in form of a thick oil as a residual feedstock in the combustion reaction. The percentage residue was obtained as per equation (2). The yield of residue is about 3.28 wt%. Liquid is a main product resulting from the condensation of the lightest gas product and it is calculated according to equation (3). The yield of liquid is found to be about 42.54 wt%. The resulted liquid was analyzed with the GC-MS to determine their fractions such as biogasoline, kerosine, and heavy hydrocarbon fuel. The largest side yield is the gas that disappeared during the catalytic activation. The determination of percentage gas is calculated as in equation (4). The amount of gas yield is 52.07 wt%. All the side products such as coke, residue, and gas are difficult to collect and hence cannot determine their fractions and compositions.

Figure 8 
                  Total products resulted from the hydrocracking process.
Figure 8

Total products resulted from the hydrocracking process.

3.3 Conversion of liquid to biofuel

The ability of NiMoO4/activated carbon catalyst in the conversion of palm oil into biofuel is an indication of the successful catalytic process. Many numbers of peaks present in the figure show the effectivity of the catalyst in the catalytic hydrocracking. Figure 9 shows the GC spectra of the liquid product obtained at different temperatures. Figure 9(a–c) describes the distribution of peaks at the temperatures of 150, 250, and 350°C, respectively. Different number of peaks are shown in each of the temperature. At a temperature of 150°C, the number of the peak at low retention time in the range of 2–10 min is more dominant compared to other hydrocracking temperatures. This result proves that the hydrocracking temperature of 150°C is predominantly biogasoline. However, Figure 9(a) and (b) shows the reduction in the number of peaks at low retention time and shifts to higher retention time in the range of 10–20 min. The reason is that the increase in temperature to 250 and 350°C increases the kerosine (C11–C16) and heavy hydrocarbon fraction (>C17) product. The effectiveness of the catalyst of NiMoO4/activated carbon in the conversion of palm oil to biofuel was influenced by the temperature which was supported with hydrogen gas and an active site of the catalyst. Temperature of the hydrocracking may initiate the breakdown of carbon–carbon to form free radicals resulting in an increasing gas and light oil product.

Figure 9 
                  GC-MS spectra of liquid product resulted at different temperatures of (a) 150°C, (b) 250°C, and (c) 350°C.
Figure 9

GC-MS spectra of liquid product resulted at different temperatures of (a) 150°C, (b) 250°C, and (c) 350°C.

The presence of hydrogen in the catalytic process is very important to support the formation of the product. At high temperatures, the hydrogen is easily split into free radicals, which are dispersed on the active site of the catalyst. However, the active site of a catalyst consisting of metallic NiMoO4 and a porous structure of activated carbon has a dual function as an acidic site for an increase of the cracking process and as metal sites for the hydrogenation process. The combination of free radicals resulted from hydrogen and carbon inhibits serious cracking and facilitates the condensation of free radicals. This process suggested that temperature of 150°C is the optimum condition for producing of a shorter-chain-hydrocarbon compound as a biofuel product. However, at a higher temperature, the yield of the catalytic hydrocracking is a heavy fraction such as kerosene and coke.

Figure 10 shows the percentage of the liquid product determined from the GC data. The result was classified according to carbon contents such as biogasoline (C5–C10), kerosine (C11–C16), and heavy product (>C18). The highest conversion was obtained at a temperature of 150°C consisting of biogasoline (37.83 wt%), kerosine (61.33 wt%), and heavier hydrocarbon (0.83 wt%). A temperature of 250°C shows decrease in biogasoline and kerosene products to 10.67and 58.91 wt%, respectively, and an increase in the heavy product (30.42 wt%). However, at the temperature of 350°C, the product of biogasoline increases to 20.41 wt% followed by decrease in kerosene (67.10 wt%) and heavier products (12.49 wt%). This study suggests that the optimum condition of the hydrocracking process is obtained at a temperature of 150°C. Increasing the temperature from 250 to 350°C may accelerate the formation of free radicals from hydrogen and carbon. Incorporation of free radicals through isomerization might create a new hydrocarbon fuel with smaller carbon content. The condensation of free radicals may form hydrocarbon fuels such as biogasoline and kerosene. However, the formation of a heavy hydrocarbon fuel such as coke is due to the ineffective catalyst to facilitate the isomerization process. This result was compared with the previous study [18] and shows a similar optimum temperature (150°C) with the highest gasoline products. This result can be assumed that the conversion of palm oil into biogasoline can be recommended at a temperature of 150°C.

Figure 10 
                  Types of liquid fractions at different temperatures: biogasoline (C5–C10), kerosine (C11–C16), and heavy hydrocarbon fuel (C17–C24).
Figure 10

Types of liquid fractions at different temperatures: biogasoline (C5–C10), kerosine (C11–C16), and heavy hydrocarbon fuel (C17–C24).

3.4 Conversion of biofuel to hydrocarbon fraction

The liquid fraction of the hydrocracking process can be separated into biogasoline (C5–C10), kerosine (C11–C16), and heavy hydrocarbon fuel (C17–C24). The prediction of fraction compounds was determined by GC-MS supported with the Similarity Index. Table 1 shows the distribution of liquid fractions at different temperatures. At the temperature of 150°C, the primary products in the biogasoline are n-nonane (C9) and 1-heptene (C7). This result was confirmed from a previous study that biogasoline consists of alkanes and alkenes compounds [26]. Based on the GC-MS analysis, the kerosine fraction primarily consists of n-pentadecane (C15) and 2-undecene (C10). This result is assumed from the conversion of unsaturated fatty acid into fatty acid and followed by the conversion into shorten-chain-hydrocarbon using decarboxylation and hydrodeoxygenation process [27]. The increase in the temperature to 250°C decreased the biogasoline and kerosine yield to 10.67 and 58.91%, respectively. At the hydrocracking temperature of 350°C, the percentage fraction of the biogasoline is 20.41% with a large number of n-decane (C10) compounds. Meanwhile, the kerosine fraction increases to 67.1% consisting of a high n-pentadecane (C15). The percentage of heavy products is 12.49 wt% as a side product of catalytic hydrocarbon. The reduction of fraction yield is assumed that an increasing temperature caused an overheating of the catalytic process and continued splitting of hydrogen and carbon–carbon bond to form free radicals. The formation of the incorporation of free radicals may create new heavy hydrocarbon product but then it continued to block the active site of the catalyst by the coke formation. Therefore, the yield of palm oil conversion is strongly influenced by the temperature of hydrocracking.

Table 1

Experiment result of biogasoline and kerosine fractions

Biogasoline (C5–C10) Kerosine (C11–C16) Heavier hydrocarbon (C17–C24)
Compound Relative content (%) Compound Relative content (%) Compound Relative content (%)
Hydrocracking temperature 150°C
1-Hexanol (C6) 3.13 1-Undecene (C11) 12.90 C17–C24 0.83
1-Heptene (C7) 8.78 4-Dodecen (C12) 7.36
Octane (C8) 5.36 Tridecane (C13) 1.69
n-Nonane (C9) 12.88 Dodecenylacetate (C14) 3.57
Decane (C10) 7.68 Pentadecane (C15) 21.01
Hexadecene (C16) 14.81
37.83 61.34 0.83
Hydrocracking temperature 250°C
1-Hexanol (C6) 0.75 1-Undecene (C11) 2.26 (C17–C24) 30.42
1-Heptene (C7) 1.23 4-Dodecen (C12) 1.82
Octane (C8) 1.46 Tridecane (C13) 6.82
Nonane (C9) 2.65 Tetradecane (C14) 3.16
Decane (C10) 4.58 Pentadecane (C15) 41.58
Hexadecane (C16) 3.27
10.67 58.91 30.42
Hydrocracking temperature 350°C
Pentane (C5) 0.33 1-Undecene (C11) 2.87 (C17–C24) 12.49
Hexane (C6) 1.04 1-Dodecene (C12) 13.94
Heptane (C7) 2.62 Tridecane (C13) 10.18
Octane (C8) 4.46 Tetradecane (C14) 12.15
Nonane (C9) 5.37 Pentadecane (C15) 18.46
Decane (C10) 6.59 Hexadecane (C16) 9.50
20.41 67.10 12.49

4 Conclusion

Characterization of NiMoO4/activated carbon was carried out using XRD, FTIR, and SEM-EDX mapping and shows that the catalyst has favorable properties for the hydrocracking process. The application was used for the conversion of palm oil shells into biofuel at different hydrocracking temperatures. The optimum condition of the reaction was obtained at a temperature of 150°C resulting in 37.83% of biogasoline and 67.34% of kerosine. The primary fractions for biogasoline are n-nonane (C9) and 1-neptene (C7), and for kerosene are pentadecane (C15) and hexadecene (C16). However, an increase in the reaction temperature to 250 and 350°C decreases the percentage of biogasoline and kerosine products. Most of the heavy hydrocarbon fraction has a low percentage due to the ineffective active site of the catalyst. The result of these studies can be concluded that the NiMoO4/activated carbon performs an important role and is a promising catalyst for heterogeneous catalyst.


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  1. Funding information: The authors would like to thank The Ministry of Education, Culture, Research, and Technology (Kemdikbudristek) for research funding through The Higher Education Leading Basic Research Scheme (PDUPT) 2021: No. 003/DirDPPM/70/DPPM/PDUPT-Kemendikbudristek/VII/2021.

  2. Author contributions: A. Allwar: conceived and designed the experiments, analyzed and interpreted the data, and wrote the article; N. Indriyani: interpreted the data and reviewed the article; R. Maulina and F. Rahmawati: conducted the experiment and analyzed the results.

  3. Conflict of interest: The authors declare no conflict of interest regarding this publication.

  4. Ethical approval: The conducted research is not related to either human or animal use.

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Received: 2022-09-27
Revised: 2022-12-15
Accepted: 2022-12-18
Published Online: 2022-12-31

© 2022 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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