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Optimization of FAME production from blends of waste cooking oil and refined palm oil using biomass fly ash as a catalyst
Abstract
One of the problems associated with biomass combustion is the amount of fly ashes generated and its subsequent management. The search for ways of valorizing these ashes has been a challenge for the academic and industrial community. On the other hand, used cooking oils are wastes which management is quite difficult, by they have a very important energetic potential. The goal of this work was to optimize the Fatty Acid Methyl Esters (FAME) process, recovering two residual materials (waste cooking oils (WCO), and biomass fly flash (BFA)). The optimization of the process was achieved using the response surface methodology and a Box-Benhken experimental design applied to mixtures of WCO and refined palm oil (RPO), using BFA as catalyst. The influence on FAME yield of four variables (catalyst loading, methanol/oil molar ratio, RPO/WCO ratio and reaction temperature) was studied. The higher FAME yield achieved was 73.8% for the following operating conditions: 13.57 wt% of catalyst loading, 6.7 of meth-anol/oil molar ratio, 28.04 wt% of RPO in the oil mixture with WCO and 55 C for the reaction temperature. The reusability of the BFA catalyst in the process was also studied through three successive usage cycles finding no loss of catalytic activity.
... Globally, energy is renowned as one of the key provisions for socio-economic prosperity. Due to the non-renewable and environmentally dangerous nature of fossil resources, biodiesel as a renewable energy has grown significantly worldwide [1]. However, 70− 95 % biodiesel production cost depends on the price of feedstock. ...
... A thinner peak corresponds to the larger crystal, whereas the broader peak resembles a smaller crystal, presence of defect, or it might be naturally amorphous (a solid lacking perfect crystallinity). From Fig. 2 K.D. Mekonnen and K. Hailemariam diffraction peaks observation, the formation of higher stable polymorph of calcite and Portlandite were observed due to the interaction of combustion products with atmospheric CO 2 and ambient moisture through carbonation and/or hydroxylation, respectively [1,31]. Furthermore, incomplete combustion of the material at a lower temperature might lead to "not much difference between the precursor and the calcined products"; if this is the case, the following alternative auxiliary reactants and reactions can be expected/predicted from the bleach production systems although their formulations were secured. ...
... As a matter of degree of agreement with the reference/pure chemical spectra, all the three coded catalysts were in the order with CaCO 3 > Ca(OH) 2 > CaO with some exceptional differences. The band assignments at 3643 and 1794 cm − 1 is assigned to the O-H bond, because of the absorption of hydroxyl/water molecules adhered to the particle surface to form Ca(OH) 2 [1,35]. The band at 1408 cm − 1 denotes asymmetric C-O bond stretching vibrations of carbonate ions/groups (CO 2− 3 ), which formed due to the chemisorption of atmospheric CO 2 over the catalyst surface. ...
One of the main problem related with liquid bleach production from calcium hypochlorite is the amount of precipitates generated and its consequent management. As a result, academic and industrial communities have been challenged with searching of a means for its valorization. Therefore, this research explores the application of the precipitate as a viable source of Ca-based heterogeneous catalyst development for the production of waste cooking oil methyl esters for the first-time. The catalyst was prepared by dividing the precipitates into three forms, viz. raw untreated (RC), heat treated (RC-TB), and NaOH impregnated plus thermally activated (RC-ITB). The prepared catalysts were efficiently characterized by XRF, XRD, FTIR, SEM, and BET techniques. The characterization results indicated that the catalysts are mainly composed of calcium metal in the form of oxides (CaO), calcite (CaCO3) and Portlandite (Ca(OH)2), which are the promising constituents of basic catalysts. The BET inspection of RC, RC-TB, and RC-ITB revealed the specific surface area of 8.509, 9.089, and 9.312 m²/g, respectively. At the same reaction conditions, the maximum biodiesel yield of 76.05 % was achieved by RC-ITB compared to RC-TB (62.57 %) and RC (19.74 %), because it's larger specific surface area and highest basic nature (pH = 12.65 at 1:5 w/v) improves the reaction catalysis through better catalyst-substrates interactions. The lower biodiesel yield was attained through the RC catalyst due to its untreated surface, lower specific area, and weak alkaline nature (pH value = 10.66 at 1:5 w/v). Furthermore, regardless of the amount of yield, almost similar fuel properties and functional groups of the products over the coded catalysts were observed. Generally, the possibility of calcium hypochlorite precipitate as a precursor of Ca-based heterogeneous catalyst has been effectively proven in this research, which could be very important for environmental safety and industrial resource integration.
... These agricultural wastes derived catalysts contain oxides and carbonates of alkali and alkaline earth metals [38]. Waste passion fruit peel [39], fermented kola nut and palm kernel shell husk [40], Enterolobium cyclocarpum [41,42], biomass fly ash [43], potato peel [44], waste ginger leaves [45], Delonix regia [46], mixture of cocoa, kola nut and fluted pumpkin husks [47], mixture of Musa acuminate, Cucurbita pepo and Citrullus lanatus peels powder [48], mixture of Musa acuminate and Citrullus lanatus peels [49], Theobroma cacao pod husks [50], etc. are some of the reported heterogeneous catalysts. ...
... Falowo et al. [47] also transesterified an equivalent mixture of yellow oleander and rubber oil using a mixture of catalysts developed from the waste of cocoa, kola nut, and pumpkin pod husks. Biomass fly ash was employed as a heterogeneous catalyst by Vargas et al. [43] for the optimization of biodiesel synthesis from the blend of refined palm oil and waste cooking oil. Such biodiesel production from mixed oils using agro-waste catalysts is advantageous in terms of economical point of view and environmental friendliness issues. ...
... This may possibly be due to the presence of only 14.1 % of K in their catalyst compared to 44.15 % of K in the M. chinensis peel catalyst. Fly ash catalyst was also studied by Vargas et al. [43] for binary oil mixture-based biodiesel synthesis and reported only 73.8 % conversion in 120 min of reaction time. This low efficiency might be due to the occurrence of CaCO 3 (71.0 ...
In this study, efficient solid catalysts from the post-harvest Musa chinensis peel, trunk and rhizome were prepared and applied effectively for the production of biodiesel from the quinary oil mixture (soybean oil, sunflower oil, canola oil, jatropha oil and pongamia oil). Catalyst characterization exhibited a highly basic character with the micro-mesoporous and polycrystalline nature of the material. This work investigated the effect of catalyst load, different catalysts from different parts of the plant, MRMO (molar ratio of methanol to oil) and temperature on the reaction. The calcined M. chinensis peel catalyst was found to be the best with 44.15 wt% of K occurring as its carbonate and oxide, which successfully yielded 95.82 % biodiesel at optimized conditions of 5 wt% catalyst amount and 9:1 MRMO at temperature of 65 • C in 11 min. The highest basicity was observed in calcined peel catalyst (0.93 mmol g − 1) in comparison to that of trunk (0.15 mmol g − 1) and rhizome catalysts (0.2 mmol g − 1). This study also displayed a turnover frequency of 16.85 h − 1 (peel), 7.025 h − 1 (trunk) and 2.317 h − 1 (rhizome). The activation energy of the quinary oil mixture-based biodiesel synthesis with the peel catalyst was 53.625 kJ mol − 1. In this work, the catalyst was found to be highly effective, reusable and produced good quality biodiesel that conforms to the international standards, and thus, it may be considered a potential renewable catalyst for biodiesel industries.
... This shows that the addition of SiO 2 causes a reduction in average pore radius in the mesoporous range as a result of impurities. However, there was an increase in the micro-pore volume of sample A from -0.000121 cm 3 /g to 0.000582 cm 3 /g in sample C. The surface area and average pore radius of sample C are higher than the 17.542 m 2 /g and 32.59 Å reported when raw FA was impregnated by Calcium metal and calcined at a temperature of 500 °C for 4 hours as reported by Arif et al. [61] and BET surface area of 9.028 m 2 /g and pore volume of 0.01055 cm 3 /g reported for biomass fly ash by Vargas et al. [62]. The increase in pore volume lends credence to the view that new mesopores can be formed not only by the activation process but also by the addition of supports [61,63]. ...
... The BET surface area is an important physical property that determines the catalytic activity of a solid particle. In this case, a high BET surface area of 35.1102 m 2 /g will aid its catalytic activity for the adsorption and desorption of molecules such as triglycerides, glycerin, and green diesel [62,64]. ...
... Similar results were also reported by Sharma et al. [65], Ho et al. [66], Bhandari et al. [67], and Maneerung et al. [68]. These results show a high possibility of using sample C as a potential catalyst for the conversion of waste plastic oil to diesel [61,62,69] ...
... Moreover, it is estimated that up to 70% of biomass ash may be landfilled worldwide , in opposition to circular economy principles. To this day, some possible valorisation strategies for biomass fly ash have been proposed, including incorporation in construction materials (Cuenca et al., 2013;Saeli et al., 2019), application as soil amendment (Alvarenga et al., 2019;Cruz et al., 2017;Ribeiro et al., 2018Ribeiro et al., , 2017b, or catalysis of biodiesel production (Vargas et al., 2021). ...
... For both types of G BFA , the predominant elements determined by EDX were Ca, K, Si, O, Fe, Al, Cl and Mg. This is in accordance with typical BFA composition, reflecting the original biomass composition (Ribeiro et al., 2017a;Vargas et al., 2021). Both types of G BFA presented silicon oxide, calcium carbonate, potassium chloride and potassium aluminium silicate, corresponding, respectively, to reference codes 04-016-2085, 04-012-8072, 04-005-7123, and 00-001-0705 of the ICDD PDF4+ database. ...
The work describes the combination of granulated biomass fly ash (GBFA) with Fenton process to enhance the removal of adsorbable organic halides (AOX) from pulp bleaching wastewater. At optimal operating conditions, wastewater's chemical and biochemical oxygen demand (COD and BOD5, respectively) and colour was also quantified, and operating cost of treatment assessed. For the first time, raw pulp bleaching wastewater was used to granulate BFA, instead of water, reducing the water footprint of the treatment. Five wastewater treatment setups were studied: (i) conventional Fenton process; (ii) GBFA application; (iii) simultaneous application of GBFA and Fenton process; (iv) sequential treatment by GBFA followed by Fenton process; (v) sequential treatment of Fenton process followed by GBFA. The latter yielded the highest AOX removal (60–70%), whilst COD was also reduced (≈15%) and wastewater biodegradability (BOD5/COD) was enhanced from 0.075 to a maximum of 0.134. Another positive feature of the proposed solution was that GBFA were successfully recovered and reused without regeneration, yielding similar AOX removal compared with fresh GBFA. The operating cost of removing 1 g of AOX from the pulp bleaching wastewater by the optimal treatment setup (60–70% removal of AOX) was 14–26% lower than the operating cost of conducting Fenton process alone (50% removal of AOX).
... During the production of FAME, triglycerides undergo transesterification with methanol, while retaining a high oxygen content, as well as double bonds of the original fatty acids [33]. At the same time, in the production of HVO, complete hydrogenation of fatty acids takes place with the removal of heteroatoms and the saturation of double bonds. ...
... For stand-alone plants, capital and operating costs were calculated using the methods mentioned without modification. Table 5 Evaluation of various types of raw materials for the production of biodiesel fuels in Russian Federation [33] Type of raw material Advantages Disadvantages ...
Current petroleum issues, quickly raising its costs and uncertainties regarding petroleum fuels availability endanger the renewable and sustainable challenge of the worldwide economy. Both the ecological consideration and availableness of fuels highly impact fuel directions for transport vehicles. The current paper introduces the Prospects for producing hydrotreated vegetable oil (HVO) and fatty acid methyl esters (FAME) biodiesel fuels and their applications. The potential of raw material supply for the production biodiesel in Russia was examined, including sunflower oil, soybean oil, rapeseed oil, tall oil, and used cooking oil. Additionally, an economic evaluation of biodiesel production in Russia was performed. Likewise, Russia has launched the process of developing low-carbon strategies for the energy transition, but the country is placing more emphasis on the electrification and gasification of transport. The results reported that HVO is a promising low-carbon component of biological nature than FAME, according to it has a high calorific value, and great chemical stability. Furthermore, the results indicated that the most promising feedstock for biodiesel production in Russia is rapeseed oil, as rapeseed retains a higher yield growth potential. Finally, the most preferable option is the hydroprocessing of oils in a separate unit with a capacity of 500,000 tons/year for oil. Large capacity is probably redundant given the limited resources of advanced raw materials up to 100–150,000 tons of waste oils and up to 150–200,000 tons of tall oils.
Graphical abstract
... characterization of BFA ( Fig. 29(a-c)) it is evident that the CaCO 3 and CaO are present in bulk and very much supportive in transesterification of waste cooking oil to FAME (fatty acid methyl aster) production. The reusability test showed that the BFA catalyst is capable for 3 cycles FAME yield up to 83% (Fig. 29(d) [239]. ...
... (a-c) SEM micrograph and EDX of BFA catalyst (d) XRD analysis of BFA and inset d1 express the reusability of the BFA under 13.575 catalyst loading, 6.7 methanol/oil ratio, 55 • C reaction temperature. Recreated with permission from Ref.[239]. ...
To reduce greenhouse emissions, the utilization of biomass is a proficient path for producing power and its impact on accumulative carbon footprint. Generation of power using biomass produces residue majorly in the form of ash. However, as electrical demand rises, the utilization of biomass as feedstock surges, resultantly the
quantity of ash from power plants increases. Production of the ash in biomass-fired power plants arise multiple problems exclusively handling of ash and its utilization. The continuous rise in ash quantity will challenge ash�storing facilities while increasing management, transferring and disposal cost. Direct disposal to the land sites may also effects the soil nutrient and its structure. This review investigated the basic challenges in biomass ash production, environmental concerns and handling issues. Furthermore, the study explores the various oppor�tunities in biomass ash utilization in conventional applications such as agriculture, construction, and cement industry. Moreover, the status and prospects of ash utilization in novel application such as nanotechnology in industrial catalysis and environmental applications have been well elucidated. Finally, the recommendations were also derived to pave the path for efficient utilization of biomass ash to improve the overall economy of the
biomass operated power plants and sustainable development.
... characterization of BFA ( Fig. 29(a-c)) it is evident that the CaCO 3 and CaO are present in bulk and very much supportive in transesterification of waste cooking oil to FAME (fatty acid methyl aster) production. The reusability test showed that the BFA catalyst is capable for 3 cycles FAME yield up to 83% (Fig. 29(d) [239]. ...
... (a-c) SEM micrograph and EDX of BFA catalyst (d) XRD analysis of BFA and inset d1 express the reusability of the BFA under 13.575 catalyst loading, 6.7 methanol/oil ratio, 55 • C reaction temperature. Recreated with permission from Ref.[239]. ...
To reduce greenhouse emissions, the utilization of biomass is a proficient path for
producing power and its impact on accumulative carbon footprint. Generation of power
using biomass produces residue majorly in the form of ash. However, as electrical
demand rises, the utilization of biomass as feedstock surges, resultantly the quantity of
ash from power plants increases. Production of the ash in biomass-fired power plants
nurture multiple problems exclusively handling of ash and its utilization. The continuous
rise in ash quantity will challenge ash-storing facilities while increasing management,
transferring and disposal expenses. Direct disposal to the land sites may also disturb
the soil nutrient and structure. This review investigated the basic challenges in biomass
ash production, environmental concerns and handling issues. Furthermore, the study
explores the various opportunities in biomass ash utilization in conventional
applications such as agriculture, construction, and cement industry. Moreover, the
status and prospects of ash utilization in novel application such as nanotechnology in
industrial catalysis and energy applications have been well elucidated. Finally, the
recommendations were also derived to pave the path for efficient utilization of biomass
ash to improve the overall economy of the biomass operated power plants.
... The quality of the regression model was expressed by the coefficient of determination R 2 , R 2 adj , and by the Lack of Fit. The residuals plots analysis was performed to validate the model assumptions (normality and randomness of residuals) (Ribeiro et al., 2020;Vargas et al., 2021). All statistical analyses were performed with StatSoft Statistica® v. 8.0 software. ...
The raw materials for the tanning industry, namely hides and skins, are preserved (curing stage) and carried with common salt, i.e., sodium chloride (NaCl). Proceeding to conversion into leather, pickling is a key stage of the tannery process, which entails high demand of water and salt. In this work, the salt-derived brine (SdB) generated from the curing of hides was treated by iron-driven electrocoagulation (EC), aiming at its later application in the pickling stage of the tanning industry, promoting a transition to zero waste emission policy. Focusing on reducing the brine's total organic carbon (TOC), central composite rotational design and response surface methodology were adopted to study the effect of electrolysis time (6.2-14.2 min) and current density (74-431 A m-2) on the treatment of the SdB (≅ 7.5 % wt. NaCl). The quality of the treated brines was then assessed in pickling trials and compared with virgin brine. 68-83% removal of TOC from the SdB were achieved under electrolysis time ranging 6.2-14.2 min and current density ranging 126-252 A m-2. Under these operating ranges the quality of the wet-blue leathers was guaranteed. Lowest power consumption (0.44 kWh·m-3) was achieved under electrolysis time of 6 min and current density of 126 A m-2, yielding 68% removal of TOC. Moreover, the shrinkage temperature of the hides was improved with treated brine (103.5 °C-110.5 °C) compared to virgin brine (103.0 °C). The present study provides strong evidence that contaminated salt from the curing stage can be valorised within the tanning industry through electrocoagulation treatment and then used in another production stage, instead of being landfilled.
... The use of JPW facilitates the transformation of waste into a useful catalytic material product with low-cost preparation and biodiesel production, as well as a reduction of waste disposal in the environment. (Abuhabaya et al., 2013;Aga et al., 2020;Atabani et al., 2012;Hajjari et al., 2017;Ruhul et al., 2015;Vargas et al., 2021). ...
This study aims to develop and convert jackfruit (Artocarpus heterophyllus) peel waste (JPW) into a new solid catalyst suitable for biodiesel synthesis. The calcination process of JPW ash was carried out for 2 h at various temperatures ranging from 500, 600, 700, and 800 ◦C, and the results showed that ash calcined under 500 ◦C produced the highest yield of 92.38%. Based on the characterization result, potassium, calcium, and magnesium were significant components in the prepared catalyst. These components are desirable in biodiesel synthesis, making the catalyst a promising candidate for this process. The response surface methodology (RSM) revealed that the optimum conditions for the synthesis process include an oil-methanol molar ratio of 1:9, a catalyst weight of 12% (w/w), a reaction time of 105 min, and a constant temperature of 65 ◦C, yielding a methyl ester content of 98.88%. The reusability result indicated that the JPW catalyst could be used three times with the highest yield of 93.33%. Moreover, the WCO biodiesel properties were analyzed and found to fulfill ASTM D 6751 requirements. This study demonstrated that JPW can be successfully employed as a solid catalyst for biodiesel synthesis.
... The use of JPW facilitates the transformation of waste into a useful catalytic material product with low-cost preparation and biodiesel production, as well as a reduction of waste disposal in the environment. (Abuhabaya et al., 2013;Aga et al., 2020;Atabani et al., 2012;Hajjari et al., 2017;Ruhul et al., 2015;Vargas et al., 2021). ...
This study aimed to examine the potential of banana peel ash calcined at temperatures of 500 °C, 600 °C, and 700 °C for 4, 5, and 6 h to be utilized as a heterogeneous base catalyst in transesterification reactions to convert triglycerides into methyl esters. X-Ray Diffraction was utilized to ascertain the crystalline phase of the prepared catalyst, whereas Fourier Transform Infra-Red was used to identify the functional groups. The experimental results showed that the optimum parameter conditions were achieved at a calcination temperature of 700 °C for 4 h, with a biodiesel yield of 98.06%. Furthermore, based on the FT-IR analysis, the most significant functional group of the catalyst was from alkaline earth metal oxides. This was also confirmed by the XRD analysis, which showed that K2O compounds have the potential as green catalysts for future use.
... Vargas et al [180]. explored the utility of fly ash as the catalyst for the synthesis of biodiesel from the mixture of refined palm oil and WCO. ...
Biodiesel is considered eco-friendly, biodegradable, non-toxic, and carbon-neutral fuel. It is made from edible or non-edible oil feedstocks including other triglyceride sources. The production of biodiesel depends on the availability of a particular feedstock and the cost of desired raw materials. Biodiesel is mainly produced by the transesterification process using a suitable catalyst preferably a heterogeneous catalyst as it is more beneficial in terms of reusability, recovery, product purity, and production cost as well. Various reactors are developed to produce cost-effective biodiesel at the commercial level. The latest trend in biodiesel synthesis is the application of the machine learning (ML) technique to optimize the process parameters. The application of a mixture of two or more oils as feedstock either non-edible or edible oil is emphasized for biodiesel synthesis and is presently getting more importance. In this paper, the production of biodiesel from various mixed oil (hybrid oil) is reviewed and the effects of mixed oil on the reaction, physicochemical properties, fatty acid composition, and fuel quality of the product are discussed. The study highlighted the activity of various catalysts in the reaction of mixed oil and the economic feasibility. It was found that the ratio of mixed oil is an important factor in terms of conversion and quality of biodiesel. It is also revealed that the application of the ML technique is essentially useful to optimize production efficiency. The utilization of mixed oils will overcome the issues related to the non-availability of feedstocks and reduce the overall cost with improved quality of biodiesel. This approach enhances the production possibility of biodiesel at a large-scale and may boost the biorefinery sector satisfying the future energy demand if the research at the advanced level goes in the right direction.
... The high BET surface area of 35.1102 m 2 /g will support the addition of SiO2 and CFA's catalytic activity for the adsorption and desorption of triglycerides, glycerine, and HDRD [32]. The results of the BET analysis of the catalyst samples has shown their acceptability as a low-cost and biowaste catalyst for hydrogenation of UCO into HDRD [33]. ...
The search for alternate energy to proffer permanent solutions to energy crises, fossil fuel depletion, and global warming
is a pressing task. In this study, hybridized used cooking oil (UCO) was explored for hydro-processing using locally
sourced biowaste catalyst. The coal fly ash (CFA) heterogeneous catalyst was reinforced into silica oxide (SiO2) in a ratio
of 60 wt% to 40wt%. The Parr reactor was used for hydroprocessing and conversion of UCO into hydrogenation-derived
renewable diesel (HDRD). The value of the micropore volume of -0.0001 cm3 increased to 0.0014 cm3, and the external
surface area increased from 0.8611 to 41.2571 m2/g, total surface area 0.5928 to 45.2771 m2/g, and pore volume of 0.0053
increased to 0.1564 cm3/g. This property showed the potential biowaste catalyst for hydrogenation. The fractionated biocrude product known as HDRD exhibits excellent fuel properties than conventional biodiesel. The total yield of bio-crude
product was 67.15%. The product's high yield and excellent quality confirmed the potentials of CFA reinforced with SiO2
as a suitable catalyst. Hydrogenation of UCO into HDRD using an optimal catalyst is a promising technology that will
enhance commercialization addition, and the product is carbon-free, environmentally friendly, and economically viable.
KEYWORDS: CFA, Hybridized UCO, Hydro-Processing, HDRD & Fuel Properties
... Numerous studies have tested biomass ash-based catalysts with the basic properties in biodiesel production such as banana [9,10] and orange [11] peel ash, pineapple [12] and sugarcane leaves ash [13], Brassica nigra plant ash [14], wheat bran ash [15], coconut [16] and rice [17] husk ash, palm oil mill boiler ash [18], biomass bottom [19] and fly ash [20], wood ash [21], Tamarindus indica fruit [22] and walnut shell ash [23] as well as acai seed ash [24]. In addition, the biomass ashes can be used as catalyst support, such as rice husk ash [17,25] and arecanut husk ash [26]. ...
Hazelnut shell ash was investigated as a new base catalyst for the transesterification of used cooking sunflower oil to biodiesel. To understand its catalytic properties, the prepared ash was characterized by EDX, XRD, TGA/DTA, Hg porosimetry, N2 physisorption, FE-SEM, and basic strength measurements. The effects of the catalyst loading in the range of 1–5% of the oil weight and the methanol-to-oil molar ratio of 6:1–18:1 on the kinetics of the fatty acid methyl esters synthesis were established. Moreover, the leaching and reusability of the catalyst were assessed. The obtained results revealed that hazelnut shell ash was mostly composed of K, Ca, and Mg. The highest ester content (98%) was achieved at the catalyst loading of 5%, the methanol-to-oil molar ratio of 12:1, and the reaction time of 10 min. The contribution of homogeneous catalysis because of the catalyst leaching was confirmed but did not determine the overall reaction rate. The catalyst can be reused after the recalcination at 800 °C for 2h achieving the high methyl esters content (>96%) in 30 min after three subsequent runs. The overall reaction followed the pseudo-first-order kinetics with respect to triacylglycerols. A linear relationship between the apparent reaction rate constant and the catalyst loading and the methanol-to-oil molar ratio was determined. The determined value of the reaction rate constant was 0.0576 dm⁶/(min·mol²).
... The higher the surface area the better the catalytic activity in terms of mild cracking and for more interactions with the reactants [25]. However, a high surface area of 45.2771 m2/g will speed up its catalytic activity for the adsorption and desorption of molecules such as triglycerides, glycerine, and green diesel [44,45]. The outcome of the Hydroprocessing of used Cooking Oil Into Green Diesel www.tjprc.org ...
The need for alternative fuels to replace fossil-based fuels has been given more attention by various stakeholders. Commercial catalysts are a major component required for hydro processing of vegetable oil into hydrocarbon. However, the high cost of commercial catalysts hinders the commercialization of green diesel. This research work investigates the viability of biowaste fly ash collected from Eskom with supports like SiO2, Al2O3, and CaO. These three support catalysts and BBTPPFS were pulverized, calcinated, and subjected to Brunauer-Emmett-Teller, thermal, spectroscopic, scanning electron microscope. A significant increase in the value of catalytic properties was noticed when 60 g BBTPPFS (sample D) was reinforced by adding 40 g of SiO2 (Sample A) to obtain sample A1. The value of the micropore volume of-0.0001 cm3 increased to 0.0014 cm3, and the surface area(external) increased from 0.8611 to 41.2571 m2/g, total surface area 0.5928 to 45.2771 m2/g and pore volume of 0.0053 increased to 0.1564 cm3/g. This combination showed properties that reveal it to be a potential green catalyst for hydrogenation and capable of mild cracking to achieve a green diesel range of C15-C18. 1.0 INTRODUCTION The sustained increase in demand for renewable energy across the globe has challenged researchers to develop and implement technologies for processing vegetable oils (edible and inedible) and animal fats into green diesel. The increase in energy demand can be traced to increased socioeconomic activities, industrialization, urbanization, modernization, and population growth [1]. The resulting increase in greenhouse gases (GHGs), and the depletion of fossil-based oil, has triggered the opinion for the search for alternative fuels that offer a pollution free environment and are sustainable. In recent years, the stakeholders have paid much attention to an effort to reduce the atmospheric temperature with policies to curb the effect, the members of legislative body otherwise known as the lawmakers have targeted pollution generated by automobile as major contributor to the GHGs which is one area to pay attention to. Despite the effort of the governments to offer a permanent solution to the threat posed by non-renewable energy and, depletion of oil reserves, the challenge is still on the increase and has attracted the attention of stakeholders globally. Hydrogenation-derived renewable diesel (HDRD), otherwise known as green diesel has emerged as the only feasible and sustainable automobile fuel. Hence, the pressing need for a transportation fuel that is suitable for a compression ignition engine without modifications. Therefore, more research is required by the scholars to investigate the resource availability to produce HDRD that can will offer zero carbon to the environment. The tailpipe emissions generated by trucks and stationary engines are the major contributor to GHGs. Transportation sector is the second largest source to global warming [2]. About 92 million automobiles were produced globally in 2019 compared with about 56 million automobiles produced in 2001 [3]. Environmental Protection Agency (EPA), United States reported, carbon IV oxide (CO2) gases increased by 9 %, Methane emission decreased by 6% between 1990 and 2014. About 20 % of carbon dioxide discharged to the environment can be traced to daily activities such as transport-related emissions, which will continue to rise in the future [4]. Thermal power plants stations are set up to convert heat energy to electrical energy to meet the energy demands of society [5]. The waste generated from a power plant is usually referred to as coal ash, this is the end product of the burning of coals; the highest percentage is fly ash, while the coarse materials that settle at the base of the heating chamber are known as base or bottom ash. The fly ash product generated from burning any form of agricultural waste is known as Bio-Based Thermal Power Plant fly ash [6]. Elemental composition of bio-based ash is determined by the source of biomass and combustion technology. Therefore, BBTPFSs are different from coal ash in terms of their chemistry and mineralogy [7]. Several researchers have investigated and reported the adaptation of catalysts sourced from waste such as eggshell, mud shell, and soda-lime as being active catalysts for decarboxylation [8]. The motivation of the current research work is the addition of CaO, Al2O3, and SiO2 to BBTPPFS to obtain a mixture that possesses optimal catalytic properties that can adequately mild crack used cooking oil (UCO) into the green diesel range. This study focuses on the evaluation of the optimal catalyst properties for hydrogenation. This research is set to determine the effect of calcinated support catalysts with freshly prepared BBTPPFS heterogeneous catalysts, in order to characterize and evaluate the optimal properties for hydrogenation purposes. The scope of this study was to admixture a catalyst and its support, calcinate, and characterize the effect on the hydroprocessing of UCO. Compression ignition (CI) engines in metro vehicles, stationary engines, agricultural machinery, etc. are the mainstay in power generation, transportation, and agriculture sectors. Carbon dioxide (CO2) comprises 74 % of GHG emissions, with about 89 % of CO2 emissions emanating from fossil fuel consumption in lighting, heating, transportation, and industrialization. Methane, nitrous oxide, and fluorinated gases make up 17.3 %, 6.2 %, and 2.1 % of total GHG emissions from agriculture, waste treatment, and industrial processes, respectively [9]. Figure 1 shows the consumption rate and CO2 emission in South Africa from 2009 to 2019. From this figure, it is evident that the consumption rate drops between 2015 to 2018 and rose in 2019, but there is a steady increment in the emission per million tons. Figure 1: Fuel Consumption (per capita) and CO2 Emission (tons) in South Africa from 2009 to 2019 [10]. Catalytic hydro processing of vegetable oils for converting low-grade oils into HDRD has continued to attract more attention in recent years [11]. Utilization of biowaste catalysts for renewable diesel production has become more significant especially when it is generated or derived from waste materials [12]. The selection of a suitable catalyst offers good product with better properties; hence, selecting an appropriate catalyst for hydroprocessing purposes becomes a challenge. Hence, the need to critically study and evaluate the right catalyst that contains the properties suitable for the production of HDRD. The primary objective of catalyst activities in hydro-processing of a feedstock is to ensure adequate triglyceride conversion to a high quality and high yield of biofuel products by lowering the activation energy [13]. In South Africa, about 109 tons of coal is used per year by Eskom power stations, and about 25 million tons of ash is generated. However, 1.2 tons of coal fly ash are supplied to Lafarge for chemical additives in the cement industry. The bottom ash is a fine spherical particle, which has high pozzolanic activity (or reactivity), with unusually high consistency. Apart from the benefit of high quality and concrete economy fly ash also serve as a material for brick making and dam building. The construction of Katse Dam project received a supply of 250 000 tons of coal ash from Lethabo Power Station(LPS), In India, 90 metric tons of fly ash is generated per year and only 3% is used, while Germany used 80% of the coal fly ash product [14]. In most of the BBTPFS thermal power plant producing industries, the method of disposal adopted is either landfill without any restriction [8]. Waste generated and accumulated in an open space causes significant pollution in the environment that can impose health challenges in the geographical area. Indiscriminate disposal of waste products has a significant negative effect on underground water, then the land space occupied inhibits the use of large surface areas for other purposes. Solid waste produced by thermal power plants can be harnessed and used as a green catalyst that will significantly reduce the total cost of production of biofuel. As stated, BBTPFS is also usable by cement production companies [15, 16]. The volume of BBTPFS generation is increasing globally, which also increase the cost of waste management. In South Africa, this waste can be harness as potentials green catalyst resources [17]. The sulfur content in BBTPFS is lower, because is generated from biomass that has low sulfur content. In addition, this will further
... In this case, a high BET surface area of 35.1102 m 2 /g will aida combination of SiO2 and CFA's catalytic activity for the adsorption and desorption of molecules such as triglycerides, glycerin, and green diesel [30,32]. The outcomes of the BET analysis of the samples are a testimony to their suitability as a low-cost and green catalyst for the conversion of waste cooking oil into green diesel by hydrogenation [33,34]. ...
The prohibitive cost of commercial catalysts has inhibited the production and utilization of biofuel as a reliable alternative to fossil-based fuel. Researchers have suggested the conversion and development of wastes as a panacea for this challenge. Towards this end, this study investigated the effects of silica oxide (SiO2) as support for coal fly ash (CFA) as a heterogeneous catalyst for green diesel production was investigated. CFA, sourced from a power plant, was pulverized and developed into a fine powder while SiO2 was obtained from a commercial supplier. Three samples, namely CFA, commercial SiO2, and CFA reinforced with SiO2, were subjected to thermal, spectroscopic, Brunauer-Emmett-Teller (BET), and X-ray diffraction characterization processes. The results showed that CFA reinforced with SiO2 showed the most potential for catalytic applications as it attained thermal equilibrium at 700 ℃ and withstood temperatures as high as 950 ℃ without thermal degradation. The BET surface area, pore-volume, and micropore volume of CFA increased due to the addition of SiO2to the CFA. Also, the spectroscopic analysis showed that the CFA sample reinforced with SiO2showed distinctive peaks at 430 cm-1 , 705 cm-1, and 831 cm-1 which revealed the presence of Al-O-Si and Si-O-Si bending vibrations, and (Si, Al)-O-(Si, Al) symmetric stretching. The percentage of quartz, mullite, and calcite in CFA increased from 33%, 11.78%, and 1% to 87%, 39%, and 5% respectively in the SiO2 reinforced sample. Judging by the outcome of the characterization, reinforcing CFA with SiO2 has the capacity to improve its catalytic performance in green diesel production.
... Fly ash is used as a catalyst for catalytic cracking or catalytic upgrading of waste plastics, which can realize the comprehensive recycling of waste plastics and fly ash. [64,65] Gaurh et al. [66] used fly ash (FA) as raw material to synthesize catalysts (FA, FA-600, FA-700, FA-800 and FA-900) at different temperatures. The catalyst effectively produced valuable aromatic hydrocarbons such as benzene, toluene, ethyl benzene and xylene (BTEX) from waste PE. ...
Development of inexpensive catalysts for biodiesel production has long been favored by researchers. In the present study, the ash from burned discarded Karanja seed shells (KSS) has been found to be one of the most economically and environmentally sustainable materials as a heterogeneous base catalysts for biodiesel production. The catalytic activity of Karanja seed shells ash as a heterogeneous catalyst in biodiesel production was studied using soybean oil methanolysis. Various methods characterized catalysts, such as XRD, WD-XRF, SEM–EDX, FT-IR, BET, and TGA. Soybean oil biodiesel was converted under the following experimental conditions, as determined by 1H NMR, FT-IR, and GC–MS: a catalyst dose of 2 wt%, methanol to oil molar ratio of 10:1, a reaction temperature of 65 °C, a reaction time of 60 min. The reuse of a catalyst was also evaluated, keeping a high biodiesel yield for up to four cycles.
Possibilities of using waste plum stones in biodiesel production were
investigated. The plum kernels were used as a source to obtain oil by the
Soxhlet extraction method, while the whole plum stones, the plum stone shells
that remained after the crashing, and the plum kernel cake that remained
after the oil extraction, were burned off to obtain ashes. The collected
ashes were characterized by elemental composition, porosity, and base
strength and tested for catalytic activity in transesterification of
esterified plum kernel oil. Dominant elements were potassium, calcium, and
magnesium at different contents in the three obtained ashes. The most active
catalyst was the plum stone shell ash, so the effect of temperature (40, 50,
and 60°C) on the reaction rate was investigated. The reaction rate constant
increased with the reaction temperature with the activation energy value of
58.8 kJ mol-1. In addition, the plum stone shell ash can be reused as a
catalyst after recalcination.
The use of a mixture design technique to maximize the energy content of waste cooking oil (WCO) from catering establishments in Iran to make solid alcohol biofuel (SABF) was investigated. Original waste cooking oil (O–WCO) was centrifuged to obtain a supernatant (S–WCO) and a bottom phase (B–WCO) for biodiesel and SABF production, respectively. Micromorphology analysis showed the presence of fatty acid solid salts homogeneously scattered in ethanol at 100 °C and created a three-dimensional porous polycrystalline network after chilling, that enclosed the ethanol molecules and generated SABF. Optimal reaction conditions were 0.2 wt.% alcohol, 0.0275 wt.% NaOH, 0.7725 wt.% B–WCO, and 45 minutes reaction time, for a maximum energy content of 8715.23 kcal/kg (36.46 MJ/kg), similar to natural gas, and higher than control groups, including SABF based on O–WCO, S–WCO, and butter, or some fossil fuels. Furthermore, this study investigates how the SABF heating value rose when the WCO's iodine value declined. This study demonstrated the feasibility of using SABF and candle wax, which has many advantages such as a high melting point, is environmentally friendly, produces no harmful gas emissions, has a long combustion time, leaves little combustion residue, is perfectly hygienic, and is easy to transport and storage.
Biodiesel synthesis from waste cooking oil (WCO) and hone (Calophyllum inophyllum) seed oil (HSO) blend with heterogeneous (calcined Ba(OH)2 and calcined biomass waste (CBW) from Enterolobium cyclocarpum) and homogeneous (KOH) catalysts via two-step irradiated-transesterification process was evaluated in this study. The modeling and optimization of the two processes were studied using Taguchi orthogonal array technique. The factors considered for the esterification process were methanol/WCO-HSO ratio (10:1 - 30:1), time (2 - 8 min), heating power (150 - 450 W), and H2SO4 dosage (0.5 - 1.5 wt.%). In contrast, the factors considered for the transesterification process were methanol/WCO-HSO ratio (6:1 - 12:1), time (1 - 7 min), heating power (150 - 450 W), and catalyst dosage (1 - 2.5 wt.%). Minimum FFA of 0.50% was attained using methanol/WCO-HSO ratio of 30:1, time of 2 min, heating power of 150 W, and H2SO4 dosage of 1.5 wt.%. For the transesterification of WCO-HSO blend, the optimum values are methanol/WCO-HSO ratio of 6:1, time of 1 min, heating power of 450 W, and KOH dosage of 1.75 wt.% with a biodiesel yield of 99.4 wt.%; methanol/WCO-HSO ratio of 6:1, time of 1 min, heating power of 300 W, and calcined Ba(OH)2 dosage of 1.75 wt.% with a biodiesel yield of 98.8 wt.%; and methanol/WCO-HSO ratio of 6:1, time of 4 min, heating power of 450 W, and CBW dosage of 1.75 wt.% with a biodiesel yield of 100 wt.%. The processes catalyzed with synthetic KOH and Ba(OH)2 reached maximum biodiesel yield faster than the crude CBW. The biodiesel quality obtained in this study showed that all three fuels met the American standard specifications and could thus serve as substitutes for fossil diesel.
In this study, thermodynamic analysis of the syngas production using biodiesel derived from waste cooking oil is studied based on the chemical looping reforming (CLR) process. The NiO is used as the oxygen carrier to carry out the thermodynamic analysis. Syngas with various H2/CO ratios can be obtained by chemical looping dry reforming (CL-DR) or steam reforming (CL-SR). It is found that the syngas obtained from CL-DR is suitable for long-chain carbon fuel synthesis while syngas obtained from CL-SR is suitable for methanol synthesis. The carbon-free syngas production can be obtained when reforming temperature is higher than 700 °C for all processes. To convert the carbon resulted from biodiesel coking and operate the CLR with a lower oxygen carrier flow rate, a carbon reactor is introduced between the air and fuel reactors for removing the carbon using H2O or CO2 as the oxidizing agent. Because of the endothermic nature of both Boudouard and water-gas reactions, the carbon conversion in the carbon reactor increases with increased reaction temperature. High purity H2 or CO yield can be obtained when the carbon reactor is operated with high reaction temperature and oxidizing agent flow.
Gas adsorption is an important tool for the characterisation of porous solids and fine powders. Major advances in recent years have made it necessary to update the 1985 IUPAC manual on Reporting Physisorption Data for Gas/Solid Systems. The aims of the present document are to clarify and standardise the presentation, nomenclature and methodology associated with the application of physisorption for surface area assessment and pore size analysis and to draw attention to remaining problems in the interpretation of physisorption data.
For many years, the cost of production has been the main barrier in commercializing biodiesel, globally. It has been well researched and established in the literature that the cost of feedstock is the major contributor. Biodiesel producers are forced to choose between edible and non-edible feedstock. The use of edible feedstock sparks concern in terms of food security while the inedible feedstock needs additional pretreatment steps. On the other hand, the wide availability of edible feedstock guarantees the supply while the choice of non-edible results in a non-continuous or non-ready supply. With these complications in mind, this review attempts to identify possible solutions by exploring the potential of waste edible oils and waste catalysts in biodiesel preparation. Since edible oils are available and used abundantly, waste or used edible oils have the potential to provide plentiful feedstock for biodiesel. In addition, since traditional homogeneous catalysts are less competent in transesterifying waste/used oils, this review includes the possibility of heterogeneous catalysts from waste sources that are able to aid the transesterification reaction with success.
Heterogeneous transesterification of waste cooking palm oil (WCPO) to biodiesel over Sr/ZrO2 catalyst and the optimization of the process have been investigated. Response surface methodology (RSM) was employed to study the relationships of methanol to oil molar ratio, catalyst loading, reaction time, and reaction temperature on methyl ester yield and free fatty acid conversion. The experiments were designed using central composite by applying 24 full factorial designs with two centre points. Transesterification of WCPO produced 79.7% maximum methyl ester yield at the optimum methanol to oil molar ratio = 29:1, catalyst loading = 2.7 wt%, reaction time = 87 min and reaction temperature = 115.5 °C.
A fly ash supported heterogeneous CaO catalyst has been developed using waste egg shell for transesterification of soybean oil to yield fuel grade biodiesel. The active metal precursor Ca(OH)2 of the catalyst has been economically derived from waste egg shell calcination and the mesoporous, high activity strong base catalyst has been prepared using wet-impregnation method. X-ray diffraction (XRD), scanning electron microscope (SEM), low temperature N2 adsorption–desorption (BET) and BJH method studies manifested the well-dispersed presence of CaO over the fly ash framework. The specific surface area of 0.701 m2/g, pore volume of 0.0044 cm3/g, 5.2 nm pore diameter and 1.6 mmol HCl/g catalyst basicity rendered high catalyst activity which could be demonstrated through high biodiesel yield from refined soybean oil by transesterification with methanol. A three factor–three level face centered central composite design (FCCD) has been used to evaluate the effects of process parameters on yield of fatty acid methyl ester (FAME). Optimal parametric values computed using response surface methodology (RSM) corresponding to maximum (i.e. 96.97%) FAME yield were CaO loading of 30 wt.%, 1.0 wt.% catalyst concentration and 6.9:1 methanol/oil molar ratio. The developed catalyst exhibited higher reusability characteristic and superior catalytic activity compared to unsupported CaO catalyst derived from egg shell. An effective waste valorization avenue could, thus, be procreated through preparation of a novel low cost heterogeneous catalyst from these industrial and municipal wastes for synthesis of fuel grade biodiesel.
This paper presents results about the characterisation of the biomass fly ashes sourced from a thermal power plant and from a co-generation power plant located in Portugal, and the study of new cement formulations incorporated with the biomass fly ashes. The study includes a comparative analysis of the phase formation, setting and mechanical behaviour of the new cement-fly ash formulations based on these biomass fly ashes. Techniques such as X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), thermal gravimetric and differential thermal analysis (TG/DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and environmental scanning electron spectroscopy (ESEM) were used to determine the structure and composition of the formulations. Fly ash F1 from the thermal power plant contained levels of SiO(2), Al(2)O(3) and Fe(2)O(3) indicating the possibility of exhibiting pozzolanic properties. Fly ash F2 from the co-generation plant contained a higher quantity of CaO ( approximately 25%). The fly ashes are similar to class C fly ashes according to EN 450 on the basis of chemical composition. The hydration rate and phase formation are greatly dependant on the samples' alkali content and water to binder (w/b) ratio. In cement based mortar with 10% fly ash the basic strength was maintained, however, when 20% fly ash was added the mechanical strength was around 75% of the reference cement mortar. The fly ashes contained significant levels of chloride and sulphate and it is suggested that the performance of fly ash-cement binders could be improved by the removal or control of these chemical species.
The present work reconnoitres the feasibility of utilizing class F fly ash and calcined animal bone powder (CABP) as raw material for the synthesis of heterogeneous solid base catalyst with varying ratios (CABP of 10, 20, and 30 mass%), that is subsequently used for transesterification of mustard oil. Physicochemical characterization of CABP revealed crystalline behavior, signifying one of the components as hydroxyapatite (HAP); when calcined at 900 °C transforms to β–tricalcium phosphate having a specific surface area of 100 m ² g ⁻¹ . The synthesized catalyst showed improved catalytic activity when compared to the parental species and the optimal value to achieve the highest conversion of 90.4% would be at CABP loading of 10 mass%, 5.5:1 methanol to oil molar ratio, and 10 mass% catalyst concentration for 6 h. The prepared biodiesel had a calorific value of 36.2 MJ kg ⁻¹ with ash content < 0.01 mass%. The catalyst could be reused five times with no loss in its activity. Results indicated that calcium enriched waste materials when impregnated in fly ash might be a potential source of catalyst in biodiesel production.
More than 95% of biodiesel production feedstocks come from edible oils, however it may cause some problems such as the competition of land use between food production and biodiesel production. The waste cooking oils (WCO) are an alternative feedstock for biodiesel production; its usage reduces significantly the cost of biodiesel production and has environmental benefits, e.g., a waste recovery instead of its elimination. This work aims to produce a low-cost efficient solid catalyst for fatty acid methyl esters (FAME) production using mixtures of refined palm oil (RPO) and WCO. Four low cost catalysts were prepared (biomass fly ashes, natural dolomite rock, chicken eggshells and polyethylene terephthalate - PET), characterized (by SEM, EDX, XRD, BET, FT-IR and Hammett indicators) and tested regarding their performance in FAME production. The maximum yield of FAME achieved was around 96%wt. for biomass fly ashes catalyst at 60 °C, 9:1 (mol/mol) of methanol to oil mixture, 10%wt. catalyst to oil mixture, over 180 min in batch reactor. The results point out for promising bifunctional catalysts able to achieve also conversion of free fatty acids up to 100% using mixtures of RPO and WCO.
Low thermal stability and insufficient Brønsted acidity are the deficiencies of conventional metal-organic-frameworks (MOFs), which would greatly limit their applications particularly for high temperature and pressure reactions such as dehydration of carbohydrates. This work has successfully demonstrated the development of a composite of MOF and activated fly ash, and their catalytic application in the xylose-to-furfural dehydration process. The composite is capable of maintaining high stability under severe hydrothermal conditions and even in the acidic medium. In addition, the composite shows its excellent catalytic performance for ten consecutive reaction cycles, which is much better than the bare MOF catalyst, MIL-101 (Cr), obtaining the furfural yield and selectivity of 71% and 80%, respectively. It is proposed that such catalytic activity is mainly attributed to the mutual contribution from the Cr atoms of MIL-101 (Cr) and hydroxyl groups of activated fly ash, acting as Lewis acid centers and Brønsted acid sites, respectively. Besides, the effect of salt concentration on the efficiency of xylose conversion has been studied. The product yield can be enhanced to 78% in the presence of trace amount of sodium chloride solution (35 ppt). This provides a promising direction towards the applications when seawater is used as the reaction media. In summary, the work shows that the incorporation of fly ash as the composite material not only reduces the cost of synthesis, but also mitigates the fly ash disposal problems to some extent.
Global energy crisis are as a result of gradual depletion of fossil fuel reserves, coupled with population growth in developing countries. Besides, fossil fuels are not environmentally benign as they are associated with problems, i.e. global warming, high toxicity and non biodegradability, hence it is considered as non sustainable source of energy. Without doubt, biofuel-based energy is a promising long-term energy source that can reduce the over dependence on fossil fuels as a result of feedstocks availability and renewability. However, biodiesel production from vegetable oil using the traditional homogeneous catalytic system is no longer defensible by industries in the near future, particularly due to food-fuel rivalry and ecological problems related to the conventional homogeneous catalytic system. This review presents a comprehensive step by step process of converting waste cooking oil (WCO) to biodiesel, using modified waste egg shell catalyst. The modified waste egg shell derived bi-functional catalyst could easily be removed from the fatty acid methyl esters (FAME) with limited environmental effects. The new modified catalytic system is able to convert the high free fatty acid (FFA) content waste cooking oil to FAME efficiently under moderate reaction conditions. Utilization of waste cooking oil as a feedstock for biodiesel production will reduce the food security issues that stem the biodiesel production from food-grade oil. Moreover, it will reduce the total production cost of the FAME due to its low cost. The major objective of this article is to demonstrate the current state of the use of heterogeneous bifunctional acid/base catalyst to produce biodiesel from green and non-edible waste cooking oil. At the end of the article, perspectives and future developments are also presented.
Transesterification of vegetable oils or animal fats with methanol in the presence of catalysts produces fatty acid methyl esters (FAME) and glycerol as a co-product. This study was focused on a comparative study of the transesterification of refined, bleached and deodorized palm oil (RBD palm oil) using a heterogeneous catalysts CaO with and without γ-alumina (γ-Al2O3) as a support. The results were also compared to that using sodium hydroxide (NaOH), which is a homogenous catalyst. Parameters like the amount of catalyst, the molar ratio of methanol to oil, reaction time and reaction temperature that affect methyl ester and glycerol formation were analyzed and the optimum conditions were determined. The FAME and glycerol content (96.75% and 92.73% respectively) obtained using CaO were lower in purity compared to that using CaO/Al2O3 (97.66% and 96.36% respectively). In the second phase of our work, wood ash from two different sources (birch bark & flyash from a biomass based power plant), which were calcined at 800 °C were studied for their potential use as a cheap renewable alternative heterogeneous catalyst. Both the wood ash samples were found to have good potential for use in such production process, but needs to be optimized further to obtain biodiesel which meets fuel biodiesel specifications. Both CaO and CaO supported on alumina produces FAME to levels that meet the fuel specifications required for blending with diesel. However, the latter produces a purer form of byproduct glycerol that can be easily converted to value added products, without the need for purification. On this basis the supported catalyst is recommended for use in industry as it can add to profits in integrated plants which produces biodiesel and simultaneously uses the byproduct glycerol for value added products.
In the present research work, esterification reaction of waste fish oil (WFO) catalyzed by sulfonated activated carbon under ultrasound irradiation was studied. The application of this catalyst, in addition to the elimination of purification process, leads to the green biodiesel production. The influences of various operating variables such as catalyst loading (1–12 wt%), methanol to oil molar ratio (6–15), and ultrasonic power (100–400 W) on the esterification conversion have been investigated. Response surface methodology (RSM) based on Box–Behnken design (BBD) has been employed. 88% conversion for the esterification reaction has been obtained under the best conditions (i.e., catalyst loading of 11.4 wt%, ultrasonic power of 296.09 W, and methanol to oil molar ratio of 14.85). An accurate mathematical correlation has been developed for the prediction of the esterification conversion. 56% conversion for the esterification reaction has been obtained in the same operating conditions in the absence of ultrasound irradiation.
Biodiesel, which could be derived from plant oils and animal fats, is considered as a promising substitute for petroleum diesel fuel because of its advantages, such as renewability, biodegradability, less environmental toxicity, and superior combustion efficiency. The feedstock used for biodiesel production primarily include edible oils, non-edible oils, waste oils, and animal fats. Consistent scientific investigations are performed to locate innovative oil resources and minimize the utilization of expensive food-grade oils for biodiesel production. The extensive research information is available on the determination of physico-chemical properties of different plant oils. This review will present a general information related to the existing varieties of oil feedstocks, their lipid content, and fatty acid composition.
The aim of this research work is to study the influence of an alkaline activating agent on the preparation of adsorbent/catalyst materials from fly ashes derived from the combustion of Eucalyptus Globulus bark in the energy plant of a pulp mill located in Northern Spain. Different fly ash pre-treatments carried out in previous studies had provided a range of precursors with a high content in unburned carbon and good textural properties. The fraction with a grain size larger than 500μm was selected as it seemed the best precursor for obtaining adsorbent/catalysts materials due to its higher unburned carbon content and better textural properties. This precursor was chemically activated with several alkaline hydroxides and carbonates at different activating agent/precursor weight ratios and under diverse experimental conditions of activation: an activation temperature of from 600 to 900°C, and a nitrogen flow of 150 and 500 ml·min-1. The materials obtained were characterized both chemically and texturally. The results show that it is possible to obtain adsorbent/catalyst materials by chemical activation using a rich-unburned carbon fly ash fraction as precursor (>500 microns). A BET specific surface area of up to 2108 m2g-1 and total pore volume of 1.120 cm3g-1 were achieved. KOH and NaOH were found to be the best activating agents. The materials obtained were mainly microporous. In general, the development of mesoporosity was promoted by NaOH chemical activation. The parameters that had the greatest influence on the textural development of the materials were the activating agent/precursor ratio and the final activating temperature.
Wood ash is a highly alkaline material comprises of inorganic constituents. A limited information on use of wood ash as catalyst is available in literature. The present study was undertaken to investigate the catalytic activity of wood ash for transesterification of Jatropha oil. The thermal treatment (calcination) of wood ash was carried out at temperature in the range of 500–1200 °C to produce calcined wood ash catalysts (CWC). The wood ash was also chemically activated with K2CO3 and CaCO3 by double carbonate solid state reaction to yield activated wood ash catalysts (AWC). The prepared catalysts were characterized by analytical techniques for surface morphology, crystalline phases, textural characteristics and alkalinity. Methyl ester conversion of Jatropha oil was achieved in the range of 97–99% with CWC and AWC catalysts. The synthesized Jatropha methyl esters using CWC and AWC catalysts have been found meeting the critical physico-chemical properties of ASTM D-6751 standards of biodiesel. The present study revealed the possibility of producing potential heterogeneous catalyst from wood ash for biodiesel synthesis, which can find a way to utilize abundant wood ash and reduce the overall cost of biodiesel production.
The main aim of this research is to develop environmentally and economically benign heterogeneous catalysts for biodiesel production via transesterification of palm oil. For this propose, calcium oxide (CaO) catalyst has been developed from bottom ash waste arising from woody biomass gasification. Calcium carbonate was found to be the main component in bottom ash and can be transformed into the active CaO catalyst by simple calcination at 800 °C without any chemical treatment. The obtained CaO catalysts exhibit high biodiesel production activity, over 90% yield of methyl ester can be achieved at the optimized reaction condition. Experimental kinetic data fit well the pseudo-first order kinetic model. The activation energy (Ea) of the transesterification reaction was calculated to be 83.9 kJ mol−1. Moreover, the CaO catalysts derived from woody biomass gasification bottom ash can be reutilized up to four times, offering the efficient and low-cost CaO catalysts which could make biodiesel production process more economic and environmental friendly.
Biodiesel production has become an intense research area because of rapidly depleting energy reserves and increasing petroleum prices together with environmental concerns. This paper focused on the optimization of the catalytic performance in the esterification reaction of oleic acid for biodiesel production over the bifunctional catalyst organotriphosphonic acid-functionalized ferric alginate ATMP-FA. The reaction parameters including catalyst amount, ethanol to oleic acid molar ratio and reaction temperature have been optimized by response surface methodology (RSM) using the Box-Behnken model. It was found that the reaction temperature was the most significant factor, and the best conversion ratio of oleic acid could reach 93.17% under the reaction conditions with 9.53% of catalyst amount and 8.62:1 of ethanol to oleic acid molar ratio at 91.0°C. The research results show that two catalytic species could work cooperatively to promote the esterification reaction, and the bifunctional ATMP-FA is a potential catalyst for biodiesel production.
A palm oil mill fly ash supported calcium oxide (CaO) catalyst was developed to be used as a heterogeneous base catalyst in biodiesel synthesis from crude palm oil (CPO). The catalyst preparation procedure was optimised in terms of final calcination temperature and duration. The optimum catalyst preparation conditions were determined as final calcination at 850 °C for 2 h with 45 wt.% loading of calcined calcium carbonate (CaCO3). A maximum biodiesel yield of 75.73% was achieved for this catalyst under fixed transesterification conditions. Characterisation tests showed that the catalyst had higher surface area and basic sites which favoured transesterification. The effects of catalyst loading, methanol to oil molar ratio, reaction temperature and reaction time on biodiesel yield and fatty acid methyl ester (FAME) conversion were also investigated. It was determined that transesterification conditions of 6 wt.% catalyst loading, 12:1 methanol to oil molar ratio, 45 °C reaction temperature, 3 h reaction time and 700 rpm stirring speed resulted in biodiesel yield and FAME conversion of 79.76% and 97.09%, respectively. Experimental kinetic data obtained from the heterogeneous transesterification reactions fitted the pseudo-first order kinetic model. The activation energy (Ea) of the reaction was calculated to be 42.56 kJ mol−1. Key physicochemical properties of the produced biodiesel were measured and found to be within the limits set by EN 14214. The developed catalyst could feasibly be used up to three consecutive cycles after regeneration using methanol washing followed by recalcination at 850 °C for 2 h.
The ultrasound-assisted sunflower oil methanolysis using KOH as a catalyst was studied at different reaction
conditions. A full factorial experiment 33with replication was performed. The effects of three reaction
variables, methanol-to-oil molar ratio, catalyst loading and the reaction temperature on fatty acid methyl
ester yield were evaluated by the analysis of variance and the multiple regression. At the 95% confidence
level all three factors and the interaction of the reaction temperature and methanol-to-oil molar ratio were
effective on fatty acid methyl ester formation, the most important factor being the catalyst loading. The
relationship between the factors and their interactions was modeled by the second-order polynomial
equation.
Application of ultrasound-assisted biodiesel production process from Jatropha oil catalyzed by activated carbon-supported tungstophosphoric acid catalyst was studied. Influences of ultrasonic energy on different process variables were elucidated. Reaction variables i.e. reaction time (10–50 min), reactants' molar ratio (5:1–25:1), ultrasonic amplitude (30–90% of the maximum sonifier power) and catalyst amount (2.5–4.5 w/w oil) were studied. A mathematical representation for biodiesel yield was successfully generated. A yield of 91% was achieved in just 40 min at a moderate ultrasonic amplitude (∼60%), high molar ratio (25:1) and low reaction temperature (65 °C). Interactions between the variables were also validated statistically. Leaching study revealed that the reaction was predominately heterogeneous in nature.
The use of ultrasonic processor in the heterogeneous transesterification of palm oil for biodiesel production has been investigated. Response surface methodology was employed to statistically evaluate and optimize the biodiesel production process catalyzed by two alkaline earth metal oxide catalysts i.e. BaO and SrO. SEM, surface analysis, AAS analysis and the Hammett indicator methods were used for characterization of the catalysts. Four different variables including reaction time (10–60 min), alcohol to oil molar ratio (3:1–15:1), catalyst loading (0.5–3.0 wt.%) and ultrasonic amplitude (25–100%) were optimized. Mathematical models were developed and used to predict the behavior of the process. The models were able to accurately predict the biodiesel yield with less than 5% error for both catalysts. The basic strength of the catalysts was the main reason of their high activities. This study confirmed that the ultrasonic significantly improved the process by reducing the reaction time to less than 50 min and the catalyst loading to 2.8 wt.% to achieve biodiesel yields of above 95%. The optimum alcohol to oil ratio was found to be at 9:1 while the best amplitudes were ∼ 70 and ∼ 80% for the BaO and SrO catalysts, respectively.
Solid acid catalysts are normally used to catalyze the transesterification of oil with high free fatty acid (FFA) to biodiesel. However, the immiscible phases of methanol-oil-catalyst in the initial reaction mixture usually lead to slow reaction rate and long reaction time. One possible way to overcome this limitation is by using co-solvent that has high solubility in oil and methanol. Therefore, in the present study, the use of biodiesel as co-solvent for transesterification reaction catalyzed by SO42-/SnO2–SiO2 (solid acid catalyst) was investigated. It was found that with the use of biodiesel as co-solvent, a high FAME yield of 88.2% (almost 30% higher than without using co-solvent) can be obtained in a shorter reaction time (1.5 h) using the following reaction conditions; reaction temperature of 150 °C, methanol to oil ratio of 15 and catalyst loading of 6 wt.% (weight of oil).
This study aims to develop an optimal continuous process to produce fatty acid methyl esters (biodiesel) from waste cooking oil in a reactive distillation column catalyzed by a heteropolyacid, H3PW12O40·6H2O. The conventional production of biodiesel in the batch reactor has some disadvantage such as excessive alcohol demand, short catalyst life and high production cost. Reactive distillation combines reaction and separation to simplify the process operation. The reaction catalyzed by H3PW12O40·6H2O overcomes the neutralization problem that occurs in conventional transesterification of waste cooking oil with high free fatty acid (FFAs) and water content. Response surface methodology (RSM) based on central composite design (CCD) was used to design the experiment and analyzed four operating parameters: total feed flow, feed temperature, reboiler duty and methanol/oil ratio. The optimum conditions were determined to be 116.23 (mol/h) total feed flow, 29.9°C feed temperature, 1.3kW reboiler duty, and 67.9 methanol/oil ratio. The optimum and actual free fatty acid methyl ester (FAME) yield was 93.98% and 93.94%, respectively, which demonstrates that RSM is an accurate method for the current procedure.
BA (boiler ash) (empty fruit bunch ash) was used as a source of pseudo-homogeneous base catalyst for transesterification of palm olein. BA successfully transesterified palm olein at mild reaction conditions (3wt.% dried BA, 15:1 methanol:oil molar ratio, reaction temperature of 60°C and reaction time of 30min) to produce 90% methyl esters. Although BA works very well as a catalyst for transesterification, it is not reusable as the active species in the catalyst tend to leach out of the system during reaction. BA was prepared for transesterification by drying in oven at 105±2°C to constant weight.
In this study, waste cooking oil has subjected to transesterification reaction by potassium hydroxide (KOH) catalytic and supercritical methanol methods obtaining for biodiesel. In catalyzed methods, the presence of water has negative effects on the yields of methyl esters. In the catalytic transesterification free fatty acids and water always produce negative effects since the presence of free fatty acids and water causes soap formation, consumes catalyst, and reduces catalyst effectiveness. Free fatty acids in the waste cooking oil are transesterified simultaneously in supercritical methanol method. Since waste cooking oil contains water and free fatty acids, supercritical transesterification offers great advantage to eliminate the pre-treatment and operating costs. The effects of methanol/waste cooking oils ratio, potassium hydroxide concentration and temperature on the biodiesel conversion were investigated.
Biodiesel is a low-emissions diesel substitute fuel made from renewable resources and waste lipid. The most common way to produce biodiesel is through transesterification, especially alkali-catalyzed transesterification. When the raw materials (oils or fats) have a high percentage of free fatty acids or water, the alkali catalyst will react with the free fatty acids to form soaps. The water can hydrolyze the triglycerides into diglycerides and form more free fatty acids. Both of the above reactions are undesirable and reduce the yield of the biodiesel product. In this situation, the acidic materials should be pre-treated to inhibit the saponification reaction. This paper reviews the different approaches of reducing free fatty acids in the raw oil and refinement of crude biodiesel that are adopted in the industry. The main factors affecting the yield of biodiesel, i.e. alcohol quantity, reaction time, reaction temperature and catalyst concentration, are discussed. This paper also described other new processes of biodiesel production. For instance, the Biox co-solvent process converts triglycerides to esters through the selection of inert co-solvents that generates a one-phase oil-rich system. The non-catalytic supercritical methanol process is advantageous in terms of shorter reaction time and lesser purification steps but requires high temperature and pressure. For the in situ biodiesel process, the oilseeds are treated directly with methanol in which the catalyst has been preciously dissolved at ambient temperatures and pressure to perform the transesterification of oils in the oilseeds. This process, however, cannot handle waste cooking oils and animal fats.
This paper explores the feasibility of converting Cerbera odollam (sea mango) oil into biodiesel. The first part of this study focused on the extraction of oil from the seeds of C. odollam fruits, whereas the second part focused on the transesterification of the extracted oil to fatty acid methyl esters (FAME). The transesterification reactions were carried out using three different catalysts; sodium hydroxide (NaOH) as a homogenous catalyst, sulfated zirconia alumina and montmorillonite KSF as heterogeneous catalysts. The seeds were found to contain high percentage of oil up to 54% while the yield of FAME can reach up to 83.8% using sulfated zirconia catalyst.
Flyash-based base catalyst was used in the transesterification of sunflower oil with methanol to methyl esters in a heterogeneous manner. Catalyst preparation variables such as, the KNO3 loading amount and calcination temperature were optimized. The catalysts were characterized by powder XRD. The catalyst prepared by loading of 5 wt.% KNO3 on flyash followed by its calcination at 773 K has exhibited maximum oil conversion (87.5 wt.%). The influence of various reaction parameters such as % catalyst loading, methanol to oil molar ratio, reaction time, temperature, reusability of the catalyst on the catalytic activity was investigated. K2O derived from KNO3 might be an essential component in the catalyst for its efficiency.
Various solid acid catalysts were evaluated for the production of biodiesel from low quality oil such as waste cooking oil (WCO) containing 15 wt.% free fatty acids. The zinc stearate immobilized on silica gel (ZS/Si) was the most effective catalyst in simultaneously catalyzing the transesterification of triglycerides and esterification of free fatty acid (FFA) present in WCO to methyl esters. The optimization of reaction parameters with the most active ZS/Si catalyst showed that at 200 °C, 1:18 oil to alcohol molar ratio and 3 wt.% catalysts loading, a maximum ester yield of 98 wt.% could be obtained. The catalysts were recycled and reused many times without any loss in activity.
In the present study, 21 polycyclic aromatic hydrocarbon (PAH) congeners were measured in the exhaust stack of 3 types of restaurants: 9 Chinese, 7 Western, and 4 barbeque (BBQ). The total PAH concentration of BBQ restaurants (58.81 ± 23.89 μg m(-3)) was significantly higher than that of Chinese (20.99 ± 13.67 μg m(-3)) and Western (21.47 ± 11.44 μg m(-3)) restaurants. The total benzo[a]pyrene potency equivalent (B[a]P(eq)) concentrations, however, were highest in Chinese restaurants (1.82 ± 2.24 μg m(-3)), followed by Western (0.86 ± 1.43 μg m(-3), p<0.01) and BBQ-type restaurants (0.59 ± 0.55 μg m(-3), p<0.01). We further developed a probabilistic risk model to assess the incremental lifetime cancer risk (ILCR) for people exposed to carcinogenic PAHs. Because the exhaust stack directly affected the back-door neighbors of these restaurants, we were concerned with the real exposure of groups near the exhaust stack outlets of these restaurants. The ILCRs for total exposure of the neighbors (inhalation+dermal contact+ingestion) were 2.6-31.3, 1.5-14.8, and 1.3-12.2 × 10(-6) in Chinese, Western, and BBQ restaurants, respectively. We suggest that the maximum acceptable exposure time to the exhaust stack outlet area for Chinese, Western, and BBQ restaurants ranges between 5-19, 17-42, and 18-56 h month(-1), respectively, based on an ILCR of less than 10(-6).
A recent rise in crab aquaculture activities has intensified the generation of waste shells. In the present study, the waste shells were utilized as a source of calcium oxide to transesterify palm olein into methyl esters (biodiesel). Characterization results revealed that the main component of the shell is calcium carbonate which transformed into calcium oxide when activated above 700 degrees C for 2 h. Parametric studies have been investigated and optimal conditions were found to be methanol/oil mass ratio, 0.5:1; catalyst amount, 5 wt.%; reaction temperature, 65 degrees C; and a stirring rate of 500 rpm. The waste catalyst performs equally well as laboratory CaO, thus creating another low-cost catalyst source for producing biodiesel. Reusability results confirmed that the prepared catalyst is able to be reemployed up to 11 times. Statistical analysis has been performed using a Central Composite Design to evaluate the contribution and performance of the parameters on biodiesel purity.
Determinaci on del índice de acidez y de la acidez
- Icontec
- Y Aceites Grasas
- Y Vegetales
- Animales
ICONTEC, NTC 218, Grasas Y Aceites Vegetales Y Animales, Determinaci on del
índice de acidez y de la acidez., Colombia, 2011. https://tienda.icontec.org/
wp-content/uploads/pdfs/NTC218.pdf. (Accessed 15 February 2019).
Grasas y aceites animales y vegetales, Determinaci on del índice de saponificaci on
ICONTEC, Grasas y aceites animales y vegetales, Determinaci on del índice de
saponificaci on, NTC 335 (1998).
ASTM Standard D446e07, Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers
- S Specifications
S. Specifications, ASTM Standard D446e07, Standard Specifications and
Operating Instructions for Glass Capillary Kinematic Viscometers, ASTM Int.
ASTM Standard D446-07, Standard Specifications and Operating Instructions for Glass Capillary Kinematic Viscometers, ASTM Int. 100 Barr Harb
- S Specifications