Methanolysis of Crude Jatropha Oil using Heterogeneous Catalyst from the Seashells and Eggshells as Green Biodiesel

Kinetics and deactivation of a dual-site heterogeneous oxide catalyst during the transesterification of crude jatropha oil with methanol

Ti-incorporated SBA-15 mesoporous silica as an efficient and robust Lewis solid acid catalyst for the production of high-quality biodiesel fuels

Biodiesel (methyl esters) has been produced using numerous catalysts to enhance its quality and related productivity. Generally, the raw materials for biodiesel production and its catalysts significantly impact the produced biodiesel’s quality. In addition, the heterogeneous catalysts are promising as catalysts in the transesterification for biodiesel production and can be used continuously during this production. In particular, these catalysts are essential for green biodiesel production because of their high activity, thermal stability, and reusability. Hence, several homogeneous and heterogeneous (acidic and alkaline) catalysts for biodiesel production, particularly the naturally derived heterogeneous catalysts, are reviewed in this article. Further, the different heterogeneous catalysts for biodiesel production have been studied extensively as replacements for the respective homogeneous catalyst. Specifically, this replacement is aimed at the simultaneous esterification and transesterification of the nonedible and low-cost biomasses under moderate conditions producing biodiesel. Moreover, this study analyzes biodiesel’s impact and long-term performance in various applications. Finally, it also reports the advancements in biodiesel production in terms of the catalysts used in it and its processes to aid further developments in biodiesel production.

A heterogeneous catalyst, FeOx/SiO2, prepared by the pore‐filling method, was found to be active in the transesterification of crude Jatropha oil with methanol. When the transesterification reaction was carried out with a reaction temperature of 220 °C, a catalyst amount of 15 wt%, a methanol/oil molar ratio of 218:1, and a reaction time of 3 h, the yield of fatty acid methyl esters (FAME) in the product exceeded 99.0 %, and met with EN standards for allowable contents of glycerine and mono‐, di‐, and tri‐glycerides. The correlation between the FAME production activity and measured acidity of the FeOx/SiO2 catalysts showed that the transesterification reaction was promoted via the acidic function of these catalysts, which are less inhibited by coexisting free fatty acids in the feedstock triglycerides.

Transesterification of crude jatropha oil with methanol was investigated using a heterogeneous catalyst derived from waste marble. The barium enhanced waste marble catalyst was prepared via precipitation/impregnation methods and showed high performance to methyl ester conversion when calcined at 830 o C for 4 h. The high activity of the solid oxide catalyst resulted from the basic-sites generated from the synergetic composite formed with high dispersion of the active species as indicated from characterization data with Brunauer-Emmett-Teller (BET) surface area, 56.01 m 2 /g, average pore size, 123.63A, and pore volume, 0.17 cm 3 /g. The methyl ester content of 70.36% was achieved over the catalyst within 4 h under the optimal transesterification conditions of methanol/oil molar ratio of 15:1, catalyst amount of 5 wt % and reaction temperature of 65 o C. The research provides insight into application of waste marble enhanced with barium as potential catalyst in the heterogeneously catalyzed transesterification of crude jatropha oil in mild conditions. http://dx.doi.org/10.4314/njt.v34i1.15

The transesterification of crude jatropha oil (CJO) to biodiesel using Bi-ZnO (bi-zinc oxide) as a solid catalyst was investigated. The catalyst was prepared by co-precipitation technique, calcined and characterized with XRD, TEM and the surface area, pore volume and pore size distribution of the developed catalyst were measured using BET method to give insights into its performance. It was established that sample loading of 2.0 wt.% Bi on ZnO could exhibit the highest catalytic activity when the transesterification reaction was carried out at reflux of methanol (65°C), with a 12:1 molar ratio of methanol to oil and a catalyst amount of 4 wt.%, the conversion of jatropha oil was 95%during 1 h of reaction. The utilization of the catalyst for transesterification of non-edible oil will reduce dependence on food-grade oil for industrial application. The catalyst when washed using methanol and oven dried at 80°C, can be reused for further tranesterification of the oil. Original Research Article Olutoye et al.; AIR, 7(1): 1-8, 2016; Article no.AIR.20716 2

Heterogeneous base catalysts: Synthesis and application for biodiesel production – A review

The relevance of heterogeneous catalysis in biodiesel production cannot be overemphasized, as heterogeneous catalysts have eliminated the demerits associated with a homogeneous catalysts. Some heterogeneous catalysts experience drawbacks such as partial recoverability and reusability, energy and waste conservation issues during biodiesel processing and leaching of active catalyst sites. This paper highlights and summarizes several heterogeneous catalysts used in biodiesel production. The catalyst preparation, reaction conditions, feedstock, and biodiesel yield for the heterogeneous base and acid catalysts were emphasized. The inability of heterogeneous base catalysts to trans-esterify low-grade oil with high free fatty acid (FFA) is a primary concern; the cost of processing low-grade oil with high FFA using heterogeneous acid catalysts is also a big issue. Nano-doped heterogeneous catalysts with unique properties were recommended because they can process oil with high FFA transesterification, improve reaction efficiency, simplify production, reduce the leaching of active sites, enable better biodiesel yield by minimizing energy and waste, and increase catalyst recoverability, activity, selectivity and durability.

Current status and challenges in the heterogeneous catalysis for biodiesel production

Transesterification of crude Jatropha oil by activated carbon-supported heteropolyacid catalyst in an ultrasound-assisted reactor system

The duck and chicken eggshell wastes were applied as raw materials for the preparation of heterogeneous catalyst in biodiesel production. Prior to use, the calcium carbonate (CaCO3) content in the waste shell was converted to calcium oxide (CaO) by calcining at 600-900C for 4h. The physicochemical properties of the solid oxide catalyst were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM) and the Brunauer-Emmett-Teller (BET) method. The catalytic activity of the catalyst in transesterification of palm oil with methanol was evaluated, and the fuel properties of obtained biodiesel were measured. The effect of reaction time, reaction temperature, methanol/oil molar ratio, catalyst loading, and reusability of catalyst was also investigated. Eggshell waste is a bioresource for the production of heterogeneous base catalyst that can be successfully utilized for the synthesis of biodiesel with high purity.

As a promising renewable fuel, biodiesel has gained worldwide attention to replace fossil-derived mineral diesel due to the threats concerning the depletion of fossil reserves and ecological constraints. Biodiesel production via transesterification involves using homogeneous, heterogeneous and enzymatic catalysts to speed up the reaction. The usage of heterogeneous catalysts over homogeneous catalysts are considered more advantageous and cost-effective. Therefore, several heterogeneous catalysts have been developed from variable sources to make the overall production process economical. After achieving optimum performance of these catalysts and chemical processes, the research has been directed in other perspectives, such as the application of non-conventional methods such as microwave, ultrasonic, plasma heating etc, aiming to enhance the efficiency of the overall process. This mini review is targeted to focus on the research carried out up to this date on microwave-supported heterogeneously catalysed biodiesel production. It discusses the phenomenon of microwave heating, synthesis techniques for heterogeneous catalysts, microwave mediated transesterification reaction using solid catalysts, special thermal effects of microwaves and parametric optimisation under microwave heating. The review shows that using microwave technology on the heterogeneously catalysed transesterification process greatly decreases reaction times (5–60 min) while maintaining or improving catalytic activity (>90%) when compared to traditional heating.

Ultrasound-assisted transesterification of crude Jatropha oil using cesium doped heteropolyacid catalyst: Interactions between process variables

The need for fossil fuels and the emissions generated from these fuels are increasing daily. Researchers are concerned with global warming as well as climate change; and energy sustainability and material usages are important issues today. Waste cooking oil (WCO) can be processed into biodiesel as an alternative fuel to replace diesel. Production of biodiesel using WCO as the feedstock has been of growing interest for the last two decades. A number of research papers related to the improvements in production, raw materials and catalyst selection have been published. This paper reviews the various types of heterogeneous solid catalyst in the production of biodiesel via the transesterification of WCO. The catalysts used can be classified according to their state presence in the transesterification reaction as homogeneous or heterogeneous catalysts. Homogeneous catalysts act in the same liquid phase as the reaction mixture, whereas heterogeneous catalysts act in a solid phase with the reaction mixture. Heterogeneous catalysts are non-corrosive, a green process and environmentally friendly. They can be recycled and used several times, thus offering a more economic pathway for biodiesel production. The advantages and drawbacks of these heterogeneous catalysts are presented. Future work focuses on the application of economically and environmentally friendly solid catalysts in the production of biodiesel using WCO as the raw material.

Biodiesel is an alternative fuel to mineral diesel. It is produced from abundant and easily available renewable resources of animal fats and vegetable oil. However, the cost of oil feedstock is the major obstacle towards production and commercialization of biodiesel. In this study, an economical and environmental friendly heterogeneous catalyst derived from Tamarindus indica fruit shells (TIFSs) was prepared by calcination method, and it was used in transesterification of Parinari curatellifolia seeds oil (PCSO) to produce biodiesel. The seeds were characterized by having high oil content 36.2%, which makes the feedstock a reasonable candidate for biodiesl production. The catalyst was prepared by calcination of TIFSs at 800 °C in muffle furnace for 3 hours to obtain Tamarindus indica fruit shells ash (TIFSA), a heterogeneous catalyst. Various techniques were used to analyze physicochemical properties of TIFSA. The catalyst exhibits high basic strength (pH>9.7), with the mesoporous structure of pore diameter d = 3.2 nm, high specific area 378.2 m2/g, pore volume of 0.203 cm3/g and CaO crystals as a major active phase of the catalyst. The calcinated catalyst TIFSA was tested in the production of biodiesel through transesterification process using PCSO to obtain Parinari curatellifolia methyl ester (PCUME). During production, the best operating parameters were 5% wt. catalyst loading, 2 hours reaction time and 9:1 methanol to oil molar ratio with the maximum yield of 96.2%. In addition, the catalyst was easily separated and reused again four more times with biodiesel yield above 74%. Furthermore, the produced biodiesel was analyzed by Gas Chromatography-Mass Spectrometry (GC-MS) and composed mainly of unsaturated acids 63.6% and saturated acid 36.39%. Also, fuel properties of produced PCUME were investigated as per ASTM methods and compared to ASTM D6751 standard limits and mineral diesel. Most of the determined fuel properties were observed to be in good agreement with the global standards. Therefore, Parinari curatellifolia seeds oil and Tamarindus indica fruit shell are ideal feedstock for low-cost biodiesel and catalyst production respectively.