Recent Advances of Nanoparticle-Based Heterogeneous Catalysts forBiodiesel Production
Aya Md Saada, Hosam H Abdelhady and Mohamed S El-Deab*
Department of Chemistry, Faculty of Science, Cairo University, Egypt
Submission: December 14, 2019; Published: January 03, 2020
*Corresponding author: Mohamed S El-Deab, Department of Chemistry, Faculty of Science, Cairo University, Cairo, Egypt
How to cite this article: Aya Md Saada, Hosam H Abdelhady, Mohamed S El-Deab. Recent Advances of Nanoparticle-Based Heterogeneous Catalysts for Biodiesel Production. Recent Adv Petrochem Sci. 2020; 7(1): 555703 DOI: 10.19080/RAPSCI.2020.07.555703
Abstract
Biodiesel is a promising candidate fuel for traditional petroleum diesel fuel (derived from crude oil). The efficient production of biodiesel depends on various parameters which are involved in its preparation from its constituents, i.e., oil, methanol, catalyst and the total energy input (reaction time and temperature). This review highlights some recent developments in nanoparticles-based heterogeneous catalysts in biodiesel production. This involves the use of CaO-based catalysts derived from various sources. The operating conditions as well as the biodiesel yield are concisely highlighted.
Keywords: Biodiesel Renewable energy Heterogeneous catalysis Nanostructures
Background
Biodiesel is a promising alternative fuel for diesel vehicles and machines. Biodiesel is a renewable fuel which is characterized by low emission of the harmful nitrogen oxides and sulfur oxides gases, i.e., NOx and SOx compared to the traditional petroleum diesel. Thus, the use of biodiesel supports cleaner environment when it comes out the exhaust pipes and thus helps reduce global warming. Biodiesel production is growing world-wide due to the increasing desire for energy, and interest in environmentally friendly fuel production. It is gradually replacing petroleum diesel in several city buses, and some governmental fleets in the united states and elsewhere. It is basically the methyl ester of fatty acids which is prepared via the reaction between oil (triglyceride-fatty acid source) and methanol in such a way that methanol replaces the glycerol in what-is-called a trans-esterification process according to the following equation: Several parameters control the speed of the forward reaction towards the production of biodiesel. These include the amount of methanol, reaction temperature and time in addition to the presence of catalyst. Figure 1 above shows that a stoichiometric ratio of oil to methanol should be at least 1 to 3. Thus, a considerably sufficient amount of methanol should be added to the reaction mixture to ensure the high conversion of oil (triglyceride) to biodiesel. Also, each gallon of produced biodiesel requires at least one gallon of oil feedstock.
Keywords: Biodiesel Renewable energy Heterogeneous catalysis Nanostructures
Catalytic Aspect of Biodiesel Production
The kinetics of this un-catalyzed reaction (Figure 1) is slow. That is a catalyst should be used to push the forward reaction towards biodiesel production in a measurable rate. In this context, several catalysts were suggested including homogeneous catalysts (e.g., KOH and H2SO4) and heterogeneous catalysts (mainly basic oxides, e.g., CaO, MgO). The use of homogeneous catalysts furnishes the advantage of short reaction time and high reaction yield of biodiesel could be achieved [1-2]. But a major disadvantage is the corrosion of the reaction container, foaming (soap formation) together with the difficulty of separation of the homogeneous catalyst from the produced biodiesel and the huge amount of wastewater resulting from its washing, leading to a substantial increase in the overall cost of the process [3]. This is where heterogeneous catalysts show their superiority as a promising alternative particularly basic metal oxide (e.g., CaO, MgO, …. etc.). Thus, CaO-based catalysts showed a significant potential performance towards the forward direction of the trans-esterification process. CaO obtained from agricultural and industrial waste residues are introduced as commercial sources of CaO-based catalysts. The use of CaO solid based catalysts safes the environment, on the one hand, and high biodiesel production efficiency, on the other hand [4-5]. Recently the trans-esterification of vegetable oils to biodiesel has been successfullyachieved [6-9] using residues of paper mill industry [10], eggshell [5,11], sea creatures shell [12,13], animal bones [14-16] and plant ashes [17-19]. Recently, sugar beet agro-industrial waste showed superior activity towards biodiesel production via the transesterification reaction of sunflower oil with methanol [20]. The sole role of CaO is the acceleration of the replacement of glycerol by methanol via catalyzing the several elementary steps involved in the trans-esterification process [20].
The use of nanoparticle-based materials has been emerged as efficient catalysts in several chemical as well as electrochemical reactions. This is because of the high surface area associated with the use of materials in nanometer scale dimensions, e.g., nanoparticles, nanorods, nanospheres, nano cubes. Moreover, the electronic as well as the surface properties of materials are significantly differing in this tiny dimensions. For instance, gold nanoparticles based (AuNPs) catalysts showed a superb catalytic enhancement for low temperature oxidation of carbon monoxide as reported by Haruta et.al. [21]. Furthermore, AuNPs showed excellent electrocatalysis for the oxygen reduction reaction in alkaline, acidic and neutral media [22-24]. Using the virtues of nanoscale material, CaO-based catalysts were prepared in thistiny size dimension to catalysis the trans-esterification of oil to biodiesel (Figure 1). Abdelhady et. al. [20] prepared CaO-based nanocatalysts from sugar beet agro-industrial residue by thermal treatment. They showed that the calcination temperature plays a prominent role in determining the particle size, chemical composition as well as the surface area of the prepared catalyst. The optimum conditions for biodiesel production are shown using 1 wt% CaO nanoparticle-based catalyst (calcined at 800oC) after refluxing oil/methanol blend (molar ratio of 0.22) for 1 hour at 75oC. Whereas, Empikul et. al. [25] utilized 10 wt% of CaO-based catalyst (obtained from eggshell waste) for biodiesel production using palm olein oil and a high methanol to oil ratio (18:1) yielding ca. 94% in 2 hours and at 60°C. Similarly, Li. et. al. [11] utilized 6 wt% of CaO obtained from paper mill industry waste for transesterification of peanut oil into biodiesel (94%) under similar reaction conditions. Also, Correia et. al. [26] used crab shell residue as a source of CaO for the transesterification of sunflower oil in the presence of methanol with a biodiesel yiled of ca. 83% after reflux for 4 hours at 60°C. Additionally, Smith et. al. [17] used bovine bone as a source of CaO-based catalyst (with 8 wt% loading level) and a biodiesel yield of about 97% was obtained after 4 hours’ reflux at 65oC.
Concluding Remarks
This review highlights the significant advances in the use of Ca oxide-based catalysts derived from natural sources (e.g., wastes and residues from several agricultural and industrial activities) as promising heterogeneous catalysts for the production of biodiesel employing various oil feedstocks in the presence of methanol at acceptable reaction conditions expressed in reaction time and temperature. The suggested CaO-based heterogeneous catalysts showed superior activity towards biodiesel production compared to homogeneous catalysts (i.e., in solution phase) in terms of reusability, ease of separation, and milder aggressive corrosive effects on the reaction vessel and operating apparatus.
References
- Shan R, Chen G, Yan B, Shi J, Liu C (2015) Porous Cao-Based Catalyst Derived From PSS-Induced Mineralization For Biodiesel Production Enhancement. Energy Convers Manag 106: 405-413.
- Marchetti JM, Miguel VU, Errazu AF (2007) Possible methods for biodiesel production. Renew Sustain Energy Rev 11(6): 1300-1311.
- Fonseca JM, Teleken JG, Almeida VC, da Silva C (2019) Biodiesel from waste frying oils: Methods of production and purification. Energy Convers Manag 184: 205-218.
- Witoon T, Bumrungsalee S, Vathavanichkul P, Palitsakun S, Saisriyoot M, Faungnawakij K, et al. (2014) Biodiesel production from transesterification of palm oil with methanol over CaO supported on bimodal meso-macroporous silica catalyst. Bioresour Technol 156: 329-334.
- Devaraj K, Veerasamy M, Aathika S, Mani Y, Thanarasu A, et al. (2019) Study on effectiveness of activated calcium oxide in pilot plant biodiesel production. Journal of cleaner Production 225: 18-26.
- Marwaha A, Rosha P, Mohapatra SK, Mahla SK, Dhir A (2018) Waste materials as potential catalysts for biodiesel production: Current state and future scope. Fuel Process Technol 181: 175-186.
- Sharma YC, Singh B, Korstad J (2011) Latest developments on application of heterogenous basic catalysts for an efficient and eco friendly synthesis of biodiesel: A review. Fuel 90(4):1309-1324.
- Joshi G, Rawat DS, Lamba BY, Bisht KK, Kumar P, et al (2015) Transesterification of Jatropha and Karanja oils by using waste eggshell derived calcium based mixed metal oxides. Energy Convers Manag 96: 258-267.
- Shan R, Zhao C, Lv P, Yuan H, Yao J (2016) Catalytic applications of calcium rich waste materials for biodiesel: current state and perspectives. Energy Convers Manag 127: 273-283.
- Correia LM, Saboya RMA, Campelo N de S, Cecilia JA, Castellón ER, et al. (2014) Characterization of calcium oxide catalysts from natural sources and their application in the transesterification of sunflower oil. Bioresour Technol 151: 207-213.
- Li H, Niu S, Lu C, Liu M, Huo M (2014) Use of lime mud from paper mill as a heterogeneous catalyst for transesterification. Sci China Technol Sci 57: 438-444.
- Wei Z, Xu C, Li B (2009) Application of waste eggshell as low-cost solid catalyst for biodiesel production. Bioresour Technol 100: 2883-2885.
- Yaşar F (2019) Biodiesel production via waste eggshell as a low-cost heterogeneous catalyst: Its effects on some critical fuel properties and comparison with CaO. Fuel 255: 115828.
- Borah MJ, Das A, Das V, Bhuyan N, Deka D (2019) Transesterification of waste cooking oil for biodiesel production catalyzed by Zn substituted waste eggshell derived CaO nanocatalyst. Fuel 242: 345-354.
- Birla A, Singh B, Upadhyay SN, Sharma YC (2012) Kinetics studies of synthesis of biodiesel from waste frying oil using a heterogeneous catalyst derived from snail shell. Bioresour Technol 106: 95-100.
- Roschat W, Siritanon T, Kaewpuang T, Yoosuk B, Promarak V (2016) Economical and green biodiesel production process using river snail shells-derived heterogeneous catalyst and co-solvent method. Bioresour Technol 209: 343-350.
- Smith SM, Oopathum C, Weeramongkhonlert V, Smith CB, Chaveanghong S, et al. (2013) Transesterification of soybean oil using bovine bone waste as new catalyst. Bioresour Technol 143: 686-690.
- Corro G, Sánchez N, Pal U, Bañuelos F (2016) Biodiesel production from waste frying oil using waste animal bone and solar heat. Waste Manage 47: 105-113.
- Farooq M, Ramli A, Naeem A (2015) Biodiesel production from low FFA waste cooking oil using heterogeneous catalyst derived from chicken bones. Renew Energy 76: 362-368.
- Abdelhady H, Elazab H, Saber M, El-Deab MS (2020) Efficient Catalytic Production of Biodiesel Using Nano-Sized Sugarbeet Agro-Industrial Waste. Fuel 261: 116481.
- Haruta M (1997) Size- and support-dependency in the catalysis of gold. Catal Today 36(1): 153-166.
- El-Deab MS, Ohsaka T (2002) An extraordinary electrocatalytic reduction of oxygen on gold nanoparticles-electrodeposited gold electrodes. Electrochem Commun 4(4): 288-292.
- El-Deab MS, Sotomura T, Ohsaka T (2006) Oxygen reduction at Au nanoparticles electrodeposited on different carbon substrates. Electrochim Acta 52(4): 1792-1798.
- El-Deab MS. Sotomura T, Ohsaka T (2005) Oxygen reduction at electrochemically deposited crystallographically oriented Au(100)-like gold nanoparticles. Electrochem Commun 7(1): 29-34.
- Viriya-empikul N, Krasae P, Nualpaeng W, Yoosuk B, Faungnawakij K (2012) Biodiesel production over Ca-based solid catalysts derived from industrial wastes. Fuel 92(1): 239–244.
- Correia LM, Saboya RMA, de Sousa CN, Cecilia JA, Rodríguez-Castellón E, et al. (2014) Characterization of calcium oxide catalysts from natural sources and their application in the transesterification of sunflower oil. Bioresour Technol 151: 207-213.