|Noor Ridha Yanti||Department of Natural and Environmental Resources Management, Graduate Program, University of Lambung Mangkurat, Banjarbaru 70714, Indonesia|
|Hesty Heryani||Department of Agro-industrial Technology, Faculty of Agriculture, University of Lambung Mangkurat, Banjarbaru 70714, Indonesia|
|Meilana Dharma Putra||Department of Chemical Engineering, Faculty of Engineering, University of Lambung Mangkurat, Banjarbaru 70714, Indonesia|
|Agung Nugroho||Department of Agro-industrial Technology, Faculty of Agriculture, University of Lambung Mangkurat, Banjarbaru 70714, Indonesia|
Glycerol, an abundant by-product of biodiesel production, is urgently considered to increase its usage. Triacetin produced from glycerol is an important material, used in polyester, cryogenics, cosmetics and as a biodiesel additive. Using homogeneous catalysts in triacetin production involves high product separation costs. The purpose of this study is to synthesize heterogeneous catalysts based on alumina and silica from peat clay for use in the production of triacetin from glycerol. The conversion of glycerol for triacetin production using such alumina and silica catalysts yielded levels of 82.7% and 87.4% respectively. These values were greater than the conversion value of 71.2% using a sulfuric acid homogeneous catalyst. An optimum conversion of 91% was obtained at the mole ratio of glycerol to acetic acid of 8.9. The potential heterogeneous catalysts were confirmed by the results of SEM, XRD and BET characterization. Therefore, the production of triacetin using heterogeneous silica catalyst could be an alternative approach in commercial processes which currently using homogeneous catalysts.
Glycerol; Heterogeneous catalyst; Peat clay; Triacetin
Much attention is being paid to the limitations of fossil energy such as oil and coal, leading to the development of renewable energy. For the last two decades, alternative fuels have been developed to meet the rapidly increasing energy consumption needs. Biodiesel, one of the promising alternative and renewable fuels, has been viewed with increasing research interest in recent years as a form of renewable energy (Srithar et al., 2017). Tests on the use of biodiesel in diesel engine performance have been conducted (Susila et al., 2012) using a mixture of diesel fuel with biodiesel from vegetable oil sources, i.e rubber seed oil. Engine tests have shown that the B-20 (rubber seed oil methyl ester catalytic method dry wash system) mixture produced the best engine performance at 2550 rpm. The emission levels produced were more environmentally friendly than those from diesel fuel. Biodiesel production would generate about 10% (w/w) glycerol as the main byproduct; in other words, every gallon of biodiesel generates approximately 1.05 pounds of glycerol (San Kong et al., 2016). Glycerol as a by-product of biodiesel products, which is effective to be a useful chemical, is needed to reduceenvironmental pollution (Srithar et al., 2017).
A study on glycerol conduct by Saksono et al. (2012) investigated the effectiveness of plasma electrolysis on hydrogen product quantity and energy consumption. Their results showed that an increase in voltage led to increased hydrogen production and energy consumption, and that the addition of glycerol resulted in a decrease in hydrogen production, but an increase in energy consumption. Moreover, according to Slamet et al. (2015), alternative method with metal oxide and non-metallic oxide, which has been developed in the modification of TiO2 photocatalyst from a mixture of glycerol-water to produce H2 with conversion from glycerol.Crude glycerol can be utilized for production of pyrolyzed oil using a microwave heating technique with a coconut shell-based activated carbon catalyst. The derived liquid and gaseous pyrolysis products in the range of 15?42% and 55?82% could be potential alternative fuels in combustion systems (Leong et al., 2016). Recently, the conversion of glycerol into products such as triacetin through an esterification process has been under development. Triacetin is of particular interest due to its wide applications in polyester, cryogenics, cosmetics, as an additive in biodiesel, and as a fuel additive to waste cooking biodiesel (Khayoon & Hameed, 2011; San Kong et al., 2016; Zare et al., 2016).
Production of triacetin from glycerol can be easily processed using homogeneous acid catalysts such as H2SO4, HCl, HNO3 or H3PO4 (Khayoon & Hameed, 2011). However, the catalyst could cause corrosion in industrial equipment and also have a toxic impact on the environment (San Kong et al., 2016). Moreover, such a catalyst involves a complex separation process, thus contributing to the high costs. Various heterogeneous catalysts have been studied to produce triacetin from glycerol and their efficiencies classified into different groups: ion exchange resin, zeolites, heteropolyacids, metal oxides, mesoporous silica, amberlist, carbon, alumina, zirconia and the nano-silica (SiO2) co-precipitation method using a high-energy grinding technique (Zhou et al., 2012; Jalil et al., 2016; Rane et al., 2016; San Kong et al., 2016). However, the use of these commercial synthesis catalysts has a major disadvantage, its high cost (Zhou et al., 2012). The price of commercial synthesis catalysts in the chemical industry was USD 0.98 – 1.65/kg (San Kong et al., 2016). However, since the industry's needs are growing rapidly, the price of catalysts reaches USD 20-40/kg.
One potential resource that can be considered as a heterogeneous catalyst is peat clay. This is a crystal-shaped and layered structure with particles smaller than 2 µm. It is located under peat soil at a depth of 1.5–3 meters below ground level and contains alumina and silica, hence its potential use as a catalyst or support (Uddin, 2017). The peat clay in South Kalimantan, Indonesia has characteristics such as weight of soil volume of 0.964 g cm-3; specific gravity of 1.381; void ratio of 6.891; organic contents 95.380%; fiber contents 61.330%; ash content 4.620 %; acidity of pH 3-5; and moisture content 67.732% at 60°C (Nurdin, 2011; Ma'ruf & Yulianto, 2016).
The purpose of this study is to synthesize alumina and silica based heterogeneous catalysts derived from peat clay. The study also characterizes these catalysts, including their catalyst components, crystallinity, pore size and morphology. The catalysts are further tested for the production of triacetin from glycerol and acetic acid.
The authors thank the Graduate Program at Lambung Mangkurat University for supporting the work.
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