Article http://sciencetechindonesia.com Article History Received: 12 February 2017 Received in revised form: 15 May 2017 Accepted: 25 May 2017 DOI: 10.26554/sti.2017.2.3.76-79 ©2017 Published under the term of the CC BY NC SA license Science & Technology Indonesia p-ISSN: 2580-4405 e-ISSN: 2580-4391 Sci. Technol. Indonesia 2 (2017) 67-69 PREPARATION OF CALCIUM OXIDE FROM CATTLE BONES AS CATALYST FOR CONVER- SION OF WASTE COOKING OIL TO BIODIESEL Sabat Okta Ceria Sitompul1, Risfidian Mohadi1* 1 Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Sriwijaya, Indralaya, OI 30622 Indonesia *Corresponding Author : email: risfidian.mohadi@unsri.ac.id ABSTRACT Preparation of calcium oxide from cattle bones by thermal decomposition for 3 hours using various temperature at 400°, 500°, 800°, 900°, 1000°, and 1100°C. Calcium oxide was characterized using X-Ray Diffractometer. The results of XRD pattern showed of diffraction similar to CaO standard from JCPDS at 2θ: 32.2°; 37.3°; 53.8°; 64.1° and 67.3°. The CaO from heating cattle bones at 1000°C resulting of 2θ: 32.3°; 53.8° and 64.1°. Then, the metal oxide was characterized by FT-IR which showed the existence of CaO at wave number 362.2 cm-1 from CaO vibration. The CaO from cattle bones applied as catalyst on biodiesel synthesis from waste cooking oil and resulting viscosity value of biodiesel 5.93 cSt, density 0.876 g/cm3, acid value 0.561 mg/KOH and iod number value 16.92 g/100 g, respectively all in the range of SNI standard. Keyword: cattle bones, calcium oxide, catalyst, biodiesel, waste cooking oil INTRODUCTION The use of petroleum for various activities has led to the depletion of petroleum stocks. Therefore another alternative must be sought as a substitute for petroleum. One of the alternative fuels that have been developed over the years is biodiesel. Biodiesel is one of the attractive alternative fuels that can be produced from renewable sources. The stan- dard process for biodiesel processing is by transesterification process. The synthesis of biodiesel by transesterification reaction will not take place without a catalyst. One type of catalyst used to synthesize biodiesel from triglycerides with alcohol, the base catalyst (Verma et.al, 2016). Alkaline catalysts often used as NaOH, KOH, and calcium hydroxide (Ca(OH) 2 ) is a homogeneous alkaline catalyst system. However, the use of such catalysts has a disadvantage, i.e., the separation of the catalyst from the product is quite complicated. Other basic catalysts commonly used are metal oxide catalysts such as CaO, MgO (Lee et.al., 2014). The base catalyst of this metal oxide class has a heterogeneous system. The use of heterogeneous catalysts offers many advantages because this catalyst is separated from the product and can be reused. But the price of these met- al oxide catalysts is expensive. Therefore, the research effort to find the source of the cheap heterogeneous catalyst obtained from nature and also friendly to the environment. There are several sources of calcium such as eggshells, mollusks, and bones. Bone consists of organic and inorganic materials. Approximately 20% of the bones are water, and the rest consists of inorganic materials such as calcium phosphate (65-70%), protein and collagen matrix (30-35%). Inorganic materials of natural sources contain the main components of calcium phosphate and calcium carbonate, with little magnesium, fluoride, and sodium, phosphorus, manganese, tin and copper (Prasuna et.al, 2004). Sources of raw materials for synthesizing biodiesel include vegetable oils such as jatropha seeds, rubber, palm oil. Another source that can be used into biodiesel is waste cooking oil. The waste cooking oil is the rest of the household provided abundant forms the basis of an attractive and increase economic value into biodiesel. Ho et.al. (2014) have synthesized biodiesel with raw materials from waste cooking oil using heterogeneous base catalyst which CaO derived from snail shells (Achatina fulica) calcinated at a temperature of 700 oC. The research shows the ratio of methanol and transesterification of waste cooking oil (40: 100) at a temperature of 65 ° C to form methyl ester is an average of 35 mL. In this study synthesized CaO catalyst from cattle bones was applied to transesterification reaction of biodiesel manufacture from wasteland oil to be utilized as a catalyst for an industrial process other than biodiesel (Minaria and Mohadi, 2017. EXPERIMENTAL SECTION Chemicals and Instrumentation The instrumentations are used in this research glasses flask, reflux ap- paratus, viscometer, water bath, pycnometer, Shimadzu Lab X-6000 X-ray diffractometer, Shimadzu FTIR Prestige-21, and SEM Jeol JED-2300. The materials used are cattle bone, phosphoric acid, methanol, phenol- phthalein, potassium hydroxide, oxalic acid, Hanus solution (Iodine-Bro- mide Reagent), 15% potassium iodide, starch, chloroform, ethanol, so- dium thiosulfate. Methods Base catalyst preparation from cattle bone Cattle bone is taken from several locations in a traditional market in Palembang City. The cattle bones that have been obtained are washed and dried in an oven at a temperature of 100 °C to remove water. Cattle bones are crushed and sifted to a 100 mesh size. Preparation of waste cooking oil sample Waste cooking oil was taken from food stalls in the Indralaya Dis- trict. Waste cooking oil was filtered using Whatman No.40 filter paper to clean it. The filtered oil is store in a plastic container. Fatty acids determination in waste cooking oil by titration Cooking oil of 5 grams is weighed, then added with 96% ethanol of 10 mL, refrigerated to boiling, then shaken until completely dissolved. The resulting sample is titrated with PP indicator using a KOH titrant to pro- duce a pink color. Fatty acid formula: = Standardization of KOH A total of 102 mg of oxalic acid were included in a 250 mL Erlen- meyer, then 25 mL aquadest were added. The mixture is added with PP indicator and titrated with 0.1 N KOH which will be standardized until the solution is pink in color. Iteration was performed three times. Sitompul et al. 2017/Science & Technology Indonesia 2 (3) 2017:76-79 © 2017 Published under the term of the CC BY NC SA 4.0 license 77 Determination of iodine number in waste cooking oil by Hanus method The waste cooking oil is weighed as much as 0.5 g and then loaded into Erlenmeyer. 10 ml of chloroform solution and 25 ml of Hanus solution (Iodine-Bromide Reagent) are added, shaken until all oil is well blended and let stand in a dark room for 30 minutes. 10 ml of 15% KI solution added. Titration is done with a solution of Na 2 S 2 O 3 0.1 N and the indi- cators used are starch 1%, titration until a clear solution. Na 2 S 2 O 3 0,1N use was recorded. Iod Numbers Where : A = Number of mL thio solution for the titration of the sample B = Number of mL thio solution for blank titration Preparation and characterization of base catalyst cattle bones Cattle bones that pass a 100 mesh sieve as much as 100 grams of cal- cined with a furnace in oxygen atmosphere conditions at various tempera- ture variations. The temperature variations used were 400, 500, 800, 900, 1000, and 1100 ° C for 3 hours. After the cold solids are then it stored in the desiccator for 24 hours. Characterization is performed by using X-ray diffraction. The result of the obtained characterization compared with JCPDS data which is standard for XRD diffraction pattern data. Study of transesterification of cooking oil with preparation catalyst Into biodiesel The transesterification reaction was performed using a 500 mL three- neck flask equipped with a pumpkin flap. A total of 100 mL of waste cooking oil was added 40 mL of anhydrous methanol followed by the addition of a basic catalyst of cattle bone as much as 0.2 g. The reaction was heated at 65 ° C. for 3 hours. The reaction is stopped by using ice water. The reaction product was left overnight to obtain multiple phases, followed by separation by addition of 1 mL H 3 PO 4 for the neutralization process. Determination of viscosity value of biodiesel product The sample is inserted into the viscometer, then covered with a rubber ball, then the lid is opened, and the sample is allowed to flow. The sample flow time is recorded from the first line to the second line in seconds. If the flow time is less than 200 seconds, then the determination is repeated using a viscometer that has a smaller factor. The same treatment is done for biodiesel after distillation. Viscosity formula: KV = F x t Where: KV = Kinematic Viscosity F = The viscometer factor used T = Flow time of example Determination of density value of biodiesel product Density measurements carried out in the water bath at a temperature of 40 °C empty pycnometer first weighed, then pycnometer filled with a biodiesel product that is obtained, then weigh it. Repetition is done three times. The same test performed for aquadest as a comparison. RESULTS AND DISCUSSION Identification of CaO metallic oxide of preparation from cattle bone using XRD Calcium oxide analysis resulting from the calcination process using XRD. Data XRD diffractogram generates patterns derived calcium com- pounds include CaO, Ca(OH) 2 and CaCO 3 as the main compound. Pat- tern diffractogram produced consistent with the patterns of calcium oxide released by the Joint Committe on Powder Diffraction Standard (JCPDS) as pre- sented in Table 1. Characteristics of calcium compounds at any tempera- ture variation is analyzed through the observation of 2θ according to the standards. In accordance to the JCPDS diffractogram in the Figure. 2, the selec- tion of CaO to be used as a base catalyst in the synthesis of biodiesel from cooking oil through a transesterification reaction process is the cattle bone heated at a temperature of 1000ºC. This can be seen from the resulting CaO peaks approaching the standard JCPDS diffractogram for CaO. The 2θ value of cattle bones 1000ºC heating is 32.3°; 53.8° and 64.1° with the intensity values sequentially by 117.13 and 15. A value of 2θ from cattle bones 1100ºC heating is 32.2°; 53.2° and 64.1° with successive intensity values of 165.33 and 17. Identification of calcium oxide that results from the preparation of cattle bones decomposition with analysis using FT-IR spectroscopy In this study, cattle bone heating at 1000 ° C was analyzed by FT- IR. The measured FT-IR spectra are presented in Figures 3. In Figure 3 shows that the presence of functional groups in the region 400-4000 cm -1 wave number. The wave number range can be divided into two main areas namely in the range of 400-1000 cm -1 wave numbers as an area for identification of inorganic compounds and local wave number range 1000-4000 cm -1 as a base uptake organic compounds to facilitate the ob- servation. In the wave number around 3400 cm-1 contained in the cattle bone as shown in Figure 3 which shows the -OH group. This indicates the presence of crystal water formed at CaO where the wavelength indicates the shifting vibration of the -OH group. A number range calcium carbon- ate and hydroxide legible at 400-1000 cm -1 (Tang et.al, 2013). Figure 1. Difactogram of CaO Table 1. Data 2θ (JCPDS) for the compounds of CaO, Ca(OH) 2, CaCO 3 Compounds 2θ CaO 34.2º 37.3º 53.8º 64.1º 67.3º CaCO 3 29.4º 39.4º 43.2º 47.4º 48.5º Ca(OH) 2 28.6º 34.1º 47.1º 50.8º - Figure 2. Diffractogram of Cattle bones Heating Results at Various Temperatures Sitompul et al. 2017/Science & Technology Indonesia 2 (3) 2017:76-79 © 2017 Published under the term of the CC BY NC SA 4.0 license 78 Calcium oxide is the expected target solids in this study was observed in the range of 250-400 cm -1 wave number. FT-IR spectra of cattle bones heating at a temperature of 1000 ° C and FT-IR spectra of standard CaO is presented in Figure 3 shows the peaks that appear to vibration almost identical between the standard cattle bones and CaO. CaO absorption bands in cattle bone decomposition at temperatures of 1000 °C seen in the area around 362.2 cm-1 that indicates vibration of the metal oxides CaO preparation results. OCO bond stretching of carbonate appears at wave number 1465.9 cm-1. Early identification of cattle bone using SEM-EDX analysis The result of SEM-EDX analysis for the bone of cattle bone can be seen in Figure. 4 and Figure. 5. the surface morphology of cattle bone before heating with 1000x magnification is seen not homogeneous due to different composition between cattle bone. The composition of cattle bone can be seen from EDX data in Fig- ure 8 which is carbon 64.14%, oxygen equal to 24.82%, sodium equal to 0.25%, magnesium equal to 0.24%, posfor equal 3.64% and calcium 6.92%. The EDX data of cattle bone before heating process at various tem- perature variation obtained low calcium element content. Although cal- cium is not the main component in cattle bones a but can be used as a candidate to obtain CaO. SEM-EDX analysis on cattle bones heated at 1000 °C Cattle bones that have been through the process of heating at various temperatures and have done XRD analysis that produces the best CaO from cattle bones at a temperature of 1000 °C subsequently analyzed by SEM-EDX. The results of SEM-EDX analysis for cattle bones at 1000 °C can be seen in Figure 6 and 7. In Figures 6, there is a significant difference with cattle bones before heating process. Cattle bones composition, from heating at 1000 °C can be seen from the data in Figure 7 namely EDX carbon by 11.21%, 44.21% oxygen, sodium at 2.01%, amounting to 1.14% magnesium, phosphorus amounted to 14.37 % And calcium by 24.83%. The high carbon content initially decreased, but the calcium content grew by 6.91% to 24.83%. From the SEM-EDX data in Figures 6 and 7 it is clear that the structure of the heating cattle bone has a higher homogeneity than before heating. The application of CaO from cattle bone as a catalyst in the synthe- sis of biodiesel from cooking oil The transesterification process is carried out for 3 hours through a re- flux process to achieve the value or the maximum amount of methyl esters formed. The use of pure H 3 PO 4 was added as a solvent reactant strongly acidic alkaline neutralizing acidic conditions in the transesterification pro- cess. Methyl ester which is biodiesel obtained through transesterification reaction with heated CaO catalyst is 20 mL, with calculation yield obtained is 14.28%. The value of fatty acid number of biodiesel product The result of the determination of fatty acid number on biodiesel pro- duction from waste cooking oil by titration method got the average value of repetition 3 times equal to 0.561 mg/KOH using CaO catalyst from cattle bone. According to the data of SNI 04-7182-2006, the maximum value of fatty acid number found in biodiesel is 0.8 mg/KOH. The data shows that the biodiesel product has a value that is in accordance with the standard. High acid numbers can cause sediment in the fuel system and corrosion of the media. The higher the acid number the lower the quality of biodiesel (Pinyaphong, 2011). Iod value of biodiesel product The result of the determination of Iodine number of biodiesel prod- uct obtained average value from repetition 3 times is 16.92 g/100 g for cattle bone catalyst. The result of the analysis shows that iodine number in biodiesel from synthesis according to standard biodiesel value determined by SNI (Lesbani et.al, 2015). Biodiesel with a high content of iodine num- ber exceeds constant biodiesel quality standard maximum of 115 g/100 g will lead to a tendency to polymerization and formation of deposits on in- jectors noozle and piston rings at the start of combustion. Density value of biodiesel product Density provides information on how the fuel will work in diesel en- gines. According to the standard ASTM D-1298 (1999), a specific gravity of diesel fuel specifications in the range of 0.85 to 0.89 g / cm 3. The test was performed on methyl ester with measurement according to ASTM standard with laboratory scale. The use of high temperature to the transes- terification reaction will increase the saponification reaction. The presence of impurities such as glycerol from the saponification reaction so that the impurities formed form the mass of the biodiesel species to become larger. High mass types indicate some impurities contained in biodiesel (Pinyaphong, 2011). The results of the analysis of methyl ester density were measured with three repetitions of the average values obtained are 0.8844g/cm 3 for cattle bones catalyst. These results indicate that the re- sulting product meets the ASTM standard of density used. Figure 3. FT-IR spectra of CaO from Cattle bones heating at 1000 °C and CaO Standards. Figure 5. EDX Analysis Results from Cattle bones Figure 4. Results of SEM photograph of Cattle bones Sitompul et al. 2017/Science & Technology Indonesia 2 (3) 2017:76-79 © 2017 Published under the term of the CC BY NC SA 4.0 license 79 Viscosity value of biodiesel product Viscosity is defined as fluid resistance to the flow rate of a mm-sized capillary. The test results obtained after three times the viscosity repetition obtained an average of 5.93 cSt and 6.03 cSt. The recommended restric- tion is ASTM D-445 with a viscosity of diesel fuel specification that is in range 2.3 – 6.0 cSt. If the price of viscosity is too high it will be big friction losses in the pipeline, the pump work will be heavy, the filtration is difficult and the possibility of the dirt come too big, and difficult to disregard the fuel. Conversely, if the viscosity of biodiesel it will result a thin lubrication. CONCLUSION Cattle bone heating at a temperature of 1000 °C was produced CaO as a catalyst. 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