Preparation and research on properties of castor oil as a diesel fuel additive

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1 Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 Peer-reviewed & Open access journal The primary version of the journal is the on-line version ATI - Applied Technologies & Innovations Volume 6 Issue 1 March 2012 pp Preparation and research on properties of castor oil as a diesel fuel additive Nurbakhit Imankulov M.Auezov South Kazakhstan State University, Kazakhstan igic@rambler.ru postal address: avenue Tauke Khan 5, Shymkent, Kazakhstan The research shows an opportunity of preparing biodiesel fuel on the basis of local diesel fuel and the bioadditive - castor oil. Limiting optimum concentration of introduction of the bioadditive equal was established as 5% mass ratio. The castor oil released from seeds of Palma Christi grown on experimental field. All physical and chemical characteristics of the oil including IR-spectra were determined. Operating conditions of castor oil introduction (temperature, solubility, concentration, etc.) were determined. The received biofuel was tested at oil refinery and its bench tests with a positive effect were also carried out. Technical requirements and technological regulation (temporary) on manufacture of this biodiesel fuel were prepared. Keywords: Biodiesel, castor oil, diesel fuel additive The necessity of development and application of alternative fuels is caused with a fast exhaustion of global stocks of oil and with deterioration of ecological environmental conditions. Maintaining the modern rates in extraction and consumption the proven oil reserves, as expected by experts, will suffice for the nearest years. It forces to explore perspectives for replacement of oil use in the production of motor fuels using on alternative sources of raw materials. Nowadays oil is practically a unique source of motor fuels production which consumes more than 70% of extracted petroleum. Such consumption of oil in production of motor fuels is caused by fast growth of vehicle fleets: statistically for each two seconds a new vehicle descends in the world from the conveyor. By 2001 the European Commission has approved three alternative replacements for motor fuels - natural gas, biofuel and hydrogen. Each of above mentioned kinds of fuel can reach a level over 5% in the fuel market by 2020: biofuel - 15 %, the natural gas - 10%, liquefied oil gas - 5%, hydrogen - less than 5 % (EU, 2003). An application of biofuels reduces the issue of practically all harmful substances in comparison with use of oil diesel fuels. For pure biofuels the content of unburned hydrocarbons is reduced down to 56%, of firm particles - to 55%, carbon oxide - to 43%. In connection with above-stated the current article considers the issue of castor oil receiving, research of its physical and chemical properties and an opportunity of its application as the additive (Imankulov, 2008) to diesel fuel with the ultimate purpose of getting biodiesel fuel with the improved characteristics (Imankulov and Balabekov, 2009). The product of diesel production at Shimkent oil refinery (Open Company Petro Kazakhstan oil Products ) was used as the initial diesel fuel; its which physical and chemical characteristic are shown in Table 1. The product corresponds to safety requirements according to the certificate of conformity No.КК Prague Development Center

2 Applied Innovations and Technologies Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 The castor oil is the representative of group of completely non-drying liquid oils. It is applied not only to the medical purposes, but also as lubricant oil and for manufacturing of alizarin oil. Its particular value is a less significant change of viscosity with the change of temperature when compared with other oils. According to viscosity the castor oil surpasses all other known fats. Its viscosity by Engler at 20 С is equal to At absolute scale of units the viscosity of castor oil at different temperatures is characterized as follows: η 20 С =9.6; η 30 С =4.6; η 40 С =2.3; η 50 С =1.3 и η 100 С =0.19 Castor oil is extracted from seeds of Palma Christi, the annual plant Ricinus communis and its other versions belonging to Euphorbiaceae family and cultivated almost in all tropical and subtropical countries. The seed contains up to 55% of the oil, when released from a peel it contains up to 69%. The oil is manufactured mainly using pressing technology. The presence of a large number of ricinoleic acid glycerides in the oil is the reason of good solubility of castor oil in alcohol and of a bad solubility in petroleum ether. Palma Christi seeds contain the poisonous alkaloid ricin. Physical constants: Density d Temperature of hardening, С -18 Factor of refraction nd Chemical constants: Number of saponification mg КОН/g 176 Acetyl number 146 Iodine number, g J2/100 g 82 Radon number 81 Average molecular weight of fat acids 290 Chemical composition (% mass): Stearin acid (together with dioxystearin acid) 3.0 Oleic acid 8.0 Linoleic acid 3.0 Ricinoleic acid 80.0 Castor oil differs from other fats in solubility and some other properties - high density, big viscosity, and high acetylic number. Different requirements are set to castor oil depending on its application (Table 2). Castor oil is an expensive and scarce reagent and is delivered from Russia. For the needs of import replacement the Palma Christi (castor) plant was planted at experimental plot of Shimkent Region of Republic of Kazakhstan; the crop was grown and harvested. 300 kg of castor oil was released it Shimkent oil-fat factory. The physical and chemical characteristics of the received oil are shown in Table 3. Figure 1 presents the basic technological circuit of castor oil manufacturing from seeds of Palma Christi. The raw material comes into special capacity (1) through the industrial bunker (2); then it comes to capacity (3) where it is cleared of a shell, mechanical and organic impurities; then with the help of adjective (4) and distributive (5) screws it gets in a 2012 Prague Development Center

3 Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 crusher (6) where the seeds are crushed; then through a sieve (7) it gets into a sieve-separator (8) where it undergoes additional clearing of a peel. The cleared fraction of castor oil seeds gets into a brazier (9) where seeds are exposed to thermal processing and are filtered through the filter-press (10). The finished goods (technical castor oil) come in the corresponding capacity (11), while an oil cake - into the special bunker (12). FIGURE 1. THE BASIC TECHNOLOGICAL CIRCUIT OF CASTOR OIL RECEPTION INSTALLATION 1 - the capacity for raw material, 2 - industrial bunker, 3 - clearing of mineral and organic substances, 4 - transfer screw, 5 - distributive screw, 6 - crusher, 7 - sieve, 8 - sieve-separator for peel separation, 9 - brazier 10 - filter, 11 - finished goods, 12 - oil cake To obtain a full characteristic of the oil its IR-spectrum was taken and written down at spectrophotometer SPECORD 75IR in the area of sm -1. Oil samples were pressed into tablets with КBr to proceed the spectra realization. In a spectra of castor oil there are strips of absorption at 1150 and 1725 sm -1 corresponding to valent fluctuations of carboxyl υ (C=O) and υ (C-CO-CO), accordingly. The wide strip with a maximum at 3400 sm -1 corresponds to valent fluctuations of hydroxyl group s υ (OH) of ricinoleic acid which also allows distinguishing it from other fat acids, and also castor acid itself from other natural substances. Narrow long strips with maxima at 2840 and 2915 sm -1 correspond to valent symmetric (υs) and valent dissymetric (υas) fluctuations of СН 2 groups. Two peaks of identical intensity at sm -1 correspond to deformation (δs) and dissymetric (δаs) fluctuations of СН 3 groups. And the narrow strip of average intensity at 710 sm -1 concerns with the deformation fluctuations (δ) of (СН 2 ) х groups. To receive the biodiesel fuel having improved ecological characteristics on the basis of local diesel fuel the following castor oil concentrations were used: 0.5; 1.0; 2.0; 3.0; 4.0; 5.0 mass %. In laboratory the operational conditions of the Prague Development Center

4 Applied Innovations and Technologies Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 bioadditive introduction into the fuel were determined: the room temperature (about 20 0 С), the bioadditive is well dissolved in diesel fuel therefore it was entered into fuel without additional solvent. The mixture of fuel with castor oil was dissolved with formation of true solutions; optimum concentration of oil was 5%. When the fuel contained more oil it did not meet the standards in temperature of hardening and turbidity, and required the introduction of depression additive. Results of the carried out analyses of biofuel produced on the basis of diesel fuel with addition of castor oil in various concentrations are shown at Table 4. It appears from data that the density of fuel at introduction of the additive changed insignificantly but within the limits of State standards norms. The density of initial diesel fuel was kg/m 3 but when added with bioadditive it increased in the following line: from up to kg/m 3 being not more than the limit of State standards norm kg/m 3. Its fractional structure did not change, the temperature of hardening at addition of 0.5% of castor oil was identical to initial diesel fuel С; but at addition of 5% mass of castor oil this temperature increased up to -7 0 С. Value of coking capacity of 10% the residue was within the limits of norm. Viscosity and the maintenance of sulfur also satisfied the limits of norm (Imankulov, 2010). The carried out research has shown an opportunity of receiving of biodiesel fuel on the basis of local diesel fuel and the bioadditive - castor oil. Limiting optimum concentration of introduction of the bioadditive equals to 5% of mass. The received biofuel was tested at oil refinery, and its bench tests resulted with a positive effect. Technical requirements and technological regulation (temporary) on manufacturing of this biodiesel fuel were prepared. References EU, Directive 2003/30 of EU Parliament and the Council of EU. On the promotion of the use of biofuels or other renewable fuels for transport. May 8 Imankulov, N., Castor oil as a component of biodiesel fuel [Kastorovoye maslo kak komponyent biodizyelnogo topliva], in Russian, Collected Scientific articles at 6th International Scientific Conference, Vol.1, Ufa (Russia), pp Imankulov, N. and Balabekov, O., Alternative fuels on the basis of plant raw materials [Alternativnoe toplivao na osnove rastitelnogo sirya], in Russian, Shymkent (Kazakhstan) Imankulov, N., International standards on biodiesel fuel, VI International scientificpractical conference Vĕdecký Pokrok na Rozmezi Tisicileti, Prague, Czech Republic, pp Prague Development Center

5 Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 Appendix TABLE 1.THE PHYSICAL AND CHEMICAL CHARACTERISTIC OF THE SUMMER FUEL The name Parameters Cetane ratio 45 Fractional composition: 50 % are overtaken at temperature, up to, С, 96 % are overtaken at temperature, С Viscosity kinematic at 20 С, mm 2 /s Temperature of hardening, С -12 Temperature of turbidity, С -6 The flash temperature determined in a closed crucible, С 40 Mass fraction of sulfur, in fuel of the 1 kind 0.1 Mass fraction of sour sulfur 0.02 Content of hydrogen sulfide absent Test for a copper plate satisfactory Content of mechanical impurity absent Content of water-soluble acids and alkalis absent Mass fraction of water absent Acidity, mg of КОН for 100 sm 3 of fuel 5 Iodine number, g of iodine for 100 g of fuel 6 Ash content, % 0.02 Coking capacity of 10 % of residue 0.3 Factor of filterability 3.0 Density at 20 С, kg/m Prague Development Center

6 Applied Innovations and Technologies Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 TABLE 2. REQUIREMENTS TO CASTOR OIL Physical and chemical parameters Color at 20 С Transparency at 20 С Smell and taste at 20 С Transparency and sediment at 20 С Medical oil Aviation oil Technical oils Colorless or with a weak yellowish shade Completely transparent With peculiar to castor oil a smell, medical oil - without bitterness or extraneous smack Without dregs and a deposit, completely transparent; and aviation oil besides contains no moisture and mechanical impurities; in technical oil - the traces of dregs are supposed Density at 15 С Iodine number Saponification number Acid number no more than Acid number at С at normal pressure Viscosity by Angler at 50 C, not less than Flash by Pensky-Martens, not less than Full in absolute ethanol in all proportions Full in 96 % ethanol in equal volumes Not taken into account 15 Not taken into account 240 Flash by Brenken, not less than 275 Mineral acids Resinous substances Absent Ashes, not more than 0.01% Temperature of thickening, о С Prague Development Center

7 Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 TABLE 3. PHYSICAL AND CHEMICAL CHARACTERISTICS OF THE CASTOR OIL PRODUCED The name of parameters Size Temperature of fusion, С -12 Density at 15 С, g/sm 3 0,909 Number of saponification, mg КОН/g 176 Iodine number, g J2/100 g 82 Viscosity at 100 С, mm 2 /s 5.9 Temperature, С: of flashing (in open crucible) of hardening Parameter of refraction, n 20 D Index of viscosity (GOST ) 90.7 Coking capacity, % 0.19 Acid number, mg КОН/g 1.18 Ash content, % Color, in units of CNL 1.5 Name of acids Content, % mass Palmitic acid (0)* 2.0 Stearic acid (0)* 3.0 Oleic acid (0)* 8.0 Ricinoleic acid (1)* 80.0 Linoleic acid (2)* 3.0 Note: * - the number of double bonds in a molecule of the acid Prague Development Center

8 Applied Innovations and Technologies Preparation and research on properties of castor oil as a diesel fuel additive ATI, March 2012 TABLE 4. RESULTS OF DIESEL FUEL S ANALYSIS CARRYING OUT AT ADDITION OF CASTOR OIL Names of parameters Initial diesel fuel Amount of added castor oil, % mass 0.6% 1.0% 2.0% 3.0% 4.0% 5.0% Cetane number, not less than Fractional structure 50% are distilled at temperature С, not higher than 96% are distilled at temperature С, not higher than Viscosity kinematic at 20 С, mm 2 /s, within the range The temperature of hardening, С, not higher than The temperature of turbidity, С, not higher than The temperature of the flash determined in closed crucible, С, not lower than A mass fraction of sulfur, % no more, in fuel of the 1 type Fraction of mercaptan sulfur, %, not more than The maintenance of hydrogen sulfide, % absent absent absent absent absent absent absent Test on copper plate The maintenance of satisfying satisfying satisfying satisfying satisfying satisfying satisfying absent absent absent absent absent absent absent contamination The maintenance of water absent absent absent absent absent absent absent soluble acids & alkalis The maintenance of water absent absent absent absent absent absent absent Acidity, mg КОН per 100 sm of fuel, not more than Iodine number, g per 100 g of fuel, not more than Ash content, %, not more than Coking capacity, 10% of residue, not more than Factor of filterability Density at 20 С, the kg/m 3, max Prague Development Center