Minia J. of Agric. Res. & Develop. Vol. (36), No. 2, pp. 245-269, 2016

FACULTY OF AGRICULTURE

USE OF WASTEWATER AND TREATED WATER FOR Jatropha curcas CULTIVATIONAND THE POSSIBILITY OF OIL SEED USEAS A BIOFUEL

Gamal-Fakhry1, Nabil, A. E. Azazz1, Ahmed Abdel-Monem2, Abdel-Raddy Mohamedin2

1Minia Faculty of Agriculture, Minia University 1Demiat Faculty of Agriculture, Demiat University, 2Faculty of Agriculture, Al-Azar University, Assuit Branch

Received: 9March (2016) Accepted: 4 June (2016)

ABSTRACT In the present work, eight water mixtures were used for germination and cultivation of Jatropha in pot experiments. The results showed that germination percentages of Jatropha seed ranged from 54 to 87% and the highest percent was recorded when irrigation with untreated drainage water (100%UDW) was used and the lowest one (54%) was observed for sample irrigated with 50% tap water+50% untreated drainage water (50%TW+50%UDW). Generally, higher germination percentages were recoded when untreated drainage water (raw) was applied and lower ones were reported when tap water was used. Characteristic fuel properties of Jatropha oil were studied to assess compatibility of blends with diesel. The relative density at 150C of raw Jatropha oil is 0.876 higher than that determined for diesel (0.839). The values of the kinematic viscosity of raw Jatropha oil and diesel at 400C are found to be 5.8 and 3.08 respectively. The cetane number of Jatropha raw oil determined in the present study was ranged from 46 to 70. The flash and fire point of Jatropha oil was found to be 1280C and 1360C respectively. Our results showed that higher heating value (HHV) of Jatropha oil ranged from 39.24 to 41.87 and the lower heating value (LHV) ranged from 36.53 to 38.94. The heating value (MJ/kg) for Jatropha biodiesel is lower than those reported for petro diesel, nucleus dates biodiesel and olive biodiesel but higher than those reported for castor biodiesel and coconut biodiesel. Gamal-Fakhry et al., 2016

Determination of iodine number of Jatropha crude oil revealed to high iodine number to be 101. Sulphur weight % in Jatropha oil determined in the present work which was 0.0024%. Specific heat capacity (SHC) of Jatropha oil determined which was 0.80 Jk-1g-1 . Fractionation of fatty acids process was done using GC. Jatropha oil had more than 19% saturated fatty acids (C16:0, C17:0, C18:0, and C20:0) and more than 80% unsaturated fatty acids (C16:1, C17:1, C18:1, C18:2, C18:3 and C20:1). Levels of total saturated fatty acids (TSFA) in Jatropha sample are 19.16 and the most abundant fatty acid in Jatropha was palmitic acid (C16:0) followed by stearic (C18:0) and the lowest one was arachidic acid (C20:0). These results also, showed existence of odd chain saturated fatty (OCS-FAs) margaric acid C17:0 with level of 0.29. Results showed that levels of total unsaturated fatty acids (TUSFA) in Jatropha sample was 80.81 and the most abundant fatty acid in Jatropha oil was linoleic acid C18:2 followed by oleic acid C18:1 and the trienoic acid (linolenic acid C18:3) which was the lowest one. Key words: Biofuel, Fatty acids fractionation, Jatropha oil, Jatropha, Jatropha curcas, L. wastewater

INTRODUCTION composition of biodiesel that would Biodiesel is a non-toxic, enhance the combustion process. It biodegradable, and renewable diesel was observed that the fuel properties fuel and can be used neat or blends of biodiesel play a significant role in with petroleum diesel fuels. Biodiesel the combustion process. One of such has many advantages compared to properties is cetane number, (CN) diesel fuels. It has higher cetane influence the combustion process and number than diesel fuel, and contains engine performance. The CN is a no aromatics, almost no sulfur and 10- commonly used indicator for the 12% oxygen by weight. Biodiesel- determination of diesel fuel ignition fueled engines produce less CO, HC the quality. It measures the readiness and particulate emissions than of the fuel to auto-ignite when injected petroleum diesel-fueled engines into the engine (Bamghoye and (Graboski and McCormik 1998 and Hansen, 2008). Many performance Tomasevic and Marinkovic 2003). characteristics such as density, heating Biodiesel improves the lubricity, value are related to cetane number which results in longer engine (Lakshmi et al., 2008). Cetane number component life (Boehman, 2005; is the parameter used to determine the Kinast, 2001 and Gerpen, 2005). quality of biodiesel; it is proportionate Attempts have been made by various to the fuel ignition delay time in CI researchers to determine the best engines. A fuel’s CN rating can be

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Gamal-Fakhry et al., 2016 applied to determine ignition 2009) and 4- the aptitude of the characteristics of biodiesel fuels Jatropha oil extraction residue to (Knothe et al., 2003). recover infertile land (Gübitz et al., As the future lack of petroleum 1999). will be a current concern, that The leaves of J. curcas are used biodiesel seems to be “part of the in traditional medicine against coughs solution”, by replacing partial or or as antiseptics after birth, and the totally petro-diesel fuel in diesel branches are chewing sticks (Gübitz et engines. This reason, added to an al. 1999). The latex produced from the increasing environmental concern, branches is useful for wound healing creates a scenario in which biodiesel and others medical uses. Each fruit production is expected to have a big contains 2-3 oblong black seeds which development over the next few years. can produce oil. The seed kernel oil Biodiesel is an alternative fuel contained 40-60% (w/w) oil (Makkar produced from different types of et al. 1997). The seed oil extracted is renewable vegetable oil, animal fats or found useful in medicinal and different types of recycled cooking oil, veterinary purposes, as insecticide, for by transesterification reaction. In soap production and as fuel substitute conventional processes, biodiesel is (Gübitz et al. 1999). manufactured by alkaline catalyzed Jatropha curcas L., commonly transesterification of oil, in methanol known as Jatropha, physic nut, or (Murugesan et al., 2009). The alkalis purging nut, belongs to the family frequently used are KOH, NaOH or Euphorbiaceae. It is a perennial oilseed their corresponding alkoxides. Some shrub that originated in Tropical and solid catalysts were also assayed (Vyas Subtropical America. J. curcas is a et al., 2009). drought-resistant non-edible tree that The oil to produce biodiesel can can thrive in a wide range of soils and be obtained from different crops such climates. For these reasons, it is as soy, rapeseed, Jatropha curcas L. considered as the most promising and others. Nowadays, Argentinian biodiesel feedstock worldwide. J. biodiesel is largely made out of soy curcas is a fast growing crop and can oil, but the industry is considering the produce seeds for up to 50 years possibility of using Jatropha oil (Achten et al., 2008) The full potential (Falasca and Ulberich, 2008). The of J. curcas has however not been main differences are: 1- the Jatropha realized due to several technological seeds, due to its toxicity, are not edible and economic reasons (Divakara et al., (Cai-Yan et al., 2010), 2- Jatropha 2010) .J. curcas seed kernel contains crop can tolerate harder climate 40–60% (w/w) oil (Makkar et al., conditions than soy and rapeseed 1997), and the oil contains around (Jones and Miller 1992), 3- the 80% unsaturated fatty acid which Jatropha seeds can give four times makes it suitable for biodiesel more oil than soy (Aceites and Grasas, production J. curcas oil can be

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Gamal-Fakhry et al., 2016 converted to biodiesel using used as fuel in furnace and boiler. It transesterification, the production can be upgraded to higher grad fuel by depends on the free fatty acid content trans esterification process (Kamrun of the oil (Jain and Sharma 2010 and and Hampton 2011). Patel, et al., 2010). The resulting The main objectives of the present biodiesel can be used as a substitute investigation are (a) to study the for petroleum diesel fuel. The seed possibility of cultivation of Jatropha cake remaining after oil extraction is curcas on wastewater (b) to study an excellent source of plant nutrients Jatropha curcas seed oil properties (Martınez-Herrera et al., 2006). and the possibility of its use as a The composition of J. curcas oil biofuel. from Nigeria consists of main fatty acid such as palmitic acid (13%), MATERIALS AND METHODS stearic acid (2.53%), oleic acid Jatropha cultivation (48.8%) and linoleic acid (34.6%) It was conducted experiment (Martínez-Herrera et al., 2006). J. using a randomized complete block curcas oil contains high percentage of design, Jatropha plants irrigated with unsaturated fatty acid which is about mixture drainage water: Fresh 78- 84%. This made the oils suitable water,(1) Irrigation using tap water for biodiesel production. However, the (100%), (2) Irrigation using (100%) chemical compositions of the oil vary untreated drainage water (3) Irrigation according to the climate and locality. utilizing treated drainage water J. curcas was cultivated in Egypt (100%), (4) Irrigation using (50%) in Luxor, Sohag and Suez (OEJC, water tap + (50%) utilizing treated raw 2008) the plant seeds generally used wastewater,(5) Irrigation using (50%) for the purpose of extracting oil which water tap + (50%) treated water,(6) primary source from which the oil is Irrigation using (75%)water tap+(25%) extracted. Oil has very high utilizing treated raw wastewater, saponification value and being (7)Irrigation using (25%) water tap + extensively used for making soap in (75%) utilizing treated raw wastewater some countries. Also oil is used as in water,(8)Irrigation using (25%) water illuminant in lamps as it burns without tap + (75%) treated water . emitting smoke. It is also used as fuel Physicochemical properties of in place of, or along with kerosene Jatropha oil;- stoves. Jatropha oil cake is rich in Some of the physical properties nitrogen, phosphorous and potassium of oil extracted from the Jatropha and can be used as organic manure. By seeds were determined using different thermodynamic conversion process, kinds of machines. In the present work pyrolysis, useful products can be ten characteristic properties of obtained from the Jatropha oil cake. Jatropha raw oil were determined. The The liquid, solid and gaseous products characteristic fuel properties such can be obtained. The liquid can be as:(1)-relative density, (2)-kinematic

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Gamal-Fakhry et al., 2016 viscosity, (3)-flash and fire point, (4)- 1976. The experiment was performed cetane number, (5)-higher heating at 380C. Kinematic viscosity was value, (6)-lower heating value, (7)- calculated using the relationships specific heat capacity (SHC) (8)- given by Guthrie, (1960). 179 sulphur weight% (9)-iodine V = 0.26 t - number(10)-acid number of Jatropha k t oil were studied to assess compatibility when 34 < t< 100 and of blends with diesel. 50 Vk = 0.24 t - (1)-Relative density at 150C t (gm/cm3):- when t > 100 The relative density of the fuels where: at 150C was determined as per IS: Vk = Kinematic viscosity in centistokes t = Time for flow of 50 ml sample iv second 1448 [P: 32]: 1992 and detailed by Shambhu et al., (2013). The empty 3- Flash and fire point pyknometers of 50 ml capacity were The flash and fire point of the weighed. The pyknometers were then fuel samples was determined as Per IS: filled with fuel samples and weighed. 0 1448 [P: 32]: 1992. A Pensky Martin The samples were maintained at 15 C Flash Point (closed) apparatus was by keeping them in a Saveer used to measure the flash and fire Biotechmake walk-in temperature point of the fuel samples. The sample control chamber. The weights of the was filled in the test cup up to the empty pyknometers were subtracted specified level and was heated and from the weights of the filled ones to stirred at a slow and constant rate. The get the weight of the fuel samples. temperature was measured with the Density is the mass per unit volume of help of a thermometer. At every 10C any liquid at a given temperature. This temperature rise, flame was introduced value when divided by the volume of for a moment with the help of a the fuel sample gave the density (ρF) shutter. The temperature at which a of the fuel sample at 150C. The density 0 flash appeared in the form of sound of distilled water (ρw) at 15 C was and light was recorded as flash point. also determined. The fire point was recorded as the Density of the temperature at which fuel vapour fuel/15 0C Relative density = catches fire and stays for minimum of Density of the water/15 0C five seconds. 2- Kinematic viscosity Flash point: 150 ml of extracted Kinematic viscosity of samples oils was poured into a metal container and heated at a controlled rate was measured by using Redwood o Viscometer [WISWO make]. Time of temperature of 36 C after, which, the gravity flow in seconds of a fixed flame being passed over the surface of volume of the fluid (50ml) was the extracted oils was observed at a measured as Per IS: 1448 [P : 25] regular intervals of 5 secs for 1 min. The flash point was determined by

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ASTM D-93 method (Shambhu et al., from saponification value (SV) and 2013). The flash point temperature of iodine value (IV) of oil.

Cetane number(CN)=46.3 ( ) biodiesel fuel is the minimum

HHV)=49.43- ) Higher Heating Value temperature at which the fuel will ignite (flash) on application of an 6- Lower heating value: ignition source. The Lower heating value of Jatropha Fire point is the lowest temperature at oil was determined according to which a specimen will sustain burning ASTM D240. for 5 seconds. These two parameters 7- Specific heat capacity (SHC): have great importance while A copper calorimeter was determining the fire hazard weighed and recorded. 150 ml quantity (temperature at which fuel will give of oil was also weighed and its off inflammable vapour). Flash point temperature which is 15oC was noted of the samples were measured in the and transferred to the calorimeter. A temperature range of 60 to 190°C by known volume of water (53 ml) was an automated Pensky-Martens closed heated to a temperature of 20oC above cup apparatus. that oil, the hot water was transferred 4- Cetane number:- to the oil in the calorimeter, which was Cetane number is measured using closed and stir until it reaches the blends of two reference fuels, namely equilibrium temperature and it was n-cetane (100 CN) and recorded. Specific heat capacity was heptamethylnonane (15 CN). Cetane calculated using the following number of the test fuel is the equation: C=t/m where C = SHC of percentage by volume of n-cetane in a calorimeter, (kJ/kg/K), t = heat loss, blend of n-cetane (100 CN) and (oC), m = mass of oil, (ml). Ambient heptamethylnonane (15 CN) having temperature, Ta = 20.1oC (degree to the same ignition quality when tested minimize error due to heat transfer to in the same engine under the same test or from the surroundings). conditions Bamgboye and Hansen 8- Determination sulphur weight % (2008). Determination of sulphur content 5- Determination of Cetane Number of Jatropha oil combustion was done and Higher Heating Value in a bomb calorimeter. The washings The Cetane number (CN) and were collected and titrated with higher heating value (HHV) (MJ/Kg of standard sodium carbonate followed oil) of the biodiesel was determined by neutralization with aqueous using ASTM D 613 standard ammonia. Solution was boiled, filtered procedures through the following and 10ml of concentrated HCl was empirical formula as described by added. 10% Barium chloride was Cocks and Vanrede, (1984), and added whilst boiling the solution. Eshetu and Gabiyye (2013). The Solution was then covered and calculation was based on the results precipitate allowed to settle for an hour after which it was filtered through an

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Gamal-Fakhry et al., 2016 ash-less filter paper. After several RESULTS AND DISCUSSION washings, the filter paper and sample Cultivation of Jatropha curcas:- was placed in a weighed crucible and In the present experiment, eight ignited (Mohammed and Adamu, water mixtures were used for 2009). cultivation and germination of 9- Iodine number Jatropha in pot experiments, these Jatropha oil (0.2 g) was weighed combinations water mixture are given accurately by transfer method into a in Table (1) and Fig (1). The results 250 mL iodine flask and dissolved in showed that germination percentages chloroform (20 mL). Wij’s reagent (20 of Jatropha seed ranged from 54 to mL) was added by means of a pipette. 87% and the highest percent was The flask was stoppered and kept in recorded when irrigation with darkness for one hr. with intermittent untreated drainage water (100%UDW) shaking. Then 15% of potassium was used and the lowest one (54%) iodide solution (10 mL) and 50 mL of was observed for sample irrigated with distilled water were added to the flask 50%tap water+50% untreated drainage and mixture was shaken well. The water (50%TW+50%UDW). liberated iodine was titrated with 0.1 N Generally, higher germination sodium thiosulphate solution using percentages were recoded when fresh starch solution as indicator. A untreated drainage water (raw) was blank titration was also conducted side applied and lower ones were reported by side (Nayak and Patel 2010). when tap water was used (Fig. 2). 10- Acid Value Drainage water contains salts and Acid value is, therefore, an heavy metals in varied degrees led to important characteristic to be oxidative stress in plant irrigated with measured. The acid value or number waters and cause several physiological defined as the mg KOH required to changes due to chance in metabolic neutralize the free fatty acid present in pathway (Lee et al., 2001 and Panda one gram of oil sample. The total acid and Upadhyay, 2003). value of Jatropha sample was It was conducted experiment measured as per method describe by using a randomized complete block Cox and Pearson (1962). A known design, Jatropha plants irrigated with amount of sample was dissolve in 50 mixture drainage water:, and Irrigation ml of the neutral solvent (neutral utilizing treated wastewater and solvent is the mixture of 25 ml ether, Irrigation utilizing treated raw 25 ml alcohol and 1 ml of 1% wastewater and Jatropha plants phenolphthalein solution and titrated irrigated with % freshwater. with aqueous solution of KOH of 0.1 Hussein et al., (2013) concluded N. The total acidity was calculated and that, even if oxidative stress is induced a blank titration was also conducted in Jatropha plants irrigated with 25, 50 side by side. and 75% industrial waste water, application of NPK could be provide

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Gamal-Fakhry et al., 2016 protection against this oxidative stress Jatropha plants. Therefore, the by increase the antioxidant protective irrigation of Jatropha plants by mean system, which involved as one of the of industrial west water at 75% (v/v) is factors responsible for salt tolerance of possible when fertilized with NPK.

Table (1): Water mixtures used in germination and cultivation of Jatropha seeds No Treatment (%) 1 Irrigation with tap water (100%TW) 65±2 2 Irrigation with untreated drainage water (100%UDW) 87±4 3 Irrigation utilizing treated drainage water (100% TDW) 79±2 4 Irrigation with 50%tap water+50% untreated drainage 54±1 water (50%TW+50%UDW) 5 Irrigation with 50% tap water + 50% treated drainage 75+±2 water (50%TW+50%TDW) 6 Irrigation with 75% tap water + 25% untreated drainage 83±3 water (75%TW+25%UDW) 7 Irrigation with 25% tap water + 75% untreated drainage 68±2 water (25% TW+75%UDW) 8 Irrigation with 25% tap water + 75% treated drainage 65±2 (25%TW+75%TDW) Mean ± SD of SE

Fig. (1): Effect of use of drainage water on the Jatropha seed germination

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Preparation of soil of Jatropha seed Germination of Jatropha seed in pots

Irrigation with 100% treated drainage Irrigation with 100% untreated water drainage water

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Irrigation with 100% untreated Irrigation with 100% tap water drainage water

Irrigation Irrigation with 75% tap water + 25% with50%tapwater+50%treated drainge treated drainge water water

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Irrigation with 25%tapwater + 75% Irrigation with 75%tapwater + 25% untreated drainage water untreated drainage water

Irrigation with 25%tapwater + 75% Irrigation with 50%tapwater + 50% untreated water. treated drainage water. Fig. (2): Germination of Jatropha seed

Rajaona, et al., (2012) concluded reported to be salt sensitive, the use of that in the global context, it is evident waste water while controlling soil that effluent reuse in agriculture will salinity has to be considered, even if increase in water scarce countries in the nutrient and water supply can be the near future, particularly in the satisfied. The feasibility of such an vicinity of cities. This is necessary to irrigation system depends to a large release precious freshwater resources extent on environmental factors, such for the drinking water supply of the as climate, soils and the overall water growing urban areas and to ensure availability, and thus, transferability of irrigation. Since Jatropha has been

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Gamal-Fakhry et al., 2016 the model results presented here needs of biofuels output from these plants, it to be studied further. can be deduced that the most suitable According to the present plants for producing the biofuels in comparisons (Table 2) between plants Egypt are caster and Jatropha due to in terms of productivity per acre, the following reasons prices and various chemical properties Table (2): Comparisons between the average productivity of previous plants/acre and price. Plant Production/Acre Oil per ton Price* Jatropha 600-800 kg of 180-272 L 13-17$ for 1kg/oil, 2-2.5$ for seeds 1kg/seed Caster 1-1.5 ton of seeds 600L 7$ for 1kg/oil 0.7$ for 1kg/seed Coconut 400 kg of copra 420 L/ton copra 10$ for 1L/oil Dates nucleus 600 kg of nucleus Not available Not available Olive 3 ton/acre 170 L 5$ for 1L/oil 0.7$ for 1 kg/ (after 9 years) seed *In accordance with the prices in the Egyptian market. Comparisons between the considered as a renewable energy average productivity of previous plants (clean energy). per acre showed that The heating value Physicochemical properties of and the flash point for the biofuels Jatropha oil;- output from the previous oil plants are Results given in Table (3) show compared with those values of petro ten physicochemical properties of oil diesel as in figs. 1and 2. It is shown extracted from the Jatropha seeds in that the petrol diesel oil has higher compared to diesel. In the present heating value and lower flash point work the characteristic fuel properties compared with the other biofuels. On of Jatropha oil were studied to assess the other hand the biofuels oil can be compatibility of blends with diesel.

Table (3): Physicochemical properties of Jatropha oil Properties Values of Jatropha oil Values of Diesel 1. Relative density at 150C (gm/cm3) 0.876 0.839 2. Kinematic viscosity at 40°C 5.8 3.08 3. Flash point (°C) 128 63.2 4. Fire point 136 235.2 5. Cetane number 46 to 70 38.0* 6. Higher heating value (HHV) 39.21 39.24 – 41.87 7. Lower heating value LHV) 36.55 36.53 – 38.94 8. Iodine value (Iv) 101 60 – 135 9. Acid value (Av) 101 60 – 135 10. Sulphur weight % 0.0024 0.0165** *Sivaramakrishnan and Ravikumar, (2012), ** Barua, (2011).

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Relative density at 150C (gm/cm3):- typical diesel fuel range. The value of The relative density at 150C of cetane number is found to generally raw Jatropha oil is 0.876 higher than increase with increasing carbon chain those determined for diesel (0.839) and length. It was observed from the tables these results are in a good agreement that vegetable oils have a low cetane with those found by Shambhu et al., number; this is due to the presence of (2013).Density is an important bulkier molecules in the triglycerides property of biofuel and our results also which have a high viscosity. Babassu showed that relative density of raw oil records the highest CN of 63. Sun Jatropha oil is 4.41% percent higher flower oils have a lowest of 37.1. than that of diesel. The results are also Methyl esters (biodiesel) are observed in line with the findings of Foidl et al. to possess a higher CN when (1996) who have reported the relative compared to their corresponding oils. density of ethyl and methyl ester of The babassu oil methyl ester has the Jatropha oil to be 0.886 and 0.879 highest CN, whereas soybean methyl respectively. ester records the lowest among the oils Kinematic viscosity:- tested. Methyl esters have a lower The values of the kinematic viscosity than their corresponding viscosity of raw Jatropha oil and diesel vegetable oils. Biodiesel records high at 400C are given in Table (3). Values CN values; these values are higher of kinematic viscosity of raw Jatropha than that of diesel fuel with CN of 52. oil and diesel were found to be 5.8 and The high CN of biodiesel may be 3.08 respectively. These results are influenced by their characteristics of lower than reported by Foidl et al. the feed stock. Factors that affect the (1996) and much lower than those CN in the biodiesel are, e.g. the recently reported by Shambhu et al., number of carbon atoms of the original (2013) who reported that kinematic fatty acids, the number of double viscosity of raw Jatropha oil diesel at bonds and the ester yield 380C 32.67 (Sivaramkrishnan and Ravikumar, Cetane number in Jatropha oil;- 2012). It can also be observed from the The cetane number of Jatropha readings that non edible oils blends raw oil determined in the present study have CN values close to those of the was ranged 46 to 70. The ignition diesel fuel samples; this is due to the quality of a fuel can be deduced presence of diesel in blends. It is clear through its cetane number. A fuel with that, the higher the density the lower good ignition quality has a high cetane the Cetane number. number, where the ignition delay The cetane number (CN) of the period between the start of fuel fuel is one such important parameter injection and the onset of auto ignition which is responsible for the delay is short. Cetane number of biodiesel period. Cetane number of a fuel is varies with the feed stock used, but it defined as the percentage by volume of is generally in the higher end of the normal cetane in a mixture of normal

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Gamal-Fakhry et al., 2016 cetane and α-methyl naphthalene Flash and fire point:- which has the same ignition The flash and fire point of characteristics (ignition delay) as the Jatropha oil was found to be 1280C test fuel, when combustion is carried and 1360C respectively (Fig. 3). The out in a standard engine under observed results on flash and fire point specified operating condition. A fuel are not in accordance with the findings of higher cetane number gives lower of Foidl et al. (1996) who reported delay period and provides smoother flash point of Jatropha oil as 2400C. engine operation. Biodiesel has a The observed results are lower than higher CN than petrodiesel because of those reported by Ouedraogo et al. its higher oxygen content. The cetane (1991). Shambhu et al., (2013) number is one of the most commonly recorded very high values for flash and cited indicators of diesel fuel quality. fire point of Jatropha raw oil, these It measures the readiness of the fuel to were 229.3 and 235.2. Flash point autoignite when injected into the varies inversely with the fuel’s engine. It is generally dependent on volatility. Minimum flash point the composition of the fuel and can temperatures are required for proper impact the engine’s startability, noise safety and handling of diesel fuel. level, and exhaust emissions.

250 210 174 200 161 145 128 150 115

100 68.3

Flash point Flash 50

0 Petro diesel Castor boidieselJatropha biodieselJatropha biodieselNucleus 2015 datesOlive boidiesel boidiesel Coconout biodiesel

Fig. (3): The flash point of petro diesel and biofuels from plant oils

Flash point is the lowest mixture above the sample to ignite. temperature at which application of the Flash point specifies the temperature test flame causes the vapor and air to which a fuel needs to be heated for

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Gamal-Fakhry et al., 2016 the vapour and air above the fuel could Iodine number: be ignited. The flash points of the Determination of Iodine number biodiesels are generally higher than of Jatropha crude oil revealed to high that of geodiesel. It is higher than Iodine number to be 101. These results 900C, and is thus safer than diesel from are in a good agreement with those the standpoint of fire-hazards (Sarma, reported by Nayak and Patel (2010). 2006). The Iodine value (IV) is a measure of The flash point is related to the the average amount of unsaturation of safety requirement in handling and fats and oils and is expressed in terms storage of fuel however, Jatropha oils of the number of milligrams of iodine have very high flash point values. This absorbed per gram of sample (Gerhard makes them safer to handle and store. 2002). The oil shows a high iodine When compared with standard base value due to its high content (80%) of oil, it was discover that base oil of unsaturated fatty acids (Table 1). The 240oC was higher than the two IV has found applications to various extracted oils of 145oC and 113oC chemical and physical properties of respectively. But the two sampled oils fats and oils, having physiological are good and can be use (Olasheu et applications, and serving as a quality al., 2015). control method for hydrogenation, Higher and lower heating value: these applications include use in Our results are given in Fig. (4) standards for biodiesel and in and Table (3) showed that higher assessing oxidative stability. Jatropha heating value (HHV) of Jatropha oil collected from rural area of Bardoli reached to be 39.21 and the lower (Gujarat) has nearer iodine value 106 heating value (LHV) is 36.53. These to that reported 105.2 in Nigerian and recorded values are within the range of 135.85 in Malaysian (Salimon and diesel fuel. The heating value (MJ/kg) Abdullah 2008). for Jatropha biodiesel is lower than Sulphur weight % those reported for petro diesel, nucleus Sulphur weight % in Jatropha oil dates biodiesel and olive biodiesel but determined in the present work is higher than those reported for castor 0.0024%. This result given in Table biodiesel and coconut biodiesel Fig (3) is lower compared with petroleum (2). Biodiesel is a mixture of esters of diesel (0.0165%). These results is not short chain alcohols, produced as an in a good agreement with those alternative fuel for mineral diesel reported by Barua, (2011) who stated substitution. It is originated from that sulphur content % in Jatropha is renewable sources (fats and oils) and is 0.0094.Sulphur content in the less pollutants. But for its biodiesel is important parameter and it implementation, it is necessary to can be evaluated using energy analyze some important quality dispersive X-ray Fluorescence parameters (Oliveira and Da Silva, Spectrometry (XRF). This testing 2013). method covers the measurement of

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Gamal-Fakhry et al., 2016 sulphur in naphtha, kerosene, diesel, counts from previously prepared fuel oils, lube base oils and crude oils. calibration samples. To protect the The applicable concentration range is environment from sulfur dioxide 0.015 to 5.00 mass% sulphur and time emission, the sulfur content in diesel, taken for testing is 5 minutes per petrol, etc. are restricted to certain sample. The conventional lamp or maximum value. Also, in processing bomb method usually takes 8 hours. the hydrocarbon, different types of The sample is placed in the beam catalysts are used, some of which are emitted from an X-ray source. The poisoned by sulfur. Sulfur creates resultant excited characteristic X- corrosion problems and hence its radiation is measured and the tolerance is limited. accumulated count is compared with

Fig. (4): Comparative study of heating value among Jatropha curcas, some common plant biodiesel and petro diesel.

Specific heat capacity with those reported by Olasheu et al., Specific heat capacity (SHC) of (2015) who stated that the specific heat Jatropha oil determined in the present capacity for Jatropha oil that was work given in Table (4) is 0.80 Jk-1g-1 0.080 kJ/kg/K. these results are in a good agreement

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Table (4): Specific heat capacity Analyte/parameter Test method Description Specific heat capacity ACAL-APR-10-00 Value :0.80 Jk-1g-1 Analytical chemistry unit (ACAL) The use of Jatropha oil as diesel and boiler. It can be upgraded to fuel depends on its characteristics fuel higher grade fuel by transesterification properties. The fuel property, such as, process (Kamrun and Hampton 2011). viscosity, ash content, carbon residue, Fractionation of fatty acids in flash point and acid value of Jatropha Jatropha oil: oil was found to be far greater than Fractionation of fatty acids that of petro diesel and therefore, make process was done using GC. Soybean it unsuitable for use as fuel in diesel oil contains 10 fatty acids Table (5). engines. Esterification of Jatropha oil Two of these fatty acids linoleic to methyl and ethyl ester brought the (C18:2), and linolenic (C18:3), are fuel properties closer to that of petro considered essential fatty acids diesel. The viscosity of methyl ester, because the human body cannot ethyl ester and their blends with diesel synthesize it. A lack of the daily was within the recommended limit. It requirements of these fatty acids leads could also be concluded from the to serious health problems (Chapkin, study of the physical and chemical 1992). Many healthcare professionals properties of Jatropha biodiesel are in recommend replacing saturated fats agreement with those of petro diesel with unsaturated fats. Jatropha oil has and meet the existing standards for more 19% saturated fatty acids (C16:0, vegetable oil derived fuel. Therefore, it C17:0, C18:0, and C20:0) and more can be used as an alternate fuel in than 80% unsaturated fatty acids compression ignition engines after (C16:1, C17:1, C18:1, C18:2, C18:3 esterification. and C20:1). These results are in good Oil has very high saponification agreement with those reported by value and being extensively used for Salimon and Abdullah (2008) and also making soap in some countries. Also similar with those reported by Neff oil is used as in illuminant in lamps as and List (1999) and Gamal-Fakhry et it burns without emitting smoke. It is al., (2016). also used as fuel in place of, or along Given results in Table (5) showed with kerosene stoves. Jatropha oil cake that levels of total saturated fatty acids is rich in nitrogen, phosphorous and (TSFA) in Jatropha sample were 19.16 potassium and can be used as organic and the most abundant fatty acid in manure. By thermodynamic Jatropha was palmitic acid (C16:0) conversion process, pyrolysis, useful followed by stearic acid (C18:0) and products can be obtained from the the lowest one was arachidic acid Jatropha oil cake. The liquid, solid and C20:0. These results also, showed gaseous products can be obtained. The existence of odd chain saturated fatty liquid can be used as fuel in furnace (OCS-FAs) margaric acid C17:0 with

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Gamal-Fakhry et al., 2016 value of 0.29. The role of C17:0 in carbon, followed by the removal of the human health has recently been terminal carboxyl group. reinforced following a number of Differentiation human adipocytes important biological and nutritional showed a distinct increase in the observations (Jenkins et al., 2015). concentration of OCS-FAs, which was Historically, odd chain saturated fatty possibly caused through α-oxidation. acids (OCS-FAs) were used as internal Further evidence for an endogenous standards in GC-MS methods of total pathway, is in human plasma, where fatty acids and LC-MS methods of the ratio of C15:0 to C17:0 is intact lipids, as it was thought their approximately 1:2 which is concentrations were insignificant in contradictory to the expected levels of humans. One possible mechanism for C15:0 to C17:0 roughly 2:1 as the endogenous production of OCS- detected in dairy fat (Jenkins et al., FAs is α-oxidation, involving the 2015). activation, then hydroxylation of the α- Table (5): Fatty acids composition of Jatropha Fatty acid Test results of fatty acid Palmitic C16:0 13.84 Margaric acidC17:0(OCS-FAs) 0.29 Stearic C18:0 4.84 Arachidic acidC20:0 0.19 Total saturated fatty acids (TSFA) 19.16 Palmitoleic acidC16:1 1.19 cis-10-Heptadecenoic acid C17:1 0.40 Oleic C18:1 34.81 Linoleic C18:2 44.03 Linolenic C18:3 0.28 Paullinic acidC20:1 0.10 Total unsaturated fatty acids (TUSFA) 80.81 C17:0= Heptadecanoic acid, OCS-FAs= odd chain saturated fatty acids, C20:0= Eicosanoic acid, C22:0= Docosanoic acid

Given results in Table (6) showed C17:1are relatively rare in mammals that levels of total unsaturated fatty but common in plants and marine acids (TUSFA) in Jatropha sample is organisms. Odd chain fatty acids are 80.81 and the most abundant fatty acid oxidized in the same way as even in Jatropha oil is linoleic C18:2 chained fatty acids up until the followed by oleic C18:1 and the formation of propionyl CoA. trienoic acid (linolenic C18:3) is Propionyl CoA is converted into lowest one. succinyl CoA which then enters into Monounsaturated fatty acids with the citric acid cycle. cis-10- an odd number of carbon atoms Heptadecenoic acid has been claimed

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Gamal-Fakhry et al., 2016 to be a minor component of ruminant for biodiesel production. However, the fats (Alves et al. 2006). cis-10- chemical compositions of the oil vary Heptadecenoic acid has been shown to according to the climate and locality. have some inhibitory activity against To date, Malaysian varieties of J. human cancer cells HL-60 although curcas oil have yet to be characterized. less than some other saturated long Fatty acids composition of the chain fatty acids (Fukuzawa et al., Malaysian J. curcas oil is rich in oleic 2008). This fatty acid has a cis double and linoleic acids and the oil can be bond at an even carbon (carbon 10) classified as unsaturated oil. Hence the and therefore cannot be enzymatically Malaysian J. curcas oil has a great degraded via the usual beta-oxidation potential for oleochemical application pathway. Instead, a reductase- such as surface coating and low pour isomerase or an epimerase pathway point biodiesel. Therefore, it is must be employed in the metabolism convivial to have more research on J. of this fatty acid (Allenbach and curcas seed oil in the future to explore Poirier 2000). its potentials for future industrial Oils with a higher saturated fatty oilseeds crop (Salimon and Abdullah acid content (C18:0) have increased 2008). melting temperatures. Interesterified Jatropha curcas oil was extracted oils, high in C18:0 can be processed using n-hexane as solvent in the into softer margarines that have Soxhlet extraction method. The suitable spread ability, sensory physicochemical properties of characteristics, and acceptable oil-off Malaysian Jatropha curcas oil were properties. Such products are favorable evaluated by Salimon and Abdullah when low trans acid contents are (2008). The result showed that the required (List et al., (1979). Jatropha seeds consist of 60% (dry Jatropha oil contains 40% dienoic w/w) crude oil. The physicochemical and trienoic acids, amounts that are properties showed that the seed oil large enough to influence formation of contained low moisture level of 0.02 considerable levels of trans isomers of ±0.01%, acid value of 1.50±0.07%, linoleic and linolenic acids (Table 5). iodine value of 91.70±1.44 mg/g, These results disagree those reported peroxide value of 0.66±0.04 by Boskou and Elmadfa (1999). miliequivalence/kg and saponification The composition of J. curcas oil value of 208.5±0.47 mg/g. Gas from Nigeria consists of main fatty chromatography analysis showed that acid such as palmitic acid (13%), oleic acid (O) (46.00±0.19%) appears stearic acid (2.53%), oleic acid as dominant fatty acid in seed oil (48.8%) and linoleic acid (34.6%) followed by linoleic acid (L) (Martínez-Herrera et al. 2006). J. (31.96±0.19%) and palmitic acid (P) curcas oil contains high percentage of (13.89±0.06%). High performance unsaturated fatty acid which is about liquid chromatography (HPLC) results 78-84%. This made the oils suitable showed that the dominant

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Gamal-Fakhry et al., 2016 triacylglycerols present were PLL petro diesel, wastewater used to (20.40%), OOL (17.98%), POO irrigate these plants does not need a lot (15.02%), OOO (14.89%) and OLL of water difficulties facing extraction (14.00%). of biofuels from other plants, such as:- difficulty of extracting the oil from the CONCLUSIONS dates nucleus. -high prices of olive and Jatropha curcas L. can be a coconut crops are edible. -productivity revolutionary crop in Egyptian of the olive harvest begins in biodiesel industry, by replacing or abundance after the 9thyear. In the complementing the use of soy to irrigation process, these plants need produce the renewable fuel. It has clean water at a time when the world is many advantages in comparison to soy suffering water shortages where and rapeseed, (e.g. it does not compete Jatropha plants can be irrigated by for land use, it is not an edible crop wastewater. and it has more oil). Nevertheless, nowadays lack of information about REFERENCES some crucial aspects, like vulnerability Aceites, A. and Grasas, G. (2009): El to national pests, diseases and climatic aceite de jatrofa. 3: pp, 414-418. adaptability, are the main obstacle to Achten, W., Verchot L, Franken YJ, its large scale development. The main Mathijs E, Singh VP, Aerts R, difference between Jatropha’s and and Muys B (2008) Jatropha bio- other oil sources for fuel production is diesel production and use. the higher acid number, which affects Biomass Bioenerg 32, 1063– the processing for biodiesel 1084. production. About the Jatropha cake Allenbach and Poirier (2000): obtained by pressing, three different "Analysis of the alternative uses can be pointed out: 1- as animal pathways for the beta- oxidation feed (studies should be performed); 2- of unsaturated fatty acids using as fertilizer for exhausted lands, and 3- transgenic plants synthesizing as boiler fuel. polyhydroxyalkanoates in In this study we introduce peroxisomes", Plant Physi., Jatropha oil as solution in the next ten 124(3), 2000, pp. 1159-1168 decades because of the following Alves, J.M.; Souza, A.A. deA.Silva, properties, suitable heating value, S.R.G. da, Lopes, G.N.; Smideri, suitable flash point, and low L.E.O. J., and Uchoa, S.C.P., agriculture cost, non-edible, farming (2006): Pinhao-Manso: Uma conditions are visualizations with the Alternati vapara Producao de conditions of agriculture in Egypt. Biodiesel na Agricultura Familiar Seeds contain a large amount of oil, da Amazonia Brasileira. extracting oil simply, reasonable price Agro@mbiente On-line, 2, n. 1, in the Egyptian market, better p.57-68. properties when they are mixing with

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إستخدام مياه الصرف الصحى الخام و المعالجة فى زراعة الجاتروفا وامكانية إستخدام زيت بذور الجاتروفا كوقود حيوى

3 2 1 جمال فخري عبد النعيم ) (, مصطفى دمحم إبراهيم) (, نبيل عبد الخالق عيد عزاز) (

5 4 , أحمد عبد المنعم) (, عبد الراضيدمحمين) (

2 2 2 ) ( قسم الكيمياء الحيوية, كمية الزراعة, جامعة المنيا- ) ( قسم المحاصيل, كمية الزراعة, جامعة األزىر فرع أسيوط – ) ( كمية زراعة 5 4 دمياط, جامعة دمياط -) ( قسم المحاصيل, كمية الزراعة جامعة األزىر فرع أسيوط – ) ( قسم المحاصيل فرع الكيمياء, كمية الزراعة جامعة األزىر فرع أسيوط

تم فى ىذا البحث دراسة إمكانية ز ارعة الجاتروفا باستخدام مياه الصرف الصحى فى الرى حيث تم تنفيذ التجربو فى أصص وذالك باستخدام ثمانية معامالت من مخاليط الماء المستخدمة لرى وانبات بذور الجاتروفا. أظيرت النتائج أن نسبة اإلنبات تتراوح من 54- 87% . كما أشارت النتائج إلى أن أعمى نسبة إنبات سجمت عند إستخدام ماء صرف غير معالج فى الرى 87%. بينما أقل نسبة إنبات لبذور الجاتروفا سجمت )54%( عند إستخدام المعاممو %52 ماء صنبور + 52% ماء صرف غير معالج. تطرقت الدراسة أيضا إلى دراسة خصائص ومميزات زيت الجاتروفا ومدى قابميتو لمخمط مع وقود الديزل البترولى وتشير النتائج إلى أن الكثافو النسبية لزيت الجاتروفا الخام )27876( و ىي أعمى من تمك التى قدرت فى وقود الديزل البترولى والتى تبمغ )2.829( وكانت المزوجو الكيناميتيكية فى زيت الجاتروفا الخام )5728( بينما فى وقود الديزل البترولى )2728( كما تم تقدير رقم السيتان لزيت الجاتروفا الخام والذى تتراوح نسبتو ما بين 46- 72. كما 0 0 أشارت النتائج إلى أن كال من نقطة الوميض واالحتراق C 228 و C 226عمى التوالى . كما أظيرت النتائج ان القيمة الحرارية العميا لزيت الجاتروفا تتراوح من 29724-42787 وأن القيمة الحرارية السفمى من -26752 MJ/kg) 28794) كما تشير النتائج إلى أن القيمة الحرارية لزيت الجاتروفا أقل من تمك التى قدرت فى وقود الديزل البترولى وزيت النخيل وزيت الزيتون بينما كانت أعمى من تمك التى وجدت فى زيت الخروع وزيت جوز اليند. كما أوضحت النتائج أن الرقم اليودى لزيت الجاتروفا الخام)222) كما تم تقدير الكبريت كنسبو مئويو حيث بمغت نسبتو -1 -1 272224%. كما تبين من النتائج أن الحرارة النوعية لزيت الجاتروفا تصل إلى Jk g (2782( . تم تفريد األحماض الدىنيو بواسطة GC و اظيرت النتائج ان زيت بذور الجاتروفا يحتوى عمى أكثر من 29% أحماض دىنيو مشبعة (palmetic C16:0, margaric C17:0, stearic C18:0, and arachidic C20:0). كما يحتوى عمى أكثر من 82% أحماض دىنيو غير مشبعو.(C16:1, C17:1, C18:1, C18:2, C18:3 and C20:1). تصل نسبة األحماض الدىنيو المشبعو إلى 29726% أكثرىا وفره فى الزيت ىو حمض البالمتيك (C16:0). ويميو حمض اإلستياريك (C18:0) بينما اقل األحماض الدىنيو المشبعو تواجداً فى زيت الجاتروفا ىو حمض األراشيديك C20:0 . كما تشير النتائج إلى وجود حمض دىنى مشبع فردى السمسمو الكربونيو وىو حمض المارجاريك ..(C17:0 (0.29) . كما توضح النتائج أن نسبة األحماض الدىنيو غير المشبعو تصل إلى 82782% وأكثرىا تواجدٍا فى الزيت ىو حمض المينوليك ويميو حمض األوليك . بينما أقميا تواجداً ىو حمض المينولينك 7

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