Tobacco Leaves Pyrolysis for Repellent Active

International Journal of Applied Engineering Research ISSN 0973-4562 Volume 9, Number 21 (2014) pp. 9739-9749 © Research India Publications http://www.ripublication.com

Tobacco Leaves Pyrolysis for Repellent Active Compound Production Misri GOZAN1, Yasman2, Praswasti P.D.K. WULAN1, Ellen DAWITRI1 1

Chemical Engineering Department, Engineering Faculty, Universitas Indonesia, Depok 16424, Indonesia, Phone: +62-21-7863516; Fax: +62-21-7863515, E-mail: [email protected]; 2Biology Department, Faculty of Math and Natural Science, Universitas Indonesia, Depok 16424, Indonesia.

Abstract Tobacco is the major raw material for cigarettes production. It is known to have a big potential as a pesticide or repellent. On the other side, commercial mosquito repellent which is used by public, contain DEET as its active compound, a synthetic substance which can be absorbed to human body and cause some systemic poisoning. This research study further potential of repellent on tobacco leaves, to make a repellent that is safe for human. Bio-oil was extracted from tobacco leaves using fast pyrolysis at temperature of 500oC, 600oC, and 700oC to evaluate the effect of temperature. Bio-oil was then made into bio-mass based repellent. Bio-oil was characterized using GCMS, while the repellent was tested directly to human to evaluate the effects on the skin and the effectivity as a repellent. Optimum yield of bio-oil was found on 600oC at 24% wt. The active compound of repellent found was nicotine, dLimonene, indole, and pyridine. Nicotine was the highest substance from biooil at 31,1%; 16,7%; and 18,92%, respectively. Bio-oil was added to repellent mixture as active compound with different concentration (0%; 0,5%; 1,5%; and 3%), all in %wt. Repellent tested showed a desired result, where not only the repellent didn’t take effect on human skin, the effectivity of each concentration was 38,09%; 45,82%; 46,41%; and 57,07%, respectively. Keywords: Tobacco Leaves; Pyrolysis; Bio-Oil; Mosquito Repellent; Pesticide

Introduction Tobacco is the major raw material for cigarettes production. Cigarette industry is one of the industries that continue to increase each year. In 2011, the production in

Paper Code: 26929 - IJAER

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Indonesia reached 270,3 billion cigarettes [1]. It makes cigarettes industry as one of the industry is irreplaceable in Indonesia, although in fact many people want a termination of this industry because of the negative impact brought by smoking. But when cigarettes industry is stopped, it is bad for the tobacco farmer’s life in Indonesia. In addition to the danger that itas as raw materials for cigarettes, tobacco has other functions that are not yet well known, namely as repellent or pesticide. Another experiment done before, using the exact same method show that bio-oil produced from tobacco pyrolysis can kill insects. Compounds that function as pesticides was nicotine, d-limonene, pyridine, and indole, with the most one was nicotine with totalof 37,5% [2] Mosquito repellent was a ingridient which can act locally or from faraway, to prevent mosquitos come near or bite human[3].DEET (N,N-dietil-m-toluamida) was the most used active ingridient in comercial repellent[4]. According to the ethics of commercial insect repellent , DEET content should notbe more than 14%, but in the reality, most of the repellent contain more [5]. DEET can be absorbed into the body, and high dosed usage of DEET can cause sensoric and motoric nerve disturbance, neurodegeneration, and systemic poisoning [6]. Main chemical composition of tobacco leaf extract consists of phenolic compounds, nicotine, and diterpen.The tobacco leaf itself actually has many benefits other than for the manufacture of cigarettes. One of them is able to function as a biopesticide Farmers themselves have many utilize the other parts of tobacco such its stem that had often become waste and discarded, to eradicate the pest plants, onions and chili. While on the leaves of tobacco, nicotine content is labeled as hazardous materials that can serve as a pesticide. Nicotine levels ranged from 0.6-3.0% of dry weight of tobacco. Characterization of tobacco as the biomass has been mostly done [7-9]. However, the production of bio-oil by pyrolysis of tobacco very little published. The potential of bio-oil as a pesticide from tobacco is an area of research that needs to be traced further. This research is producing pesticides and examine the content and nature of the biopesticide produced from pyrolysis of tobacco.

Method Preparation Tobacco leaves used is an old leaves with yellowish green colored with varying sizes. Tobacco leaves was taken from Kerinci, Jambi. First the leaves were washed to remove dirt and dust from the surface. Then the leaves were dried on the sun and the continued by oven or a furnace at temperature of 60oC until it was completely dried. The dried leaves then grinded in a blender, then filtered using a mesh to obtain a homogeneous size about 60 μm Pyrolysis of Tobacco At this stage pyrolysis will be done using dried tobacco leaves that had been prepared before to produce bio-oil. The reactor used in pyrolysis was a cylindrical reactor made of stainless steel with a diameter of 8 cm and a length of about 40 cm. The reactor

Tobacco Leaves Pyrolysis for Repellent Active Compound Production

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will be heated in a furnace, and the pyrolysis itself was carried out in two different temperatures, that is 500oC and 600oC. Inert gas used to subtitute the presence of oxygen was nitrogen, and the tobacco leaves dust used was 250 gram. Gas coming out from the reactor was condensed to get the bio-oil. Bio-Oil Characterization Bio-oil from tobacco leaves pyrolysis was characterized through GC-MS analysis to identified the composition of bio-oil. Analysis was done at Police Headquarters Forensic Laboratory Center, South Jakarta. A HP 6890 series gas chromatography system with a mas selective detector was used to analyze the bio-oil composition, and the column model Agilent 19091S-433 with injection volume 1,0 microliters. Mosquito Repellent Making The repellent was made by mixing cream base with the bio-oil. It was made in variouskind of bio-oil concentration, that is 0%; 0,5%; 1,5%; and 3%. The method used was emulsion of water and oil. The oil phase was a mixture of stearic acid, glycerl monostearate, isopropyl myristic, dimeticon, and propyl paraben, that was heated at temperature of 70-80oC. While the water phase was a mixture of methyl paraben, trietanolamine, PEG 400, propylenglycol, and aquadest. The oil phase was mixed into water phase with homogenizer at temperature of 70oC, when the temperature reach 40oC citric acid 20% solution was dropped slowly into the mixture together with aquadest, antioxidant, and bio-oi. Then the stirring continued with a speed of 1000 rpm for another 15 minutes. Evaluation of Mosquito Repellent The evaluation was divided into 3 steps, that is the stability of the repellent lorion, sensitivity of human skin to the repellent, and effectivity of the repellent to prevent mosquito bites. Repellent Stability Test This test was done to evaluate the stability of the cream lotion. The lotion was put into centrifugation in a speed of 3750 rpm for 5 hours or 5000 to 10000 rpm for 30 minutes, then observation was done to see if there was a separation of the phase in the lotion. Sensitivity Test This test was to observe the effect of repellent on human skin. The repellent used was the one with 3% of bio-oil concentration. It was smeared into the panelist arm in 5 x 5 cm wide,then a patch was put on it for 24 hours. After 24 hours, the observation was done in the area where the repellent was put. Positive irritation reaction was signified by erythema, itchiness, or edema on the skin. The data collected was the processed to get index of skin irritation with equation below: ∑ ∑ index of irritation = (1)

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Effectivity Test This test was done to observe the effevtivity of mosquito repellent. The test was done to 10 volunteer for 3 days, with a test using 25 mosquitoes, using both hands of the volunteer, which only one of the hands was using the repellent and the other was used as control. The test was carried out for 6 hours and using each concentration to compare the effectiveness . The protection was calculated by the formula below: ∑ − ∑ 100% (2) ∑ .

Result and Discussion Pyrolysis Result Figure 1 show the diagram of pyrolysis system. Size reduction was done to tobacco leaves before pyrolysis to speed up the pyrolysis reaction [10]. Products of pyrolysis are in a form of gas, liquid, and solid in a form of carbon or char. Decomposition of biomass happened in temperature of 400-500oC will tend to produce liquid oil on short residence time.

Figure 1. Diagram of Pyrolysis System During pyrolysis process, the moisture will evaporate first at a temperature of 100oC, later followed by cellulose decomposition (240-340oC) and lignin (280500oC). The higher the heating rate, the faster the formation of volatile compounds, increasing the pressure, shorter residence time from the volatile products inside the reactor, and higher liquid product [10]. The main product wanted was the liquid with a strong odor of tobacco. It was originally homogeneous thick liquid with black colour. After a few hours the fluid start to separate and form two fraction. The top fraction was a black viscous liquid, while the lower one has a form like cooking oil butmore watery. The top fraction did not dissolve in water and the lower fraction was soluble in water..


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There are a difference on the total bio-oil produced from each temperature. The total volume each fraction is also different. Liquid product from temperature 500oC has the most volume, and it was decreased as the temperature increased. This proved that in fast pyrolysis, as the temperature was

Figure 2. Comparison of Bio-Oil Yield

Increased, the yield of liquid productwill decreased because of cracking and gasification [12]. Table 1 shows the total volume and weight of each pyrolysis liquid product. The amount of biopoil top fraction increased from 500oC to 600oC, then decreased at 700oC. Most of liquid product from temperature of 600oC was the top fraction with the yieald at almost 24%. This show that pyrolysis was the most optimum at temperature of 600oC. The increasing temperature at pyrolysis will also increased the gas product ant amount of water while decreasing the char [11]. This was also occured insome other experiments [11-12]. Figure 2 shows the comparison of the liquid yield from pyrolysis. Table 1. Total Volume and Weight of Pyrolysis Product 500oC 600oC 700oC Total Volume (mL) 70 61 59 Top FractionVol. (mL) 33,3 47,7 38,3 Lower Fraction Vol (mL) 36,7 13,3 19,7 Total Mass (gram) 73,37 60,3 54,38

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GC-MS Analysis The component insinde bio-oil then analyzed by using GC-MS analysis. Each sample was analyzed to get the content in fractions above and below it to determine of the component differences between the top and lower fractions. The results of GC-MS graph was shown in Figure 3. Tobacco bio-oil from pyrolysis contained various compounds. The top fraction was dominated by heavy hydrocarbons, some aromatics, organic acids, and other oxygenated compounds. While the lower fraction was dominated bt organic acids and pyridine derivatives. The most dominant compounds from tobacco bio-oil was nicotine, with the comparison of each temperature of each fraction seen in Figure 4. GC-MS result on tobacco bio-oil show that there were some components that have a function as insect repellent, that were the main component in this experiment. They were: d-limonene D-limonene is used as the active and inert ingredients in pesticide products, and as an ingredient in food products, soaps, and perfumes. As the active ingredient, dlimonenen used as an insecticide, insect and animal repellent. While as an inert, these compounds can be used as a solvent and fragrance [13]. Indole Indole, is an active ingredient found naturally in nature. These compounds are commonly used in the synthesis of perfume or essential oil in low concentrations. . Indole can be used in biochemical pesticides at low concentrations as an attractant, but showed very low levels of toxicity [14]. Nicotine Nicotine, derived from tobacco, has been used as a pesticide since at least the 15th century. Type the use of nicotine as an insecticide is a pesticide, which is used only on ornamental plants and flowers and is not recommended in food crops [15]. Pyridine Piridine is a compound that is often used as a solvent and is used to make a variety of products such as medicines, vitamins, food flavorings, pesticides, and other. Its use as an intermediate in the manufacture of various insecticides and herbicides for agricultural use were just start to widely produced since the 20th century [16].


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Figure 3. GC-MS of Tobacco Bio-Oil (Top: 500oC, Middle: 600oC, Bottom: 700oC)

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Figure 4. Comparison of Nicotine Amount

Evaluation of Mosquito Repellent The lotion was in a form of homogeneous white cream. The three repellent that has bio-oil in it was white cream lotion with distinctive odor. The higher the concentration of the bio-oil used, the odor was stronger. Stability Test The test was done byusing centrifugation with a speed of 3750 rpm within some redius of centrifugation for 300 minutes. This test could be treated the same as the effect of gravitational force to the lotion for the storage of more or less one year [17]. The observation indicate that there were no separation on the repellent after the centrifugation was done. Sensitivity Test After 24 hours of test done to 10 panelist, patch was removed and observation was done on the skin where the repellent was applied, and the data were processed according to the erythema and edema score happened to the panelist’s skin showedin table 2. Using equation (1), then we will get:


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Table 2. Sensitivity Test Result Panelis Erithema Score Edema Score 1 0 0 2 0 0 3 0 0 4 1 0 5 0 0 6 0 0 7 0 0 8 0 0 9 0 0 10 0 0

According to respond category then the effect of mosquito repellent to panelist can be categorized as “meaningless” Effectivity Test The test was carried out for 6 hours and done with each concentration to compare the effectivity of each concentration. Protection average result of each formula was shown by table 3. As shown, the higher the concentration of bio-oil in the repellent, the higher the protection. In general, repellent will manipulate the smell and taste from skin by resisting the lactate acid receptor in mosquito, so it will prevent the mosquito to come near the skin, usually by adding some dominant smell on mosquito repellent such as orange skin or lavender. This principle also applied to tobacco mosquito repellent, where beside it has a potential as pesticide, tobacco bio-oil also had a dominant smell so it can manipulate mosquito by covering CO2 smell that was produced by human skin. Comparison with Other Bio-Oil Study to another bio-oil or essence oil as repellent are also done, one of them was using the mixture of lemongrass and eucalyptus oil to repel Ae. Aegypti [18]. The experiment gave a satisfying result,where the mixture of those essence oil could gave a protection in (98,66+11,56) minute. The protection parameter was the mosquitoes that was landed on the skin is not more than 2. This time is relative short compare to industrial mosquito repellent, where according Thai Industrial Standards Institute (TISI), the protection given should be more than 120 minute. The experiment using repellent containing tobacco bio-oil show much more better result. Protection given from tobacco mosquito repellent with 3% bio-oil concentration in it last along the experiment period, that is 6 hours, where to the most panelist, there were just less than 2 mosquitoes land on the volunteer’s hand.

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Misri GOZAN et al Table 3. AverageProtection by Tobacco Mosquito Repellent Formula Average Protection F1 ( 0%) 38,09 % F2 (0,5%) 45,82 % F3 (1,5%) 46,41 % F4 (3%) 57,07 %

Conclusion From this experiment, it can be concluded that:  The incresing temperature on fast pyrolysis will decrease the yield of liquid, by cracking and gasification reaction  The compound that act as pesticide/mosquito repellent on the bio-oil was nicotine, d-limonene, pyridine, and indole.  Nicotine was the most dominant compound on all result of bio-oil, where it was 31,1% on 500oC; 16,77% on 600oC; and 18,92% on 700oC.  Mosquito repellent that had bio-oil in it had a relative hight effectivity, that is 57,07% on the one with 3% bio-oil concentration.  The repellent was proved harmless to human skin. It is proved by the sensitivity test where there are no effect on the volunteer skin.

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