Characterization of Coconut Shell Liquid Volatile Matter (CS-LVM) by Using Gas Chomatroghaphy

Generally, the coconut shell is only used for the fuel of furnace or is just burnt in which this will just create pollution. One way of solving this problem is by re-processing the coconut shell as raw materials for making liquid volatile matter (LVM) by pyrolysis method. Coconut shell is part of the coconut fruit at which having biological function to protect fruit core and is located on the inner side of the fiber with a thickness ranging from 3-6 mm. Coconut shell is classified as hardwood, mainly composed of lignin, cellulose, and hemicellulose, with water content of approximately 6-9 %. Coconut shell is more suitable for pyrolysis process, since they contain less amount of ash, more amount of volatile matter and available with lower cost in rural areas during all the sessions of the year. This research was aimed at determining the influence of pyrolysis temperature towards the LVM volume of coconut shell. LVM was made of condensing the smoke of pyrolysis result from the coconut shell while the analysis of compound composition of LVMcoconut shell used Gas Chromatography. Based on the result of the research, it was known that the pyrolysis, at the temperatures of 400°C, 500°C, 600°C and 700°C can create LVM volume as many as 204.167 mL kg-1, 208,33 mL kg-1 and 216.67 mL kg-1. The LVM created from the pyrolysis at 400°C was made of ammonia (12. 41%), acetic acid (37.27%), phenol (31.66%), furfural (4.16%), and alcohol (5.01%). The LVM created from the pyrolysis at 500°C was made ofammonia (12.22%), hydrazine (5.61%), acetic acid (40.96%), phenol (32.82%), and alcohol (3.10%), furfural (5.30%). The LVM created from the pyrolysis at 600°C was made of ammonia (15.49%)), acetic acid (36,01%), phenol (32.85%)), alcohol (6.75%)), and furfural (4.62%). The LVM created from the pyrolysis at 700°C was made of ammonia (15,.), acetic acid (35.20%), phenol (22.60%), alcohol (5.07%), and furfural (4,90%). From this result, it can be seen that LVM has big advantages for food flavor and other specific flavor as well as for preservative because of its antimicrobe and anti-oxidant characteristics.


Introduction
Biomass, defined as any hydrocarbon material mainly consisting of carbon, hydrogen, oxygen, nitrogen and some other components in small proportions [1], includes wood and its derived wastes, different organic wastes (including biodegradable MSW), agricultural and crop wastes, animal wastes, energy plantations, among others. Cashew nut (CNS) and coconut shells (CcNS) are part of this family [2]. Coconut shell is part of the coconut fruit at which having biological function to protect fruit core and is located on the inner side of the fiber with a thickness ranging from 3-6 mm [3]. Coconut shell is classified as hardwood, mainly composed of lignin, cellulose, and hemicellulose, with water content of approximately 6-9 % [3].
Coconut shell is more suitable for pyrolysis process, since they contain less amount of ash, more amount of volatile matter and available with lower cost in rural areas during all sessions of the year [4]. Pyrolysis is a thermo-chemical process in which organic material is converted into a carbon rich solid (char) and volatile matter (liquids and gases) by heating in the absence of oxygen [5]. Lignocellulosic biomass basic components are hemicellulose, cellulose and lignin. Researchers have already confirmed that lignin starts decomposing at low temperatures (160-170°C) and continues to decompose at low rate until approx. 900 °C. Hemicellulose is the second component to start 524 A. Tsamba reported that decomposing, followed by cellulose, in a narrow temperature interval from about 200 to 400°C. This is the interval in which the main decomposition takes place and accounts for the greatest decomposition in the biomass pyrolysis process consisting of degradation reactions. Beyond 400 °C, the most important reaction leads to the aromatisation process, at low mass loss rate [6]. Up to now, pyrolisis is commonly equipped by conventional heater (electric heater or furnace). Recently, the use of microwave radiation as a substitute for the conventional heating for synthesizing organic [7][8][9][10] ceramic processing [11][12][13], and accelerate a chemical reaction and atomic diffusion [14][15][16][17]. Microwave is not only shortening processing time but also improving material properties such as microstructure and hardness [18][19]. The heating with a microwave depends more on the molecular characteristics and the condition of reactions compared to a conventional heating. The use of this microwave energy for pyrolysis and processing biomass based materials has been performing in Halu Oleo University and will be reported in separated papers.
Smoke is defined as a suspension of solid and liquid particles in a gas medium. The smoke is produced by the pyrolysis process by means of incomplete combustion at which involving reaction of constituent polymers decomposition into organic compounds with low molecular weight due to the effects of heat include oxidation reaction, decomposition, polymerization, and condensation [20]. Liquid smoke is a solution of the result of condensation of vapor of wood smoke which is burned with limited air at high temperatures [21]. Liquid smoke contains many compounds that are formed due to the pyrolysis of three components of wood, namely cellulose, hemicellulose and lignin [22].
Coconut shell pyrolysis process produces three fractions, namely fraction of solid in the form of charcoal, the weight fraction of tar, and the light fraction of gas [23]. More than 400 chemical compounds in the smoke have been successfully identified. These components are found in varying amounts depending on the type of wood, age of the plant of wood sources, and wood growing conditions such as climate and soil. These components include acid, carbonyl, and phenol. Acids affect the taste, pH, and storage duration of smoked products. Carbonyl reacts with proteins to form brown staining. Phenol is a major framer of aroma and showed antioxidant activity [24].
Chromatography is a powerful and versatile tool for separating closely related chemical species. In addition, it can be used for the qualitative identification and quantitative determination of separated species. [24].Some detectors are universal; that is they are sensitive to practically every compound that elutes from the column. On the other hand, there are discriminating (selective) detectors that are sensitive only to specific compounds, yielding a very uncomplicated chromatogram. The ideal situation to quantify an analytic, would be to have a detector which sees only this analytic. They can be also categorized as destructive or non-destructive of the analytic. Detectors are classified into two groups depending on whether they lead only to a single information such as the retention time and those which yield, besides retention time, structural information of the analytic concerned. For this reason, some gas chromatographs are equipped with two or three detectors linked in series. Nonetheless, the response of all detectors is dependent on the molar concentration or on the mass of analytic in the carrier gas [25].

Material and Method 2.1 Materials and Tools
Materials used for the manufacture of liquid smoke is a coconut shell waste . The main equipment used to obtain the coconut shell liquid smoke is pyrolysis , and liquid smoke produced in identification using Gas Chromatography Agilent brands.

Sample Preparation
Preparation of the material in this study is the material taken from the wild form of coconut shell cleaned from coir and cut into small pieces (size 2 -3 cm) and then dried in the sun for 7-10 days.

Pyrolysis process
Pyrolysis process is done by using a pyrolysis reactor equipment with the following procedures: 1). Coconut shell sample is weighed as much as 1200 grams, 2) . The sample is introduced into a pyrolysis reactor tube, 3). Pyrolysis appliance connected to the electric current, 4). The process temperature is set by means Termocouple until it reaches a temperature variations 400°C, 500 o C, and 600 o C .for 1 hour, 5). Smoke coming out has been condensed and collected in a bottle, 6). After selesasi process , the reactor is cooled, 7). The resulting liquid volatile matter volume was analyzed using GC .

Pyrolysis results
Results coconut shell waste pyrolysis produces liquid distillate in the form of smoke and charcoal residue. It also obtained the gases which can not be condensed by cooling, so it could not be accommodated in the liquid reservoir. Most of these gases are trapped in the container while others apart from the reservoir through the conduit of smoke and escape into the atmosphere .
The volume of liquid smoke produced is an important parameter to determine the outcome of a process. Liquid smoke in this study were generated through a process of condensing the smoke released pyrolysis reactor. During the pyrolysis process of evaporation of various kinds of compounds. Volume smoke liquid smoke produced from each temperature are presented in Table 1 . Based on Table 1 the average volume of liquid smoke produced from each successive temperature are 204.167 ml.kg -1 , 208.33 ml.kg -1 and 216.67 ml.kg -1 . In this case the amount of liquid smoke generated in the pyrolysis process is very dependent on temperature pyrolysis and condensation systems used. That is appropriate condition for the formation of liquid smoke used water as the cooling medium so that the heat exchange process can occur relatively quickly. Pyrolysis at temperatures high and too long will lead to the formation of liquid smoke is reduced as the temperature of the cooling water is increasing so that the smoke generated is not completely condensed.
The quality of liquid smoke is very dependent on the composition of the chemical compounds they contain. Criteria for a good quality liquid smoke flavor and aroma as a characteristic possessed the smoke is determined by the class of chemical compounds it contains. Chemical compounds contained in liquid smoke is very dependent on the pyrolysis conditions and raw materials used . In addition, the process of pyrolysis of a material that does not last perfect can cause chemical components generated in the liquid smoke less complete. Chemicals component that have been identified in the liquid smoke include compounds phenol, carbonyl, carboxylic acid, furan, hydrocarbon, alcohol and lactone.

Chemical components of LVM
LVM generated in the pyrolysis process of waste coconut shall beforehand dissolved in methanol for chemical content are further identified. Determination of the compounds contained in liquid smoke is done by using GC equipment. Depictions of the chromatogram pattern shaped curve as a function of time. Chromatograms in Figures 1 to 3 show that the liquid smoke is generated in the pyrolysis process of waste coconut shell shows the separation of the chemical components through chromatogram peaks appearing in gas chromatography. Results chromatogram liquid smoke at a temperature of 400 o C peak chromatogram start appearing at a retention time from 1.86 to 19.27 minutes ( Figure 1) and identified as many as 20 compounds. Results chromatogram liquid smoke at a temperature of 500 o C chromatogram peaks begin to appear on the retention time from 1.82 to 19.27 minutes ( Figure 2) and identified as many as 14 compounds. While the results of the chromatogram liquid smoke at a temperature of 600°C peak cromtogram began to appear on the retention time of 1.85 to 19.27 minutes ( Figure 3) and identified as many as 14 compounds.  The compounds are believed to have the name and structure as listed in Table 2 .  From the results of the above identification is found phenol. Where the phenolic compounds can be applied as a food preservative.

Conclusion
Results pyrolysis cocoa shell with temperature variations 400 o C, 500 o C and 600 o C gained an average volume of liquid smoke respectively 204.167 ml kg -1 , 208.33 ml kg -1 , and 216.67 ml kg -1 . Results of the Gas Chromatography identification of unknown chemical components of liquid smoke cocoa shell has ammonia, acetic acid, propanone, furfural, and phenol. Phenol compounds can be used as a preservative applications