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ISSN: 2155-9872
Journal of Analytical & Bioanalytical Techniques
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Using GC-MS to Analyze Bio-Oil Produced from Pyrolysis of Agricultural Wastes - Discarded Soybean Frying Oil, Coffee and Eucalyptus Sawdust in the Presence of 5% Hydrogen and Argon

Zeban Shah1*, Renato Cataluña Veses1 and Rosangela da Silva2

1Federal University of Rio Grande do Sul, Av. Bento Gonçalves, Porto Alegre, RS, Brazil

2Pontifical Catholic University of Rio Grande do Sul, Av Ipiranga, Porto Alegre, RS, Brazil

*Corresponding Author:
Zeban Shah
Federal University of Rio Grande do Sul
Av. Bento Gonçalves 9500
91501-970 Porto Alegre, RS, Brazil
Tel: +555134340123
E-mail: [email protected]

Received Date: January 26, 2016; Accepted Date: February 17, 2016; Published Date: February 24, 2016

Citation: Shah Z, Veses RC, Silva R (2016) Using GC-MS to Analyze Bio-Oil Produced from Pyrolysis of Agricultural Wastes - Discarded Soybean Frying Oil, Coffee and Eucalyptus Sawdust in the Presence of 5% Hydrogen and Argon. J Anal Bioanal Tech 7:300. doi:10.4172/2155-9872.1000300

Copyright: © 2016 Shah Z, et al. This is an open-access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited..

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Abstract

Pyrolysis is a thermal process for converting various biomasses, wastes and residues to produce high-energydensity fuels (bio-oil). In this paper, we have done some important analysis of bio-oil which is obtained from the pyrolysis of agricultural wastes - discarded soybean frying oil, coffee and eucalyptus sawdust in the presence of 5% Hydrogen and Argon. The bio oil was obtained in one step pyrolysis in which temperature of the system kept 15°C and then increased up to 800°C but in two step condensation processes. 1st condensation step is done on temperature 100°C and 2nd is done on 5°C. So we got two types of fractions, HTPO (Oil condensed at high temperature 100°C after pyrolysis) and LTPO (Oil condensed at low temperature 5°C after pyrolysis). After pyrolysis the thermal cracking is done for both types of oil on the same two temperatures, then we again got two type of fractions HTCO (high temperature 100°C condensed oil after cracking) and LTCO (Low temperature 5°C condensed oil after cracking), these fractions are distillated and analyzed in GC-MS. The resulted compounds are given in the paper and are explained with the help of graphs and tables. The ultimate aim of hydrogenation and Argon is to improve stability and fuel quality by decreasing the contents of organic acids and aldehydes as well as other reactive compounds, as oxygenated and nitrogenated species because they not only lead to high corrosiveness and acidity, but also set up many obstacles to applications.

Keywords

Chromatographic analysis; GC/MS; Biomass pyrolysis; Bio-oil production

Abbreviations

CSSB: Bio-oil produced from coffee, sawdust and discarded soybean frying oil; GC/MS: Gas chromatogram/mass spectrometer; HTPO: Oil condensed at 100°C high temperature after pyrolysis; LTPO: Oil condensed at 5°C low temperature after pyrolysis; HTCO: Oil condensed at 100°C high temperature after cracking; LTCO: Oil condensed at 5°C Low temperature after cracking

Introduction

Now-a-days Bio-Oils (Biodiesel or Biofuels) are becoming more famous and attractive for the people in all over the world because of their good aspects for the people and environment around us. Biodiesel is an oxygenated fuel consisting of long chain fatty acid which contain 10-15% oxygen by weight [1,2] and it contains neither sulfur, nor aroma. These facts lead biodiesel to enhance more complete combustion and less emission of particulate matter. The biomass pyrolysis process is an economically feasible option for producing chemicals and/or fuels [3,4]. The bio-oil resulting from the pyrolysis process consists of a mixture of more than 300 organic compounds [5]. In terms of environmental issue biodiesel is more adoptable compare to fossil fuel as it forms low carbon and smoke which are responsible for global warming [6,7]. On the other hand biodiesel has higher molecular weight, density, viscosity and pour point than conventional diesel fuel [8,9]. Higher molecular weight and viscosity of biodiesel causes low volatility and poor fuel atomization, injector coking, piston ring sticking and leading incomplete combustion [10] as well as it has cold flow property which is a barrier to use it in cold or chill weather [11] anyhow the best benefit of Bio-oils is that they are preparing from renewable sources like corpse, plants, trees and residues etc. Approximately 100 years ago, Rudolf Diesel tested Bio oil as the fuel for his engine that was available with him [12,13]. According to scientists and researchers there are 350 oil containing crops and plants identified, among them only soybean, rapeseed, coffee, sunflower, cottonseed, peanut, safflower, and coconut oils are considered that they have the potential and quality of alternative fuels for diesel engines [14,15]. Bio oils have the capacity to substitute for a part or fraction of the petroleum products, distillates and petroleum based petrochemicals in the future. Due to being more expensive than petroleum, bio-oil fuels are nowadays not petroleum competitive fuels. However, due to the misuse, high expenditure and increases in petroleum prices and the uncertainties concerning petroleum availability, there is renewed interest in using Bio-oils in Diesel engines [16]. The emergence of transesterification can be dated back as early as 1846 when Rochieder described glycerol preparation through methanolysis of castor oil and since that time, alcoholysis has been studied in many parts of the world. Scientists, researchers have also investigated the important reaction conditions and parameters on the alcoholysis of triglycerides, such as tallow, fish oils, sunflower, soybean, rapeseed, linseed oils, cottonseed, sunflower, safflower, and peanut [17,18]. Soybean oil was transesterified into ethyl and methylesters, and comparisons of the performances of the fuels with diesel were made [19,20]. Also, methylesters have been prepared from palm oil by transesterification using methanol in the presence of a catalyst (NaOH) or (KOH) in a batch reactor [21]. Ethan oil is a preferred alcohol in the transesterification process compared to methanol because it is derived from natural agricultural products and is renewable and biologically less objectionable in the environment. The success of rapeseed ethylester production would mean that biodiesel`s two main raw materials would be agriculturally produced, renewable and environmentally friend [22].

Methyl, ethyl, 2-propyl and butyl esters were prepared from canola and linseed oils through transesterification using KOH and/or sodium alkoxides as catalysts. In addition, methyl and ethyl esters were prepared from rapeseed and sunflower oils using the same catalysts [23,24].

Experimental

Materials: Discarded soybean frying oil, coffee, eucalyptus sawdust and other reagents

Discarded soybean frying oil, coffee grounds and eucalyptus sawdust were collected from Porto Alegre a Brazilian city. The biooil was obtained by pyrolysis of a mixture (1:1:1 in mass) of discarded soybean frying oil, coffee grounds and eucalyptus sawdust. The frying oil was mixed to the solids after their granulometric reduction (till 0.21 mm). Calcium oxide was added to this mixture (at 20% in mass) and sufficient amount of water to produce a malleable mass that could be fixed and conformed in cylinders (50 mm × 180 mm). After building the cylinders, they were dried at environmental temperature during 3 days. Before the pyrolysis, the system is purged during 20 minutes with Argon with 5% of hydrogen (100 mL/min). The ultimate aim of hydrogenation and Argon is to improve stability and fuel quality by decreasing the contents of organic acids and aldehydes as well as other reactive compounds, as oxygenated and nitrogenated species because if we were not used H and Ar then we found above species which not only lead to high corrosiveness and acidity, but also set up many obstacles to applications.

Production of CSSB

The bio-oil was produced from the pyrolysis of discarded soybean frying oil, coffee grounds and eucalyptus sawdust in the presence of 5% hydrogen and argon. A round block shape structure of sample was made inside the filter paper from (filter paper as side wall of the sample block to keep the biomass tight) biomass, while the weight of this sample is kept 400 g after preparation of this sample block it was kept inside a stainless steel chamber of pyrolysis system which is further connected to two other chambers which are shown in diagram in Figure 1.

analytical-bioanalytical-techniques-Biomass-pyrolysis

Figure 1: Biomass pyrolysis system.

The temperature of chamber which has biomass was increased from 15°C to 800°C with help of heater, temperature controller cabinet, and condenser, through which biomass was converted to biogas and then the biogas was condensed in other two chambers which condensed fractions of biogas to bio-oil on temperature 100°C and 5°C respectively, the two condensed fractions from these chambers (HTPO and LTPO) were collected and introduced to further analysis.

GC-MS analysis of HTPO and LTPO (CSSB)

The bio-oil identification and composition determination were performed on a GC Agilent series 6890 with a Agilent mass selective detector of series 5973. A capillary polar wax column, polyethylene glycol (PEG)-coated (length of 30 m, internal diameter of 0.25 mm, and film thickness of 0.25 μm).

Chromatographic conditions were as follows:

Injection volume of 0.2 μL, oven at 40°C (1 min) 6°C min−1 up to 300°C (10/Min) split mode with a ratio of 100:1 and injection temperature of 290°C. Time taken was 54.3 minutes, He (helium) as carrier gas with a flow rate of 2.9 mL min−1.

GC-MS chromatograms of CSSB

Below Figures 2 and 3 are different chromatograms of HTPO and LTPO respectively which show different peaks which show different compounds in both cases.

analytical-bioanalytical-techniques-split-less-mode

Figure 2: Done with split-less mode where different peaks show different compounds in HTPOat different retention time.

analytical-bioanalytical-techniques-different-peaks

Figure 3: Done with split mode where different peaks show different compounds in LTPO at different retention time.

Results and Discussion

Chemical composition of CSSB

CSSB is a dark and sticky liquid the compounds detected in CSSB can be classified into hydrocarbons, alcohols, phenol, ethers, aldehydes, ketones, carboxylic acids, and other esters. But large peaks of GC/MS mostly shows aromatic, aliphatic and cyclic hydrocarbons while small peaks show other groups. Library match used for identification of compounds based on probability score and each compound was detected very clearly and with high probability value. According to GC/MS analysis summarized in Tables 1 and 2 mostly aromatics and aliphatic groups were enriched in the sample. After GC/MS analysis each peak of chromatogram was matched with library one by one, where different peaks showed different Aliphatic and Aromatic compounds.

No Name Formula Retention time
1 Benzene, 1-ethyl-3-methyl- C9H12 8.18
2 Benzene, 1,2,3-trimethyl- C9H12 9
3 Decane C10H22 9.15
4 2-Decene, (Z)- C10H20 9.32
5 cis-3-Decene C10H20 9.52
6 Benzene, 1,2,3-trimethyl- C9H12 9.72
7 Benzene, 2-propenyl- C9H10 9.82
8 Indane C9H10 10.17
9 Indene C9H8 10.3
10 Benzene, butyl- C10H14 10.52
11 Benzene, 1,2-diethyl- C10H14 10.72
12 2,4-Dimethylstyrene C10H12 11.3
13 Undecane C11H24 11.7
14 3-Undecene, (Z)- C11H22 11.82
15 3-Undecene, (Z)- C11H22 12.05
16 Benzene, 4-ethenyl-1,2-dimethyl- C10H12 12.67
17 1H-Indene, 2,3-dihydro-4-methyl- C10H12 12.95
18 Benzene, pentyl- C11H16 13.15
19 Naphthalene, 1,2,3,4-tetrahydro- C10H12 13.25
20 Benzene, (1-methylbutyl)- C11H16 13.35
21 Azulene C10H8 13.75
22 Dodecane C12H26 14.15
23 6-Dodecene, (Z)- C12H24 14.25
24 3-Dodecene, (Z)- C12H24 14.5
25 Benzene, hexyl- C12H18 15.55
26 Benzene, (1-methylpentyl)- C12H18 15.7
27 Naphthalene, 1-methyl- C11H10 16.35
28 Tridecane C13H28 16.47
29 3-Tridecene, (E)- C13H26 16.57
30 1H-Indene, 1-ethylidene- C11H10 16.75
31 Naphthalene, 2-methyl- C11H10 16.85
32 1-Isopropenylnaphthalene C13H12 16.95
33 Tetradecane C14H30 18.65
34 3-Tetradecene, (E)- C14H28 18.75
35 Pentadecane C15H32 20.72

Table 1: Aliphatic and Aromatic Hydrocarbons detected in HTPO with their retention time.

No Name Formula Retention time
1 3-Undecene, (Z)- C11H22 11.45
2 Undecane C11H24 11.65
3 5-Undecene, (Z)- C11H22 11.8
4 3-Dodecene, (Z)- C12H24 13.9
5 3-Dodecene, (Z)- C12H24 14.05
6 Dodecane C12H26 14.15
7 3-Dodecene, (E)- C12H24 14.25
8 3-Dodecene, (Z)- C12H24 14.5
9 2-Tridecene, (Z)- C13H26 16.3
10 Tridecane C13H28 16.45
11 3-Tridecene, (E)- C13H26 16.55
12 3-Tetradecene, (E)- C14H28 18.5
13 Tetradecane C14H30 18.65
14 3-Tetradecene, (E)- C14H28 19
15 Pentadecane C15H32 20.72
16 Hexadecane C16H34 22.7
17 Heptadecane C17H36 24.58

Table 2: Aliphatic hydrocarbons in CSSB and their retention time.

Enrichment of chemicals in CSSB sample

According to GC/MS analysis summarized in Tables 1 and 3, C11-C17 alkanes, alkene, cyclic hydrocarbons and aromatic hydrocarbons were enriched in the CSSB sample.

No Name of compound Formula Retention time
1 Benzene, 1-methyl-4-(1-methylethyl)- C10H14 11.3
2 3-Undecene, (Z)- C11H22 11.45
3 Undecane C11H24 11.65
4 5-Undecene, (Z)- C11H22 11.8
5 Benzene, 4-ethenyl-1,2-dimethyl- C10H12 12.65
6 1H-Indene, 2,3-dihydro-5-methyl- C10H12 12.9
7 7-Methyl-1,2,3,5,8,8a-hexahydronaphthalene C11H16 13
8 2-Methylindene C10H10 13.1
9 Benzene, pentyl- C11H16 13.13
10 Naphthalene, 1,2,3,4-tetrahydro- C10H12 13.25
11 Benzene, (1-methylbutyl)- C11H16 13.38
12 Naphthalene C10H8 13.75
13 3-Dodecene, (Z)- C12H24 13.9
14 3-Dodecene, (Z)- C12H24 14.05
15 Dodecane C12H26 14.15
16 3-Dodecene, (E)- C12H24 14.25
17 3-Dodecene, (Z)- C12H24 14.5
18 2-Ethyl-2,3-dihydro-1H-indene C11H14 14.95
19 Benzene, hexyl- C12H18 15.55
20 Benzene, (1-methylpentyl)- C12H18 15.7
21 2-Tridecene, (Z)- C13H26 16.3
22 Naphthalene, 1-meth yl- C11H10 16.35
23 Tridecane C13H28 16.45
24 3-Tridecene, (E)- C13H26 16.55
25 1H-Indene, 1-ethylidene- C11H10 16.75
26 Benzene, heptyl- C13H20 17.9
27 1-Methyl-2-n-hexylbenzene C13H20 18
28 Naphthalene, 2-ethyl- C12H12 18.6
29 3-Tetradecene, (E)- C14H28 18.5
30 Tetradecane C14H30 18.65
31 3-Tetradecene, (E)- C14H28 19
32 Naphthalene, 1,7-dimethyl- C12H12 19.15
33 Pentadecane C15H32 20.72
34 n-Nonylcyclohexane C15H30 21.8
35 Hexadecane C16H34 22.7
36 Cyclopentane, undecyl- C16H32 22.8
37 Heptadecane C17H36 24.58

Table 3: Aliphatic and Aromatic Hydrocarbons detected in LTPO with their retention time.

Enrichment of C11-C17 aliphatic hydrocarbons (alkane, alkene, cyclic): As Tables 1 and 4 shows, aliphatic hydrocarbons with C11–C17 are predominant in the sample with a % area of 51.255, 34.843, and 31.204 in LTCO, LTPO and HTCO respectively. Figure 4 and Table 2 show only aliphatic hydrocarbons in CSSB.

analytical-bioanalytical-techniques-aliphatic-hydrocarbons

Figure 4: Shows only aliphatic hydrocarbons peaks.

No Name Formula Retention time
1 Benzene, 1-methyl-4-(1-methylethyl)- C10H14 11.3
2 Benzene, 4-ethenyl-1,2-dimethyl- C10H12 12.65
3 1H-Indene, 2,3-dihydro-5-methyl- C10H12 12.9
4 7-Methyl-1,2,3,5,8,8a-hexahydronaphthalene C11H16 13
5 2-Methylindene C10H10 13.1
6 Benzene, pentyl- C11H16 13.13
7 Naphthalene, 1,2,3,4-tetrahydro- C10H12 13.25
8 Benzene, (1-methylbutyl)- C11H16 13.38
9 Naphthalene C10H8 13.75
10 2-Ethyl-2,3-dihydro-1H-indene C11H14 14.95
11 Benzene, hexyl- C12H18 15.55
12 Benzene, (1-methylpentyl)- C12H18 15.7
13 Naphthalene, 1-methyl- C11H10 16.35
14 1H-Indene, 1-ethylidene- C11H10 16.75
15 Benzene, heptyl- C13H20 17.9
16 1-Methyl-2-n-hexylbenzene C13H20 18
17 Naphthalene, 2-ethyl- C12H12 18.6
18 Naphthalene, 1,7-dimethyl- C12H12 19.15
19 n-Nonylcyclohexane C15H30 21.8
20 Cyclopentane, undecyl- C16H32 22.8

Table 4: Main Aromatic compounds detected in CSSB and their retention time.

Enrichment of aromatic hydrocarbons: As Table 4 and Figure 5 show only aromatic hydrocarbons detected in CSSB and also occupied large part of the CSSB with in the sample with a % area of 0.246, 30.008, 32.241, 24.892 in HTPO, LTCO, LTPO and HTCO respectively.

analytical-bioanalytical-techniques-aliphatic-hydrocarbons

Figure 5: Shows only aliphatic hydrocarbons peaks.

Enrichment of other compounds: Alcohols, Aldehydes, Ketones, Ethers, Esters, Phenols, and Nitrogenous also contained some part of the CSSB while in these classes Phenols and ketones were occupied more space as compared to others as shown in Table 5. Which mean that in these we also have Phenols and ketones, which need to be separated.

Figure 6 shows % area of alcohols, ethers, ketones, phenols, N-compounds, aliphatic, aromatic and cyclic compounds in HTPO (blue) and LTPO (red) while Figure 7. Shows % area of alcohols, ethers, ketones, phenols, N-compounds, aliphatic, aromatic and cyclic compounds in HTCO (blue) and LTCO (red) and their detail is also given in Table 5.

analytical-bioanalytical-techniques-HTPO-blue

Figure 6: % area of compounds in HTPO (blue) and LTPO (red).

analytical-bioanalytical-techniques-HTCO-blue

Figure 7: % area of compounds in HTCO (blue) and LTCO (red).

Different Classes  of compounds % Area
HTCO LTPO LTCO HTPO
Alcohols n.d 0.894 0.168 10.930
Aldehydes n.d. 0.416 1.289 n.d.
Ketones 9.088 7.92 6.526 30.827
Ethers 1.459 n.d. 0.468 6.263
Esters 0.921 n.d. n.d. n.d.
Phenols 4.018 6.809 4.458 2.858
Nitrogenous n.d. 0.354 n.d. 45.779
Aromatics hydrocarbons 24.892 32.241 30.008 0.246
Cyclic hydrocarbons 28.319 16.420 5.829 3.096
Aliphatic hydrocarbons 31.304 34.843 51,255 n.d.

Table 5: % area of different compounds detected in CSSB and its Graphical representation.

Conclusion

More than 120 compounds were detected in the CSSB. Among them, aromatic, aliphatic and cyclic hydrocarbons, especially alkanes, alkenes and benzene containing compounds were dominant. A laboratory scale effort is made in this work however to improve efficiency and process thus, this process can be successfully applied in large-scale operations because the demand for liquid transportation fuels is increasing day by day, and biofuels might be one of the best solutions for this problem. Technologies for converting biomass to biodiesel also are at various stages of development, which include the pretreatment of biomass. Although cost of biomass may be high or the costs of processing it can be high but for the time being it may be an alternative for fossil fuels, Future work is going to improve the recovery of phenols, ketones and other chemicals from the CSSB.

Acknowledgements

The authors want to thank CNPq, Brazil.

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  1. Salim
    Posted on Aug 04 2016 at 2:40 pm
    The article discusses the various advantages of hydrogenation and application of argon in order to improve stability, quality and usability of the biofuels isolated from agricultural waste through pyrolysis. The article is highly informative and will help in the production of cost effective biofuels that can be used on a large scale.
 

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