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Separation of Phenol from Bio-oil Produced from Pyrolysis of Agricultural Wastes | OMICS International
ISSN: 2329-6798
Modern Chemistry & Applications
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Separation of Phenol from Bio-oil Produced from Pyrolysis of Agricultural Wastes

Zeban Shah1*, Renato CV1, Marco AC1 , Rosangela DS2

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, Porto Alegre, RS, Brazil
Tel: 555182634325
E-mail: [email protected]

Received date: November 02, 2016; Accepted date: December 12, 2016; Published date: January 02, 2017

Citation: Shah Z, Renato CV, Marco AC, Rosangela DS (2017) Separation of Phenol from Bio-oil Produced from Pyrolysis of Agricultural Wastes. Mod Chem Appl 5:199. doi: 10.4172/2329-6798.1000199

Copyright: © 2017 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

The aim of this study was to separate phenol from Bio-Oil obtained from the pyrolysis of agricultural wastes (BAW). The BAW was obtained in one step catalytic pyrolysis in which temperature of the reactor was kept at 30°C and then increased up to 900°C. After pyrolysis, the BAW was distillated and analyzed by Gas chromatography and Mass spectrometry (GC-MS) technique and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry detection (GC × GC/TOFMS) Where BAW showed the presence of more than 120 other important compounds and phenol. After detection, phenol was separated by solvent extraction method, where Ethyl ether (C4H10O), Caustic soda (NaOH) and Hydrochloric acid (HCl) were used to separate phenol from BAW and then Nuclear magnetic resonance spectroscopy (NMR) was done to confirm the recovery of phenol.

Keywords

NMR; GC/MS; Biomass pyrolysis; Bio-oil production; Phenol extraction

Abbreviations

BAW: Bio-oil obtained from agricultural wastes; BHTP: Bio-oil obtained at high temperature (90°C) after pyrolysis; BLTP: Bio-oil obtained at low temperature (10°C) after pyrolysis.

Introduction

Bio-oil is a complex mixture which contains a large number of organic compounds, including alcohol, organic acids, phenol, aldehyde, ketone, etc. Some of these chemicals, such as phenols are important industrial raw materials and additives [1-3]. The total amount of phenolic compounds in the pyrolysis oil varies from 20.0% to 30% depending on the biomass used and operating conditions [4,5]. Biooil contains several hundreds of chemicals as a result, it exhibits some inferior properties, such as high water content, high oxygen content, high viscosity low flash point, and strong corrosiveness [6]. These drawbacks make it difficult to be directly used as a vehicle fuel. Therefore, several upgrading technologies have been developed to improve the quality of bio-oil, including catalytic hydrodeoxygenation [7-9], catalytic cracking, steam reforming, catalytic esterification, supercritical upgrading and so on [10]. Compared with phenols derived from petroleum fuel, these phenolic compounds are renewable and easily obtained. These phenols are not only used as a replacement for phenol in phenol–formaldehyde resins but also as raw materials for developing bio-based antioxidants and many other purposes [11-15]. Pyrolysis offers the cheapest route to renewable liquid fuels. Nonetheless, many aspects of the pyrolysis pathway are still under investigation. The diverse array of research into biomass pyrolysis is multi-disciplinary and multi-dimensional and includes Pyrolysis Oil (PO) characterization, kinetic studies, new distillation systems like vacuum distillations system, computational fluid dynamics, design of new reactors, new catalytic systems, microwave-assisted pyrolysis, optimizing the pyrolysis yield, process intensification, techno-economic analysis, molecular distillation system, environmental assessment, in addition to enterprise-wide and supply chain optimization [16-22]. Now-a-day biomass has an un ignorable importance in our life and in industries as an interesting renewable resource used to provide second generation of biofuels or chemicals [23-27]. Large amount and CO2 neutrality with low sulfur and nitrogen contents make biomass a sustainable and eco-friendly energy source [28-32]. Recently bio-oil has been paid attention to provide fuels and chemicals and the residues of pyrolysis could be used as soil fertilizer [33-38]. Biomass is a CO2, H2 and syngas neutral energy source that has considerable stockpile. It can replace fossil feedstock in the production of heat, electricity, transportation fuels, chemicals, soil fertilizers and other important materials [39-41]. Liquid bio-fuels, which are considered to be substitutes for traditional fossil fuels, can be produced from biomass in different ways, such as high-pressure liquefaction, fast pyrolysis and Hydro-thermal pyrolysis [42-45]. Pyrolysis is a technology that can efficiently convert biomass stockpile into liquid biofuels. The liquid obtained from fast pyrolysis, which is also called crude bio-oil, may be used as burning oil in boilers or even as a transportation fuel after upgrading [46,47]. In fast pyrolysis, lignocellulosic molecules of biomass are rapidly decomposed to short chain molecules in the absence of oxygen [48]. Under conditions of high heating rate, short residence time, and moderate pyrolysis temperature, pyrolysis vapor and some char are generated. After condensation of the pyrolysis vapor, liquid product can be collected in a yield of up to 65- 75% on a dry weight basis [49,50].

Experimental

Materials discarded sawdust and other reagents

The BAW was obtained by pyrolysis of a mixture (3:1 in mass) of sawdust (Pterocarpus, Eucalyptus and Kapok ect) and CaO. The sawdust was mixed with the water after their granulometric reduction Calcium oxide was added to this mixture. After preparation, the mixture was dried at environmental temperature for 24 hours.

Production of BAW

The BAW was produced from the pyrolysis of sawdust in the presence of 25% CaO as catalyst. The biomass sample was kept inside a stainless steel reactor of pyrolysis system which was connected to two other glass chambers as shown in Figure 1. The temperature of the chamber which had biomass was increased from 30°C to 900°C with the help of electric heater, temperature controller cabinet, and two condensers. In this system through biomass was converted to biogas and then condensed to bio-oil at temperatures 90°C and 10°C respectively. The two condensed fractions BHTP and BLTP were collected and introduced for further analysis (Figure 2).

modern-chemistry-applications-Biomass-pyrolysis-system

Figure 1: Schematic diagram of Biomass pyrolysis system.

modern-chemistry-applications-Chromatograph-operated-splitless

Figure 2: Chromatograph operated in splitless mode.

GC-MS analysis of BHTP and BLTP (BAW)

The bio-oil identification were performed on a GC Agilent series 6890 with an 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: 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 (Figure 3).

modern-chemistry-applications-Chromatograph-operated-split

Figure 3: Chromatograph operated in split mode.

Extraction of phenols

A feasible separation route to isolate phenolic fraction from biooil was investigated. A certain amount of Ethyl ether (C4H10O) and 20 ml of 10% solution of Caustic soda (NaOH) was added to bio-oil to separate the water and phenol from the bio-oil by reacting with phenol to form Sodium phenoxide (NaOH+C6H6O=NaOC6H5+H2O). The phase splitting was initiated and two phases occurred, a bottom aqueous layer which was a little bit clear and transparent brown compared to an upper layer that was very viscous and dark. The formed bottom layer was separated and 20 ml of 10% solution of HCl was added to it, to react with NaOC6H5 in solution to form NaCl and phenol (NaOC6H5+HCl=C6H6O+NaCl) and after pH test, the water was evaporated through hot air and the remaining compound (phenol) was washed with liquid NaCl and introduced to NMR to confirm the recovery of phenol from bio-oil as shown in Figure 4 and a simple sketch in Figure 5. While reactions and mechanisms are shown in Figure 6.

modern-chemistry-applications-chromatogram-presence-phenol

Figure 4: NMR chromatogram showing the presence of phenol.

modern-chemistry-applications-sketch-phenol-bio-oil

Figure 5: The simple sketch above shows how to recover phenol from bio-oil step by step.

modern-chemistry-applications-reaction-mechanism-Phenol

Figure 6: The reaction steps and mechanism above show how NaOH reacts with Phenol.

Results and Discussion

Chemical composition of BAW

BAW was a dark and sticky liquid mixture of more than 120 of organic compounds. The compounds detected in BAW can be classified into hydrocarbons, alcohols, phenol, ethers, aldehydes, ketones, carboxylic acids, and other esters. But large peaks of GC/ MS mostly showed aromatic, aliphatic, and cyclic hydrocarbons while small peaks showed other groups, Library match was used for identification of compounds based on probability score and each compound was detected very clearly and with a 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 as well as other important compounds like phenol and ketone (Figures 7 and 8).

NO Compound’s Name Formula Retention time
1 Benzene, 1-ethyl-3-methyl C9H12 8.18
2 Benzene, 1,2,3-trimethyl C9H12 9.00
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 10.30
10 Benzene, butyl C10H14 10.52
11 Benzene, 1,2-diethyl C10H14 10.72
12 Benzene, 1-methyl-4-(1-methylethyl) C10H14 11.30
13 Undecane C11H24 11.65
14  5-Undecene, (Z) C11H22 11.80
15 Benzene, 4-ethenyl-1,2-dimethyl C10H12 12.65
16 1H-Indene, 2,3-dihydro-5-methyl C10H12 12.90
17 7-Methyl-1,2,3,5,8,8a-hexahydronaphthalene C11H16 13.00
18 2-Methylindene C10H10 13.10
19  Benzene, pentyl C11H16 13.13
20 Naphthalene, 1,2,3,4-tetrahydro C10H12 13.25
21 Benzene, (1-methylbutyl) C11H16 13.38
22 Naphthalene C10H8 13.75
23 3-Dodecene, (Z) C12H24 13.90
24 3-Dodecene, (Z) C12H24 14.05
25 Dodecane C12H26 14.15
26 3-Dodecene, (E) C12H24 14.25
27  3-Dodecene, (Z) C12H24 14.50
28 2-Ethyl-2,3-dihydro-1H-indene C11H14 14.95
29 Benzene, hexyl C12H18 15.55
30 Benzene, (1-methylpentyl) C12H18 15.70
31 2-Tridecene, (Z) C13H26 16.30
32 Naphthalene, 1-meth yl C11H10 16.35
33 Tridecane C13H28 16.45
34 3-Tridecene, (E) C13H26 16.55
35 1H-Indene, 1-ethylidene C11H10 16.75
36  Benzene, heptyl C13H20 17.90
37 1-Methyl-2-n-hexylbenzene C13H20 18.00
38  Naphthalene, 2-ethyl C12H12 18.60
39  3-Tetradecene, (E) C14H28 18.50
40 Tetradecane C14H30 18.65
41  3-Tetradecene, (E) C14H28 19.00
42 Naphthalene, 1,7-dimethyl C12H12 19.15
43 Pentadecane C15H32 20.72
44 n-Nonylcyclohexane C15H30 21.80
45  Hexadecane C16H34 22.70
46 Cyclopentane, undecyl C16H32 22.80
47 Heptadecane C17H36 24.58

Table 1: Aliphatic and Aromatic hydrocarbons identified in BAW.

NO Compound’s Name Formula Retention time (Min)
1 pentanol C5H12 9.50
2 pentanone C5H10O 7.63
3 hexanone C6H12O 9.50
4 octanone C8H16O 20.83
5 heptanone C7H14O 15.77
6 Hexenol C6H12O 13.89
7 cyclopentanone C5H8O 11.23
8 cyclopentanone, C1  C6H10O 13.63
9 cyclopentanone, C2 C7H12O 16.03
10 cyclohexenone, C1 C7H10O 19.77
11 heptanone C7H14O 15.77
12 cyclopentenone, C3  C8H12O 22.57
13 acetophenone C8H8O 24.97
14 cyclohexenyl, ethanone C8H12O 26.03
15 cyclopentenone, C4 C9H14O 26.83
16 cyclohexanone, ethylidene C8H12O 28.17
17  cyclopentenone, C3 methylene C9H12O 31.50
18  indenone, hexahydro C9H12O 37.50
19 ethane, diethoxy C6H14O2 9.23
20 furanmethanol C5H6O2 17.37
21 furan, C2 C6H8O 22.97
22 phenol C6H6O 23.37
23 phenol, C1 C7H8O 24.97
24 pyrrole C4H5N 9.63
25 pyrrole, C1 C5H7N 10.43
26 piperidine, C1 C6H13N 11.37
27 piperidine, C1 C6H13N 11.50
28 piperidine, C2 C7H15N 15.37
29 pyridine, C1 C6H7N 15.50
30 pyridine, C3 C8H11N 21.10
31 imidazole, C4 C7H12N2 15.77
32 pyrazine, C2 C6H8N2 16.43
33 pyrazine, C3 C7H10N2 21.23
34 pyrazine, C4 C8H12N2 25.37
35 pyrazine, C5 C9H14N2 29.50
36 pyrazine, C6 C11H18N2 29.90
37 pyrrolidinone, C2 C6H11NO 26.83
38 piperidinone, C4 C9H17NO 27.23
39 pentanamide, C1 C6H13NO 28.30
40 pyrazine, C6 C10H16N2 33.37
41 imidazole, C3 C6H10N2 31.23
42 pyrazole, C3 C6H10N2 33.23
43 pyrazole, C4 C7H12N2 33.37
44 imidazole, C4 C7H12N2 33.50
45 pyridine, C1 propenyl C10H13N 34.97
46 pyrrolidinone, C2 methylidene C7H11NO 36.18

Table 2: Compounds of other groups detected in BAW.

modern-chemistry-applications-aliphatic-hydrocarbon-peaks

Figure 7: Shows only aliphatic hydrocarbon peaks.

modern-chemistry-applications-aromatic-hydrocarbon-peaks

Figure 8: Shows only aromatic hydrocarbon peaks.

Hydrocarbons in BAW

Tables 2 and 3 show C8–C17 hydrocarbons and other classes were enriched in the BAW. As shown in Table 1. Aliphatic and aromatic hydrocarbons with C8–C17 are predominant in the BAW sample with a % area of 53.99

NO Name Formula Retention time (Min)
1 Undecane C11H24 11.65
2  5-Undecene, (Z) C11H22 11.80
3 3-Dodecene, (Z) C12H24 13.90
4 3-Dodecene, (Z) C12H24  14.05
5 Dodecane C12H26 14.15
6 3-Dodecene, (E) C12H24 14.25
7  3-Dodecene, (Z) C12H24 14.50
8 2-Tridecene, (Z) C13H26 16.30
9 Tridecane C13H28 16.45
10 3-Tridecene, (E) C13H26 16.55
11  3-Tetradecene, (E) C14H28 18.50
13 Tetradecane C14H30 18.65
14  3-Tetradecene, (E) C14H28 19.00
15 Pentadecane C15H32 20.72
16  Hexadecane C16H34 22.70

Table 3: Shows Aliphatic compounds identified in BAW.

Alcohols, Aldehydes, Ketones, Ethers, Esters, Phenols, and Nitrogenous compound also present in BAW while in these classes, Phenols and ketones occupied more space compared to others as shown in Table 4 and 5. Above Figure 9 is the graphical representation of both fractions BHTP (blue) and BLTP (red) Show % area of all groups present in BAW.

NO Name Formula Retention time (min)
1 Benzene, 4-ethenyl-1,2-dimethyl C10H12  12.65
2 1H-Indene, 2,3-dihydro-5-methyl  C10H12 12.90
3 7-Methyl-1,2,3,5,8,8a-hexahydronaphthalene C11H16 13.00
5 2-Methylindene  C10H10 13.10
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 15.70
13 Naphthalene, 1-methyl  C11H10  16.35
14 1H-Indene, 1-ethylidene C11H10 16.75
15  Benzene, heptyl C13H20  17.90
16 1-Methyl-2-n-hexylbenzene C13H20 18.00
17  Naphthalene, 2-ethyl C12H12 18.60
18 Naphthalene, 1,7-dimethyl C12H12 19.15
19 n-Nonylcyclohexane  C15H30  21.80

Table 4: Shows Aromatic compounds identified in BAW.

Different Classes of compounds % Area
BLTP BHTP
Alcohols 0.889 11.110
Aldehydes 0.501 1.123
Ketones 7.02 25.827
Ethers n.d. 6.263
Esters n.d. 1.923.
Phenols 7.109 4.858
Nitrogenous 0.354 40.779
Aromatics hydrocarbons 33.001 2.246
Cyclic hydrocarbons 17.420 3.096
Aliphatic hydrocarbons 35.121 0.101

Table 5: % area of deferent classes of compounds identified in BAW.

modern-chemistry-applications-compounds-BHTP-blue

Figure 9: % area of compounds in BHTP (blue) and BLTP (red).

Catalytic optimization

Numerous reaction were carried out in which the amount of biomass was remained the same while catalyst (CaO) was varying to choose a suitable ratio of catalyst with biomass at which maximum pyrolysis yield while less amount of residue is obtained. At different ratio of CaO and biomass the pyrolysis reactions were carried out, finally 3:1 of biomass and CaO respectively were found proper for a good pyrolysis yield (Figures 10-12).

modern-chemistry-applications-Distillation-curve-BLTP

Figure 10: Distillation curve for BLTP.

modern-chemistry-applications-Distillation-curve-BHTP

Figure 11: Distillation curve for BHTP.

modern-chemistry-applications-BAW-NMR-spectra

Figure 12: BAW H.NMR spectra.

Conclusions

After different process and analyzing techniques, more than 120 compounds were detected in the BAW. Among them, aromatic, aliphatic and cyclic hydrocarbons, especially alkanes, alkenes and benzene containing compounds were dominant but other important compounds like phenol were also present. A laboratory scale effort is made in this work to recover phenol from BAW, however, to improve efficiency, this process can be successfully applied in largescale operations because phenol is an important compound used in the preparation of resins, dyes, explosives, lubricants, pesticides and plastics. It is indirectly useful in the preparation of plywood. Phenol is also used as an organic solvent to dissolve other alcohols as well as for medicinal purposes. Future work is going to test light fraction (80- 160°C) in diesel engine and heavy fraction (160-240°C) in a jet engine by mixing them in normal diesel fuels and aviation fuels respectively (Figure 13).

modern-chemistry-applications-Phenols-NMR-spectra

Figure 13: Phenols H.NMR spectra.

Acknowledgements

The financial support of CNPq, Brazil was acknowledged.

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