GC×GC-TOF/MS Analysis of Bio-Oils Obtained from Pyrolysis of Acuri and Baru Residues

Cardoso, Claudia Andrea L.; Machado, Maria Elisabete; Maia, Franksteffen S.; Arruda, Giberto Jose; Caramão, Elina B.

doi:10.5935/0103-5053.20160081

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Short Report • J. Braz. Chem. Soc. 27 (11) • Nov 2016 • https://doi.org/10.5935/0103-5053.20160081 copy

GC×GC-TOF/MS Analysis of Bio-Oils Obtained from Pyrolysis of Acuri and Baru Residues

Authorship SCIMAGO INSTITUTIONS RANKINGS

Bark of acuri and endocarp of baru are residues generated during the processing of these fruits. One alternative to consider is the pyrolysis of these materials to generate bio-oils, opening the perspective for the production of environment-friendly, added value products. Samples of acuri and baru were subjected to laboratorial scale pyrolysis. At the optimized pyrolysis conditions, the bio-oils yields (m/m) were 30% for bark of acuri and 29% for endocarp of baru. Next, the obtained bio-oil was submitted to proximate analysis and GC×GC-TOF/MS (two-dimensional gas chromatography with time-of-flight mass spectrometric detection). The bio-oil generated from the bark of acuri proved to be of the highest complexity with 113 identified compounds, while the bio-oil generated from the endocarp of baru sample led to 71 identified compounds. A total of 29 compounds were confirmed using standards in the acuri bark bio-oil, while 23 compounds were confirmed for endocarp of baru bio-oil. There was a predominance of phenols and ketones for the bio-oil generated from acuri bark, and hydrocarbons and phenols for the bio-oil from baru endocarp.

Keywords:
bio-oil; Attalea phalerata; Dipteryx alata

¹t_R^a a 1tR = Retention time in the first dimension; / min	²t_R^b b 2tR = retention time in the second dimension; / min	Name	Formula	RI^c c RI = retention index calculated; RIN = retention index obtained NIST 69 (reference 40).	RIN^d
6.70	2.64	benzene	C₆H₆	-	685
6.82	2.44	heptane	C₇H₁₆	700	700
8.52	3.12	toluene	C₇H₈	786	784
9.00	2.44	octane	C₈H₁₈	800	800
11.43	3.55	xylene	C₈H₁₀	876	877
12.33	2.61	nonane	C₉H₂₀	900	900
13.33	3.47	hexanoic acid, methyl ester	C₇H₁₄O₂	929	931
15.45	4.59	phenol	C₆H₆O	994	-
16.17	2.72	decane	C₁₀H₂₂	1000	1000
19.95	5.14	phenol, 2-methoxy	C₇H₈O₂	1079	1084
21.17	2.83	undecane	C₁₁H₂₄	1100	1100
21.67	3.62	octanoic acid, methyl ester	C₈H₁₆O₂	1112	1111
22.93	4.70	phenol, 2,5-dimethyl	C₈H₁₀O	1166	1167
23.57	5.51	naphthalene	C₁₀H₈	1193	1194
23.83	2.87	dodecane	C₁₂H₂₆	1200	1200
26.17	4.01	phenol, 4-propyl	C₉H₁₂O	1260	1260
26.78	4.91	phenol, 4-ethyl-2-methoxy	C₉H₁₂O₂	1276	1279
27.33	2.91	tridecane	C₁₃H₂₈	1300	1300
28.17	3.68	decanoic acid, methyl ester	C₁₃H₂₆O₂	1325	1324
29.33	4.84	eugenol	C₁₀H₁₂O₂	1359	1358
29.87	4.96	phenol, 2-methoxy-4-propyl	C₁₀H₁₄O₂	1374	1374
30.80	3.04	tetradecane	C₁₄H₃₀	1400	1400
33.95	3.09	pentadecane	C₁₅H₃₂	1500	1500
34.50	3.85	dodecanoic acid, methyl ester	C₁₁H₂₂O₂	1520	1525
36.75	3.16	hexadecane	C₁₆H₃₄	1600	1600
39.55	3.22	heptadecane	C₁₇H₃₆	1700	1700
40.00	3.85	tetradecanoic acid, methyl ester	C₁₅H₃₀O₂	1719	1719
42.12	3.28	octadecane	C₁₈H₃₈	1800	1800
44.50	3.48	nonadecane	C₁₉H₄₀	1900	1900
45.17	3.97	hexadecanoic acid, methyl ester	C₁₇H₃₄O₂	1929	1927
46.83	3.34	eicosane	C₂₀H₄₂	2000	2000
49.00	4.28	octadecadienoic acid, methyl ester	C₁₉H₃₂O₂	2093	-
49.17	4.24	octadecenoic acid, methyl ester	C₁₉H₃₄O₂	2100	-
49.17	3.42	uncosane	C₂₁H₄₄	2100	2100
49.67	4.05	octadecanoic acid, methyl ester	C₁₉H₃₆O₂	2125	2128
49.83	4.53	oleic acid	C₁₈H₃₄O₂	2133	-
51.17	3.48	docosane	C₂₂H₄₆	2200	2200
53.33	3.54	tricosane	C₂₃H₄₈	2300	2300
54.00	4.17	hexadecanoic acid, 15-methyl-, methyl ester	C₁₈H₃₆O₂	2334	-
55.33	3.61	tetracosane	C₂₄H₅₀	2400	2400
57.33	3.67	pentacosane	C₂₅H₅₂	2500	2500
58.00	4.30	docosanoic acid, methyl ester	C₂₂H₄₄O₂	2520	2513
60.83	3.87	hexacosane	C₂₆H₅₄	2600	2600
62.72	3.97	heptacosane	C₂₇H₅₆	2700	2700
64.33	4.47	octacosane	C₂₈H₅₈	2800	2800

¹t_R^a a 1tR = Retention time in the first dimension; / min	²t_R^b b 2tR = retention time in the second dimension; CH = cyclic hydrocarbon; AH = aromatic hydrocarbon; OH = others hydrocarbon; SH = saturated hydrocarbon; /min	Name	Formula	Acuri bark area / %	Baru endocarp area / %	Chemical class
6.60	2.31	cyclohexane	C₆H₁₂	0.28	-	CH
6.88	2.28	acetic acid	C₂H₄O₂	2.91	0.09	acid
8.52	3.12	toluene^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₇H₈	0.25	33.19	AH
8.75	3.66	butanone, hydroxy	C₄H₈O₂	0.86	-	others ketone
8.98	2.99	butanoic acid	C₄H₈O₂	0.08	0.46	acid
9.22	3.99	cyclopentanone	C₅H₈O	0.11	0.19	cyclic ketone
9.22	4.70	propenediol	C₃H₈O₂	0.06	-	alcohol
10.38	4.46	maleic anhydride	C₄H₂O₃	0.05	0.15	anhydride
10.50	4.13	furfural	C₅H₄O₂	4.32	1.83	aldehyde furfural
10.50	4.81	cyclopentenone	C₅H₆O	3.53	2.1	cyclic ketone
10.85	3.14	furanmethanol	C₅H₆O₂	1.91	0.1	others alcohol furane
11.43	3.55	xylene^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₈H₁₀	0.48	0.34	OH
11.55	4.67	propanone, acetyloxy	C₅H₈O₃	0.04	0.15	others ketone
11.67	4.55	C1-furan	C₅H₆O	0.05	0.21	ether furan
12.95	4.81	C1-cyclopentenone	C₆H₈O	1.89	-	cyclic ketone
13.18	4.77	ethanone, furanyl	C₆H₆O₂	0.91	2.2	ketone furanone
13.18	6.41	butyrolactone	C₄H₆O₂	0.17	-	lactone
13.65	5.01	cyclopentanedione	C₅H₆O₂	0.13	0.45	cyclic ketone
14.33	4.51	C3-benzene	C₉H₁₂	0.05	0.24	AH
14.93	3.79	C3-benzene	C₉H₁₂	0.19	-	AH
15.00	4.69	butanone, acetyloxy	C₆H₁₀O₃	0.39	-	othres ketone
15.17	3.77	C3-benzene	C₉H₁₂	0.11	0.12	AH
15.28	4.77	C1-furan	C₅H₆O	0.14	0.23	ether furan
15.45	5.31	C1-cyclopentenone	C₆H₈O	0.68	0.16	cyclic ketone
15.45	4.59	phenol^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₆H₆O	3.68	4.46	phenol
16.17	2.71	decane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₀H₂₂	0.15	0.04	SH
16.33	4.97	cyclohexenedione	C₆H₆O₂	0.05	0.23	cyclic ketone
16.33	4.92	C2-cyclopentenone	C₇H₁₀O	0.81	-	cyclic ketone
16.50	5.49	C2-furanone, dihydroxy	C₆H₈O₂	0.21	-	ketone furanone
17.27	4.47	C1-benzene, methoxy	C₈H₁₀O	0.25	0.1	methoxy ether
17.50	5.11	C2-cyclopentenone	C₇H₁₀O	0.87	0.06	cyclic ketone
17.50	5.15	C1-cyclopentadione	C₆H₁₀O	1.23	0.8	cyclic ketone
17.73	4.56	C2-furan	C₆H₈O	0.25	-	ether furanone
18.08	5.17	C2-cyclopentenone	C₇H₁₀O	0.14	1.52	cyclic ketone
18.20	3.83	C2-cyclopentenone	C₇H₁₀O	0.13	1.2	cyclic ketone
18.67	3.86	C4-benzene	C₁₀H₁₄	0.11	0.04	AH
18.67	4.71	C1-phenol	C₇H₈O	1.65	0.06	phenol
18.90	4.95	C1-phenol	C₇H₈O	0.07	0.38	phenol
19.02	4.71	C2-cyclopentenone	C₇H₁₀O	0.18	0.04	cyclic ketone
19.13	4.79	C2-cyclohexenone	C₈H₁₂O	0.05	0.48	cyclic ketone
19.13	5.37	acetophenone	C₈H₈O	0.11	-	acetophenone
19.60	4.66	C1-phenol	C₇H₈O	1.99	0.33	phenol
19.60	4.54	C2-phenol	C₈H₁₂O	0.11	1.69	phenol
19.95	5.14	phenol, 2-methoxy^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₇H₈O₂	18.67	14.06	methoxy phenol
20.18	6.22	C1-pentanal	C₆H₁₂O	-	0.23	aldehyde
20.18	2.79	undecane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₁H₂₄	0.02	1.54	SH
20.18	4.31	C2-phenol	C₈H₁₀O	0.02	0.89	phenol
20.53	4.91	C2-phenol	C₈H₁₀O	3.91	-	phenol
21.00	4.96	C2-cycloptentenone, hydroxy	C₇H₁₀O₂	0.29	-	cyclic ketone alcohol
21.67	4.65	C2-phenol	C₈H₁₀O	1.19	0.22	phenol
21.83	5.41	benzene, dimethoxy	C₈H₁₀O₂	0.19	-	methoxy ether
21.93	4.56	C3-cyclopentanedione	C₈H₁₂O₂	0.07	-	cyclic ketone
22.00	4.78	naphthalene, dihydroxy	C₁₀H₁₀	0.73	-	OH
22.28	4.77	C2-phenol	C₈H₁₀O	0.15	0.28	phenol
22.93	4.70	phenol, 2,5 dimethyl^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₈H₁₀O	1.97	-	phenol
23.17	4.97	C- phenol, methoxy	C₈H₁₀O₂	0.79	-	methoxy phenol
23.33	5.05	C2-phenol	C₈H₁₀O	0.1	1.24	phenol
23.33	5.10	C1-phenol, methoxy	C₈H₁₀O₂	0.88	-	methoxy phenol
23.57	5.51	naphthalene^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₀H₈	0.05	1.26	OH
24.17	4.81	C2-benzofuran	C₁₀H₁₀O	0.06	0.04	benzofuranone
24.27	3.89	C3-phenol	C₉H₁₂O	0.75	-	phenol
24.62	6.69	dianhydro-α-d-glucopyranose	C₆H₈O₄	0.11	3.66	anhydride
25.43	4.68	benzenediol	C₆H₆O₂	0.21	-	phenol diol
25.55	5.20	dimethoxy toluene	C₉H₁₂O₂	0.19	-	methoxy ether
25.55	4.83	C3-phenol	C₉H₁₂O	0.69	0.18	phenol
26.25	3.92	C6-benzene	C₁₂H₁₈	0.05	0.37	AH
26.25	4.67	phenol, 4-propyl^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₉H₁₂O	0.05	-	phenol
26.25	4.85	C3-phenol	C₉H₁₂O	0.11	0.17	phenol
26.48	5.16	dimethoxy toluene	C₉HsO₂	0.05	0.28	methoxy ether
26.60	4.88	C1-naphthalene, dihydroxy	C₁₁H₁₀	0.19	-	OH
26.72	4.92	C3-phenol	C₉H₁₀O	0.17	-	phenol
26.78	4.91	phenol, 4-ethyl-2-methoxy^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₉H₁₂O₂	8.01	0.05	methoxy phenol
26.78	5.51	dihydroxyacetophenone	C₈H₁₀O₂	0.18	-	acethophenone
27.53	4.79	C1-benzenediol	C₇H₈O₂	0.14	3.1	phenol diol
27.53	2.99	tridecane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₃H₂₈	0.31	0.12	SH
27.53	5.46	C1-naphthalene	C₁₁H₁₀	0.19	0.08	AH
27.77	5.26	C1-phenol methoxy	C₈H₁₀O₂	0.09	0.22	methoxy phenol
27.83	5.42	methoxy vinyl phenol	C₉H₁₀O₂	4.78	-	others phenol
28.12	4.83	C1-phenol methoxy	C₁₂H₁₆	0.09	5.81	methoxy phenol
29.33	2.77	mequinol	C₇H₈O₂	0.29	0.64	methoxy phenol
29.33	4.84	eugenol^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₀H₁₂O₂	1.54	3.22	methoxy phenol
29.63	5.18	phenol, 2,6-dimethoxy^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₈H₁₀O₃	3.69	-	methoxy phenol
29.87	4.05	C7-benzene	C₁₃H₂₀	0.17	-	SH
29.87	4.96	phenol, 2-methoxy-4-propyl^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₀H₁₄O₂	0.79	1.01	methoxy phenol
30.80	3.04	tetradecane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₄H₃₀	0.19	0.38	SH
31.00	5.04	C2-benzenediol	C₈H₁₀O₂	0.17	-	phenol diol
31.62	5.60	C2-naphthalene	C₁₂H₁₂	0.22	-	AH
32.43	6.00	trimethoxy benzene	C₉H₁₂O₃	1.1	-	methoxy ether
32.55	2.60	C6-cyclopentene	C₁₁H₂₀	0.04	4.06	CH
32.55	5.53	phenol, methoxy, propenyl	C₁₀H₁₂O₂	5.98	-	phenol methoxy
33.50	6.60	C6-cyclopentene	C₁₁H₂₀	0.21	-	CH
33.95	3.09	pentadecane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₅H₃₂	0.16	0.5	SH
34.77	5.89	C1-benzene, trimethoxy	C₁₀H₁₄O₃	0.69	-	methoxy ether
35.67	6.26	dimethoxy acetophenone	C₁₀H₁₂O₃	1.28	-	methoxyacetophenone
36.75	3.16	hexadecane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₆H₃₄	0.15	0.05	SH
38.38	6.29	phenol, dimethoxy, propenyl	C₁₁H₁₄O₃	0.05	0.34	methoxy phenol
38.97	3.36	trimethoxy benzene	C₉H₁₂O	0.15	0.67	methoxy ether
39.55	3.22	heptadecane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₇H₃₆	1.99	1.04	SH
40.25	3.87	phenoxyethanol	C₈H₁₀O₂	0.19	-	others alcohol
42.12	3.28	octadecane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₈H₃₈	0.15	0.05	SH
45.27	4.00	acetophenone, hydroxy	C₁₇H₃₄O₂	0.21	-	acetophenone
46.20	4.23	hexadecanoic acid	C₁₉H₃₈O₂	1.36	-	acid
46.83	4.01	nonadecanone	C₁₃H₂₂O	0.05	0.05	ketone
46.83	3.34	eicosane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₂₀H₄₂	0.08	0.05	SH
49.00	4.42	octadecadienoic acid, methyl ester^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₉H₃₂O₂	0.11	-	ester
49.23	3.49	heneicosane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₂₁H₄₄	0.08	0.06	SH
49.35	4.32	octadecenoic acid, methyl ester^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₉H₃₄O₂	0.19	0.04	ester
49.67	4.05	octadecanoic acid, methyl ester^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₉H₃₆O₂	0.12	0.1	ester
50.28	4.62	oleic acid^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₁₈H₃₄O₂	1.28	0.65	acid
51.45	3.54	docosane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C22H46	0.11	0.08	SH
53.55	3.62	tricosane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₂₃H₄₈	0.12	0.09	SH
55.53	3.69	tetracosane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₂₄H₅₀	0.12	0	SH
60.83	3.97	hexacosane^* * compared with standards in same conditions of analysis (GC×GC-TOF/MS).	C₂₆H₅₄	0.14	-	SH

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