EFFECT OF PYROLYSIS HEATING RATE ON THE CHEMICAL COMPOSITION OF WOOD VINEGAR FROM EUCALYPTUS UROGRANDIS AND MIMOSA TENUIFLORA

Medeiros, Lúcio César Dantas de; Pimenta, Alexandre Santos; Braga, Renata Martins; Carnaval, Tatiane Kelly de Azevedo; Medeiros Neto, Pedro Nico; Melo, Dulce Maria de Araújo

doi:10.1590/1806-90882019000400008

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ARTICLE • Rev. Árvore 43 (4) • 2019 • https://doi.org/10.1590/1806-90882019000400008 copy

EFFECT OF PYROLYSIS HEATING RATE ON THE CHEMICAL COMPOSITION OF WOOD VINEGAR FROM EUCALYPTUS UROGRANDIS AND MIMOSA TENUIFLORA

EFEITO DA TAXA DE AQUECIMENTO DE PIRÓLISE NA COMPOSIÇÃO QUÍMICA DO EXTRATO PIROLENHOSO DE EUCALYPTUS UROGRANDIS E MIMOSA TENUIFLORA

Authorship SCIMAGO INSTITUTIONS RANKINGS

ABSTRACT

Among the parameters used in the biomass carbonization process, the heating rate is one of the most important. The objective of the present work was to assess the influence of different heating rates on the chemical composition of wood vinegar (WV) from two wood species. Dried disks of Eucalyptus grandis and Mimosa tenuiflora wood were used as raw material. Carbonization runs were carried out in a laboratory muffle furnace at three heating rates (0.7, 1.0 and 1.4 °C/min), with 10 runs at each heating rate, reaching 450 °C. Yields of charcoal, pyrolysis liquids and gases were determined for all carbonization conditions. Crude pyrolysis liquid from each wood species and each heating rate was bi-distilled, yielding purified WV samples. These samples were extracted with ethyl acetate and the organic fraction was analyzed by gas chromatography-mass spectrometry to obtain qualitative and semi-quantitative data. Results showed that lower heating rates produce higher yields of charcoal, while higher heating rates lead to higher yields of pyrolysis liquids and gases. Totals of 57 and 42 chemical compounds were identified in the WV of Eucalyptus and Mimosa, respectively, divided into the following groups: alcohols, ketones, furans and pyrans, and phenolic compounds. In general, higher heating rates led to greater contents of furans and pyrans and lower concentrations of phenolic compounds.

Keywords:
Wood vinegar; Heating rate; Phenolic compounds

Table 1 Chemical and physical characterization of Eucalyptus urograndis and Mimosa tenuiflora wood.

		PROXIMATE			CHEMICAL		WOOD
		ANALYSIS			COMPOSITION		DENSITY
		(%)			(%)		(g cm^-3)
WOOD SPECIES	VM	FC	ASHES	LIGNIN	CEL	HEM
Eucalyptus urograndis	81.72	8.25	2.39	14.58	48.54	28.36	0.51
Mimosa tenuiflora	73.61	18.18	1.96	32.92	32.02	15.52	0.98

Table 2 Groups of chemical compounds identified in wood vinegar of Eucalyptus urograndis wood obtained at three heating rates.

			HEATING RATE
			(ºC min^-1)
			0.7		1.0		1.4
ELUTION	COMPOUND	MOLECULAR	RT	Area	RT	Area	RT	Area
ORDER		FORMULA	(min)	(%)	(min)	(%)	(min)	(%)
	ALCOHOLS
5	5-Hexen-3-ol-2.3-dimethyl	C₈H₁₆O	4.383	0.49	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
19	1,6-Heptadien-4-ol	C₇H₁₂O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	9.641	0.29
	KETONES
1	2-Butanone	C₄H₈O	2.874	0.78	2.875	0.77	2.873	0.47
4	3-Penten-2-one	C₅H₈O	4.117	0.11	4.104	0.41	4.119	0.09
7	2-Butanone, 3-hydroxy	C₄H₈O₂	4.902	0.11	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	4.897	0.23
9	2-methylcyclobutanone	C₅H₈O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	6.659	0.32	6.549	0.63
13	2-Methyl-2-cyclopentenone	C₆H₈O	7.308	2.05	7.288	4.13	7.3	2.39
18	3-Methylcyclopentanone	C₆H₁₀O	9.317	0.46	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	9.314	0.29
34	2-Cyclopenten-2-one, 3,4-dimethyl	C₇H₁₀O	16.185	0.23	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	15.06	0.89
35	4,4-Dimethyl-2-cyclopenten-1-one	C₇H₁₀O	15.086	0.49	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
36	2-Cyclopenten-1-one, 2,3-dimethyl	C₇H₁₀O	15.29	0.83	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
44	2-Cyclohexen-1-one, 4,5-dimethyl	C₈H₁₂O	19.503	0.44	19.468	0.24	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
56	3-Ethyl-2-hydroxy-2-cyclopenten-1-one	C₇H₁₀O₂	26.712	2.18	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	26.667	1.31
	FURANS E PYRANS
11	Furan, 2-butyltetrahydro	C₈H₁₆O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	6.113	0.18
12	2-Furanol, Tetrahydro-2-methyl	C₅H₁₀O₂	6.114	0.45	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
15	2-(methoxymethyl)-furan	C₆H₈O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	8.659	0.14	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
16	Furfural	C₅H₄O₂	8.972	8.36	8.959	12.00	8.94	4.43
20	Furan, Tetrahydro-3,5dimethoxy	C₆H₁₂O₃	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	10.595	0.46	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
21	Furan, tetrahydro-2,4-dimethoxy	C₆H₁₂O₃	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	10.608	0.19
22	Furan, Tetrahydro-2,5dimethoxy	C₆H₁₂O₃	10.605	0.34	11.192	0.26	11.231	0.93
23	Ethanone, 2-(2-furanyl)	C₆H₆O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	11.451	0.51
25	2-acetylfuran	C₆H₆O₂	11.895	3.77	11.837	2.81	11.843	4.89
28	2-furancarboxaldehyde, hydrazide	C₅H₆N₂O₂	13.152	0.53	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
29	2-Furancarboxaldehyde, 5-methyl	C₆H₆O₂	13.987	4.97	13.96	4.38	13.653	0.67
30	3-Furancarboxaldehyde, 5-methyl	C₆H₆O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	13.951	6.47
31	3-Furancarboxylic acid, ethyl ester	C₆H₆O₃	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	14.184	0.32
32	2-ethyl-5-methyl-furan	C₇H₁₀O	14.441	2.12	14.402	1.89	14.404	2.06
37	2-Furanone, 2,5-dihydro-3.5-dimethyl	C₆H₈O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	15.437	0.68
40	Ethanone, 2,2-dihydroxy-1-phenyl	C₈H₈O₃	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	18.028	0.25
	PHENOLIC COMPOUNDS
24	Phenol	C₆H₆O	11.659	5.70	11.616	3.43	11.624	6.09
39	Phenol. 3-methyl	C₇H₈O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	17.388	0.20
41	Phenol, 4-methyl	C₇H₈O	18.762	0.26	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
42	Phenol, 2-methyl	C₇H₈O	17.898	0.62	17.97	1.43	18.653	0.78
43	2-Methoxyphenol (guaiacol)	C₇H₈O₂	19.158	15.82	19.121	22.74	19093	5.23
45	Phenol. 2,3-dimethyl	C₈H₁₀O	19.66	0.41	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	19622	0.53
46	1,3-Dimethylphenol	C₈H₁₀O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	20.491	1.38	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
47	2,4-Dimethylphenol	C₈H₁₀O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	21.516	1.59	21.351	0.97
48	Phenol, 2-methoxy-4-methyl	C₈H₁₀O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	22.365	1.46	22.352	1.78
49	Phenol, 4-methoxy-3-methyl	C₈H₁₀O₂	22.976	4.43	27.171	1.11	22.663	0.22
50	2,6-dimethoxy-phenol (syringol)	C₉H₁₂O₃	23.276	13.93	23.358	20.40	23.214	1.63
51	Phenol, 2,3,6-trimethyl	C₉H₁₂O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	24.195	2.76	23.338	0.12
52	Phenol, 3-methoxy-4-methyl	C₈H₁₀O₂	22.379	1.37	24.353	2.82	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
54	Phenol, 4-ethyl-2-methoxy	C₉H₁₂O₂	26.034	6.92	26.037	2.36	26.006	5.02
55	Phenol, 3-ethyl-2-methoxy	C₉H₁₂O₂	26.27	11.16	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	26.227	8.49
57	Phenol, 4-ethyl-3-methoxy	C₉H₁₂O₂	26.902	2.19	26.682	2.29	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
	OTHER COMPOUNDS
2	Methyl-propionate	C₄H₈O₂	3.361	1.50	3.364	1.98	3.373	1.06
3	Cyclobutylamine	C4H9N	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	3.902	0.29
6	Propanoic acid, 2-methyl-methyl ester	C₅H₁₀O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	4.386	0.25	4.384	0.33
8	Butanoic acid, methyl ester	C₅H₁₀O₂	5.265	0.58	5.254	0.36	5.273	0.60
10	Tetrachloroethylene	C₂C_l4	7.949	0.32	7.95	0.22	7.954	0.32
14	4-Hydroxy-pyridine	C₅H₅NO	8.468	0.08	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	8.236	2.05
17	2-methyl-1-pyrrole	C₅H₇N	9.129	0.37	9.101	0.70	9.111	0.71
26	1.3-Pentadiene, 3-methyl	C₆H₁₀	12.869	1.00	12.861	0.59	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
27	1-isopropyl-1-cyclopentene	C₈H₁₄	16.955	1.41	16.916	3.12	12.592	0.18
33	Pentanoic acid, 4-oxo, methyl ester	C₆H₁₀O₃	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	14.858	0.31	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
38	1-Methylcycloheptene	C₈H₁₄	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	15.266	0.89	16.936	2.44
53	Benzene, 1,2-dimethoxy	C₉H₁₂O₂	24.411	3.23	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	24.371	2.77

Table 3 Groups of chemical compounds identified in wood vinegar of Mimosa tenuiflora wood obtained at three heating rates.

			HEATING RATE
			(ºC min^-1)
			0.7		1.0		1.4
ELUTION	COMPOUND	MOLECULAR	RT	Area	RT	Area	RT	Area
ORDER		FORMULA	(min)	(%)	(min)	(%)	(min)	(%)
	ALCOHOL
13	1,6-Heptadien-4-ol	C₇H₁₂O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	9.589	0.21	11.949	0.28
	KETONES
5	Cyclopentanone	C₅H₈O	7.259	0.95	7.255	1.19	7.282	1.03
10	Cyclohexanone	C₆H₁₀O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	11.099	0.27
15	2-Heptene-4-one	C₇H₁₀O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	12.845	0.60	13.137	0.26
20	2-Cyclopenten-1-one, 2,3-dimethyl	C₇H₁₀O	16.852	1.26	15.291	0.35	15.299	0.89
	FURANS AND PYRANS
11	Furfural	C₅H₄O₂	11.546	8.13	11.574	8.34	11.604	11.33
12	Ethanone, 1-(2-furanyl)	C₆H₆O₂	11.75	3.42	11.78	2.60	11.792	2.72
16	2-Furancarboxaldehyde, 5-methyl	C₆H₆O₂	13.84	2.46	13.865	3.03	13.887	2.36
17	3-Furancarboxylic acid, methyl ester	C₆H₆O₃	14.343	0.84	14.351	0.75	14.371	0.91
28	1-Propanone, 1-(5-methyl-2-furanyl)	C₈H₁₀O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	20.58	0.39	20.488	0.13
	PHENOLIC COMPOUNDS
18	Phenol	C₆H₆O	14.482	3.17	14.586	4.18	14.655	2.98
21	Phenol, 2-methyl	C₇H₈O	17.418	2.38	17.505	2.15	17.552	2.12
22	Phenol, 3-methyl	C₇H₈O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	18.368	4.64	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
23	Phenol, 4-methyl	C₇H₈O	18.234	4.72	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	18.416	3.75
24	2-Methoxyphenol (guaiacol)	C₇H₈O₂	18.925	39.92	19.059	38.32	19.108	32.07
26	Phenol, 2,3-dimethyl	C₈H₁₀O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	19.56	2.07	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
27	Phenol, 2,6-dimethyl	C₈H₁₀O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	19.593	0.55
29	Phenol, 2,5-dimethyl	C₈H₁₀O	21.029	1.83	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
30	Phenol, 3.4-dimethyl	C₈H₁₀O	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	21.894	0.26	21.132	2.43
31	Phenol, 2-methoxy-4-methyl	C₈H₁₀O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	22.315	1.24	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
32	Phenol. 3-methoxy-4-methyl	C₈H₁₀O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	22.327	1.67
33	Phenol, 4-methoxy-3-methyl	C₈H₁₀O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	22.597	1.14	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
34	2-Methoxy-5-methylphenol	C₈H₁₀O₂	22.285	2.21	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	22.61	1.19
35	2,6-dimethoxy-phenol (syringol)	C₈H₁₀O₃	22.819	15.56	22.911	14.74	22.942	18.46
38	Phenol, 4-ethyl-2-methoxy	C₉H₁₂O₂	25.915	4.18	25.961	2.90	25.982	5.52
39	Phenol, 3,4-dimethoxy	C₈H₁₀O₃	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	28.391	0.81	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
41	Phenol, 2,6-dimethoxy	C₈H₁₀O₃	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	28.402	0.39
42	Phenol, 2-methoxy-4-propyl	C₁₀H₁₄O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	28.954	0.43	28.982	0.52
	OTHER COMPOUNDS
1	Methyl propionate	C₄H₈O₂	3.346	0.96	3.347	0.67	3.36	0.40
2	Propanoic acid, 2-methyl, methyl ester	C₅H₁₀O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	4.366	0.21	4.394	0.14
3	Butanoic acid, methyl ester	C₅H₁₀O₂	11.899	0.75	5.253	0.26	5.272	0.22
4	Pyridine	C₅H₅N	5.812	0.59	5.799	0.56	5.822	0.32
6	4-Hydroxy-pyridine	C₅H₅NO	8.768	3.31	8.808	3.02	8.823	2.92
7	3-Methyl-3-hexene	C₇H₁₄	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	9.293	0.10
8	Propanoyl chloride, 2-methyl	C₄H₇C_lO	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	9.608	0.15
9	3-Hexyne, 2-methyl	C₇H₁₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	10.127	0.12
14	1-Methylcycloheptene	C₈H₁₄	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	12.855	0.22
20	1H-Pyrrole-2-carboxaldehyde, 5-methyl	C₆H₇NO	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	15.574	0.23	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.
25	Cis-1.4-dimethyl-2-methylenecyclohexane	C₉H₁₆	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	19.451	0.19	19.485	0.36
37	1H-Pyrrole, 3-methyl-	C₅H₇N	24.107	0.60	24.151	0.77	24.167	0.41
36	Benzene, 1,2-dimethoxy-	C₈H₁₀O₂	23.023	2.76	23.084	3.18	23.114	3.21
40	3,4-Dimethoxytoluene	C₉H₁₂O₂	^* *()** compounds with concentration under detection limit.	^* *()** compounds with concentration under detection limit.	24.433	0.24	24.448	0.37

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