滇池藻水热液化成油特性研究

doi:10.3969/j.issn.1673-5854.2020.06.008

Abstract

Abstract:

Bio-crude oil was produced from algae in Dianchi lake by hydrothermal liquefaction. The effects of process parameters on the reaction of hydrothermal liquefication and the effects of reaction temperature on the product distribution of hydrothermal liquefication and characteristics of bio-crude oil were analyzed.The highest bio-crude yield of 14.82% was obtained at reaction temperature 300 ℃, reaction time 60 min and the mass fraction of solid in raw material 20%. The highest energy recovery was 54.11%, the carbon recovery and hydrogen recovery were 49.65% and 24.83%, and the HHV of bio-crude oil is 35.79 MJ/kg. The results of GC-MS analysis mainly showed that the hydrocarbons, organic acids, nitrogenoxides and esters were 22.4%, 34.3%, 21.1% and 5.47%. The reaction temperature had great effecs on the GC content changes of nitrogenoxides, esters, organic acids, hydrocarbons and phenols in bio-crude oil components. The highest H/C and the lowest N/C of bio-crude oil were respectively 1.39 and 0.05, the highest conversion efficiency of 83.87% was obtained at 380 ℃ and the HHV was 36.76 MJ/kg.

Key words: hydrothermal liquefaction, bio-crude oil, temperature, algae

CLC Number:

TQ35
TK6

Pengtao CHOU, Chunyan TIAN, Yanmei LI, Xueyuan BAI. Characteristics of Bio-crude Oil from Hydrothermal Liquefaction of Algae in Dianchi Lake[J]. Biomass Chemical Engineering, 2020, 54(6): 45-52.

Figures/Tables 7

Fig.1

Fig.2

Fig.3

Table 1

Table 2

GC-MS analysis results of bio-crude oil at different temperatures"

时间/s time	化合物名称 compound name	化学式 chemical formula	GC含量GC content/%
时间/s time	化合物名称 compound name	化学式 chemical formula	260 ℃	300 ℃	340 ℃	380 ℃
6.014	2-丁酮2-butanone	C₄H₈O	—	—	—	0.88
19.529	2，3-二甲基-2-环戊烯-1-酮2-cyclopenten-1-one, 2, 3-dimethyl-	C₇H₁₀O	—	—	—	0.74
20.979	2，3，4-三甲基-2-环戊烯-1-酮2-cyclopenten-1-one, 2, 3, 4-trimethyl-	C₈H₁₂O	—	—	—	0.97
23.262	7, 7-二甲基-2, 4-双四氢吡喃基-1, 3, 5-环庚三烯 loheptatriene, 2, 4-bis(tetrahydropyranyl)-7, 7-dimethyl-	C₂₁H₃₂O₄	—	—	—	0.80
27.455	六甲基三环十二烷基-5, 11-二烯 1, 3-hexamethyltricyclododeca-5, 11-diene-	C₁₈H₂₄O₂	—	—	—	1.07
29.183	2-(2-异丙烯基-5-甲基-环戊基-甲氧基)四氢吡喃 2-(2-isopropenyl-5-ethyl-cyclopentyl-methoxy)	C₁₅H₂₆O₂	1.15	—	—	—
31.05	5, 9-二甲基螺[3.5]壬-1-酮 5, 9-dimethylspiro[3.5]nonan-1-one	C₁₁H₁₈O	1.08	—	—	—
20.379	苯酚phenol	C₆H₆O	—	0.77	—	3.38
21.799	2-甲基-苯酚phenol, 2-methyl-	C₇H₈O	—	—	—	2.61
22.809	4-甲基-苯酚phenol, 4-methyl-	C₇H₈O	—	1.51	—	4.81
23.978	2-乙基-苯酚phenol, 2-ethyl-	C₈H₁₀O	—	—	—	5.94
25.296	4-乙基-苯酚phenol, 4-ethyl-	C₈H₁₀O	0.88	1.68	2.23	4.46
27.475	4-乙基-2-甲氧基苯酚4-ethyl-2-methoxyphenol	C₉H₁₂O₂	1.22	—	—	5.44
30.536	二丁基羟基甲苯butylated hydroxytoluene	C₁₅H₂₄O	0.75	—	—	2.50
23.899	(4-异丙基-1-甲基-6, 7-二甲基双环[3.2.1]辛-8-基)甲醇 (4-isopropyl-1-methyl-6, 7-dimethylenebicyclo[3.2.1]oct-8-yl)methanol	C₁₅H₂₄O	—	—	—	0.97
26.164	1, 5, 8a-四甲基- 1, 4-甲基偶氮烯-7-醇 1, 4-methanoazulen-7-ol, 1, 5, 8a-tetramethyl-	C₁₅H₂₆O	—	—	—	0.92
35.845	3, 7, 11-三甲基-1-十二醇 1-dodecanol, 3, 7, 11-trdimethyl-	C₁₅H₃₂O	0.95	2.61	—	1.10
40.966	5, 7, 10(19)三9, 10-烯断胆甾基- 9, 10-secocholesta-5, 7, 10(19)-triene-	C₂₇H₄₄O₃	4.86	—	—	1.13
38.797	14-甲基-十五酸甲酯pentadecanoic acid, 14-methyl-, methyl ester	C₁₇H₃₄O₂	1.31	1.98	—	2.66
41.413	1-(羟甲基)-十六酸酯hexadecanoic acid, 1-(hydroxymethyl)-1 ester	C₃₅H₆₈O₅	11.39	3.49	25.8	12.99
42.778	10-氧代-十八酸甲酯octadecanoic acid, 10-oxo-, methyl ester	C₁₉H₃₆O₃	13.20	—	—	—
8.64	甲苯toluene	C₇H₈	4.60	18.15	24.29	—
32.568	2, 6, 10-三甲基-十四烷tetradecane, 2, 6, 10-trimethyl-，	C₁₇H₃₆	1.59	—	—	7.60
32.658	7-十七碳烯7-heptadecene	C₁₇H₃₄	—	—	—	2.20
34.729	二十二烷docosane	C₂₂H₄₆	2.82	4.25	8.91	—
34.882	三十二烷dotriacontane	C₃₂H₆₆	0.87	—	—	3.08
7.605	乙酸acetic acid	C₂H₄O₂	—	—	—	0.81
10.017	丙酸propanoic acid	C₃H₆O₂	—	—	—	1.23
12.606	丁酸butanoic acid	C₄H₈O₂	—	2.76	—	0.98
14.203	3-甲基-丁酸butanoic acid, 3-methyl-	C₅H₁₀O₂	—	1.83	—	0.74
17.601	4-甲基-戊酸pentanoic acid, 4-methyl-	C₆H₁₂O₂	—	0.85	—	0.69
41.411	十六酸n-hexadecanoic acid	C₁₆H₃₂O₂	2.58	28.86	4.03	2.04
6.122	六氢-5(1H)-吲哚嗪酮5(1H)-indolizinone, hexahydro-,	C₈H₁₃NO	0.83	—	2.43	—
23.295	2-吡咯烷酮2-pyrrolidinone	C₄H₇NO	1.1	3.07	2.37	—
24.266	4-(2, 5-二氢-3-甲氧基苯基)丁胺 4-(2, 5-dihydro-3-methoxyphenyl)butylamine	C₁₁H₁₉NO	—	—	—	2.10
25.497	2-甲基-3-吡啶醇3-pyridinol, 2-methyl-	C₆H₇NO	2.8	3.70	2.26	1.00
26.158	3-吡啶醇3-pyridinol	C₅H₅NO	7.92	5.94	—	—
26.478	2-哌啶酮2-piperidinone	C₅H₉NO	2.44	3.13	4.46	—
27.125	3-甲酰基-4, 5-二甲基吡咯3-formyl-4, 5-dimethyl-pyrrole	C₇H₉NO	—	1.68	5.18	1.14
29.155	1-[2-丁炔基]-2-吡咯烷酮2-pyrrolidinone, 1-[2-butynyl]-	C₁₂H₁₈N₂O	—	—	1.90	—
31.207	n-[4-羟基氢化肉桂酰基]-色胺 tryptamine, n-[4-hydroxyhydrocinnamoyl]-	C₁₉H₂₀N₂O₂	—	—	—	1.83
33.198	对甲基-1-烯-3-酮,氨基脲p-menth-1-en-3-one, semicarbazone	C₁₁H₁₉N₃O	0.65	—	—	—
37.598	3, 17-二羟基-16-(甲氧羰基)-4-甲基-2, 4(1H)-环-3, 4-癸二酰胺 2, 4(1H)-cyclo-3, 4-secoakuammilanium, 3, 17-dihydroxy-16- (methoxycarbonyl)-4-methyl-,	C₂₂H₂₉N₂O₄	—	0.92	—	—
39.827	脱氧精胍菌素deoxyspergualin	C₁₇H₃₇N₇O₃	4.40	—	—	—
41.706	N, N-二庚基-N, N-二甲基-1，2-环丁二二甲酰胺 1, 2-cyclobutanedicarboxamide, N, N′-diheptyl-N, N′-dimethyl-	C₂₂H₄₂N₂O₂	4.63	—	—	—
42.955	N-庚基-2-4-甲基-氨基甲酰基-甲氧基-丁氧基-N-甲基乙酰胺 N-heptyl-2-4-[-methyl-carbamoyl-methoxy] -butoxy-N-methyl-acetamide	C₂₄H₄₈N₂O₄	4.45	—	—	—
43.145	秋水仙胺demecolcine	C₂₁H₂₅NO₅	13.98	—	—	—
47.146	吡啶羧酸pyridinecarboxylic acid	C₃₂H₃₉NO₁₀	—	2.66	—	—
21.31	2, 4, 5-三甲基-苯胺benzenamine, 2, 4, 5-trimethyl-	C₉H₁₃N	—	—	—	0.80
23.14	5, 7-二甲基吡啶1H-吲哚唑1H-indazole, 5, 7-dimethyl-	C₉H₁₀N₂	—	—	—	1.25
26.107	N, N-二甲基-2-嘧啶胺2-pyrimidinamine, N, N-dimethyl-	C₆H₉N₃	—	—	3.12	—
27.443	1-(1-环戊烯-1-基)-吡咯烷pyrrolidine, 1-(1-cyclopenten-1-yl)-	C₉H₁₅N	—	2.01	3.01	—
33.833	5, 7-二甲基-1H-吲哚1H-indole, 5, 7-dimethyl-	C₁₀H₁₁N	—	—	—	2.26
35.847	19, 20-二醇-16, 17-二氢呋喃16, 17-didehydro curan, 19, 20-diol	C₁₉H₂₄N₂	—	—	—	4.14

Table 2

Table 3

Fig.4

References 19

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反应温度/℃ reaction temperature	生物油得率/% bio-crude oil yield	转化率/% conversion efficiency	固体残渣得率/% solid residue yield	气体和水相产物得率/% gas and aqueous yield
260	12.69±0.2	74.85±0.47	25.15±0.47	62.16±0.31
300	14.82±0.35	79.97±1.30	20.03±1.30	65.15±0.36
340	11.94±1.4	82.24±0.19	17.76±0.19	70.30±2.31
380	10.81±0.34	83.87±1.17	16.13±1.17	73.86±0.63

反应温度/℃ reaction temperature	C/%	H/%	O¹⁾/%	N/%	H/C	O/C	N/C	Q_HHV/ (MJ·kg^-1)
260	70.94	7.96	13.90	6.60	1.35	0.15	0.08	32.97
300	75.20	8.41	9.85	5.58	1.34	0.10	0.06	35.79
340	77.11	8.73	8.35	4.86	1.36	0.08	0.05	37.16
380	75.88	8.80	8.87	4.62	1.39	0.09	0.05	36.76

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Characteristics of Bio-crude Oil from Hydrothermal Liquefaction of Algae in Dianchi Lake

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