云南小粒咖啡壳水热液化产物分析

doi:10.3969/j.issn.1673-5854.2023.04.007

摘要/Abstract

摘要：

以云南小粒咖啡加工过程所产生的咖啡壳废弃物为原料, 通过铁催化其水热液化, 对液化产物进行真空抽滤分离水相和固相。然后用乙醚萃取水相得到轻质生物油, 用乙醇萃取固相得到重质生物油和固体残渣生物炭。分别对2种生物油进行气相色谱-质谱分析, 鉴别出轻油产率约7%, 主要含有50%以上糠醛及其衍生物、10%以上的苯酚及其衍生物, 而重油产率约14%, 主要含有36.19%的咖啡因、41.3%的脂肪酸等物质。残渣固体为富含含氧官能团且均匀地嵌入了纳米零价铁(nZVI)的生物炭, 具有催化过硫酸盐氧化降解四环素的性能, 150 min内该生物炭可以去除水中约80%的四环素。

关键词: 咖啡壳, 水热液化, 生物油, 生物炭

Abstract:

The coffee shell waste produced by the processing of Yunnan Arabica Coffee was used as raw material, and its hydrothermal liquefaction was catalyzed by iron and the liquefaction products were extracted by solvent to obtain the coffee shell bio-oils and the residual biochars. The light bio-oil extracted from the aqueous phase with ether and the heavy bio-oil extracted from the solid phase with ethanol were analysed by gas chromatography-mass spectrometry. It was identified that the light oil yield was around 7%, mainly containing more than 50% furfural and its derivatives, more than 10% phenol and its derivatives, while heavy oil yield was around 14%, mainly containing 36.19% caffeine, 41.3% fatty acids and other substances. The solid residue was a biochar rich in oxygen-containing functional groups and uniformly embedded with nano-zero valent iron, which had the performance of catalyzing the oxidative degradation of tetracycline by persulfate, and the biochar could remove about 80% of tetracycline in water within 150 min.

Key words: coffee shells, hydrothermal liquefaction, bio-oils, biochar

中图分类号:

TQ35
TQ424

刘光蓉, 李静, 黄强. 云南小粒咖啡壳水热液化产物分析[J]. 生物质化学工程, 2023, 57(4): 53-59.

Guangrong LIU, Jing LI, Qiang HUANG. Constituent Analysis of Hydrothermally Liquefying Products of Yunnan Coffea arabica Linn. Shells[J]. Biomass Chemical Engineering, 2023, 57(4): 53-59.

图/表 8

表1

轻油的主要成分"

保留时间/min retention time	化合物 chemical compound	化学式 chemical formula	峰面积比/% peak area ratio
4.015	α-呋喃甲醛(糠醛) α-furancarboxaldehyde(furfural)	C₅H₄O₂	35.96
8.539	5-甲基呋喃醛 5-methylfuranal	C₆H₆O₂	12.63
10.196	2-吡咯甲醛 2-pyrrole formaldehyde	C₅H₅NO	2.01
11.042	苄硫醇 benzyl mercaptan	C₇H₈S	1.30
12.223	间苯酚 m-phenol	C₇H₈O	0.61
12.377	愈创木酚 guaiacol	C₇H₈O₂	1.73
15.587	邻苯二酚 catechol	C₆H₆O₂	3.56
16.107	5-羟甲基糠醛 5-(hydroxymethyl)furfural	C₆H₆O₃	1.27
17.024	3-甲基苯邻二酚 3-methylbenzene-1, 2-diphenol	C₇H₈O₂	0.54
17.086	2,6-二羟基苯乙酮 2,6-dihydroxyacetophenone	C₈H₈O₃	1.99
18.036	4-乙烯基-2-甲氧基苯酚 4-ethenyl-2-methoxyphenol	C₉H₁₀O₂	2.39
18.913	2,6-二甲氧基苯酚 2,6-dimethoxyphenol	C₈H₁₀O₃	0.65
19.913	香兰素 vanillin	C₈H₈O₃	1.95
20.983	2,6-二甲酰-4-甲基苯酚 2,6-diformyl-4-methylphenol	C₉H₈O₃	5.97
22.300	3-羟基苯酰肼 3-hydroxybenzohydrazide	C₇H₈N₂O₂	0.67
23.791	丁基香草酮 butyl vanillone	C₁₁H₁₄O₃	0.68
25.919	(E)-2,6二甲氧基-4-(1-丙烯基)苯酚 (E)-2,6 dimethoxy-4-(1-propenyl)phenol	C₁₁H₁₄O₃	0.70
26.451	松柏醛 pineal	C₁₀H₁₀O₃	1.17
26.940	1,3,4(2H,5H)三酮-6,7-二甲基-1H-吡咯并[2,3-C]吡啶 1,3,4(2H,5H)-trione 6,7-dimethyl-1H-pyrrolo[2,3-C]pyridine	C₉H₈N₂O₃	5.27
27.018	1,3,7,8-四甲基黄嘌呤 1,3,7,8-tetramethylxanthine	C₉H₁₂N₄O₂	0.55
28.381	咖啡因 caffeine	C₈H₁₀N₄O₂	2.60
36.999	2,2'-亚甲基双(4-甲基-6-叔丁基苯酚) 2,2'-methylenebis(4-methyl-6-tert-butylphenol)	C₂₃H₃₂O₂	0.83
38.685	邻苯二甲酸二(2-乙基己)酯 di(2-ethylhexyl) phthalate	C₂₄H₃₈O₄	0.92
39.881	7-(3,4-甲二氧基)-四氢苯并呋喃酮 7-(3,4-methyldioxy)-tetrahydrobenzofuranone	C₁₅H₁₂O₅	4.17
42.957	3-(2-呋喃基)-1-(4-甲基苯基)-5-苯基2-吡唑啉 3-(2-furanyl)-1-(4-methylphenyl)-5-phenyl-2-pyrazoline	C₂₀H₁₈N₂O	0.80

表1

表2

图1

图2

图3

图4

图5

表3

参考文献 15

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保留时间/min retention time	化合物 chemical compound	化学式 chemical formula	峰面积比/% peak area ratio
4.356	二丙酮醇 diacetone alcohol	C₆H₁₂O₂	0.50
16.143	5-羟甲基糠醛 5-(hydroxymethyl)furfural	C₆H₆O₃	1.09
28.66	咖啡因 caffeine	C₈H₁₀N₄O₂	36.19
30.578	棕榈酸 palmitic acid	C₁₆H₃₂O₂	22.22
30.901	棕榈酸乙酯 ethyl palmitate	C₁₈H₃₆O₂	1.64
33.14	亚油酸 linoleic acid	C₁₈H₃₂O₂	15.27
33.198	顺-7-十四烯醛 cis-7-tetradecenal	C₁₄H₂₆O	3.25
33.513	硬脂酸 stearic acid	C₁₈H₃₆O₂	2.79
34.459	顺丁烯二酸二(2-乙基己)酯 bis(2-ethylhexyl) (2E)-2-butenedioate	C₂₀H₃₆O₄	2.19
36.291	花生酸 peanut acid	C₂₀H₄₀O₂	1.02
38.166	棕榈酸甘油单酯 monoglycerol palmitate	C₁₉H₃₈O₄	1.46
39.889	7-(3,4-甲二氧基)-四氢苯并呋喃酮 7-(3,4-methyldioxy)-tetrahydrobenzofuranone	C₁₅H₁₂O₅	0.82
40.376	亚油酸甘油单酯 linoleic acid monoglycerides	C₂₁H₃₈O₄	2.19
40.465	全顺4,7,10,13,16,19-二十二碳六烯酸甲酯 all-cis-4,7,10,13,16,19-docosahexaenoic acid methyl ester	C₂₃H₃₄O₂	0.93
43.959	5,8,11,14,17-二十碳五烯酸正丙酯 5,8,11,14,17-eicosapentaenoic acid n-propyl ester	C₂₃H₃₆O₂	1.20
47.171	γ-谷甾醇γ-sitosterol	C₂₉H₅₀O	0.91

温度temperature/℃	k_obs/min^-1	去除率removal rate/%	η/(mg·g^-1·min^-1)	R²
20	0.021 7	85.5	14.8	0.967
40	0.023 6	82.2	15.5	0.972
50	0.025 9	78.7	16.3	0.945
60	0.026 3	79.0	16.6	0.923

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