阴离子功能化生物柴油离子液体抗氧化剂[X][C6H5COO]的制备

隋猛; 李法社; 吴学华; 王霜; 李明

阴离子功能化生物柴油离子液体抗氧化剂[X][C₆H₅COO]的制备

隋猛^{1, 2},
李法社^{1, 2, ,},
吴学华^{1, 3},
王霜²,
李明⁴

1.
冶金节能减排教育部工程研究中心, 云南昆明 650093
2.
昆明理工大学冶金与能源工程学院, 云南昆明 650093
3.
昆明理工大学理学院, 云南昆明 650093
4.
中国科学院广州能源研究所, 广东广州 510000

基金项目:

国家自然科学基金 51766007

云南省自然科学基金 2015FB128

云南省自然科学基金 2018FB092

NSFC-云南联合基金 U1602272

省部共建复杂有色金属资源清洁利用国家重点实验室自设项目 CNMRCUTS1704

云南省科技厅基金青年项目 2016FD055

详细信息

通讯作者:
LI Fa-she, Tel:15025131595, E-mail:asan97@qq.com

中图分类号: TK6
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- 文章访问数: 121
- HTML全文浏览量: 30
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- 被引次数: 0
出版历程
- 收稿日期: 2018-08-06
- 修回日期: 2018-11-06
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-01-10

Preparation of anionic functionalized ionic liquid antioxidant[X] [C₆H₅COO] for biodiesel

SUI Meng^{1, 2},
LI Fa-she^{1, 2
, ,},
WU Xue-hua^{1, 3},
WANG Shuang²,
LI Ming⁴

1.
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
2.
Engineering Research Center of Metallurgical Energy Conservation & Emission Reduction, Ministry of Education, Kunming 650093, China
3.
Kunming University of Science and Technology, Kunming 650093, China
4.
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510000, China

Funds:

the National Natural Science Foundation of China 51766007

Natural Science Foundation of Yunnan Province 2015FB128

Natural Science Foundation of Yunnan Province 2018FB092

NSFC-Yunnan Joint Fund Project U1602272

State Key Laboratory of Clean and Applied Utilization of Complex Nonferrous Metal Resources CNMRCUTS1704

Yunnan Science and Technology Department Foundation Youth project 2016FD055

摘要

摘要: 设计合成了两种阴离子功能化离子液体抗氧化剂（[MI][C₆H₅COO]、[Ch][C₆H₅COO]），采用核磁共振氢谱、傅里叶红外光谱对其结构进行了表征，并研究了两种离子液体抗氧化剂对小桐子生物柴油抗氧化性、铜片腐蚀性和油溶性能的影响。结果表明，离子液体抗氧化剂可有效提高生物柴油氧化稳定性，在添加量为0.3‰时，[MI][C₆H₅COO]的小桐子生物柴油诱导期提高了238%，超过了中国国家标准（6 h），[Ch][C₆H₅COO]的小桐子生物柴油诱导期提高了141%，未达到中国国家标准。进一步研究了两种离子液体抗氧化剂的油溶性，油溶性能从大到小的顺序为[MI][C₆H₅COO] > [Ch][C₆H₅COO] > GA（合成离子液体抗氧化剂的原料）。实验表明，合成的两种离子液体抗氧化剂中含有亲油阳离子的[MI][C₆H₅COO]综合性能明显优于含有亲水阳离子的[Ch][C₆H₅COO]。
- 离子液体 /
- 生物柴油 /
- 抗氧化剂 /
- 油溶性 /
- 氧化稳定性
Abstract: Two ionic liquid antioxidants ([MI] [C₆H₅COO], [Ch] [C₆H₅COO]) were designed, and synthesized, and measured by nuclear magnetic resonance spectra and Fourier infrared spectra.The effects of two ionic liquid antioxidants on the oxidation resistance, copper corrosion and oil solubility of Jatropha biodiesel were studied.The results show that ionic liquid antioxidants can effectively improve the oxidative stability of biodiesel. When the addition amount of[MI] [C₆H₅COO] is 0.3‰, the induction period of Jatropha biodiesel increases by 238%, exceeding the national standard (6 h). However, when the addition amount of[Ch] [C₆H₅COO] is 0.3‰, the induction period of Jatropha biodiesel increases by 141%, which does not meet the national standard. The order of oil solubility from large to small is[MI] [C₆H₅COO] > [Ch] [C₆H₅COO] > GA (raw material for synthesizing ionic liquid antioxidants).Moreover, the experiments show that the synthetic properties of[MI] [C₆H₅COO] containing lipophilic cations in the two ionic liquid antioxidants are significantly better than those containing hydrophilic cations[Ch] [C₆H₅COO].
- ionic liquid /
- biodiesel /
- antioxidants /
- oil solubility /
- oxidative stability

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图 1 生物柴油诱导期测试流程

Figure 1 Experimental setup for the oxidation stability test

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图 2 生物柴油氧化稳定性曲线

Figure 2 Test sample oxidation stability curve

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图 3 [MI][C₆H₅COO]的合成路线

Figure 3 Synthetic route of [MI][C₆H₅COO]

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图 4 [Ch][C₆H₅COO]的合成路线

Figure 4 Synthetic route of [Ch][C₆H₅COO]

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图 5 离子液体[MI][C₆H₅COO]红外光谱谱图

Figure 5 Infrared spectrum of ionic liquid [MI][C₆H₅COO]

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图 6 离子液体[Ch][C₆H₅COO]红外光谱谱图

Figure 6 Infrared spectrum of ionic liquid [Ch][C₆H₅COO]

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图 7 离子液体[MI][C₆H₅COO]核磁共振氢谱

Figure 7 Nuclear magnetic resonance spectroscopy of ionic liquid [MI][C₆H₅COO]

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图 8 离子液体核磁[Ch][C₆H₅COO]共振氢谱

Figure 8 Nuclear magnetic resonance spectroscopy of ionic liquid [Ch][C₆H₅COO]

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图 9 生物柴油诱导期随离子液体抗氧化剂含量的变化

Figure 9 Curve of induction period of biodiesel versus ionic liquid antioxidant content

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图 10 小桐子生物柴油氧化稳定性诱导期

Figure 10 Jatropha biodiesel oxidation stability induction period

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图 11 铜片腐蚀后的表面SEM照片

Figure 11 SEM image of copper sheet

(a): [MI][C₆H₅COO]+Jatropha biodiesel; (b): [Ch][C₆H₅COO]+Jatropha biodiesel; (c): Jatropha biodiesel

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图 12 铜片腐蚀等级对照

Figure 12 Copper corrosion level comparison

A: the appearance of the copper sheet after being corroded by [Ch][C₆H₅COO]+Jatropha biodiesel;
B: the appearance of the copper sheet after being corroded by [MI][C₆H₅COO]+Jatropha biodiesel;
C: the appearance of the copper sheet after being corroded by Jatropha biodiesel;
D: the original appearance of the copper

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表 1 铜片腐蚀试验后的小桐子生物柴油的酸值变化

Table 1 Acid value of Jatropha biodiesel after copper corrosion test.

Test sample	Acid value /(mgKOH·g^-1)
Jatropha biodiesel	2.96
Jatropha biodiesel after the test	8.74
[Ch][C₆H₅COO]+Jatropha biodiesel	6.43
[MI][C₆H₅COO]+Jatropha biodiesel	3.42

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表 2 抗氧化剂在生物柴油中的油溶性

Table 2 Oil solubility of antioxidants in biodiesel

Antioxidants	Solubility/(g·(100 mL)^-1)	Oil soluble/(mL·g^-1)
[MI][C₆H₅COO]	0.0372	2673
[Ch][C₆H₅COO]	0.0014	71428
GA	0.0005	200000

下载: 导出CSV

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