酯化改性玉米秸秆吸油材料的制备与性能

doi:10.16085/j.issn.1000-6613.2023-1784

摘要/Abstract

摘要：

以玉米秸秆（RCS）为原料，经碱性过氧化氢预处理后，在微波辅助作用下，以甲酸为催化剂、乙酸为溶剂和酯化剂改性得到酯化玉米秸秆（ECS）吸油材料。采用Box-Behnken法进行响应面实验设计，得到制备ECS的最佳条件为：甲酸质量分数为7%、固液体积比为1∶40、微波功率为400W、反应温度为100℃，反应时间为20min，制备的ECS对机油的吸油倍率达到25.47g/g，与回归模型预测值25.80g/g相差1.27%，表明该模型模拟良好。通过红外光谱仪、元素分析仪、扫描电镜、X射线衍射仪、热重分析仪和接触角测量仪的表征和测试表明，ECS的红外谱图中有新峰出现，O和H元素含量减少，表明成功发生酯化反应，表面粗糙，结晶度为42.54%，失重速率最大的温度由改性前的310.1℃提高到352.1℃，疏水角由改性前的0°提高到97.2°。相比RCS，ECS的吸油倍率有明显的提高，在重复使用9次之后，ECS对不同油品的吸油倍率均能保持70%以上。本文为废弃玉米秸秆资源化利用和含油废水的处理提供一种方法。

关键词: 玉米秸秆, 改性, 酯化, 吸油倍率

Abstract:

The oil absorption material for esterified corn straw (ECS) was prepared by esterification modification under microwave assistance with raw corn straw (RCS), alkaline hydrogen, formic acid and acetic acid. The optimal preparation conditions were determined by response surface design with the Box-Behnken method, that was, the mass fraction of formic acid was 7%, the solid-liquid ratio was of 1∶40, the microwave power was of 400W, the reaction temperature was of 100℃ and the reaction time was 20min. The oil absorption ratio of ECS for engine oil attained 25.47g/g, which was 1.27% lower than the predicted value of 25.80g/g by regression model and indicated that the model was well simulated. The structures and properties were characterized and tested via infrared spectroscopy, elemental analyzer, the scanning electron microscopy, X-ray diffraction, thermogravimetric analyzer and contact angle measurement instrument. The analysis results showed that there were new peaks in the infrared spectrum of ECS, and the content of O and H elements was reduced, indicating that the esterification reaction had successfully occurred, the surface was rough, its crystallinity was of 42.54%, the temperature of the maximum weight loss rate was increased from 310.1℃ before modification to 352.1℃ after modification, and the hydrophobic angle was increased from 0° before modification to 97.2° after modification. Compared with RCS, the oil absorption rate of ECS was significantly improved. After reuse 9 times, the oil absorption rate of ECS for different oil products could remain more than 70%. This paper can provide a method for the resource utilization of waste corn straw and the treatment of oily wastewater.

Key words: raw corn straw, modification, esterification, oil absorption ratio

中图分类号:

TQ352.9

赵凯月, 朱春山, 张宾朋, 赵美箐, 何昱铤, 王明锐. 酯化改性玉米秸秆吸油材料的制备与性能[J]. 化工进展, 2024, 43(11): 6483-6492.

ZHAO Kaiyue, ZHU Chunshan, ZHANG Binpeng, ZHAO Meijing, HE Yuting, WANG Mingrui. Preparation and oil absorption properties of oil-material for corn straw by esterification modification[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6483-6492.

图/表 16

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来源	平方和	自由度	均值	F值	P值	显著性
模型	186.91	14	13.35	34.10	<0.0001	**
A	2.76	1	2.76	7.06	0.0188	*
B	6.42	1	6.42	16.41	0.0012	**
C	2.79	1	2.79	7.13	0.0183	*
D	11.86	1	11.86	30.29	<0.0001	**
AB	0.0289	1	0.0289	0.0738	0.7898	—
AC	0.5041	1	0.5041	1.29	0.2756	—
AD	10.96	1	10.96	27.98	0.0001	**
BC	0.2352	1	0.2352	0.6007	0.4512	—
BD	4.64	1	4.64	11.86	0.0040	**
CD	0.3364	1	0.3364	0.8591	0.3697	—
A²	60.49	1	60.49	154.47	<0.0001	**
B²	106.32	1	106.32	271.54	<0.0001	**
C²	17.23	1	17.23	44.01	<0.0001	**
D²	22.50	1	22.50	57.46	<0.0001	**
残值	5.48	14	0.3916	—	—	—
失拟	4.68	10	0.4684	2.35	0.2130	不显著
纯差	0.7977	4	0.1994	—	—	—
总和	192.39	28	—	—	—	—

来源	平方和	自由度	均值	F值	P值	显著性
模型	186.91	14	13.35	34.10	<0.0001	**
A	2.76	1	2.76	7.06	0.0188	*
B	6.42	1	6.42	16.41	0.0012	**
C	2.79	1	2.79	7.13	0.0183	*
D	11.86	1	11.86	30.29	<0.0001	**
AB	0.0289	1	0.0289	0.0738	0.7898	—
AC	0.5041	1	0.5041	1.29	0.2756	—
AD	10.96	1	10.96	27.98	0.0001	**
BC	0.2352	1	0.2352	0.6007	0.4512	—
BD	4.64	1	4.64	11.86	0.0040	**
CD	0.3364	1	0.3364	0.8591	0.3697	—
A²	60.49	1	60.49	154.47	<0.0001	**
B²	106.32	1	106.32	271.54	<0.0001	**
C²	17.23	1	17.23	44.01	<0.0001	**
D²	22.50	1	22.50	57.46	<0.0001	**
残值	5.48	14	0.3916	—	—	—
失拟	4.68	10	0.4684	2.35	0.2130	不显著
纯差	0.7977	4	0.1994	—	—	—
总和	192.39	28	—	—	—	—

实验次数	甲酸质量分数/%	固液体积比	微波功率/W	反应温度/℃	反应时间/min	吸油倍率/g·g^-1
1	7	1∶40	400	100	20	25.16
2	7	1∶40	400	100	20	25.53
3	7	1∶40	400	100	20	25.72
平均	—	—	—	—	—	25.47

实验次数	甲酸质量分数/%	固液体积比	微波功率/W	反应温度/℃	反应时间/min	吸油倍率/g·g^-1
1	7	1∶40	400	100	20	25.16
2	7	1∶40	400	100	20	25.53
3	7	1∶40	400	100	20	25.72
平均	—	—	—	—	—	25.47

样品	C/%	H/%	O/%	N/%
PCS	42.923	6.248	47.503	0
ECS	43.465	6.217	46.081	0