Preparation and oil absorption properties of oil-material for corn straw by esterification modification

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

Abstract

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

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

CLC Number:

TQ352.9

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.

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.

Figures/Tables 16

References 33

1	鞠春红. 含油废水常用的处理方法及超疏水材料的应用[J]. 黑龙江科学, 2023, 14(8): 128-129, 149.
	JU Chunhong. Application of super-hydrophobic material and the treatment of oily wastewater[J]. Heilongjiang Science, 2023, 14(8): 128-129, 149.
2	赵诗琳, 孟范平, 林雨霏, 等. 二甲苯吸附剂及其在泄漏事故水域的适用性评述[J]. 化工进展, 2019, 38(6): 2813-2824.
	ZHAO Shilin, MENG Fanping, LIN Yufei, et al. Sorbents for seprating xylene and their applicability in waters after the accidental spills: A review[J]. Chemical Industry and Engineering Progress, 2019, 38(6): 2813-2824.
3	叶泽权, 吴青芸, 顾林. 纤维素基油水分离材料研究进展[J]. 化工进展, 2022, 41(6): 3038-3050.
	YE Zequan, WU Qingyun, GU Lin. Recent progress in cellulose-based materials for oil-water separation[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3038-3050.
4	李小菊, 武芸, 李惠成, 等. 酯化改性葵花秸秆吸油性能研究[J]. 当代化工, 2023, 52(4): 794-800.
	LI Xiaoju, WU Yun, LI Huicheng, et al. Study on oil absorption performance of esterified modified sunflower straw[J]. Contemporary Chemical Industry, 2023, 52(4): 794-800.
5	王磊, 刘昌见. 水稻秸秆水热处理-酯交换改性制备吸油材料[J]. 化工进展, 2017, 36(5): 1811-1817.
	WANG Lei, LIU Changjian. Hydrothermal treatment and transesterification modification of rice straw for oil spill absorption material[J]. Chemical Industry and Engineering Progress, 2017, 36(5): 1811-1817.
6	李亚婧, 孙晓锋, 王广征, 等. 秸秆的改性及吸油能力[J]. 化工进展, 2012, 31(8): 1847-1851.
	LI Yajing, SUN Xiaofeng, WANG Guangzheng, et al. Modification of straw and its oil absorbency[J]. Chemical Industry and Engineering Progress, 2012, 31(8): 1847-1851.
7	TANG M X, ZHANG R, PU Y W. Wheat straw modified with palmitic acid as an efficient oil spill adsorbent[J]. Fibers and Polymers, 2018, 19(5): 949-955.
8	王帅, 杨晨曦. 疏水/亲油改性柚子皮纤维的制备及其性能研究[J]. 应用化工, 2019, 48(6): 1321-1325.
	WANG Shuai, YANG Chenxi. Preparation and properties of hydrophobic/lipophilic modified grapefruit fiber[J]. Applied Chemical Industry, 2019, 48(6): 1321-1325.
9	王旭, 王晓丽, 彭世涛, 等. 香蕉果皮酯化改性制备吸油材料[J]. 化工新型材料, 2020, 48(1): 257-261.
	WANG Xu, WANG Xiaoli, PENG Shitao, et al. Preparation of oil-absorbing material by esterification of banana peel[J]. New Chemical Materials, 2020, 48(1): 257-261.
10	王艳敏, 丁文明, 蔡静. 改性木屑对海上溢油的吸附[J]. 环境工程学报, 2017, 11(5): 2705-2710.
	WANG Yanmin, DING Wenming, CAI Jing. Adsorption of oil spill by modified sawdust[J]. Chinese Journal of Environmental Engineering, 2017, 11(5): 2705-2710.
11	闫红芹, 郑文瑞, 张桂玉, 等. 疏水/亲油丝瓜络制备及在油水分离中的应用[J]. 化工进展, 2021, 40(5): 2893-2899.
	YAN Hongqin, ZHENG Wenrui, ZHANG Guiyu, et al. Preparation of hydrophobic/oleophilic luffa and its application in oil-water separation[J]. Chemical Industry and Engineering Progress, 2021, 40(5): 2893-2899.
12	高文中, 张佳, 付存亭, 等. 玉米秸秆的水热酸处理工艺技术研究[J]. 化工设计通讯, 2019, 45(8): 80-81.
	GAO Wenzhong, ZHANG Jia, FU Cunting, et al. Study on hydrothermal acid treatment of corn stover[J]. Chemical Engineering Design Communications, 2019, 45(8): 80-81.
13	葛秀, 谭凤芝, 刘兆丽, 等. 秸秆接枝丙烯酸丁酯制备吸油树脂[J]. 大连工业大学学报, 2012, 31(2): 132-135.
	GE Xiu, TAN Fengzhi, LIU Zhaoli, et al. Synthesis of oil-absorption resin with corn straw graft butyl acrylate[J]. Journal of Dalian Polytechnic University, 2012, 31(2): 132-135.
14	陈鹤男. 玉米秸秆吸油材料的制备与研究[D]. 大连: 大连海洋大学, 2019.
	CHEN Henan. Preparation and research of oil absorbing material of corn straw[D]. Dalian: Dalian Ocean University, 2019.
15	TAN X F, WANG H-M D, ZANG D L, et al. Superhydrophobic/superoleophilic corn straw as an eco-friendly oil sorbent for the removal of spilled oil[J]. Clean Technologies and Environmental Policy, 2021, 23(1): 145-152.
16	XU Y, YANG H Y, ZANG D L, et al. Preparation of a new superhydrophobic/superoleophilic corn straw fiber used as an oil absorbent for selective absorption of oil from water[J]. Bioresources and Bioprocessing, 2018, 5(1): 1-11.
17	任俊鹏, 汤婷, 董翠鸽, 等. 表面硅烷化改性秸秆吸油材料的制备及性能[J]. 环境化学, 2021, 40(7): 2246-2254.
	REN Junpeng, TANG Ting, DONG Cuige, et al. Preparation and properties of surface silanized modified corn stalkas nature oil sorbents[J]. Environmental Chemistry, 2021, 40(7): 2246-2254.
18	ZANG D L, ZHANG M, LIU F, et al. Superhydrophobic/superoleophilic corn straw fibers as effective oil sorbents for the recovery of spilled oil[J]. Journal of Chemical Technology and Biotechnology, 2016, 91(9): 2449-2456.
19	SHI Y L, FENG X J, YANG R H. Preparation of recyclable corn straw fiber as oil absorbent via a one-step direct modification[J]. Materials Research Express, 2021, 8(1): 015506.
20	LIU T. Direct conversion of rod-shaped corn straw to superhydrophobic absorbent by hydroxyl-driven silylation for selective removal of organic solvents and oils[J]. Journal of the Iranian Chemical Society, 2023, 20(10): 2621-2629.
21	PENG D, OUYANG F, LIANG X J, et al. Sorption of crude oil by enzyme-modified corn stalk vs. chemically treated corn stalk[J]. Journal of Molecular Liquids, 2018, 255: 324-332.
22	WANG Z, TIAN T, XU K, et al. Removal of antimony(Ⅲ) by magnetic MIL-101(Cr)-NH₂ loaded with SiO₂: Optimization based on response surface methodology and adsorption properties[J]. Chemical Papers, 2022, 76(5): 2733-2745.
23	CELLI G B, GHANEM A, S-L BROOKS M. Optimized encapsulation of anthocyanin-rich extract from haskap berries (Lonicera caerulea L.) in calcium-alginate microparticles[J]. Journal of Berry Research, 2016, 6(1): 1-11.
24	汤健, 毕明, 陈长洁, 等. 超疏水棕榈生物质材料的研发[J]. 现代丝绸科学与技术, 2019, 34(1): 12-15, 34.
	TANG Jian, BI Ming, CHEN Changjie, et al. Research and development of super hydrophobic palm biomass materials[J]. Modern Silk Science & Technology, 2019, 34(1): 12-15, 34.
25	唐明晓, 吕二盟, 张睿, 等. 常温下乙酰化小麦秸秆纤维制备高效溢油吸附剂的研究[J]. 安徽农业科学, 2018, 46(8): 183-187.
	TANG Mingxiao, Ermeng LÜ, ZHANG Rui, et al. Preparation of an efficient oil-spill adsorbent by acetylating wheat straw cellulose at room temperature[J]. Journal of Anhui Agricultural Sciences, 2018, 46(8): 183-187.
26	姜思雨, 娄春华, 于晶晶, 等. 玉米秸秆乙酰化改性对环氧树脂性能的影响[J]. 工程塑料应用, 2023, 51(3): 129-135.
	JIANG Siyu, LOU Chunhua, YU Jingjing, et al. Effect of acetylation modification of corn straw on properties of epoxy resin[J]. Engineering Plastics Application, 2023, 51(3): 129-135.
27	WARR L N, PERDRIAL J N, M-C LETT, et al. Clay mineral-enhanced bioremediation of marine oil pollution[J]. Applied Clay Science, 2009, 46(4): 337-345.
28	SETYAWAN H, FAUZIYAH M, TOMO H S S, et al. Fabrication of hydrophobic cellulose aerogels from renewable biomass coir fibers for oil spillage clean-up[J]. Journal of Polymers and the Environment, 2022, 30(12): 5228-5238.
29	范廷玉, 李文洁, 彭丹, 等. 漆酶改性玉米秸秆髓的制备及其吸油特性[J]. 中国环境科学, 2020, 40(9): 3810-3820.
	FAN Tingyu, LI Wenjie, PENG Dan, et al. Preparation of laccase modified corn stover pith as oil sorbent and its properties[J]. China Environmental Science, 2020, 40(9): 3810-3820.
30	吕福全, 孟玉霞, 张元军, 等. 成型玉米秸秆气化的热重分析及动力学研究[J]. 当代化工研究, 2019(4): 147-150.
	LV Fuquan, MENG Yuxia, ZHANG Yuanjun, et al. Study on thermogravimetric analysis and kinetics during gasification of molding corn straw[J]. Modern Chemical Research, 2019(4): 147-150.
31	PAWAR A A, KIM H. Sustainable, hydrophobic, and reusable paper waste aerogel as an effective and versatile oil absorbent[J]. Journal of Environmental Chemical Engineering, 2022, 10(2): 107356.
32	WANG J J, ZHOU J L, ZHAI R, et al. A versatile platform of corn stalk-based membranes for high performance of oil/water separation[J]. Vacuum, 2023, 210: 111862.
33	刘晓晖, 曹亚峰, 李沅, 等. 玉米秸秆基吸油材料的制备与表征[J]. 林产化学与工业, 2016, 36(5): 37-44.
	LIU Xiaohui, CAO Yafeng, LI Yuan, et al. Preparation and characterization of oil absorbent material derived from corn stalk[J]. Chemistry and Industry of Forest Products, 2016, 36(5): 37-44.

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