面向溢油污染治理的SiO2氣凝膠疏水改性的研究進展

韓松; 張添華; 肖龍恒; 郭敏; 張梅

doi:10.13374/j.issn2095-9389.2022.05.03.002

面向溢油污染治理的SiO₂氣凝膠疏水改性的研究進展

doi: 10.13374/j.issn2095-9389.2022.05.03.002

韓松^1,,
張添華^{1, 2},
肖龍恒¹,
郭敏¹,
張梅^1, ,

1.
北京科技大學冶金與生態工程學院，北京 100083
2.
中冶建筑研究總院有限公司，北京 100088

基金項目: 國家自然科學基金資助項目（U21A20321, 51972019）；國家重點研發計劃資助項目（2020YFB0606205）

詳細信息

通訊作者:
E-mail: zhangmei@ustb.edu.cn

中圖分類號: TH145.1+1;TB383
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出版歷程
- 收稿日期: 2022-05-03
- 網絡出版日期: 2022-06-19
- 刊出日期: 2023-05-31

Research progress of hydrophobic modification of silica aerogel for oil spill pollution treatment

HAN Song^1
,,
ZHANG Tian-hua^{1, 2},
XIAO Long-heng¹,
GUO Min¹,
ZHANG Mei^{1
, ,}

1.
School of Metallurgical and Ecological Engineering, University of Science & Technology Beijing, Beijing 100083, China
2.
Central Research Institute of Building and Construction Co., Ltd, MCC Group, Beijing 100088, China

More Information

Corresponding author: E-mail: zhangmei@ustb.edu.cn

摘要

摘要: 二氧化硅氣凝膠（Silica aerogel，SA）具有高孔隙率、低密度、高比表面積等特性，可成為一種良好的吸油材料，然而親水表面和珍珠項鏈的結構限制了其在吸油領域的廣泛應用。疏水改性后的疏水SiO₂氣凝膠（Hydrophobic silica aerogel，HSA）不僅具有SA的優異特性，而且疏水/親油性好，是一種優異的輕質吸油材料。本文以表面后處理法和共前驅體法制備HSA為主線，系統介紹了這兩種方法結合超臨界干燥和常壓干燥制備HSA的研究進展，分析總結了兩種方法的優缺點。其中，共前驅體法主要結合超臨界干燥工藝制備HSA，表面后處理法則常結合常壓干燥，兩種方法主要都采用硅烷化劑為疏水改性劑。表面后處理法改性不改變已形成的孔隙結構，HSA的孔徑和粒徑比較均勻，但可能存在內部改性不徹底的問題。共前驅體法在凝膠結構形成的同時完成改性，制備的HSA比表面積更大，疏水性更好，但是其孔徑不均勻，引入的疏水基團有限。此外，本文還綜述了目前常用的提高HSA機械性能的方法以及HSA吸油性能的研究進展。最后，立足于當前HSA用作吸油材料發展的趨勢，對HSA吸油材料朝著開發低成本且環境友好的原料、開發周期短的疏水改性流程、制備大塊體HSA、提高HSA的機械性能以及提高其吸油性能等發展方向進行了展望。
- SiO₂氣凝膠 /
- 表面后處理法 /
- 共前驅體法 /
- 常壓干燥 /
- 機械性能 /
- 吸油
Abstract: Oil spill pollution seriously endangers human and ecosystem health. Therefore, it is urgent to develop oil-absorbing materials to effectively remove oil spill pollution. Among the traditional oil-absorbing materials, natural organic adsorption material has low oil absorption capacity and hydrophilicity; inorganic adsorption materials are difficult to recover and have low oil absorption efficiency and high price; and although the synthetic organic adsorbent has outstanding oil absorption capacity, its biodegradation is poor. Silica aerogel (SA) has the characteristics of high porosity, low density, and high specific surface area, which make it an excellent oil-absorbing material. However, the hydrophilic surface and pearl necklace structure of SA limit its wide applications in the oil absorption field. Hydrophobically modified hydrophobic silica aerogel (HSA) has not only excellent SA characteristics but also good hydrophobic/lipophilic properties. In this paper, focusing on HSA preparation by surface posttreatment modification and coprecursor modification, the research progress on these two methods combined with supercritical drying and ambient pressure drying is systematically introduced, and the advantages and disadvantages of the two methods are analyzed and summarized. The coprecursor modification is mainly combined with a supercritical drying process to prepare HSA, while the surface posttreatment modification is often combined with an ambient pressure drying process. Both methods normally use silylating agents as hydrophobic modifiers. The surface posttreatment modification does not change the formed pore structure, and the pore size and particle size of HSA are relatively uniform. However, the modification process of surface posttreatment is long, the solvent consumption is large, and the cost is high. In addition, incomplete internal modification may be a problem. In the coprecursor modification method, wet gel is formed and modified simultaneously, shortening the modification time and saving costs. The prepared HSA of coprecursor modification has a larger specific surface area and better hydrophobicity, but its pore size is uneven, and the introduced hydrophobic groups are limited. Excessive silylating agents affect the sol–gel process of HSA. In addition, the current methods for strengthening HSA mechanical properties and the research progress on HSA oil absorption properties are reviewed. Finally, based on the current development of HSA as oil-absorbing materials, the development direction of these materials is discussed, for example, developing low-cost and eco-friendly raw materials, shortening the hydrophobic modification process, preparing bulk HSA, strengthening the mechanical properties, and improving the oil-absorbing properties of HSA.
- silica aerogel /
- surface posttreatment modification /
- coprecursor modification /
- ambient pressure drying /
- mechanical properties /
- oil absorption

HTML全文

圖 1 SA的制備流程和反應機理

Figure 1. Preparation process and reaction mechanism of SA

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圖 2 TMCS表面后處理法制備HSA的改性過程及機理^[34]

Figure 2. Modification process and mechanism of HSA prepared by TMCS surface post-treatment^[34]

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圖 3 HSA在IPA/TMCS/正己烷中的反應機理^[51]

Figure 3. Reaction mechanism of HSA in IPA/TMCS/n-Hexane solution^[51]

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圖 4 CSMA（HMDSO/TMCS、HMDSO/HMDZ和HMDZ/TMCS）改性SA的反應機理^[55]

Figure 4. Reaction mechanism of CSMA (HMDSO/TMCS，HMDSO/HMDZ, and HMDZ/TMCS) modified SA^[55]

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圖 5 DMF作為DCCA的反應機理（R為疏水基團）^[71]

Figure 5. Reaction mechanism of DMF as DCCA (R-hydrophobic group)^[71]

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圖 6 表面后處理法和共前驅體法（硅烷改性）制備HSA的流程與反應機理

Figure 6. Preparation process and reaction mechanism of HSA by surface post-treatment modification and co-precursor modification (silylating agents modification)

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表文中所用到的化合物縮寫名稱表

Table . List of abbreviated names of compounds used in this paper

Full name	Abbreviation	Full name	Abbreviation
Tetramethoxysilane (正硅酸甲酯)	TMOS	Polydiethyloxysiloxane (聚二乙氧基硅氧烷)	PDEOS
Tetraethoxysilane (正硅酸四乙酯)	TEOS	Isopropanol (異丙醇)	IPA
Dimethyldichlorosilane (二甲基二氯硅烷)	DMDCS	Phenyltriethoxysilane (苯基三乙氧基硅烷)	PTES
Dimethylchlorosilane (二甲基氯硅烷)	DMCS	Hexamethyldisilazane (六甲基二硅氮烷)	HMDZ
Trimethylchlorosilane (三甲基氯硅烷)	TMCS	Hexamethyldisiloxane (六甲基二硅氧烷)	HMDSO
Trimethylmethoxysilane (三甲基甲氧基硅烷)	TMMS	N. N-dimethylformamide (N，N-二甲基甲酰胺)	DMF
Trimethylethoxysilane (三甲基乙氧基硅烷)	TMES	3-(trimethoxysilylpropyl) methacrylate [3-（三甲氧基硅基丙基）甲基丙烯酸酯]	TMSPM
Methyltriethoxysilane (甲基三乙氧基硅烷)	MTES	2,5-divinyltrimethoxysilane (2，5-二乙烯基三甲氧基硅烷)	DVTHP
Methyltrimethoxysilane (甲基三甲氧基硅烷)	MTMS	3-methylpropenyloxypropyltrimethoxysilane (3-甲基丙烯氧基丙基三甲氧基硅烷)	MEMO
Ethyltrimethoxysilane (乙基三甲氧基硅烷)	ETMS	3-glycidyloxypropyltrimethoxysilane (3-縮水甘油氧基丙基三甲氧基硅烷)	GLYMO
Ethyltriethoxysilane (乙基三乙氧基硅烷)	ETES	Dodecyltrimethoxysilane (十二烷基三甲氧基硅烷)	DTMS
Propyltrimethoxysilane (丙基三甲氧基硅烷)	PTMS

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表 1 三種官能硅烷劑的分類^[35–36]

Table 1. Classification of monofunctional, difunctional, and trifunctional silylating agents^[35–36]

Type	Structure	R/Si	R_nSiX_4–n
Mono-functional		3	Trimethylchlorosilane (TMCS), Hexamethyldisilazane (HMDZ), Hexamethyldisiloxane (HMDSO), etc.
Di-functional		2	Dimethyldimethoxysilane (DMDMS), Dimethyldichlorosilane (DMDCS), Dimethyldimethoxysilane (DMMOS), etc.
Tri-functional		1	Methyltrimethoxysilane (MTMS), Methyltriethoxysilane (MTES), Methyltrichlorosilane (MTCS), Trimethoxysilane (TMMS), etc.

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表 2 硅源及改性劑的成本

Table 2. Cost of silicon source and silylating agents

Name		Price/yuan	Specifications
Silicon source	Tetramethoxysilane	~276.00	/Bottle, 500 g, purity 98%
	Tetraethoxysilane	~56.00	/Bottle, 500 mL, AR
	Water glass	~1800.00	/Ton
	Kaolin	1000.00–2000.00	/Ton
Silylating agents	Trimethylchlorosilane	~49.00	/Bottle, 100 mL, purity ≥98%
	Methyltrimethoxysilane	~54.00	/Bottle, 100 mL
	Methyltriethoxysilane	~76.00	/Bottle, 100 mL, purity 98%
	Hexamethyldisiloxane	~67.00	/Bottle, 100 mL, purity 99%
	Hexamethyldisilazane	~56.00	/Bottle, 100 mL, AR, purity 98%

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表 3 表面后處理法和共前驅體法對比

Table 3. Comparison between the surface posttreatment method and coprecursor method

Modification method	Common drying process	Modified object	Advantage	Disadvantage
Surface posttreatment modification (surface derivation modification)	Ambient pressure drying	Wet gel after sol–gel process	The method is simple and easy to control. The modification does not affect the original void structure. The pore size and particle size of HSA are relatively uniform	The solvent consumption of the modification project is large, the internal modification is not complete, and the process is cumbersome
Coprecursor modification (in situ modification)	Supercritical drying	Primary particles and growing aggregates in the sol–gel process	With simple process flow and low cost, HSA with a large specific surface area and better hydrophobicity can be prepared	The reaction process is not easy to control, the introduced hydrophobic groups are limited, and the pore size is uneven

下載: 導出CSV

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