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为了实现在室温条件下对水包油型原油乳液的高效破乳，提出了一种利用新发现的天然微纳硅碳矿(Si—C)矿物材料制备纳米粒子(NP)破乳剂的新方法。硅碳矿的物质组成主要为亲水性的石英和疏水性的有机碳，利用其矿物组成特点制备纳米破乳剂具有天然的优势。通过简单的氧化改性获得氧化硅碳矿破乳剂(OSi—C)，采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、扫描电子显微镜能谱(SEM-EDS)、X射线光电子能谱(XPS)、Zeta电位、界面活性、界面张力及表面润湿性等手段对改性前后的样品组成和结构进行了分析表征。结果显示，OSi—C具有良好的双亲性、界面活性及降低油–水界面张力的能力。利用瓶试法对OSi—C纳米颗粒的破乳性能进行了评价，发现OSi—C纳米颗粒具有优异的破乳性能，在破乳剂用量1000 mg/L、pH=6时OSi—C的破乳效率可达到98.94%。对纳米粒子的破乳机制进行了深入的分析和探讨，OSi—C纳米粒子优异的两亲性和界面活性使其易于达到油–水界面，并且其表面丰富的含氧官能团使纳米粒子能够通过氢键和π—π相互作用与油–水界面的沥青质等乳化分子结合，进一步借助搅拌、振荡等外部机械力作用而破坏油–水界面处的保护膜，从而实现油水分离。相关研究发现不仅为纳米破乳剂处理原油乳液提供了新的认识，而且为天然矿物材料制备纳米破乳剂开辟了新的途径。
Abstract：Introduction It is well known that crude oil is one of the most important energy sources. The oil-in-water emulsion is often produced during oil exploitation due to waterflooding and groundwater. This emulsion causes damage to the transmission pipeline and environment. Therefore, the separation of oil and water is an essential step in the petroleum industry. Chemical demulsification is currently the most widely employed due to its convenient operation and quick response. However, the extensive use of chemical emulsifiers has brought potential harm to the environment, so it is necessary to explore novel environmentally friendly demulsifiers. Recently, nanoparticle(NP) demulsifiers have been widely concerned in the application of demulsification for crude oil emulsion. NP demulsifiers usually refer to chemically synthesized nanoparticles or modified natural nanoparticle minerals. While graphene oxide and reduced graphene oxide are reported to exhibit an excellent demulsification performance of more than 99.9%, the high cost of raw materials limits their widespread use. As a result, economical mineral materials such as attapulgite, kaolinite, and nano-silica are employed to develop NP demulsifiers. Ordinary mineral nanomaterials typically consist of a single hydrophilic part(e.g., quartz, silicate, etc.). Therefore, they require complex surface modifications to adjust their hydrophilicity and hydrophobicity, enabling them to be excellent demulsifiers. Recently, researchers found a novel mineral material called Micro-nano silicon-carbon ore(Si–C). The Si–C particles consist primarily of hydrophilic quartz and hydrophobic carbon, so it is expected that they can be used to prepare a novel NP demulsifier. Methods The Nano silicon-carbon ore utilized was sourced from a mining site named Shilukeng in Fengcheng City, Jiangxi Province, China. Initially, bulk samples of Si–C were ground, and the resulting mineral particles were subsequently screened to obtain samples less than about 1 um. The demulsifiers(OSi–C) were prepared through a simple oxidation treatment. Results and discussion The major elemental composition of the Si–C includes O(40.35%), Si(35.33%), C(9.15%), Al(2.18%), Fe(1.3%), K(0.33%), and the loss on ignition is 9.57%. The average particle size of Si–C was 343.4 nm. The Zeta potential of OSi–C was considerably lower than that of the Si–C for all pH conditions. This is due to the introduction of oxygen-containing functional groups on the OSi–C surface after oxidation treatment. The content of C–OH, C–O–C, and O=C–O increased compared to that of the Si–C, suggesting that the OSi–C was successfully oxidized, resulting in increasing oxygen-containing functional groups. After oxidation, the obtained OSi–C nanoparticles showed good amphiphilicity, interfacial activity, and low interfacial tension(IFT) properties, which enable the particles easily to arrive at the oil–water interface. And it was believed that the self-assembly behavior of OSi–C at the oil-water interface is due to its good interfacial activity and the ability to reduce the oil-water IFT. At a demulsifier dosage of 1000 mg/L, OSi–C exhibited a demulsification efficiency exceeding 98.94% at pH 6, with the oil concentration in the separated water less than 97.33 mg/L. Conclusions An OSi–C nanoparticle demulsifier was prepared by a simple oxidation treatment of natural Si–C nanoparticles to achieve highly efficient demulsification for the crude oil-in-water emulsion at room temperature(25 ℃). The OSi–C nanoparticles exhibit superior demulsification performance than the original Si–C at the optimal conditions, and have a demulsification efficiency of 98.94% at pH 6. The mechanism behind emulsion breaking was revealed through analyses of Zeta potential, interfacial activity, surface wettability, dynamic IFT, self-assembling at the oil–water interface, and microscopic observation of the demulsification process. On the one hand, the OSi–C nanoparticles have good amphiphilicity, interfacial activity and the ability to self-assembly at the oil–water interface, which makes it easy to arrive at the oil–water interface. On the other hand, the OSi–C material has abundant Oxygen-containing functional groups and aromatic ring structures, which can promote the binding of nanoparticles with emulsified molecules of asphaltenes and resins at the oil–water interface through hydrogen bonding and π–π interactions. Furthermore, with the help of external forces such as stirring and oscillation, the protective film at the oil-water interface ruptures, thereby achieving oil–water separation. Therefore, the OSi–C nanoparticles can rapidly break the emulsion with high efficiency at room temperature. Due to the natural composition advantage and nontoxicity of the raw Si–C, this work provides a new approach for synthesizing environmentally friendly natural mineral NP demulsifiers.
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基本信息:
DOI：10.14062/j.issn.0454-5648.20250355
中图分类号:TE39
引用信息:
[1]杨舒钧,王先广,穆优,等.新型硅碳矿纳米破乳剂的制备及其性能[J].硅酸盐学报,2025,53(12):3611-3623.DOI:10.14062/j.issn.0454-5648.20250355.
基金信息:
江西省自然资源厅项目（ZRT-KB202205）; 国家自然科学基金资助项目（52364027）