負(fù)載型反相破乳劑的合成及性能研究
發(fā)布時(shí)間：2019-03-05 09:29
【摘要】：三元復(fù)合驅(qū)采油技術(shù)較普通水驅(qū)提高采收率達(dá)20個(gè)百分點(diǎn)以上,對(duì)保持我國主力油田后期的穩(wěn)產(chǎn)起到了重要作用,同時(shí)也產(chǎn)生了三元復(fù)合驅(qū)采出水水質(zhì)復(fù)雜、相態(tài)穩(wěn)定,油水分離難度大的難題。三元復(fù)合驅(qū)采出水處理是礦場(chǎng)油田開發(fā)和保護(hù)生態(tài)環(huán)境面臨的重要課題,成為了三元復(fù)合驅(qū)技術(shù)推廣的瓶頸之一。三元復(fù)合驅(qū)采出水處理在國內(nèi)外尚無成熟的技術(shù)可供參考,而破乳脫穩(wěn)是處理三元復(fù)合驅(qū)采出水首要解決的問題。近些年破乳劑的研究有了長足的進(jìn)展,但適合三元復(fù)合驅(qū)采出水破乳的高效破乳劑有待研發(fā)。因此,本文提出了針對(duì)三元復(fù)合驅(qū)O/W型采出水破乳與吸附協(xié)同作用的破乳劑分子設(shè)計(jì)新思路。采用表面枝接聚合法將預(yù)先制備的聚醚聚季銨鹽(PPA)反相破乳劑分子鍵合到比表面積大、多孔性的水合二氧化硅(SiO_2·n H2O、水合二氧化硅)表面,制備負(fù)載型聚醚聚季銨鹽反相破乳劑。通過單因素條件實(shí)驗(yàn)考察了反應(yīng)溫度、反應(yīng)時(shí)間、反應(yīng)原料用量、催化劑用量等條件對(duì)合成中間產(chǎn)物與最終產(chǎn)品轉(zhuǎn)化率的影響,并進(jìn)一步優(yōu)化了合成工藝。通過SEM和BET對(duì)水合二氧化硅的微觀結(jié)構(gòu)和孔結(jié)構(gòu)進(jìn)行表征,并通過FTIR、1H-NMR、SEM和XPS對(duì)合成產(chǎn)物進(jìn)行了表征。采用單一型PPA反相破乳劑進(jìn)行破乳試驗(yàn),考察了季銨鹽與甲基醚的配比(親水親油性)、破乳劑用量、破乳溫度、破乳時(shí)間等因素對(duì)破乳效果的影響,并對(duì)PPA反相破乳劑與其他商用破乳劑的破乳性能進(jìn)行了比較。試驗(yàn)結(jié)果表明,在n(環(huán)氧醚):n(甲基醚)=3:1,PPA投加量50 mg L-1,破乳溫度30 oC,破乳時(shí)間60 min條件下,PPA反相破乳劑的破乳率可達(dá)85.48%。采用PPA反相破乳劑破乳后油水分層,易于分離。采用單一型吸附劑MPS-SiO_2吸附處理含油污水,在含油濃度500 mg L-1,吸附劑投加量1.5 g L-1,吸附時(shí)間60 min,吸附溫度30 oC時(shí),MPS-SiO_2吸附除油率為46.8%。采用負(fù)載型反相破乳劑SiO_2@PPA破乳-吸附處理含油污水,在含油濃度500mg L-1,吸附劑投加量1.5 g L-1,吸附時(shí)間60 min,吸附溫度30 oC時(shí),負(fù)載型反相破乳劑SiO_2@PPA的除油率為91.6%,載體粒子吸附容量達(dá)301 mg g-1,是顆�；钚蕴�(GAC)吸附容量的6倍。研究結(jié)果表明,負(fù)載型破乳劑SiO_2@PPA載體粒子具有多孔隙結(jié)構(gòu),粒徑小、比表面積大的特點(diǎn),使得SiO_2@PPA兼具破乳與吸附功能,負(fù)載型反相破乳劑SiO_2@PPA通過破乳與吸附協(xié)同作用,可以適用于三元復(fù)合驅(qū)采出水破乳處理。負(fù)載型破乳劑SiO_2@PPA載體粒子吸附油滴的動(dòng)力學(xué)試驗(yàn)表明,其吸附過程符合偽二級(jí)動(dòng)力學(xué)方程;在等溫吸附中,Langmuir等溫吸附模型比Freundlich等溫吸附模型更能合理描述SiO_2@PPA載體粒子對(duì)油滴的吸附行為;熱力學(xué)研究表明,該吸附過程ΔG0且ΔH0,說明SiO_2@PPA載體粒子對(duì)油滴吸附是一個(gè)自發(fā)的、吸熱的過程。
[Abstract]:ASP flooding technology improves oil recovery by more than 20 percentage points compared with common water flooding, which plays an important role in maintaining stable production in the later stage of the main oil field in China. At the same time, it also produces complex water quality and stable phase state of produced water in ASP flooding. The difficult problem of oil-water separation. The treatment of produced water from ASP flooding is an important subject in oilfield development and protection of ecological environment, which has become one of the bottlenecks in the popularization of ASP flooding technology. There is no mature technology for treatment of produced water in ASP flooding at home and abroad, and demulsification is the first problem to be solved in the treatment of produced water in ASP flooding. The research on demulsifier has made great progress in recent years, but the high efficiency demulsifier suitable for ASP flooding water demulsifier needs to be researched and developed. Therefore, a new idea of demulsifier molecular design for the synergistic action of demulsification and adsorption of O / W type produced water by ternary composite flooding is proposed in this paper. The pre-prepared polyether polyquaternary ammonium salt (PPA) inverse demulsifier molecule was bonded to the surface of hydrated silica (SiO_ 2 路n H 2O, hydrated silica) with large specific surface area and porous surface area by surface grafting polymerization. The reverse demulsifier of supported polyether polyquaternary ammonium salt was prepared. The effects of reaction temperature, reaction time, amount of raw material and catalyst on the conversion of intermediate product and final product were investigated by single factor experiment, and the synthesis process was further optimized. The microstructure and pore structure of hydrated silica were characterized by SEM and BET, and the synthesized products were characterized by FTIR,1H-NMR,SEM and XPS. The demulsifying effect of quaternary ammonium salt and methyl ether, the amount of demulsifier, demulsification temperature, demulsification time and so on, were investigated by demulsifying test of single type PPA inverse demulsifier, and the effects of the ratio of quaternary ammonium salt and methyl ether on demulsification were investigated. The demulsifying properties of PPA reverse demulsifier were compared with other commercial demulsifiers. The experimental results show that the demulsifying rate of PPA reverse demulsifier can reach 85.48% under the conditions of n (epoxy ether): n (methyl ether) = 3 mg / L, PPA dosage 50 mg / L / L, demulsification temperature 30 oC, / demulsification time 60 min. It is easy to separate oil and water after demulsification with PPA reverse demulsifier. A single adsorbent MPS-SiO_2 was used to treat oily wastewater. When the concentration of oil was 500 mg / L, the dosage of adsorbent was 1.5g / L, and the adsorption time was 60 min, / L, the adsorption temperature was 30 oC. The oil absorption and removal rate of MPS-SiO_2 was 46.8%. The oily wastewater was treated with SiO_2@PPA demulsifier and adsorption. When the concentration of oil was 500mg / L, the dosage of adsorbent was 1.5g / L and the adsorption time was 60 min, the adsorption temperature was 30 oC. The oil removal rate of the supported inverse demulsifier SiO_2@PPA was 91.6%, and the adsorption capacity of the carrier particles reached 301 mg / g / g, which was 6 times higher than that of the granular activated carbon (GAC). The results show that the supported demulsifier SiO_2@PPA carrier particles have the characteristics of porous structure, small particle size and large specific surface area, which makes SiO_2@PPA have both demulsification and adsorption functions. Supported inverse demulsifier SiO_2@PPA can be applied to demulsification treatment of produced water by ternary compound flooding through synergistic action of demulsification and adsorption. The kinetic test of oil droplets adsorbed on SiO_2@PPA carrier shows that the adsorption process accords with pseudo-second-order kinetic equation. In isothermal adsorption, Langmuir isothermal adsorption model is more reasonable than Freundlich isothermal adsorption model to describe the adsorption behavior of SiO_2@PPA carrier particles to oil droplets. Thermodynamic studies show that the adsorption process 螖 G _ 0 and 螖 H _ 0 indicate that the adsorption of oil droplets by SiO_2@PPA carrier particles is a spontaneous and endothermic process.
【學(xué)位授予單位】：中國礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TE39
本文編號(hào)：2434760
[Abstract]:ASP flooding technology improves oil recovery by more than 20 percentage points compared with common water flooding, which plays an important role in maintaining stable production in the later stage of the main oil field in China. At the same time, it also produces complex water quality and stable phase state of produced water in ASP flooding. The difficult problem of oil-water separation. The treatment of produced water from ASP flooding is an important subject in oilfield development and protection of ecological environment, which has become one of the bottlenecks in the popularization of ASP flooding technology. There is no mature technology for treatment of produced water in ASP flooding at home and abroad, and demulsification is the first problem to be solved in the treatment of produced water in ASP flooding. The research on demulsifier has made great progress in recent years, but the high efficiency demulsifier suitable for ASP flooding water demulsifier needs to be researched and developed. Therefore, a new idea of demulsifier molecular design for the synergistic action of demulsification and adsorption of O / W type produced water by ternary composite flooding is proposed in this paper. The pre-prepared polyether polyquaternary ammonium salt (PPA) inverse demulsifier molecule was bonded to the surface of hydrated silica (SiO_ 2 路n H 2O, hydrated silica) with large specific surface area and porous surface area by surface grafting polymerization. The reverse demulsifier of supported polyether polyquaternary ammonium salt was prepared. The effects of reaction temperature, reaction time, amount of raw material and catalyst on the conversion of intermediate product and final product were investigated by single factor experiment, and the synthesis process was further optimized. The microstructure and pore structure of hydrated silica were characterized by SEM and BET, and the synthesized products were characterized by FTIR,1H-NMR,SEM and XPS. The demulsifying effect of quaternary ammonium salt and methyl ether, the amount of demulsifier, demulsification temperature, demulsification time and so on, were investigated by demulsifying test of single type PPA inverse demulsifier, and the effects of the ratio of quaternary ammonium salt and methyl ether on demulsification were investigated. The demulsifying properties of PPA reverse demulsifier were compared with other commercial demulsifiers. The experimental results show that the demulsifying rate of PPA reverse demulsifier can reach 85.48% under the conditions of n (epoxy ether): n (methyl ether) = 3 mg / L, PPA dosage 50 mg / L / L, demulsification temperature 30 oC, / demulsification time 60 min. It is easy to separate oil and water after demulsification with PPA reverse demulsifier. A single adsorbent MPS-SiO_2 was used to treat oily wastewater. When the concentration of oil was 500 mg / L, the dosage of adsorbent was 1.5g / L, and the adsorption time was 60 min, / L, the adsorption temperature was 30 oC. The oil absorption and removal rate of MPS-SiO_2 was 46.8%. The oily wastewater was treated with SiO_2@PPA demulsifier and adsorption. When the concentration of oil was 500mg / L, the dosage of adsorbent was 1.5g / L and the adsorption time was 60 min, the adsorption temperature was 30 oC. The oil removal rate of the supported inverse demulsifier SiO_2@PPA was 91.6%, and the adsorption capacity of the carrier particles reached 301 mg / g / g, which was 6 times higher than that of the granular activated carbon (GAC). The results show that the supported demulsifier SiO_2@PPA carrier particles have the characteristics of porous structure, small particle size and large specific surface area, which makes SiO_2@PPA have both demulsification and adsorption functions. Supported inverse demulsifier SiO_2@PPA can be applied to demulsification treatment of produced water by ternary compound flooding through synergistic action of demulsification and adsorption. The kinetic test of oil droplets adsorbed on SiO_2@PPA carrier shows that the adsorption process accords with pseudo-second-order kinetic equation. In isothermal adsorption, Langmuir isothermal adsorption model is more reasonable than Freundlich isothermal adsorption model to describe the adsorption behavior of SiO_2@PPA carrier particles to oil droplets. Thermodynamic studies show that the adsorption process 螖 G _ 0 and 螖 H _ 0 indicate that the adsorption of oil droplets by SiO_2@PPA carrier particles is a spontaneous and endothermic process.
【學(xué)位授予單位】：中國礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TE39
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 李三喜;徐妍如;王松;;SO_4~(2-)/TiO_2-HZSM-5固體超強(qiáng)酸催化劑的制備及酯化性能[J];化工進(jìn)展;2015年03期
2 劉龍偉;郭睿;解傳梅;王敏;王二蒙;;水包油型原油乳狀液破乳劑的合成與性能研究[J];石油化工;2014年09期
3 盛強(qiáng);姜巖;李東勝;李曉鷗;;制備白炭黑研究進(jìn)展[J];當(dāng)代化工;2014年01期
4 王明賢;趙圣;支恒學(xué);;白炭黑吸附甲醛實(shí)驗(yàn)研究[J];硅酸鹽通報(bào);2013年10期
5 吳亞;陳世軍;智率帥;徐家業(yè);;低聚季銨鹽與破乳劑復(fù)配提高聚驅(qū)采出液水質(zhì)的研究[J];西安石油大學(xué)學(xué)報(bào)(自然科學(xué)版);2013年04期
6 夏家祥;劉宇程;徐俊忠;陳明燕;;聲化破乳-離心分離處理廢棄油基鉆井液實(shí)驗(yàn)研究[J];石油與天然氣化工;2013年03期
7 趙秋實(shí);;三元復(fù)合驅(qū)采出水的處理工藝[J];油氣田地面工程;2013年06期
8 劉娟;趙亞溥;胡斌;任嗣利;;油水乳狀液的穩(wěn)定機(jī)理及其化學(xué)破乳技術(shù)的研究進(jìn)展[J];化工進(jìn)展;2013年04期
9 蔡奇峰;周繼柱;付增華;冷傳志;時(shí)武龍;王國瑞;;聚醚型原油破乳劑結(jié)構(gòu)與破乳性能關(guān)系的研究[J];應(yīng)用化工;2013年01期
10 魏然;;二氧化碳回注技術(shù)用于中原油田氣驅(qū)采油[J];油氣田地面工程;2012年12期
相關(guān)博士學(xué)位論文 前4條
1 孫媛媛;蘆竹活性炭的制備、表征及吸附性能研究[D];山東大學(xué);2014年
2 劉金河;聚合物驅(qū)原油乳狀液的穩(wěn)定性與破乳機(jī)理研究[D];中國石油大學(xué)（華東）;2012年
3 張瑞泉;弱堿體系三元復(fù)合驅(qū)采出液分離技術(shù)及機(jī)理研究[D];大連理工大學(xué);2008年
4 李道山;三元復(fù)合驅(qū)表面活性劑吸附及堿的作用機(jī)理研究[D];大慶石油學(xué)院;2003年
相關(guān)碩士學(xué)位論文 前7條
1 馬葉;改性活性炭吸附水中六價(jià)鉻離子的研究[D];南京林業(yè)大學(xué);2015年
2 鄭淑華;聚硅氧烷原油破乳劑的合成與應(yīng)用[D];陜西科技大學(xué);2014年
3 李曉敏;主鏈聚季銨鹽的合成及性能研究[D];西南石油大學(xué);2011年
4 劉夢(mèng)緋;油水乳狀液微波破乳機(jī)理研究[D];北京化工大學(xué);2011年
5 張秋;疏水型納米白炭黑的制備及表征[D];中北大學(xué);2009年
6 葉清;三元復(fù)合驅(qū)采出水特性分析及其處理方法研究[D];上海交通大學(xué);2008年
7 王方林;強(qiáng)堿體系三元復(fù)合驅(qū)采出水油水分離特性及處理技術(shù)研究[D];上海交通大學(xué);2007年
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