梳形聚合物對瀝青質(zhì)聚集行為和稠油高壓流變性質(zhì)的影響
發(fā)布時(shí)間：2018-09-08 21:39
【摘要】：瀝青質(zhì)的稠環(huán)芳香結(jié)構(gòu)及復(fù)雜的組裝聚集方式使其容易聚集沉積,從而使稠油表現(xiàn)為高粘、流動性低的特點(diǎn),這一特點(diǎn)使得稠油無論在開采還是運(yùn)輸過程中都面臨巨大的挑戰(zhàn)。向原油體系加入化學(xué)分散劑是改善瀝青質(zhì)的聚集狀態(tài)和提高油品流動性的一種經(jīng)濟(jì)可行的方法。開發(fā)針對稠油中瀝青質(zhì)聚集體的分散劑,應(yīng)首先從分散劑與瀝青質(zhì)間的作用力形式和強(qiáng)弱角度判斷哪種結(jié)構(gòu)的分散劑對瀝青質(zhì)的分散穩(wěn)定性和聚集行為有更好的改善效果。因此,本課題首先考察了 MAC和PMV兩組梳形聚合物對低濃度模型油中瀝青質(zhì)的分散效果及其聚集行為的影響,其次,研究了溫度、壓力及高壓CO_2對脫氣稠油的流變學(xué)特性的影響,特別是梳形聚合物與高壓CO_2的共同作用效果。本文以自由基聚合方法合成了聚(馬來酸酐-醋酸乙烯酯)(PMV)中間體,并通過側(cè)鏈胺化改性制備了兩個(gè)系列的梳形聚合物:一類是接枝了不同鏈長的鏈烷烴的PMV-8、PMV-14和PMV-18系列;另一類是接枝了苯胺、萘胺和2-氨基苯并咪唑的PMV-A、PMV-N和PMV-B系列。利用1HNMR表征了新型梳形聚合物的結(jié)構(gòu)和接枝率。在室溫及常壓下,運(yùn)用紫外-可見吸收光譜、濁度測量、激光動態(tài)光散射(DLS)和熒光顯微鏡分別探究了 MAC和PMV兩組梳形聚合物對瀝青質(zhì)的分散穩(wěn)定性(初始沉淀點(diǎn))和聚集行為的影響。結(jié)果顯示,MAC系列中以接枝萘環(huán)的NMAC對瀝青質(zhì)初始沉淀點(diǎn)的延遲效果最佳,使正庚烷體積分率增加22%;而PMV系列中以PMV-18的效果較佳,使正庚烷體積分率增加10%;顯微鏡觀察瀝青質(zhì)的聚集由原來絮狀沉淀并層層堆積的方式向更加分散的粘連態(tài)凝膠顆粒轉(zhuǎn)變。通過DLS測試溶液中析出瀝青質(zhì)的粒徑分布,發(fā)現(xiàn)幾種梳形聚合物添加劑均能使瀝青質(zhì)聚集體的平均粒徑降低為原來的一半且分布變窄,說明了幾種梳形聚合物對瀝青質(zhì)顆粒具有穩(wěn)定和分散效果。利用旋轉(zhuǎn)流變儀的高壓測試系統(tǒng),考察了溫度、靜壓力和高壓CO_2對脫氣(脫水、脫輕組分)稠油流變性質(zhì)的影響規(guī)律。溫度的升高可顯著降低脫氣稠油的零切復(fù)粘度,而靜壓力使稠油的粘度緩慢單調(diào)增加;高壓CO_2可以促使稠油的復(fù)粘度顯著降低,且在達(dá)到超臨界壓力前,其凝膠點(diǎn)對應(yīng)的模量不變,而只與剪切角頻率有關(guān);而在超臨界區(qū),壓力促使凝膠點(diǎn)的模量迅速降低,并使稠油向接近流體性質(zhì)的方向轉(zhuǎn)變。通過測試梳形聚合物與高壓CO_2的共同降粘效果,其降粘幅度大于單純的高壓C02的效果,使其在7MPa CO_2壓力下的復(fù)粘度比常壓下降低了兩個(gè)數(shù)量級,這為聚合物分散劑輔助CO_2驅(qū)的可行性提供了基礎(chǔ)試驗(yàn)研究。
[Abstract]:The dense ring aromatic structure of asphaltene and the complex assembly and aggregation mode make it easy to accumulate and deposit, which makes heavy oil show the characteristics of high viscosity and low fluidity, which makes heavy oil face great challenges in both exploitation and transportation. Adding chemical dispersant to crude oil system is an economical and feasible method to improve the aggregate state of asphaltene and increase the flowability of oil. In order to develop a dispersant for asphaltene aggregates in heavy oil, it is necessary to judge which kind of dispersant has a better effect on the stability and aggregation of asphaltene from the angle of the force between dispersant and asphaltene. Therefore, the effects of MAC and PMV on the dispersion and aggregation behavior of asphaltene in low concentration model oil were investigated firstly, and then the temperature was studied. The influence of pressure and high pressure CO_2 on rheological properties of degassing heavy oil, especially the effect of comb-like polymer and high pressure CO_2. In this paper, poly (maleic anhydride-vinyl acetate) (PMV) intermediates were synthesized by free radical polymerization. Two series of comb polymers were prepared by side chain amination modification: one is PMV-8,PMV-14 and PMV-18 series grafted with alkanes of different chain lengths; The other is the PMV-A,PMV-N and PMV-B series grafted with aniline, naphthylamine and 2-aminobenzimidazole. The structure and graft rate of the new comb polymer were characterized by 1HNMR. At room temperature and atmospheric pressure, using UV-Vis absorption spectrum, turbidity measurement, The effects of MAC and PMV on the dispersion stability (initial precipitation point) and aggregation behavior of asphaltene were investigated by laser dynamic light scattering (DLS) and fluorescence microscopy respectively. The results show that NMAC with grafted naphthalene ring has the best delay effect on the initial precipitation point of asphaltene, and the volume fraction of n-heptane is increased by 22%, while the effect of PMV-18 is better in the PMV series. The volume fraction of n-heptane was increased by 10 and the aggregation of asphaltene was observed by microscope. The particle size distribution of asphaltene precipitated in the solution was measured by DLS. It was found that several comb polymer additives could reduce the average particle size of asphaltene aggregates to half of the original size and narrow the distribution of asphaltene aggregates. The stability and dispersion effect of several comb polymers on asphaltene particles are explained. The effects of temperature, static pressure and high pressure CO_2 on the rheological properties of heavy oil were investigated by using the high pressure measuring system of rotary rheometer. The increase of temperature can significantly reduce the zero-shear complex viscosity of degassing heavy oil, while the static pressure can make the viscosity of heavy oil increase slowly and monotonously, and high pressure CO_2 can make the complex viscosity of heavy oil decrease significantly, and before reaching supercritical pressure, In the supercritical region, the modulus of the gel point decreases rapidly and the viscous oil changes to the direction close to the fluid property, but the corresponding modulus of the gel point is invariant, but only depends on the shear angular frequency of the gel point, while in the supercritical region, the pressure causes the modulus of the gel point to decrease rapidly. By testing the joint viscosity reduction effect of comb-shaped polymer and high-pressure CO_2, the viscosity reduction range of comb-shaped polymer is larger than that of pure high-pressure C02, and the complex viscosity of comb polymer under 7MPa CO_2 pressure is reduced by two orders of magnitude than that under normal pressure. This provides a basic experimental study for the feasibility of polymer dispersant assisted CO_2 flooding.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TE621
本文編號：2231772
[Abstract]:The dense ring aromatic structure of asphaltene and the complex assembly and aggregation mode make it easy to accumulate and deposit, which makes heavy oil show the characteristics of high viscosity and low fluidity, which makes heavy oil face great challenges in both exploitation and transportation. Adding chemical dispersant to crude oil system is an economical and feasible method to improve the aggregate state of asphaltene and increase the flowability of oil. In order to develop a dispersant for asphaltene aggregates in heavy oil, it is necessary to judge which kind of dispersant has a better effect on the stability and aggregation of asphaltene from the angle of the force between dispersant and asphaltene. Therefore, the effects of MAC and PMV on the dispersion and aggregation behavior of asphaltene in low concentration model oil were investigated firstly, and then the temperature was studied. The influence of pressure and high pressure CO_2 on rheological properties of degassing heavy oil, especially the effect of comb-like polymer and high pressure CO_2. In this paper, poly (maleic anhydride-vinyl acetate) (PMV) intermediates were synthesized by free radical polymerization. Two series of comb polymers were prepared by side chain amination modification: one is PMV-8,PMV-14 and PMV-18 series grafted with alkanes of different chain lengths; The other is the PMV-A,PMV-N and PMV-B series grafted with aniline, naphthylamine and 2-aminobenzimidazole. The structure and graft rate of the new comb polymer were characterized by 1HNMR. At room temperature and atmospheric pressure, using UV-Vis absorption spectrum, turbidity measurement, The effects of MAC and PMV on the dispersion stability (initial precipitation point) and aggregation behavior of asphaltene were investigated by laser dynamic light scattering (DLS) and fluorescence microscopy respectively. The results show that NMAC with grafted naphthalene ring has the best delay effect on the initial precipitation point of asphaltene, and the volume fraction of n-heptane is increased by 22%, while the effect of PMV-18 is better in the PMV series. The volume fraction of n-heptane was increased by 10 and the aggregation of asphaltene was observed by microscope. The particle size distribution of asphaltene precipitated in the solution was measured by DLS. It was found that several comb polymer additives could reduce the average particle size of asphaltene aggregates to half of the original size and narrow the distribution of asphaltene aggregates. The stability and dispersion effect of several comb polymers on asphaltene particles are explained. The effects of temperature, static pressure and high pressure CO_2 on the rheological properties of heavy oil were investigated by using the high pressure measuring system of rotary rheometer. The increase of temperature can significantly reduce the zero-shear complex viscosity of degassing heavy oil, while the static pressure can make the viscosity of heavy oil increase slowly and monotonously, and high pressure CO_2 can make the complex viscosity of heavy oil decrease significantly, and before reaching supercritical pressure, In the supercritical region, the modulus of the gel point decreases rapidly and the viscous oil changes to the direction close to the fluid property, but the corresponding modulus of the gel point is invariant, but only depends on the shear angular frequency of the gel point, while in the supercritical region, the pressure causes the modulus of the gel point to decrease rapidly. By testing the joint viscosity reduction effect of comb-shaped polymer and high-pressure CO_2, the viscosity reduction range of comb-shaped polymer is larger than that of pure high-pressure C02, and the complex viscosity of comb polymer under 7MPa CO_2 pressure is reduced by two orders of magnitude than that under normal pressure. This provides a basic experimental study for the feasibility of polymer dispersant assisted CO_2 flooding.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TE621
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