稠油催化降解及其沥青质化学性质的研究
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摘要
稠油资源是常规原油耗尽后的替代品。但稠油粘度大，难以直接开发利用，稠油井下水热催化降粘是解决此难题很有发展前景的技术之一。
论文以辽河稠油为研究对象，在高压反应釜中模拟注汽热采时井下改质条件，考察水热裂解的可行性，寻求稠油改质过程适宜的改质条件。通过检测反应前后样品的SARA组成，平均分子量、粘度和沥青质、胶质含量的变化来衡量稠油改质效果。并对稠油中沥青质的性质进行了研究。通过实验，主要结论如下：
(1)无催化剂存在条件下，在反应温度为240℃、反应24h、水油质量比0．5时，50℃粘度由原来的147．30Pa·s，降到130．40Pa·s。
(2)过渡金属离子催化降粘以及降低胶质、沥青质含量的顺序为：Fe~(2+)>Ni~(2+)>Co~(2+)>Ti~(4+)>Cr~(3+)>Mn~(2+)>Cu~(2+)>Zn~(2+)。且在260℃、反应24h条件下，Fe~(2+)最佳用量为0．20％。
(3)由沥青质和胶质XRD数据计算出辽河稠油分离产物中的沥青质芳香层间距(dm)、脂链之间间距(dr)、芳香片的直径(La)、晶胞高度(Lc)、芳香片堆积层数(Me)为别为2．32、2．91、27．9、13．6、6．9nm。
(4)测定以苯和甲苯为溶剂时沥青质平均分子量分别为3 167和2404。表明沥青质是由单元片层缔合成的的缔合体，溶剂的极性可使沥青质的缔合程度降低。
(5)溶液法通过计算得到辽河油田正戊烷沥青质的偶极矩μ=7．91。
(6)粘度法和表面张力法分别测定沥青质的沉淀起始点为41％和32％。
Heavy oil is the substitute of conventional crude oil when it is depleted. But the heavy oil is difficult to be exploited and utilizated because of it's high viscosity. Down hole catalytic aquathermolysis reaction to decreasing its viscosity is a potential technology to resolve this puzzle.
Liaohe heavy oil was used to study the feasibility of aquathermolusis reaction and seeking for suitable conditions during the process of the heavy oil upgrading in high-pressure batch reactor by imitating upgrading conditions at down well during steam injection. Upgrading effect was evaluated by comparing the composition changes before and after the reaction, average molecular weight, viscosity and the content of asphaltenes and resins. At the same time, properties of the asphaltenes were studied. The major conclutions are as following:
(1) After quathermolysis reaction at 240℃for 24 hours while water to oil ratio is 0.5, viscosity of the heavy oil at 50℃decreased from 147.30 Pa·s to 130.40 Pa·s.
(2) The sequence of transitional metal ions catalytic ability of aquathermolusis reaction and its decreasing of asphaltenes and resins are as following : Fe~(2+)>Ni~(2+)>Co~(2+)>Ti~(4+)>Cr~(3+)>Mn~(2+)>Cu~(2+)>Zn~(2+). Aquathermolusis reaction at 260℃for 24 hours, the optimal concentrations of Fe~(2+) is 0.20%.
(3) Calculating from the XRD results of asphaltenes, its dm, dr, La, Lc and Me are 2.3、2.9、27.9、3.6、6.9nm respectively.
(4) The average mocular weights of asphaltene in toluene and in benzene are 3167 and 2404. It shows that asphaltene is associated in toluene and the palarity of the solvent could reduce the degree of association.
(5) Dipole moments of the asphaltenes is 7.91tested by solvent method.
(6) Precipitation point of the asphaltenes are 41% and 32% respectively when tested by viscosity method and surface tension method.
论文以辽河稠油为研究对象，在高压反应釜中模拟注汽热采时井下改质条件，考察水热裂解的可行性，寻求稠油改质过程适宜的改质条件。通过检测反应前后样品的SARA组成，平均分子量、粘度和沥青质、胶质含量的变化来衡量稠油改质效果。并对稠油中沥青质的性质进行了研究。通过实验，主要结论如下：
(1)无催化剂存在条件下，在反应温度为240℃、反应24h、水油质量比0．5时，50℃粘度由原来的147．30Pa·s，降到130．40Pa·s。
(2)过渡金属离子催化降粘以及降低胶质、沥青质含量的顺序为：Fe~(2+)>Ni~(2+)>Co~(2+)>Ti~(4+)>Cr~(3+)>Mn~(2+)>Cu~(2+)>Zn~(2+)。且在260℃、反应24h条件下，Fe~(2+)最佳用量为0．20％。
(3)由沥青质和胶质XRD数据计算出辽河稠油分离产物中的沥青质芳香层间距(dm)、脂链之间间距(dr)、芳香片的直径(La)、晶胞高度(Lc)、芳香片堆积层数(Me)为别为2．32、2．91、27．9、13．6、6．9nm。
(4)测定以苯和甲苯为溶剂时沥青质平均分子量分别为3 167和2404。表明沥青质是由单元片层缔合成的的缔合体，溶剂的极性可使沥青质的缔合程度降低。
(5)溶液法通过计算得到辽河油田正戊烷沥青质的偶极矩μ=7．91。
(6)粘度法和表面张力法分别测定沥青质的沉淀起始点为41％和32％。
Heavy oil is the substitute of conventional crude oil when it is depleted. But the heavy oil is difficult to be exploited and utilizated because of it's high viscosity. Down hole catalytic aquathermolysis reaction to decreasing its viscosity is a potential technology to resolve this puzzle.
Liaohe heavy oil was used to study the feasibility of aquathermolusis reaction and seeking for suitable conditions during the process of the heavy oil upgrading in high-pressure batch reactor by imitating upgrading conditions at down well during steam injection. Upgrading effect was evaluated by comparing the composition changes before and after the reaction, average molecular weight, viscosity and the content of asphaltenes and resins. At the same time, properties of the asphaltenes were studied. The major conclutions are as following:
(1) After quathermolysis reaction at 240℃for 24 hours while water to oil ratio is 0.5, viscosity of the heavy oil at 50℃decreased from 147.30 Pa·s to 130.40 Pa·s.
(2) The sequence of transitional metal ions catalytic ability of aquathermolusis reaction and its decreasing of asphaltenes and resins are as following : Fe~(2+)>Ni~(2+)>Co~(2+)>Ti~(4+)>Cr~(3+)>Mn~(2+)>Cu~(2+)>Zn~(2+). Aquathermolusis reaction at 260℃for 24 hours, the optimal concentrations of Fe~(2+) is 0.20%.
(3) Calculating from the XRD results of asphaltenes, its dm, dr, La, Lc and Me are 2.3、2.9、27.9、3.6、6.9nm respectively.
(4) The average mocular weights of asphaltene in toluene and in benzene are 3167 and 2404. It shows that asphaltene is associated in toluene and the palarity of the solvent could reduce the degree of association.
(5) Dipole moments of the asphaltenes is 7.91tested by solvent method.
(6) Precipitation point of the asphaltenes are 41% and 32% respectively when tested by viscosity method and surface tension method.
引文
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