金属镍盐对牛圈湖原油水热裂解催化反应影响因素研究

Influence Factors of Nickel Salts as Catalysts on Aquathermolysis reaction of Niujuanhu Oil

李芳芳 杨胜来 王 欣 廖长霖 殷丹丹 陈 浩

LI Fang-Fang YANG Sheng-Lai WANG Xin LIAO Chang-Lin YIN Dan-Dan CHEN Hao

在高温高压反应釜中，以甲酸为供氢体、以金属镍盐催化剂组成催化体系，研究了牛圈湖原油水热裂解反应的影响因素，考察了不同催化剂体系、原油性质及反应温度对水热裂解反应后原油降黏率和原油SARA组成的影响。结果表明，油酸镍、环烷酸镍、硫酸镍催化体系对地面脱气原油的降黏率分别为65.3%、52.6%和55.7%，优选油酸镍催化体系为水热裂解反应的催化剂。水热裂解催化反应后，胶质和沥青质减少，饱和烃和芳香烃增加。原油中的重质组分越多，水热裂解反应越剧烈，原油的降黏效果越明显。水热裂解催化反应后，渣油、地面脱气原油、模拟地层油在45℃下的降黏率分别为90.41%、64.78%和55.78%。原油中胶质和沥青质含量是影响水热裂解反应的主要因素，渣油、地面脱气原油、模拟地层油中胶质、沥青质转化为饱和烃和芳香烃的转化率分别为36.50%、26.51%和16.73%。280℃、220℃、180℃、100℃反应温度下模拟地层油的降黏率分别为56.43%、55.78%、48.23%和14.14%，最佳反应温度为220℃。水热裂解反应后原油中胶质、沥青质断裂成小分子的饱和烃是原油永久性降黏的主要原因。

In high-temperature and high-pressure (HTHP) reaction kettle, with formic acid as hydrogen donor and nickel salt as catalytic system, the influence factors on aquathermolysis reaction of Niujuanhu oil were studied by considering the effects of different catalyst systems, crude oil properties and reaction temperature on oil viscosity reduction ratio and SARA changes. The results showed that viscosity reduction rate of nickel oleate, nickel naphthenate and nickel sulfate catalytic systems to stock tank oil was 65.3%, 52.6% and 55.7%. Nickel oleate was selected as optimum catalytic system. After aquathermolysis catalytic reaction, the content of colloid and asphaltene decreased, and that of saturated hydrocarbons and aromatic hydrocarbons increased. The more content of heavy hydrocarbon in oil, the stronger aquathermolysis reaction, and the more favorable viscosity reduction of oil was. After aquathermolysis catalytic reaction, the viscosity reduction rate of residuum, stock tank oil and simulated formation oil was 90.41%, 64.78% and 55.78% at 45℃. The content of colloid and asphaltene in crude oil was the basic root of aquathermolysis reaction. The conversion ratio of colloid and asphaltene converting into saturated hydrocarbon and aromatic hydrocarbon in residuum, stock tank oil and simulated formation oil was 36.50%, 26.51% and 16.73%. The viscosity reduction rate of simulated formation oil was 56.43%, 55.78%, 48.23% and 14.14% at 280℃, 220℃, 180℃ and 100℃ reaction temperature. The optimum reaction temperature was 220℃. The macromolecule bond rupture of colloid and asphaltene into small molecule saturated hydrocarbons was the main reason of permanence viscosity reduction of crude oil during aquathermolysis reaction.