考虑转化率的亚硝酸钠与氯化铵体系反应动力学  

Reaction kinetics of sodium nitrite and ammonium chloride system considering conversion rate

作　　者：战永平 罗明良[1,2] 付春丽 刘纪康[2] ZHAN Yongping;LUO Mingliang;FU Chunli;LIU Jikang(Key Laboratory of Unconventional Oil&Gas Development(China University of Petroleum(East China)),Ministry of Education,Qingdao 266580,China;School of Petroleum Engineering in China University of Petroleum(East China),Qingdao 266580,China;CNPC Offshore Engineering Company Limited,Qingdao 266520,China)

机构地区：[1]非常规油气开发教育部重点实验室(中国石油大学(华东)),山东青岛266580 [2]中国石油大学(华东)石油工程学院,山东青岛266580 [3]中国石油集团海洋工程有限公司,山东青岛266520

出　　处：《中国石油大学学报（自然科学版）》2023年第3期173-180,共8页Journal of China University of Petroleum(Edition of Natural Science)

基　　金：国家自然科学基金面上项目(51874334,51974346);山东省自然科学基金项目(ZR2018MEE010)。

摘　　要：针对现有未考虑反应物转化率的NaNO_(2)/NH_(4)Cl反应动力学方程难以有效预测生热/生氮气情况的问题,运用实验测试分析方法探究氮气生成反应的H^(+)浓度界限、反应转化率及其变化规律;采用灰色关联分析法研究各因素的影响程度;利用牛顿-拉斐逊迭代方法计算引入反应转化率的反应动力学参数,探讨生热/生氮气反应的预测方法。结果表明:NaNO_(2)/NH_(4)Cl体系氮气生成反应的H^(+)浓度界限为c_(H^(+))≤0.0225 mol/L(或pH≥1.65),且氮气生成反应转化率随着反应物和H^(+)浓度的增大,温度的升高而增大,其关联性最高的反应物浓度的关联度为0.8;考虑反应转化率的NaNO_(2)/NH_(4)Cl体系反应动力学方程为dηd t=4.74×10^(4)e^(-3389/T)c^(1.545)_(H^(+))c^(1.346)c_(0)(1-η)2.346或(1-η)^(-1.346)-1/1.346=4.74×10^(4)e^(-3389/T)c^(1.545)_(H^(+))c^(1.346)0_t,η<1,可有效、便捷地进行生热/生氮气反应预测。It is difficult to predict the heat/nitrogen generation of NaNO_(2)/NH_(4)Cl system because the reactant conversion rate is not considered in traditional reaction kinetic equation.The H^(+)concentration range,reaction conversion rate and its changeable rule for nitrogen generation reaction were investigated by experimental analysis method.The influence degree of each factor was studied by grey correlation analysis.The parameters of reaction kinetic equation introduced by reactant conversion were calculated by the Newton-Raphson method,through which the prediction method of the heat/nitrogen generation reaction were discussed.It is found that the H^(+)concentration range for nitrogen production of NaNO_(2)/NH_(4)Cl system is c_(H^(+))≤0.0225 mol/L(or pH≥1.65).And the reactant conversion rate increases with increasing of reactant,H^(+)concentration and temperature.The correlation between reactant conversion and reactant concentration is the strongest and reaches 0.8.The reaction kinetic equation with reactant conversion is dη/dt=4.74×10^(4)e^(-3389/T)c^(1.545)_(H^(+))c^(1.346)_(0)(1-η)^(2.346),or(1-η)-1.346-1/1.346=4.74×10^(4)e^(-3389/T)c^(1.545)_(H^(+))c^(1.346)_(0)t,η<1,which is effective and convenient to predict the heat/gas generation reaction status.

关 键 词：NaNO_(2)/NH4Cl体系 H+浓度界限 转化率 反应动力学方程 

分 类 号：TE39[石油与天然气工程—油气田开发工程]