集总热转化模型通用动力学实验结果.doc

12集总热转化模型通用动力学实验结果 第62页2.3 12集总反应模型对不同产地混合原料适应性考察1. 前 言为预测焦化炉管内不同截面介质产品分布,石油大学管式加热炉科研组开发了重油12集总热转化反应模型。通过静态实验得到了单一产地油样与模型常数的对应关系。为了使12集总反应模型常数适用于不同产地的原料，解决实验测定重油热裂解产物分布模型常数所需要的时间太长，过程模拟软件初始化后确定出油品在炉管出口热转化率后，现场装置原料性质又发生了变化的弊病，及时对在役焦化炉注汽及出口温度进行优化设计，本文拟开发出适合不同产地焦化原料的模型常数。2. 关联结果及分析通过特制的实验仪器，将重油从350左右快速加热到设定温度（400500），用计算机记录整个反应历程，并尽量将反应控制在温度期望值附近；用气相色谱分析裂解气组成；用模拟蒸馏得到馏出油和残渣油的馏程分布；定义总热转化率为原料油中小于510的馏份收率减去裂解油中小于510的馏份收率；用甲苯不溶物的产率表征缩合反应深度。通过不同反应温度与反应时间下实验结果，由与实验仪器相配套的软件得到模型常数，用数理统计分析理论对模型常数的线性相关性进行分析。科研组首先利用胜利、辽河、华北减压渣油对12集总反应模型的可靠性进行了考察，之后又分别对管输减渣、齐鲁减渣、沧州循环油、济南减渣、沙特轻油减渣剂循环油、大庆减渣等不同产地的原料进行了单独实验关联和线性分析。原始试验数据，参见附件。混合前各单油12集总模型回归结果见表-111，混合油12集总模型回归结果统计见表-1214。由表中数据可以看出： 单独油适应性由相关系数r检验及检验结果可以看出，单油总裂解和缩合反应都具有十分明显的线性关系（置信度99%）；裂解气、汽油及柴油馏分都具有十分明显的线性关系；除一种油的蜡油馏分只有比较显著的线性关系外，其它油的都具有十分明显的线性关系。模型用于预测窄馏分分布的规律是：10种单油热转化得到的各窄馏分产物中，辽河油的窄馏分产物窄组分18都具有十分明显的线性关系，而窄组分912只有比较显著的线性关系；胜利油的窄馏分产物窄组分13具有十分明显的线性关系，窄组分412没有明显的线性关系；华北油窄馏分产物窄组分16具有十分显著的线性关系，而窄组分712没有明显的线性关系；其它油都具有十分明显的线性关系。说明模型用于单油关联具有较好的适应性。 混合油的适应性将管输油、齐鲁油、沧州油、荆门油、济南油、沙特轻油等七种油混合后得到的总裂解、缩合、柴油、蜡油、瓦斯气及各窄组分模型常数都具有十分明显的线性关系， 7种油混合后结果变好的原因可能是实验点数增加后，人为实验误差所造成的影响反而有所降低。将管输油、齐鲁油、沧州油、荆门油、济南油、沙特轻油、胜利、华北、辽河等10种油混合后得到的总裂解、缩合、柴油、蜡油、瓦斯气及各窄组分模型常数同样具有十分明显的线性关系。 将大庆、胜利、辽河、华北、管输油、沙特轻油、济南油、齐鲁油、荆门油、沧州油等11种油混合后得到的总裂解、缩合、柴油、蜡油、瓦斯气及各窄组分模型常数同样具有十分明显的线性关系。3. 结 论由相关系数和f检验数值可以看出，12集总模型常数适用所用混合油的热转化反应过程，可以用来预测以上述油品为原料的焦化炉管内不同截面产品的分布。由单一油样的实验结果可知，必须增加实验点数及考虑重馏分二次反应以减少人为和模型误差。表-1 大庆渣油热化反应模型常数及相关系数检验项目活化能与气体常数之比/e/r指前因子/s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解27612.352.9072e+130.970.470.59239.598.60缩合46719.074.5330e+230.870.470.5950.898.60瓦斯气16492.821.1539e+050.830.470.5936.498.60汽油89477.775.9091e+490.600.470.598.898.60柴油25467.852.1015e+110.930.470.5997.298.60蜡油21598.222.5440e+090.920.470.5985.828.6021089477.775.9091e+490.600.470.598.898.6024080799.262.0834e+440.650.470.5911.538.6027066405.315.1889e+350.630.470.5910.718.6030020204.915.1347e+070.880.470.5953.458.6033034279.061.7427e+160.920.470.5986.798.6036032444.381.3626e+150.900.470.5966.948.6039023109.873.2474e+090.910.470.5981.558.6042021621.004.0348e+080.910.470.5980.628.6045018816.667.7089e+060.880.470.5953.038.6048015316.825.5458e+040.810.470.5929.678.6051017654.238.0665e+050.620.470.599.988.60 表-2胜利减渣热化反应模型常数项 目活化能与气体常数之比/e/r指前因子,s-1相关系数值备 注裂 解28486.253.36627e+13-0.93959.60有效实验点数为，置信度为时，=8.1，相关系数为.537；缩 合43770.812.93633e+21-0.94465.37气 体28314.862.95065e+12-0.94162.1929397.294.68597e+13-0.975156.6929159.881.1955e+13-0.95786.707 34045.541.19398e+16-0.962100.6029328.111.63362e+13-0.95277.6926039.751.75275e+11-0.95786.6825424.2856393345439-0.977164.8830008.863.01263e+13-0.95379.4929455.262.93705e+12-0.80414.6029455.262.93705e+12-0.80414.6029455.262.93705e+12-0.80414.6029455.262.93705e+12-0.80414.60表3辽河减渣热化反应模型常数项 目活化能与气体常数之比/e/r指前因子,s-1相关系数值备 注裂 解25825.802.02565e+12-0.979234.8有效实验点数为12，置信度为时，=10.04，相关系数为.708；缩 合208273.64.7402e+124-0.77515.0气 体26161.991.90793e+11-0.969154.928186.259.56999e+12-0.982275.829449.882.65587e+13-0.982271.27 28017.554.08419e+12-0.985323.028861.431.59753e+13-0.976201.928638.071.31622e+13-0.9961189.327330.301.91251e+12-0.9983130.425378.4499775237372-0.987367.324156.2715908603515-0.974182.020923.93133635382.2-0.95297.115020.7711962.77993-0.80017.814818.698828.849176-0.75313.1 表4华北减渣热化反应模型常数项 目活化能与气体常数之比/e/r指前因子,s-1相关系数值备 注裂 解32963.1075.42047e+16-0.961240.62有效实验点数为10，置信度为时，=11.26，相关系数为.765；缩 合65422.4855.43261e+34-0.59911.22气 体32054.0191.05173e+15-0.985654.0333968.0024.99953e+16-0.988809.9533451.6737.96691e+15-0.986673.617 33770.6801.39167e+16-0.987728.6834473.3174.73957e+16-0.9911061.2033100.6029.35176e+15-0.985633.9935726.6912.85134e+17-0.990940.9334460.6894.05549e+16-0.989861.1833395.8975.70992e+15-0.967289.8430751.5829.15415e+13-0.898165.1528629.7613.80342e+12-0.873187.1134724.2063.62679e+16-0.820400.07表-5 管输渣油模型常数及相关系数检验项 目活化能与气体常数之比/e/r指前因子/s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解25804.202.7617e+120.990.450.57725.608.45缩合54066.383.1114e+270.730.450.5718.948.45瓦斯气22824.221.3404e+090.950.450.57143.568.45汽油24859.101.0643e+110.940.450.57137.548.45柴油25487.682.7406e+110.960.450.57194.168.45蜡油23240.512.9175e+100.920.450.5789.468.4521024859.101.0643e+110.950.450.57143.568.4524027091.887.7482e+110.890.450.5763.508.4527026046.191.9920e+110.940.450.57132.058.4530024508.952.5115e+100.950.450.57144.208.4533026496.094.3082e+110.940.450.57140.508.4536024852.284.4526e+100.960.450.57210.458.4539023918.301.2751e+100.960.450.57202.738.4542022704.012.4268e+090.960.450.57182.468.4545023033.733.2316e+090.950.450.57166.768.4548021030.021.6098e+080.940.450.57133.408.4551018159.331.4451e+060.910.450.5779.158.45表-6 齐鲁减渣模型常数项目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解24550.544.8551e+110.990.430.55639.618.20缩合24047.512.5301e+090.730.430.5521.378.20瓦斯气23756.916.0702e+090.950.430.55175.788.20汽油64417.981.3876e+350.610.430.5511.568.20柴油21551.031.3573e+090.970.430.55352.918.20蜡油22704.681.3823e+100.970.430.55258.138.2021064417.981.3876e+350.610.430.5511.568.2024021171.062.4187e+080.960.430.55243.178.2027021696.305.5779e+080.970.430.55306.478.2030022071.501.0120e+090.970.430.55350.008.2033023028.643.6875e+090.980.430.55366.398.2036022560.182.0233e+090.970.430.55349.138.2039022843.563.4899e+090.970.430.55303.988.2042023143.464.9608e+090.970.430.55303.888.2045022747.001.7003e+090.750.430.5525.148.2048021481.351.3535e+080.730.430.5521.468.2051021744.269.2513e+070.760.430.5526.778.20表-7 沧州循环油模型常数项目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解24209.421.8410e+110.980.600.74203.139.21缩合59049.472.2827e+310.800.600.7415.979.21瓦斯气22726.668.9438e+080.750.600.7411.259.21汽油19871.405.9123e+070.750.600.7411.559.21柴油24912.041.0880e+110.970.600.74130.209.21蜡油21748.142.2428e+090.940.600.7472.769.2121019871.405.9123e+070.750.600.7411.559.2124025249.865.4039e+100.920.600.7452.829.2127026376.812.5746e+110.940.600.7465.789.2130024233.211.6285e+100.960.600.74121.609.2133025524.751.1882e+110.950.600.7487.519.2136024517.892.5752e+100.940.600.7473.359.2139025913.331.9269e+110.950.600.7488.559.2142017664.727.6227e+050.640.600.746.289.2145015160.331.3118e+040.700.600.748.589.214802095.194.8709e-050.100.600.740.099.21510453.144.1863e-060.030.600.740.019.21表-8 荆门减渣模型常数及相关检验项目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解29362.513.1843e+140.980.450.57334.298.45缩合35945.963.0664e+160.920.450.5787.828.45瓦斯气24819.112.2701e+100.950.450.57151.888.45汽油32427.572.9043e+150.890.450.5765.758.45柴油31579.751.2904e+150.960.450.57212.048.45蜡油32205.147.6478e+150.940.450.57121.908.4521032427.572.9043e+150.890.450.5765.758.4524035700.031.1278e+170.950.450.57166.218.4527032138.711.0055e+150.950.450.57151.208.4530031981.378.3489e+140.950.450.57144.198.4533032795.032.3434e+150.950.450.57171.798.4536033263.065.2350e+150.950.450.57168.298.4539032387.281.7136e+150.940.450.57139.228.4542032754.283.3165e+150.940.450.57127.478.4545031468.284.4742e+140.930.450.57114.638.4548031656.503.4212e+140.910.450.5784.328.4551023927.882.4433e+090.780.450.5727.268.45表-9 济南减渣模型常数及相关检验项 目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解27274.411.9079e+130.990.440.56713.758.32缩合51975.636.8035e+260.840.440.56438.32瓦斯气22091.226.0925e+080.950.440.56164.208.32汽油31848.432.1944e+150.960.440.56211.138.32柴油29866.461.4505e+140.970.440.56286.878.32蜡油21943.213.5851e+090.940.440.56141.878.3221031848.432.1944e+150.960.440.56211.138.3224028972.801.3885e+130.960.440.56219.328.3227028528.036.6145e+120.960.440.56219.338.3230032342.581.6705e+150.970.440.56243.838.3233027575.382.0595e+120.960.440.56238.488.3236025407.709.2868e+100.960.440.56211.138.3239022854.282.1561e+090.820.440.5636.328.3242024161.121.3699e+100.810.440.5634.088.3245019539.491.4595e+070.720.440.5619.648.3248010596.5118.230.510.440.566.398.325109597.032.530.600.440.569.878.32 表-10 沙轻油循环油模型常数项 目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解304763.43e+150.980.450.57457.898.45缩合286452.90e+120.860.450.5748.718.45瓦斯气198312.50e+070.960.450.57213.668.45汽油304143.38e+140.960.450.57220.258.45柴油296111.19e+140.970.450.57246.88.45蜡油285731.11e+140.90.450.5773.248.45210304143.38e+140.960.450.57213.668.45240307771.79e+140.960.450.57207.718.45270328553.55e+150.940.450.57136.138.45300276092.76e+120.960.450.57229.548.45330296865.57e+130.970.450.57245.888.45360296755.83e+130.970.450.57257.698.45390301521.25e+140.970.450.57267.398.45420302741.62e+140.970.450.57270.378.45450299841.19e+140.970.450.57261.438.45480276635.27e+120.960.450.57191.748.455102616567.53e+110.950.450.57142.828.45表-11 沙轻油减渣模型常数项 目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解30877.096.19e+150.990.530.66610.629.30缩合46807.762.92e+23-0.810.530.6622.839.30汽油26181.672.86e+11-1.000.530.661687.669.30柴油29891.222.00e+14-1.000.530.661744.279.30蜡油28789.295.00e+13-1.000.530.664546.959.30瓦斯气30005.157.89e+14-0.980.530.66227.049.3021029891.222.00e+14-1.000.530.661687.669.3024027972.404.86e+12-1.000.530.663936.919.3027029440.244.04e+13-0.990.530.66874.279.3030028994.212.44e+13-0.990.530.66840.509.3033030002.171.14e+14-1.000.530.663640.809.3036031067.035.16e+14-1.000.530.663457.369.3039031348.507.58e+14-1.000.530.665531.759.3042030562.342.90e+14-1.000.530.665966.669.3045030901.634.70e+14-1.000.530.661841.229.3048030718.613.08e+14-1.000.530.661179.139.3051024954.744.95e+10-0.910.530.6657.859.30表-12 7种原料混合后关联结果项 目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解27274.622.2936e+130.960.170.241575.656.85缩合40520.513.3930e+190.770.170.24188.456.85瓦斯气23207.022.6875e+090.910.170.24635.596.85汽油r36803.682.1302e+180.660.170.2499.436.85柴油25495.143.0479e+110.950.170.241290.716.85蜡油25307.555.9752e+110.960.170.241548.086.8521036803.682.1302e+180.660.170.2499.436.8524025242.396.2683e+100.930.170.24785.636.8527025427.519.0564e+100.950.170.241123.776.8530026447.004.3217e+110.950.170.241198.026.8533026709.696.6136e+110.950.170.241285.896.8536025718.321.7032e+110.970.170.241707.696.8539025678.711.6950e+110.950.170.241054.286.8542025718.141.8585e+110.940.170.24912.696.8545025964.382.1890e+110.880.170.24433.166.8548024191.981.1869e+100.790.170.24209.916.8551022353.844.3639e+080.760.170.24172.686.85表-13 10种原料混合后关联结果项 目活化能与气体常数之比e/r指前因子s-1相关系数rf检验实验值r95%r99%r实验f值99%f总裂解28957.472.2849e+140.930.160.221015.146.81缩合40802.315.1517e+190.780.160.22227.866.81瓦斯气24247.971.1237e+100.670.160.22123.346.81汽油r35877.965.6764e+170.950.160.221483.346.81柴油27239.253.4106e+120.940.160.221113.776.81蜡油27746.521.6428e+130.910.160.22716.246.8121035877.965.6764e+170.670.160.22123.346.8124026925.336.5009e+110.930.160.22895.266.8127027408.781.4250e+120.950.160.2