原油一步法催化裂解制低碳烯烃：实验和反应路径研究

doi:10.11949/0438-1157.20240947

摘要/Abstract

摘要：

首先通过中试实验获得大庆原油制低碳烯烃的反应规律及优选反应域；然后基于智慧炼化技术进行了分子动力学建模，模型包括原料组成、反应机理制定、反应网络生成、动力学及反应器型式。通过全局优化算法训练实验数据得到动力学参数，模型在馏分产率、气体产率、液体产品烃族组成等方面的计算值和实验值基本一致。利用模型剖析了优选实验条件下原油制低碳烯烃的分子转化路径，定量对比了理论上关键裂解主反应及副反应对低碳烯烃产率的影响，探索了消除副反应后理想情况下的产物分布情况。模型计算发现影响低碳烯烃生成的三个最关键裂解主反应路径为：烯烃中间裂解、烯烃裂解生成丙烯、丁烯及烷烃中间裂解反应；三种影响低碳烯烃产率的主要副反应为：氢转移、烯烃环化及烯烃叠合反应。利用模型对最优化实验点进行计算，模拟优化在消除所有副反应后，乙烯、丙烯及丁烯产率分别提升3.91、10.88及10.51个百分点，总低碳烯烃产率相对提高约45.5%（质量分数）。

关键词: 智慧炼化, 石蜡基原油, 催化裂解, 动力学模型, 模拟, 化学反应

Abstract:

Firstly, the preferred reaction domains and reaction pattern of light olefins from Daqing crude oil were obtained through experiment evaluation. Then a molecular-level kinetic modeling has been established based on intelligent refining technology, which includes feedstock composition, reaction mechanism formulation and reaction network generation, kinetics and reactor type. The kinetic parameters were obtained by training the experimental data with a global optimization algorithm, and the model calculated values of the fraction yield, gas yield, and hydrocarbon composition of the liquid products are in agreement with the experimental data. The model was used to analyze the molecular transformation pathway of crude oil to light olefins under the optimal experimental conditions, and the effects of the theoretical key cracking main reaction and side reaction on the light olefin yield were quantitatively compared. The product distribution under ideal conditions after eliminating the side reaction was explored. Model calculations revealed that the three most critical cracking primary reaction paths affecting light olefins are: olefin middle cracking, olefin cracking to propylene or butene, and paraffin middle cracking, the three main side reactions affecting light olefins are: hydrogen transfer, olefin cyclization and olefin polymerization. Using the model to calculate the optimal experimental point, simulation optimization after elimination of all side reactions, the ethylene, propylene and butene yields were increased by 3.91, 10.88 and 10.51 percentage points, respectively, the total light olefin yield can be relatively increased by about 45.5% (mass fraction).

Key words: intelligent refining, paraffin ease crude oil, catalytic cracking, kinetic modeling, simulation, chemical reaction

中图分类号:

TE 624.4

党法璐, 孙志国, 高照, 王刚, 陈政宇, 张霖宙, 连竞存, 刘美佳, 张忠东, 刘超伟. 原油一步法催化裂解制低碳烯烃：实验和反应路径研究[J]. 化工学报, 2025, 76(2): 667-685.

Falu DANG, Zhiguo SUN, Zhao GAO, Gang WANG, Zhengyu CHEN, Linzhou ZHANG, Jingcun LIAN, Meijia LIU, Zhongdong ZHANG, Chaowei LIU. One-step catalytic cracking of crude oil to light olefins: experimental and reaction pathway studies[J]. CIESC Journal, 2025, 76(2): 667-685.

图/表 21

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参数	数值	参数	数值
密度（20℃）/(kg/m³)	862.8	蒸馏数据
黏度（50℃）/(mm²/s)	27.2	初馏点	73.6℃
残炭/%（质量分数）	3.07	10%（质量分数）	209.2℃
蜡含量/%（质量分数）	30.2	30%（质量分数）	383.8℃
胶质含量/%（质量分数）	6.6	50%（质量分数）	448.2℃
沥青质含量/%（质量分数）	0.08	70%（质量分数）	602.2℃
镍/(mg/kg)	3.28	90%（质量分数）	707.2℃
铁/(mg/kg)	4.13	95%（质量分数）	741.2℃
钒/(mg/kg)	0.57	馏分切割
C/%（质量分数）	86.11	石脑油（C₅~200℃）	9.56%（质量分数）
H/%（质量分数）	13.55	柴油（200~350℃）	19.58%（质量分数）
S/%（质量分数）	0.12	减压馏分油（350~500℃）	26.56%（质量分数）
N/%（质量分数）	0.11	减压渣油（>500℃）	44.30%（质量分数）

参数	数值	参数	数值
密度（20℃）/(kg/m³)	862.8	蒸馏数据
黏度（50℃）/(mm²/s)	27.2	初馏点	73.6℃
残炭/%（质量分数）	3.07	10%（质量分数）	209.2℃
蜡含量/%（质量分数）	30.2	30%（质量分数）	383.8℃
胶质含量/%（质量分数）	6.6	50%（质量分数）	448.2℃
沥青质含量/%（质量分数）	0.08	70%（质量分数）	602.2℃
镍/(mg/kg)	3.28	90%（质量分数）	707.2℃
铁/(mg/kg)	4.13	95%（质量分数）	741.2℃
钒/(mg/kg)	0.57	馏分切割
C/%（质量分数）	86.11	石脑油（C₅~200℃）	9.56%（质量分数）
H/%（质量分数）	13.55	柴油（200~350℃）	19.58%（质量分数）
S/%（质量分数）	0.12	减压馏分油（350~500℃）	26.56%（质量分数）
N/%（质量分数）	0.11	减压渣油（>500℃）	44.30%（质量分数）

参数	数值	参数	数值
孔体积/(cm³/g)	0.17	粒度分布
比表面积/(m²/g)	210	20~40 μm	5.64%（质量分数）
微反活性	57	40~80 μm	19.90%（质量分数）
堆积密度/(g/cm³)	0.79	80~110 μm	48.01%（质量分数）
平均孔径/nm	6.82	>110 μm	17.58%（质量分数）

参数	数值	参数	数值
孔体积/(cm³/g)	0.17	粒度分布
比表面积/(m²/g)	210	20~40 μm	5.64%（质量分数）
微反活性	57	40~80 μm	19.90%（质量分数）
堆积密度/(g/cm³)	0.79	80~110 μm	48.01%（质量分数）
平均孔径/nm	6.82	>110 μm	17.58%（质量分数）

编号	提升管出口温度/℃	反应时间/s	剂油比
1	600	2.48	15.70
2	600	3.80	21.60
3	600	2.52	18.20
4	600	2.55	17.35
5	600	3.72	17.81
6	600	1.70	24.10
7	600	3.70	28.00
8	605	3.75	30.80
9	610	3.78	32.60
10	620	2.55	19.60
11	620	3.80	29.00
12	620	3.80	33.50
13	620	3.80	30.00
14	620	3.80	32.16
15	620	3.60	35.80
16	620	3.30	36.00
17	620	3.00	35.70
18	620	2.85	35.20
19	620	1.70	35.90
20	650	2.30	18.20
21	650	4.00	36.00
22	650	3.50	42.20