Application advances of molecular level reaction kinetic modeling for catalytic cracking/pyrolysis process

doi:10.16085/j.issn.1000-6613.2020-1988

Abstract

Abstract:

The requirements and control of catalytic cracking/pyrolysis products are gradually refined to the molecular level due to increasingly stringent environmental regulations and continuous upgrading of refined oil standard quality. A reliable molecular-scale reaction kinetics model is the key to achieve molecular management of the catalytic cracking/pyrolysis process. This article briefly describes the catalytic cracking/pyrolysis reaction mechanism and reaction types. The research progress in the construction of the reaction network and molecular-scale reaction kinetics model of catalytic cracking/pyrolysis process by different methods in the past 30 years were reviewed. This study focused on the detailed comparative analysis of the advantages and disadvantages of different model building technologies. It also pointed out the research direction of the construction of the catalytic cracking/pyrolysis reaction molecular level kinetic model, including the development of more refined petroleum molecular analysis and characterization technology, building a molecular level reaction kinetic model combined with catalyst deactivation and reactor model, and the realization of the design and process engineering scale-up of catalytic cracking/pyrolysis reactor based on molecular management. In addition, the establishment of an integrated platform for molecular set construction, reaction network construction, and kinetic parameter solving is an inevitable trend in the development of molecular-level reaction kinetic.

Key words: catalytic cracking, catalytic pyrolysis, reaction, kinetic modeling

摘要：

随着环保法规的日益严格和成品油质量标准的持续升级，对催化裂化/裂解过程的产品要求和控制逐渐精细到分子级别，可靠的分子尺度反应动力学模型是实现催化裂化/裂解过程分子管理的关键所在。本文简述了催化裂化/裂解的反应机理和反应类型，回顾了近三十年来不同方法对催化裂化/裂解过程反应网络和分子尺度反应动力学模型构建的研究进展。重点对不同模型构建技术的优缺点进行了详细的对比分析，指出了催化裂化/裂解过程分子尺度反应动力学模型构建的研究方向：开发更为精细的石油分子分析表征技术，构建与催化剂失活和反应器模型相结合的分子尺度反应动力学模型，实现基于分子管理的催化裂化/裂解过程反应器设计和工艺工程放大。此外，指出建立对分子集构建、反应网络构建和动力学参数求解的集成化平台是分子尺度反应动力学发展的必然趋势。

关键词: 催化裂化, 催化裂解, 反应, 动力学模型

CLC Number:

TQ013.2

LIU Dongyang, BAI Yu’en, ZHANG Linzhou, ZHANG Yuhao, ZHAO Liang, GAO Jinsen, XU Chunming. Application advances of molecular level reaction kinetic modeling for catalytic cracking/pyrolysis process[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2082-2091.

刘东阳, 白宇恩, 张霖宙, 张宇豪, 赵亮, 高金森, 徐春明. 分子尺度反应动力学模型构建在催化裂化/裂解过程中的应用进展[J]. 化工进展, 2021, 40(4): 2082-2091.

Figures/Tables 10

反应类型	化学反应
烷烃裂化	$C n H 2 n + 2 → C m H 2 m + 2 + C p H 2 p + 2, n = m + p$
烯烃裂化	$C n H 2 n → C m H 2 m + 2 + C p H 2 p + 2, n = m + p$
烷基芳烃脱烷基	$A r C n H 2 n + 1 → A r - H + C n H 2 n$
芳烃侧链β-断裂	$A r C n H 2 n + 1 → C m H 2 m - 1 + C p H 2 p + 2, n = m + p$
环烷烃裂化	$C n H 2 n → C m H 2 m + C p H 2 p + 2, n = m + p$
氢转移反应	$3 C n H 2 n + C m H 2 m → 3 C n H 2 n + 2 + C m H 2 m - 6, n = m + p$
环化
芳构化
异构化
缩合反应	烯烃与烯烃、烯烃与芳烃及芳烃与芳烃之间的缩合反应
烷基转移

反应类型	化学反应
烷烃裂化	$C n H 2 n + 2 → C m H 2 m + 2 + C p H 2 p + 2, n = m + p$
烯烃裂化	$C n H 2 n → C m H 2 m + 2 + C p H 2 p + 2, n = m + p$
烷基芳烃脱烷基	$A r C n H 2 n + 1 → A r - H + C n H 2 n$
芳烃侧链β-断裂	$A r C n H 2 n + 1 → C m H 2 m - 1 + C p H 2 p + 2, n = m + p$
环烷烃裂化	$C n H 2 n → C m H 2 m + C p H 2 p + 2, n = m + p$
氢转移反应	$3 C n H 2 n + C m H 2 m → 3 C n H 2 n + 2 + C m H 2 m - 6, n = m + p$
环化
芳构化
异构化
缩合反应	烯烃与烯烃、烯烃与芳烃及芳烃与芳烃之间的缩合反应
烷基转移

碳数	实验值		预测值
碳数	烯烃	烷烃+环烷烃	烯烃	烷烃+环烷烃
C₂	39	61	5	95
C₃	57	43	51	49
C₄	42	58	46	54
C₅	58	42	48	52
C₆	60	40	70	30
C₇+C₈	63	37	73	27
C₉+C₁₀+C₁₁	67	33	65	35

CH₂碳

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[15]	ZHANG Peng, PAN Yuan. Progress of single atom catalysts in electrocatalytic oxygen reduction to hydrogen peroxide [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2944-2953.