Integrated optimization of catalyst dynamic replacement and steady-state Fischer-Tropsch synthesis

doi:10.16085/j.issn.1000-6613.2025-0201

Abstract

Abstract:

In industrial coal-based Fischer-Tropsch (FT) synthesis, Fe-based catalysts coupled with slurry bed reactors are widely adopted. However, catalyst deactivation necessitates periodic replacement due to inherent limitations. To address this issue, a Matlab-Aspen Plus model was constructed, which integrated the dynamic processes of catalyst deactivation and replacement with steady-state simulation of FT synthesis. Taking an FT synthesis system with an annual capacity of 80×10⁴t/a as a case study, we analyzed the impacts of dynamic catalyst replacement conditions on key performance indicators—Specifically, specific syngas consumption and catalyst consumption per tonne of $C 3 +$ hydrocarbons. The economically optimal catalyst replacement strategy was to replace 20% catalyst every 132h. Under this condition, the specific syngas consumption and catalyst consumption were 5449m³/t and 1.65kg/t, respectively. This model offers valuable guidance for the process design, performance prediction of FT synthesis units and practical catalyst replacement operations in industrial settings. Furthermore, it provides a practical methodology for simulating process systems involving catalyst deactivation and dynamic replacement, demonstrating broader applicability in similar industrial contexts.

Key words: Fischer-Tropsch (FT) synthesis, catalyst replacement, deactivation, simulation, optimization

摘要：

工业煤基费托合成工艺一般采用铁基催化剂-浆态床反应器的技术路线。针对该工艺中催化剂易失活、需要周期性置换的问题，本文构建了一种Matlab-Aspen Plus集成模型，创新性地将催化剂失活、置换的动态过程与费托合成稳态工艺模拟进行了耦合。以产能为80×10⁴t/a的费托合成系统为例，分析了催化剂动态置换条件对关键性能指标每吨 $C 3 +$ 有效气耗和催化剂消耗的影响，并得出了经济性最优的置换条件，即每132h置换20%的催化剂，此时 $C 3 +$ 有效气耗为5449m³/t（标准状况）， $C 3 +$ 催化剂消耗为1.65kg/t。该模型对费托合成装置的工艺设计、运行预测及实际的催化剂置换操作具有一定的指导意义，同时也为存在催化剂失活与置换操作的工艺系统建模提供了一种思路。

关键词: 费托合成, 催化剂置换, 失活, 模拟, 优化

CLC Number:

TQ529.2

ZHAO Yongming, BU Yifeng, WANG Tao, DU Bing, MEN Zhuowu. Integrated optimization of catalyst dynamic replacement and steady-state Fischer-Tropsch synthesis[J]. Chemical Industry and Engineering Progress, 2025, 44(8): 4536-4544.

赵用明, 卜亿峰, 王涛, 杜冰, 门卓武. 费托合成催化剂动态置换与稳态工艺的集成优化[J]. 化工进展, 2025, 44(8): 4536-4544.

Figures/Tables 15

动力学参数	数值
k $F T 0$ /mol∙kg^-1∙s^-1∙MPa^-1	0.062
E_FT/kJ∙mol^-1	105
α_FT	5.9
β_FT	5.9
k $W G S 0$ /mol∙kg^-1∙s^-1∙MPa^-1	0.048
E_WGS/kJ∙mol^-1	125
α_WGS	2
β_WGS	2

动力学参数	数值
k $F T 0$ /mol∙kg^-1∙s^-1∙MPa^-1	0.062
E_FT/kJ∙mol^-1	105
α_FT	5.9
β_FT	5.9
k $W G S 0$ /mol∙kg^-1∙s^-1∙MPa^-1	0.048
E_WGS/kJ∙mol^-1	125
α_WGS	2
β_WGS	2

集总产物	碳数	集总数	链增长因子	烯烷比
CH₄	1	1	0.827	—
C₂H₄	2	1	0.915	0.185
C₂H₆	2	1	0.915	0.185
C₃H₆	3	1	0.890	1.920
C₃H₈	3	1	0.890	1.920
1-C₄H₈	4	1	0.930	1.894
n-C₄H₁₀	4	1	0.930	1.894
1-C₈H₁₆	8	7	0.937	1.500
n-C₈H₁₈	8	7	0.937	1.500
1-C₁₆H₃₂	16	9	0.934	0.232
n-C₁₆H₃₄	16	9	0.934	0.232
n-C₄₂H₈₆	42	61	0.928	—

模型参数	式(15)	式(16)-C₁	式(16)-C₂	式(16)-C₃	式(16)-C₄	式(16)-C₅ $+$
a₁	2.49	1.008	1.027	1.059	13.66	1.01
b₁	1481	216.1	-130.2	-547.8	-133200	39.94
c₁	557.7	1706	2425	3205	82630	2384
a₂	0.2314	0.079	0.087	0.096	0.0135	0.081
b₂	870	868.1	903.5	910.1	1541	934.4
c₂	29.92	266.7	432.3	482.2	116.3	389.6
a₃	0.4626	0.339	0.267	0.174	0.011	0.226
b₃	734.4	1837	1810	1714	899.1	1756
c₃	241.1	497.6	458	331.1	336.7	388.5
a₄	1.064
b₄	237.3
c₄	442.6

模型参数	式(15)	式(16)-C₁	式(16)-C₂	式(16)-C₃	式(16)-C₄	式(16)-C₅ $+$
a₁	2.49	1.008	1.027	1.059	13.66	1.01
b₁	1481	216.1	-130.2	-547.8	-133200	39.94
c₁	557.7	1706	2425	3205	82630	2384
a₂	0.2314	0.079	0.087	0.096	0.0135	0.081
b₂	870	868.1	903.5	910.1	1541	934.4
c₂	29.92	266.7	432.3	482.2	116.3	389.6
a₃	0.4626	0.339	0.267	0.174	0.011	0.226
b₃	734.4	1837	1810	1714	899.1	1756
c₃	241.1	497.6	458	331.1	336.7	388.5
a₄	1.064
b₄	237.3
c₄	442.6

工艺参数	数值
新鲜合成气流量（标准状况）/km³∙h^-1	550
催化剂装填量/t	110
反应温度/℃	270
反应压力/MPa	2.85
新鲜合成气n(H₂)/n(CO)	1.65
循环比	2.80
CO₂脱除比例	0.99

工艺参数	数值
CO转化率/%	97.99
CO₂选择性/%	15.96
CH₄选择性/%	2.41
$C 3 +$ 选择性/%	81.22
$C 3 +$ 有效气耗（标准状况）/m³·t^-1	5389

工艺参数	数值
CO转化率/%	97.99
CO₂选择性/%	15.96
CH₄选择性/%	2.41
$C 3 +$ 选择性/%	81.22
$C 3 +$ 有效气耗（标准状况）/m³·t^-1	5389

置换间隔/h	置换比例/%	$C 3 +$ 有效气耗（标准状况）/m³·t^-1	$C 3 +$ 催化剂消耗/kg·t^-1	全年催化剂消耗/t
48	9	5395	2.02	1616
60	11	5399	1.98	1584
72	13	5400	1.95	1560
84	15	5400	1.93	1544
96	17	5399	1.91	1528
108	19	5398	1.90	1520

置换间隔/h	置换比例/%	$C 3 +$ 有效气耗（标准状况）/m³·t^-1	$C 3 +$ 催化剂消耗/kg·t^-1	全年催化剂消耗/t
48	9	5395	2.02	1616
60	11	5399	1.98	1584
72	13	5400	1.95	1560
84	15	5400	1.93	1544
96	17	5399	1.91	1528
108	19	5398	1.90	1520

置换间隔/h	置换比例/%	$C 3 +$ 催化剂消耗/kg·t^-1	$C 3 +$ 有效气耗（标准状况）/m³·t^-1
60	8	1.48	5531
72	10	1.52	5508
84	12	1.57	5491
96	13	1.49	5511
108	15	1.53	5496
120	17	1.55	5483
132	18	1.50	5496
144	20	1.52	5484

置换间隔/h	置换比例/%	$C 3 +$ 催化剂消耗/kg·t^-1	$C 3 +$ 有效气耗（标准状况）/m³·t^-1
60	8	1.48	5531
72	10	1.52	5508
84	12	1.57	5491
96	13	1.49	5511
108	15	1.53	5496
120	17	1.55	5483
132	18	1.50	5496
144	20	1.52	5484

价格参数	数值
石脑油价格/CNY∙t^-1	7000
柴油价格/CNY∙t^-1	7000
LPG价格/CNY∙t^-1	5000
石脑油消费税/CNY∙t^-1	2100
柴油消费税/CNY∙t^-1	1000
合成气成本/CNY∙m^-3	0.5
催化剂成本/CNY∙t^-1	150000
单次活化成本/CNY∙次^-1	300000
废催化剂处理成本/CNY∙t^-1	10000

References 19

[1]	武鹏, 吕元, 郭中山, 等. 煤间接液化及产品加工成套技术开发研究进展[J]. 煤炭学报, 2020, 45(4): 1222-1243.
	WU Peng, Yuan LYU, GUO Zhongshan, et al. R&D progress of indirect coal liquefaction and product processing integrated technology[J]. Journal of China Coal Society, 2020, 45(4): 1222-1243.
[2]	孙启文, 吴建民, 张宗森, 等. 煤间接液化技术及其研究进展[J]. 化工进展, 2013, 32(1): 1-12.
	SUN Qiwen, WU Jianmin, ZHANG Zongsen, et al. Indirect coal liquefaction technology and its research progress[J]. Chemical Industry and Engineering Progress, 2013, 32(1): 1-12.
[3]	张雅琳, 张占全, 王燕, 等. 费托合成油和石油基油加工产品对比分析[J]. 化工进展, 2018, 37(10): 3781-3787.
	ZHANG Yalin, ZHANG Zhanquan, WANG Yan, et al. Comparative analysis of products from Fischer-Tropsch oil and petroleum based oil[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3781-3787.
[4]	相宏伟, 杨勇, 李永旺. 煤炭间接液化: 从基础到工业化[J]. 中国科学: 化学, 2014, 44(12): 1876-1892.
	XIANG Hongwei, YANG Yong, LI Yongwang. Indirect coal-to-liquids technology: From fundamental research to commercialization[J]. Scientia Sinica Chimica, 2014, 44(12): 1876-1892.
[5]	LI Chufu, LI Yonglong, XU Ming, et al. Studies on pathways to carbon neutrality for indirect coal liquefaction in China[J]. Clean Energy, 2021, 5(4): 644-654.
[6]	陈文迪, 吕德义, 郭中山, 等. 费托合成Fe基催化剂失活研究进展[J]. 工业催化, 2019, 27(6) :9-15.
	CHEN Wendi, Deyi LYU, GUO Zhongshan, et al. Developments on deactivation of Fe-based Fischer-Tropsch synthesis catalysts[J]. Industrial Catalysis, 2019, 27(6): 9-15.
[7]	SEHABIAGUE Laurent, LEMOINE Romain, BEHKISH Arsam, et al. Modeling and optimization of a large-scale slurry bubble column reactor for producing 10000bbl/d of Fischer-Tropsch liquid hydrocarbons[J]. Journal of the Chinese Institute of Chemical Engineers, 2008, 39(2): 169-179.
[8]	SEHABIAGUE Laurent, BASHA Omar M, HONG Yemin, et al. Assessing the performance of an industrial SBCR for Fischer-Tropsch synthesis: Experimental and modeling[J]. AIChE Journal, 2015, 61(11): 3838-3857.
[9]	王峰, 许明, 刘虎, 等. 工业费托合成浆态床反应器的模拟[J]. 化学反应工程与工艺, 2018, 34(3): 213-219, 234.
	WANG Feng, XU Ming, LIU Hu, et al. Simulation of industrial Fischer-Tropsch synthesis slurry bed reactors[J]. Chemical Reaction Engineering and Technology, 2018, 34(3): 213-219, 234.
[10]	LI Chufu. Modeling and optimization of industrial Fischer-Tropsch synthesis with the slurry bubble column reactor and iron-based catalyst[J]. Chinese Journal of Chemical Engineering, 2018, 26(5): 1102-1109.
[11]	郭中山, 赵用明, 卜亿峰, 等. 工业费托浆态床反应器扩能模拟与优化[J]. 天然气化工—C1化学与化工, 2022, 47(3): 101-108.
	GUO Zhongshan, ZHAO Yongming, BU Yifeng, et al. Simulation and optimization for production capacity expansion of industrial Fischer-Tropsch synthesis slurry reactor[J]. Natural Gas Chemical Industry, 2022, 47(3): 101-108.
[12]	GHASEMI Samira, SOHRABI Morteza, RAHMANI Mohammad. A model for the dynamic behavior of a commercial scale slurry bubble column reactor applied for the Fischer-Tropch synthesis[J]. Asia-Pacific Journal of Chemical Engineering, 2010, 5(2): 337-345.
[13]	FAN Wei, HAO Xu, XU Yuanyuan, et al. Simulation of catalyst online replacement for Fischer-Tropsch synthesis in slurry bubble column reactor[J]. Chemistry and Technology of Fuels and Oils, 2011, 47(2): 116-133.
[14]	杨加义, 赵用明, 王峰, 等. 费-托合成催化剂CNFT-1的工业试验[J]. 石油炼制与化工, 2021, 52(4): 27-32.
	YANG Jiayi, ZHAO Yongming, WANG Feng, et al. Commercial test of Fischer-Tropsch synthesis catalyst CNFT-1[J]. Petroleum Processing and Petrochemicals, 2021, 52(4): 27-32.
[15]	林泉, 卜亿峰, 孟祥堃, 等. CNFT-1催化剂的开发及工业应用[J]. 中国煤炭, 2021, 47(12): 57-65.
	LIN Quan, BU Yifeng, MENG Xiangkun, et al. Development and industrial application of CNFT-1 catalyst[J]. China Coal, 2021, 47(12): 57-65.
[16]	SEHABIAGUE Laurent, MORSI Badie I. Hydrodynamic and mass transfer characteristics in a large-scale slurry bubble column reactor for gas mixtures in actual Fischer Tropsch cuts[J]. International Journal of Chemical Reactor Engineering, 2013, 11(1): 83-102.
[17]	孙启文. 煤炭间接液化[M]. 北京: 化学工业出版社, 2012, 55-80.
	SUN Qiwen. Indirect liquefaction of coal[M]. Beijing: Chemical Industry Press, 2012, 55-80.
[18]	SHI Buchang, DAVIS Burtron H. Fischer Tropsch synthesis: Accounting for chain-length related phenomena[J]. Applied Catalysis A: General, 2004, 277(1/2): 61-69.
[19]	李为真. 费托合成催化剂失活动力学模型的研究进展[J]. 化工进展, 2019, 38(5): 2347-2352.
	LI Weizhen. Progress on the catalyst deactivation model for Fischer-Tropsch synthesis[J]. Chemical Industry and Engineering Progress, 2019, 38(5): 2347-2352.