费托合成催化剂动态置换与稳态工艺的集成优化

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

摘要/Abstract

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

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

中图分类号:

TQ529.2

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.

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.

图/表 15

图1 费托合成工艺模拟流程图1—费托合成反应器（串联CSTR）；2—蜡分离罐（flash 2）；3—换热器（heatX）；4—重质油分离罐（flash 2）；5—空冷器（heater）；6—轻质油分离罐（flash 2）；7—压缩机前缓冲罐（flash 2）；8—油水分离器（decanter）；9—脱碳系统（sep）；10—脱碳净化气缓冲罐（flash 2）；11—循环气压缩机（compr）

表1 CNFT催化剂反应动力学模型参数

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

表1 CNFT催化剂反应动力学模型参数

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

图2 工业实际烃类产物的链增长因子随碳数的变化

表2 工业条件下集总烃类产物的碳数、链增长因子、烯烷比、集总数

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	—

图3 CNFT催化剂反应物消耗及产物生成速率变化趋势

图4 CNFT催化剂的失活实验评价数据与拟合模型

表3 式(15)和式(16)的高斯函数拟合模型参数

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

表3 式(15)和式(16)的高斯函数拟合模型参数

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

图5 Matlab-Aspen Plus联用模型的计算实施流程

表4 费托合成稳态模拟的工艺参数

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

表5 费托合成稳态模拟的性能指标

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

表5 费托合成稳态模拟的性能指标

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

图6 不同置换条件下的关键性能指标模拟结果

表6 满足性能要求的不同置换间隔对应的最小置换比例

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

表6 满足性能要求的不同置换间隔对应的最小置换比例

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

表7 满足催化剂消耗限制要求的不同置换间隔对应的最大置换比例

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

表7 满足催化剂消耗限制要求的不同置换间隔对应的最大置换比例

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

表8 目标函数的价格参数设定值

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

图7 不同置换条件下的累积年利润模拟数据

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