储氢提纯和氢网络的耦合优化

doi:10.11949/0438-1157.20191548

摘要/Abstract

摘要：

基于氢网络的集成以及AB₅型储氢材料LaNi_4.75Fe_0.25及LaNi_4.85Al_0.15的特性，对储氢提纯在氢网络中的应用进行研究。综合考虑LaNi_4.75Fe_0.25及LaNi_4.85Al_0.15储氢/放氢动力学，建立了储氢提纯氢网络的优化方法，根据单位质量储氢材料提纯的节氢能力和公用工程节省量与提纯参数的关系，确定最优提纯氢源浓度、最大公用工程节省量、储氢材料量和吸氢时间。用该方法对某炼厂氢网络和储氢提纯单元进行优化，结果表明，最优提纯氢源浓度为70%，提纯后公用工程可节省23.72%； LaNi_4.85Al_0.15作为储氢提纯材料优于LaNi_4.75Fe_0.25，其消耗量为991.26 kg。

关键词: 储氢, 提纯, 优化, 氢源浓度, 氢网络

Abstract:

Based on the integration of the hydrogen network and the characteristics of the AB₅ hydrogen storage materials LaNi_4.75Fe_0.25 and LaNi_4.85Al_0.15, the application of hydrogen storage purification in the hydrogen network was studied. According to the relationship between the hydrogen-saving capacity of unit hydrogen storage material and the purification parameters, and that between utility saving and purification parameters, the optimal purification feed purity, the maximum utility saving, the amount of hydrogen storage material and the hydrogen absorption time can be determined. The proposed method is used to optimize the hydrogen network and hydrogen storage purification unit of a refinery. The results show that, in this refinery, the optimal purification hydrogen feed purity is 70% and the utility consumption can be reduced by 23.72%; more hydrogen can be saved when LaNi_4.85Al_0.15 is used in the purification unit instead of LaNi_4.75Fe_0.25, and the amount of LaNi_4.85Al_0.15 demanded in the purification unit is 991.26 kg.

Key words: hydrogen storage, purification, optimization, purification feed purity, hydrogen network

中图分类号:

TQ 021.8

李开宇, 刘桂莲. 储氢提纯和氢网络的耦合优化[J]. 化工学报, 2020, 71(3): 1143-1153.

Kaiyu LI, Guilian LIU. Coupling optimization of hydrogen-storage based purification and hydrogen network[J]. CIESC Journal, 2020, 71(3): 1143-1153.

图/表 20

图1 提纯装置

Fig.1 General hydrogen purification process

图2 LaNixM5-x平衡压力曲线

Fig.2 Equilibrium pressure diagram for LaNixM5-x alloy(1 bar=0.1 MPa)

图3 LaNixM5-x储氢材料动力学曲线

Fig.3 Kinetic curve of LaNixM5-xalloy

表1 吸氢和放氢速率常数

Table 1 Reaction rate constantsk of hydrogen absorption and desorption processes

速率常数	LaNi_4.75Fe_0.25	LaNi_4.85Al_0.15
$l n k a b s$	$3.122888 - 14475.4 R g T$	$0.467959 - 8064.6 R g T$
$l n k d e s$	$4.95603 - 23805.7 R g T$	$8.07169 - 30945.9 R g T$

表1 吸氢和放氢速率常数

Table 1 Reaction rate constantsk of hydrogen absorption and desorption processes

速率常数	LaNi_4.75Fe_0.25	LaNi_4.85Al_0.15
$l n k a b s$	$3.122888 - 14475.4 R g T$	$0.467959 - 8064.6 R g T$
$l n k d e s$	$4.95603 - 23805.7 R g T$	$8.07169 - 30945.9 R g T$

图4 提纯氢源浓度与公用工程节省量关系图

Fig.4 Quantitative relationship diagram betweencpur andΔsFu,i

图5 不同浓度下的LaNixM5-x吸氢动力学曲线

Fig.5 Absorption kinetic curve of LaNixM5-x alloy at different concentrations

图6 储氢材料用量及公用工程节省量随提纯原料浓度的变化曲线

Fig.6 Variation ofmLaNixM5-x andΔsFu,i along purification feed purity

图7 U与cpur关系图

Fig.7 Variation ofU alongcpur

图8 储氢提纯单元连续化模型

Fig.8 Continuous model of hydrogen-storage based purification unit

图9 储氢单元连续化

Fig.9 Schematic diagram of hydrogen-storage based purification unit

表2 氢源与氢阱数据[9]

Table 2 Data of hydrogen sources and hydrogen sinks[9]

流股		氢负荷/%(mol)	流量/(mol?s^-1)
氢阱
SK₁	HCU	80.61	2495.00
SK₂	NHT	78.85	180.20
SK₃	CNHT	75.14	720.70
SK₄	DHT	77.57	554.40
氢源
SR₁	HCU	75	1801.90
SR₂	NHT	75	138.60
SR₃	CNHT	70	457.40
SR₄	DHT	73	346.50
SR₅	SRU	93	623.80
SR₆	CRU	80	415.80
SR₀	fresh	95	286.82

图10 不同提纯原料浓度下LaNi4.75Fe0.25和LaNi4.85Al0.15的吸氢曲线

Fig.10 Absorption kinetic curve of LaNi4.75Fe0.25 and LaNi4.85Al0.15alloyat different purification feed purities

表3 不同提纯氢源浓度下的tabs和mLaNi4.75Fe0.25

Table 3 tabs andmLaNi4.75Fe0.25at different purification feed purities

提纯氢源浓度/%（mol）	t_abs/s	$m L a N i 4.75 F e 0.25$ /kg
100	146.84	1074.36
80	163.65	958.31
75	173.11	950.31
73	178.06	951.42
70	187.24	950.39

表3 不同提纯氢源浓度下的tabs和mLaNi4.75Fe0.25

Table 3 tabs andmLaNi4.75Fe0.25at different purification feed purities

提纯氢源浓度/%（mol）	t_abs/s	$m L a N i 4.75 F e 0.25$ /kg
100	146.84	1074.36
80	163.65	958.31
75	173.11	950.31
73	178.06	951.42
70	187.24	950.39

表4 不同提纯氢源浓度下的tabs和mLaNi4.85Al0.15

Table 4 tabs andmLaNi4.85Al0.15at different purification feed purities

提纯氢源浓度/%(mol)	t_abs/s	$m L a N i 4.85 A l 0.15$ /kg
100	94.83	693.80
80	94.38	552.68
75	95.92	526.55
73	96.52	515.74
70	97.69	495.63

表4 不同提纯氢源浓度下的tabs和mLaNi4.85Al0.15

Table 4 tabs andmLaNi4.85Al0.15at different purification feed purities

提纯氢源浓度/%(mol)	t_abs/s	$m L a N i 4.85 A l 0.15$ /kg
100	94.83	693.80
80	94.38	552.68
75	95.92	526.55
73	96.52	515.74
70	97.69	495.63

图11 镧镍系材料用量与吸氢时间随温度的变化

Fig.11 Variation oftabs andmLaNixM5-x along temperature

图12 表2所示系统的ΔsFu,SRi-cpur关系图

Fig.12 ΔsFu,SRi-cpurdiagram of system shown in Table 2

图13 mLaNixM5-x和ΔsFu随提纯氢源浓度的变化

Fig.13 Variation ofmLaNixM5-x andΔsFu along purification feed purity

图14 U与cpur关系图

Fig.14 Relationship betweenU andcpur

表5 储氢提纯单元数据

Table 5 Data of hydrogen storage unit

储氢提纯模块

m L a N i 4.85 A l 0.15

F_pur/

(mol·s^-1)

F_g/

(mol·s^-1)

表5 储氢提纯单元数据

Table 5 Data of hydrogen storage unit

储氢提纯模块

m L a N i 4.85 A l 0.15

/kg

t/s

c_pur/%(mol)

c_g/%(mol)

F_pur/

(mol·s^-1)

F_g/

(mol·s^-1)

吸氢过程

495.63

97.69

—

94.90

—

放氢过程

495.63

318.53

—

99.99

—

16.30

图15 两个储氢提纯单元的连续化模型

Fig.15 Operation of two hydrogen-storage based purification units

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