PSA-低温甲醇洗-膜分离耦合的氢气分离系统建立与模拟

doi:10.11949/0438-1157.20230895

摘要/Abstract

摘要：

氢能作为实现可持续发展的重要载体，对构建清洁低碳高效的能源体系、实现“双碳”目标具有重要意义。通过提出变压吸附（PSA）-低温甲醇洗-膜分离的耦合氢气分离系统，并借助Aspen Plus等软件进行模拟和分析，实现了多种分离技术的优势结合。多项分离工艺集成有效利用了PSA尾气中的氢气，提高了氢气回收率；打破了单一膜分离提纯氢气的纯度瓶颈，获得产品氢气浓度高达99.67%；实现了CO₂的富集和CH₄的循环回收，减少了制氢原料的损失。整个系统相比于现存的装置运行分离效果和经济性更好，为其他氢气提纯问题提供了新思路和一定的实用价值。

关键词: 氢, 分离, 变压吸附, 膜, 低温甲醇洗, 计算机模拟

Abstract:

Hydrogen energy, as an important carrier for achieving sustainable development, is of great significance for building a clean, low-carbon, and efficient energy system and achieving the “dual carbon” goals. This article designs a complete process for hydrogen separation, which is simulated and analyzed using software Aspen Plus. By proposing a coupled hydrogen separation system consisting of pressure swing adsorption (PSA), rectisol, and membrane separation, and using software such as Aspen Plus for simulation and analysis, the advantages of various separation technologies were combined. The integration of multiple separation processes has broken the purity bottleneck of single membrane separation, resulting in a product hydrogen concentration of up to 99.67%. In addition, it achieves the enrichment of CO₂ and the recycling of CH₄, reducing the loss of hydrogen production raw materials. The entire system has better separation performance compared to existing single technology, providing new insights and application potential for other gas separation problems.

Key words: hydrogen, separation, pressure swing adsorption, membranes, rectisol, computer simulation

中图分类号:

TQ 028.8

麻蓉, 张桥. PSA-低温甲醇洗-膜分离耦合的氢气分离系统建立与模拟[J]. 化工学报, 2023, 74(10): 4201-4207.

Rong MA, Qiao ZHANG. Establishment and simulation of hydrogen separation system coupled with PSA, rectisol and membrane separation[J]. CIESC Journal, 2023, 74(10): 4201-4207.

图/表 12

图1 组合分离系统流程图PSA—变压吸附; Rectisol—低温甲醇洗; MEM—膜分离

Fig.1 Flow chart of combined separation systemPSA—pressure swing adsorption; Rectisol—low-temperature methanol washing; MEM—membrane separation

表1 进料气体数据

Table 1 Data of feed gas

摩尔流率/(kmol/h)	压力/MPa	温度/K	摩尔分数/%
摩尔流率/(kmol/h)	压力/MPa	温度/K	CH₄	H₂	CO₂	CO
3430.93	2.2	313.15	7.524	73.94	18.35	0.1870

图2 双塔变压吸附流程模拟图T1, T2—吸附塔; TF, TD1, TD2, TW1, TW2, TP, TW—储气罐; VF, VF1, VF2, VP, VP1, VP2, VPURGE, VW—阀门

Fig.2 Simulation diagram of dual tower PSA processT1, T2—adsorption tower; TF, TD1, TD2, TW1, TW2, TP, TW—gas tank; VF, VF1, VF2, VP, VP1, VP2, VPURGE, VW—gas valve

表2 吸附床和吸附剂物理参数

Table 2 Physical parameters of adsorption bed and adsorbents

材料	吸附层高度/m	吸附床内径/m	颗粒间隙率
活性炭	9.530	3.2	0.36
5A分子筛	4.765	3.2	0.36

表3 变压吸附产品气及尾气数据

Table 3 Data of PSA product gas and disorbed gas

项目	摩尔流率/(kmol/h)	压力/MPa	温度/K	摩尔分数/%
项目	摩尔流率/(kmol/h)	压力/MPa	温度/K	CH₄	CO	CO₂	H₂
PRODUCT	2061.23	2.2	295.25	0.0018	0.0008	0.0322	99.96
WASTE	1377.56	0.1	296.35	18.79	0.5354	46.09	34.59

图3 低温甲醇洗流程模拟图T3—吸收塔; Y1, Y2, Y3—压缩机; C1, C2, C3—冷却器; H1, H2—加热器; V1—阀门; F1—闪蒸罐; PUMP—泵; MIX—混合器

Fig.3 Simulation diagram of rectisol processT3—absorption tower; Y1, Y2, Y3—compressor; C1, C2, C3—cooler; H1, H2—heater; V1—valve; F1—flash tank; PUMP—pump; MIX—mixer

表4 吸收塔出口气体数据

Table 4 Data of outlet gas of the absorption tower

项目	摩尔流率/(kmol/h)	压力/MPa	温度/K	摩尔分数/%
项目	摩尔流率/(kmol/h)	压力/MPa	温度/K	CH₄	CO	CO₂	H₂
产品气（S8）	475.21	0.1	298.15	0.2915	0.7194	0.5861	98.40
尾气（S14）	905.48	2.6	333.15	28.53	0.4385	70.05	0.9794

图4 二级膜分离流程图

Fig.4 Simulation diagram of two-stage membrane separation process

表5 分离膜参数及操作条件

Table 5 Separation membrane parameters and operating conditions

项目	原料侧压力/MPa	渗透侧压力/MPa	操作温度/K	渗透速率/GPU
项目	原料侧压力/MPa	渗透侧压力/MPa	操作温度/K	CH₄	CO	CO₂	H₂
一级膜分离	2.6	0.1	298.15	0.25	10.7	10.7	28.1
二级膜分离	2.5	0.1	298.15	0.25	10.7	10.7	28.1

表6 二级膜分离模拟结果

Tab1e 6　Simulation results of two-stage membrane separation

项目	摩尔流率/(kmol/h)	压力/MPa	温度/K	摩尔分数/%
项目	摩尔流率/(kmol/h)	压力/MPa	温度/K	CH₄	CO	CO₂	H₂
一级渗透气（P1）	591.52	0.1	298.15	2.456	0.5975	95.46	1.484
二级截留气（R2）	221.79	2.5	298.15	98.12	0.0117	1.863	0.0003
二级渗透气（P2）	89.05	0.1	298.15	28.39	0.4450	71.10	0.0625

表7 产品氢气数据

Table 7 Data of hydrogen product

摩尔流率/(kmol/h)	压力/MPa	温度/K	摩尔分数/%
摩尔流率/(kmol/h)	压力/MPa	温度/K	CH₄	CO	CO₂	H₂
2536.43	2.0	298.15	0.0561	0.1355	0.1359	99.67

表8 不同氢气分离工艺综合指标对比

Table 8 Comparison of comprehensive indicators of different hydrogen separation processes

项目	氢气回收率/%	回收氢气纯度/%	设备投资(相对)/%	单位产氢成本/(CNY/m³)
一段PSA	≥88.0	≥99.9	70	1.055
两段PSA耦合	≥96.3	≥99.9	110	1.012
PSA-膜分离耦合	≥96.5	≥99.9	100	1.009
PSA-低温甲醇洗-膜分离	≥99.6	≥99.7	125	1.005

参考文献 30

1	DeLuchi M A. Hydrogen vehicles: an evaluation of fuel storage, performance, safety, environmental impacts, and cost[J]. International Journal of Hydrogen Energy, 1989, 14(2): 81-130.
2	Momirlan M, Veziroglu T N. The properties of hydrogen as fuel tomorrow in sustainable energy system for a cleaner planet[J]. International Journal of Hydrogen Energy, 2005, 30(7): 795-802.
3	李非凡, 薛贺来, 李黎明, 等. 传统制氢工艺的发展与展望[J]. 化学工程与装备, 2022(4): 210-212.
	Li F F, Xue H L, Li L M, et al. Development and prospect of traditional hydrogen production process[J]. Chemical Engineering & Equipment, 2022(4): 210-212.
4	邹才能, 李建明, 张茜, 等. 氢能工业现状、技术进展、挑战及前景[J]. 天然气工业, 2022, 42(4): 1-20.
	Zou C N, Li J M, Zhang X, et al. Industrial status, technological progress, challenges and prospects of hydrogen energy[J]. Natural Gas Industry, 2022, 42(4): 1-20.
5	Bhandari R, Trudewind C A, Zapp P. Life cycle assessment of hydrogen production via electrolysis—a review[J]. Journal of Cleaner Production, 2014, 85: 151-163.
6	Barrett S. Road map to a US hydrogen economy[J]. Fuel Cells Bulletin, 2020, 2020(11): 12.
7	黄格省, 李锦山, 魏寿祥, 等. 化石原料制氢技术发展现状与经济性分析[J]. 化工进展, 2019, 38(12): 5217-5224.
	Huang G S, Li J S, Wei S X, et al. Status and economic analysis of hydrogen production technology from fossil raw materials[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5217-5224.
8	杨铮, 田桂丽. 我国氢气市场分析及发展前景研判[J]. 化学工业, 2022, 40(4): 51-57.
	Yang Z, Tian G L. Market analysis and development outlook of hydrogen in China[J]. Chemical Industry, 2022, 40(4): 51-57.
9	杨颖, 曲冬蕾, 李平, 等. 低浓度煤层气吸附浓缩技术研究与发展[J]. 化工学报, 2018, 69(11): 4518-4529.
	Yang Y, Qu D L, Li P, et al. Research and development on enrichment of low concentration coal mine methane by adsorption technology[J]. CIESC Journal, 2018, 69(11): 4518-4529.
10	Xue C L, Cheng W P, Hao W M, et al. CH₄/N₂ adsorptive separation on zeolite X/AC composites[J]. Journal of Chemistry, 2019, 2019: 1-9.
11	范鹏鹏, 刘晓, 陈贞龙, 等. 中美煤层气勘探开发现状对比及启示[J]. 现代化工, 2023, 43(8): 22-25, 30.
	Fan P P, Liu X, Chen Z L, et al. Comparison and enlightenment of current situation of coalbed methane exploration and development between China and the United States[J]. Modern Chemical Industry, 2023, 43(8): 22-25, 30.
12	钮朝阳, 江南, 沈圆辉, 等. 快速变压吸附制氢工艺的模拟与分析[J]. 化工学报, 2021, 72(2): 1036-1046.
	Niu Z Y, Jiang N, Shen Y H, et al. Simulation and analysis of rapid pressure swing adsorption for hydrogen production[J]. CIESC Journal, 2021, 72(2): 1036-1046.
13	Carta M. Gas separation[M]//Encyclopedia of Membranes. Berlin Heidelberg: Springer-Verlag, 2016.
14	Li H R, Liao Z W, Sun J Y, et al. Modelling and simulation of two-bed PSA process for separating H₂ from methane steam reforming[J]. Chinese Journal of Chemical Engineering, 2019, 27(8): 1870-1878.
15	Burgers I, Dehdari L, Xiao P, et al. Techno-economic analysis of PSA separation for hydrogen/natural gas mixtures at hydrogen refuelling stations[J]. International Journal of Hydrogen Energy, 2022, 47(85): 36163-36174.
16	Luberti M, Ahn H. Review of polybed pressure swing adsorption for hydrogen purification[J]. International Journal of Hydrogen Energy, 2022, 47(20): 10911-10933.
17	Da Conceicao M, Nemetz L, Rivero J, et al. Gas separation membrane module modeling: a comprehensive review[J]. Membranes, 2023, 13(7): 639.
18	Mao D L, Griffin J M, Dawson R, et al. Metal organic frameworks for hydrogen purification[J]. International Journal of Hydrogen Energy, 2021, 46(45): 23380-23405.
19	Gu Z L, Shi Z P, Lin G J, et al. Highly efficient and selective H₂/CH₄ separation by graphene membranes with embedded crown ethers[J]. International Journal of Hydrogen Energy, 2022, 47(59): 24835-24842.
20	张习文, 吕超, 金理健, 等. 低温甲醇洗碳捕集工艺的优化与(㶲)分析[J]. 东南大学学报(自然科学版), 2023, 53(2): 356-362.
	Zhang X W, Lyu C, Jin L J, et al. Optimization and exergy analysis of low temperature methanol washing carbon capture process[J]. Journal of Southeast University (Natural Science Edition), 2023, 53(2): 356-362.
21	杨声, 梁嘉能, 杨思宇, 等. 煤制气中甲烷化余热利用集成串级吸收式制冷新工艺[J]. 化工学报, 2016, 67(3): 779-787.
	Yang S, Liang J N, Yang S Y, et al. A novel integrated cascade absorption refrigeration technology by using waste heat in CTG’s methanation process[J]. CIESC Journal, 2016, 67(3): 779-787.
22	Wang J, Shen Y H, Zhang D H, et al. Integrated vacuum pressure swing adsorption and rectisol process for CO₂ capture from underground coal gasification syngas[J]. Chinese Journal of Chemical Engineering, 2023, 57: 265-279.
23	Ohs B, Falkenberg M, Wessling M. Optimizing hybrid membrane-pressure swing adsorption processes for biogenic hydrogen recovery[J]. Chemical Engineering Journal, 2019, 364: 452-461.
24	Li B J, He G H, Jiang X B, et al. Pressure swing adsorption/membrane hybrid processes for hydrogen purification with a high recovery[J]. Frontiers of Chemical Science and Engineering, 2016, 10(2): 255-264.
25	党凯, 艾力江, 孙镭, 等. 氢气提纯耦合工艺及其应用[J]. 天然气化工—C1化学与化工, 2021, 46(6): 86-90.
	Dang K, Ai L J, Sun L, et al. Hydrogen purification coupling process and its application[J]. Natural Gas Chemical Industry, 2021, 46(6): 86-90.
26	Park J H, Kim J N, Cho S H, et al. Adsorber dynamics and optimal design of layered beds for multicomponent gas adsorption[J]. Chemical Engineering Science, 1998, 53(23): 3951-3963.
27	Ramírez-Santos Á A, Bozorg M, Addis B, et al. Optimization of multistage membrane gas separation processes. Example of application to CO₂ capture from blast furnace gas[J]. Journal of Membrane Science, 2018, 566: 346-366.
28	乔义书. 油田伴生气多级膜分离工艺模拟及实验研究[D]. 青岛: 青岛科技大学, 2022.
	Qiao Y S. Simulation and experimental study on multistage membrane separation process of oilfield associated gas[D]. Qingdao: Qingdao University of Science and Technology, 2022.
29	许家友. CO₂膜分离过程的模拟及优化[D]. 天津: 天津大学, 2019.
	Xu J Y. Simulation and optimization of CO₂ membrane separation process[D]. Tianjin: Tianjin University, 2019.
30	陶宇鹏. 不同氢气净化提纯技术在煤制氢中的经济性分析[J]. 四川化工, 2021, 24(4): 13-16.
	Tao Y P. Economic analysis of different hydrogen purification technologies in hydrogen production from coal[J]. Sichuan Chemical Industry, 2021, 24(4): 13-16.

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