煤制甲醇耦合固体氧化物燃料电池混合系统研究

doi:10.11949/0438-1157.20250113

摘要/Abstract

摘要：

针对某大型煤化工厂产生的约15000 m³/h（标准工况）非渗透气作为废气燃料直接火炬燃烧导致的能源浪费问题，提出在原有煤制甲醇系统中引入固体氧化物燃料电池（SOFC）热电系统，开展煤化工与SOFC和透平发电技术耦合技术研究。使用仿真软件Aspen Plus建立煤制甲醇耦合SOFC系统的工艺流程，模拟SOFC进气温度、电流密度、气体利用率以及制甲醇流程弛放气循环比例对系统功率、效率的影响，并计算该耦合方案的经济成本。结果表明，与原煤制甲醇系统相比，非渗透气回收100%，其中85%用于燃料电池发电，系统额外产生13000 kW的电力，综合能量利用率提升2%，该系统在能源有效利用和缓解化工厂用电压力方面具有优越性，为现代煤化工产业绿色转型与SOFC商业化发展提供了思路。

关键词: 煤制甲醇, 固体氧化物燃料电池, 模拟技术

Abstract:

Aiming at the problem of energy waste caused by direct flare combustion of about 15000 m³/h (standard condition)impermeable gas produced by a large coal chemical plant as waste gas fuel, it is proposed to introduce solid oxide fuel cell (SOFC) thermoelectric system into the original coal-to-methanol system, and carry out research on coupling technology of coal chemical industry with SOFC and turbine power generation technology. The simulation software Aspen Plus is used to establish the process flow of SOFC coupling system for coal-to-methanol production. The influences of SOFC inlet temperature, current density, gas utilization rate and the circulation ratio of purge gas in methanol production process on the system power and efficiency are simulated, and the economic cost of the coupling scheme is calculated. The results show that compared with the original coal-to-methanol system, the non-permeate gas is recovered by 100%, of which 85% is used for fuel cell power generation. The system generates an additional 13000 kW of electricity, and the comprehensive energy utilization rate is increased by 2%. The system is superior in terms of efficient energy utilization and relieving the power pressure of chemical plants, providing ideas for the green transformation of the modern coal chemical industry and the commercial development of SOFC.

Key words: coal to methanol, solid oxide fuel cell, simulation technique

中图分类号:

TK 91

张彬怡, 孙少东, 姚谦, 蔡文河, 张惠宇, 李成新. 煤制甲醇耦合固体氧化物燃料电池混合系统研究[J]. 化工学报, 2025, 76(9): 4658-4669.

Binyi ZHANG, Shaodong SUN, Qian YAO, Wenhe CAI, Huiyu ZHANG, Chengxin LI. Study on hybrid system of coal-to-methanol coupled solid oxide fuel cell[J]. CIESC Journal, 2025, 76(9): 4658-4669.

图/表 18

图1 煤制甲醇耦合SOFC系统工艺流程

Fig.1 Process flow of SOFC system with coal-to-methanol coupling

表1 煤样工业分析和元素分析

Table 1 Industrial and elemental analysis of coal

工业分析/%				元素分析/%					热值/(MJ/kg)
M_ad	A_ad	V_ad	FC_ad	C_ar	H_ar	N_ar	O_ar	S_ar	热值/(MJ/kg)
10.7	27.41	27.1	32.85	76.62	4.74	1.11	19.68	1.83	17.3

表2 SOFC工作参数

Table 2 SOFC working parameters

参数	数值
SOFC工作压强/10⁵ Pa	1.0132
SOFC输出功率/kW	10000
SOFC工作温度/℃	800
阳极入口温度/℃	700
阴极入口温度/℃	630
阳极燃料流量/(kmol/h)	665
阴极空气流量/(kmol/h)	6400
阳极燃料气组成	H₂ 48%、CO₂ 8%、CO 7%、N₂ 33%、氩气4%
电流密度/(A/m²)	4000
燃料利用率	0.85
阴极空气利用率	0.15
单电池输出电压/V	0.63
电池有效面积/m²	5504.32
电池净发电效率	0.42
燃烧器效率	1
透平机械效率	0.99
换热器出口温差/K	10

表3 煤制甲醇系统工作参数

Table 3 Working parameters of coal-to-methanol system

参数	数值
煤炭流量/(t/h)	350
压缩机机械效率	0.99
气化炉水煤比/%	0.13
气化炉氧煤比/%	0.75
气化炉反应温度/℃	1570
弛放气循环比例	0.9
变压吸附器提纯效率	0.75
甲醇产量/(t/h)	217
综合能量利用率	0.785

表4 系统中包含的反应过程

Table 4 Reaction processes included in the system

单元	反应过程
煤气化	$C o a l + O 2$ → $C O + H 2 + C H 4 + N 2 + C O 2 + A s h$
一氧化碳变换	$C O + H 2 O$ ⇌ $H 2 + C O 2$
甲醇合成	$C O + 2 H 2$ ⇌ $C H 3 O H$
	$C O 2 + 3 H 2$ ⇌ $C H 3 O H + H 2 O$
SOFC	$2 H 2 + O 2$ → $2 H 2 O$ $2 C O + O 2$ → $2 C O 2$
	$2 H 2 + O 2$ → $2 H 2 O$ $2 C O + O 2$ → $2 C O 2$

表4 系统中包含的反应过程

Table 4 Reaction processes included in the system

单元	反应过程
煤气化	$C o a l + O 2$ → $C O + H 2 + C H 4 + N 2 + C O 2 + A s h$
一氧化碳变换	$C O + H 2 O$ ⇌ $H 2 + C O 2$
甲醇合成	$C O + 2 H 2$ ⇌ $C H 3 O H$
	$C O 2 + 3 H 2$ ⇌ $C H 3 O H + H 2 O$
SOFC	$2 H 2 + O 2$ → $2 H 2 O$ $2 C O + O 2$ → $2 C O 2$
	$2 H 2 + O 2$ → $2 H 2 O$ $2 C O + O 2$ → $2 C O 2$

表5 SOFC数学模型计算所需参数［20-21］

Table 5 Parameters required for SOFC mathematical model calculation［20-21］

参数		数值
阳极厚度/μm		20
支撑体厚度/μm		300
阴极厚度/μm		25
电解质厚度/μm		15
连接体厚度/mm		1
阳极指前因子/(A/cm²)		700000
阴极指前因子/(A/cm²)		700000
阳极活化能/(J/mol)		155000
阴极活化能/(J/mol)		110000
欧姆极化系数α/(Ω·mm)	阳极	0.0289
	阴极	0.0811
	电解质	0.0294
	内连接器	1.2
欧姆极化系数b/K	阳极	-1392
	阴极	600
	电解质	10350
	内连接器	4690
孔隙率ε		0.3
曲率τ		5
燃料利用率U_f		0.85

表6 成本分析的关键参数

Table 6 Key parameters of cost analysis

参数	数值
年工作日/d	330
年工作时间/h	8000
平均年利率/%	12
运行年限	20
维护成本因子	1.06
总能源输出/kW	13000
透平等熵效率	0.99
SOFC面积/m²	5504.32
SOFC工作温度/K	1073
透平入口气体流量/(kg/s)	3
透平进气压力/MPa	4
透平出口压力/MPa	0.1
透平出口温度/K	615
进入后燃室空气流量/(kg/s)	450
后燃室进气压力/MPa	0.1
后燃室出口压力/MPa	0.1
后燃室出口温度/K	1120

图2 计算数据与文献实验数据对比

Fig. 2 Comparison between calculated data and experimental data in literature

图3 阴极进气温度对电池电压、效率的影响

Fig. 3 Influence of cathode inlet temperature on battery voltage and efficiency

图4 阴极进气温度对输出功率的影响

Fig. 4 Influence of cathode inlet temperature on output power

图5 电流密度对电池电压、效率的影响

Fig. 5 Influence of current density on battery voltage and efficiency

图6 电流密度对输出功率的影响

Fig. 6 Influence of current density on output power

图7 燃料利用率对电池电压、效率的影响

Fig. 7 Influence of fuel utilization rate on battery voltage and efficiency

图8 燃料利用率对输出功率的影响

Fig. 8 Influence of fuel utilization rate on output power

图9 阴极空气利用率对电池电压、效率的影响

Fig. 9 Influence of cathode air utilization rate on battery voltage and efficiency

图10 阴极空气利用率对输出功率的影响

Fig. 10 Influence of cathode air utilization rate on output power

图11 弛放气循环比例对电池电压、效率的影响

Fig. 11 Effect of purge gas cycle ratio on battery voltage and efficiency

图12 弛放气循环比例对输出功率的影响

Fig. 12 Effect of purge gas circulation ratio on output power

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