Development and application of coal gasification reactor model based on Gibbs free energy minimization method

doi:10.16085/j.issn.1000-6613.2023-1493

Abstract

Abstract:

In the present study, the coal gasification module was explored by integrating the models of coal pyrolysis process and gasification process. The composition of coal pyrolysis was calculated according to the pyrolysis model. The equilibrium model was constructed with the principle of Gibbs free energy minimization. The model of coal gasification process was solved by converting the optimization problem with equilibrium constraint into an unconstrained optimization problem with the Rand method. The accuracy of the explored coal gasification model was examined with industrial data. The effects of coal slurry concentration and oxygen-coal ratio on the composition of gasification products were studied with the new coal gasification reactor module. The results indicated that the volume fraction of effective gas increased from 71.6% to 81.2% with the increase of coal slurry concentration from 52.5% to 65.5%, and it increased to 77.75% and then decreased with the oxygen-coal ratio increased from 491 to 560. The effective gas volume fraction increased with the increase of coal slurry concentration, and the fraction increased to the maximum value and then decreased with the increase of oxygen coal ratio concentration. The developed coal gasification module could accurately and reliably simulate the coal gasification process, and it had an important practical value.

Key words: coal gasification, Rand method, Gibbs free energy, reactors

摘要：

本研究开发的煤气化专有模块集成了煤气化的热解过程与气化过程模型。根据热解模型计算得到煤热解后的组成，基于吉布斯自由能最小化的原理构建平衡模型，采用Rand法将有平衡约束的最优化问题转换为无约束的最优化问题，简化煤气化过程模型的求解方法，得到煤气化反应产物的组成，并以煤气化工业数据为例，检验开发的煤气化模型的准确性。基于开发的煤气化反应器模型，考察了煤浆浓度和氧煤比对气化产品组成的影响。结果表明，当煤浆体积分数为52.5%~65.5%时，有效气体体积分数由71.6%增加至81.2%；当氧煤比由491增大到560时，有效气体体积分数增大至最大值77.75%后又逐渐减小。有效气体体积分数随着煤浆浓度增大而增大，随着氧煤比浓度增大呈先增大后减小趋势。开发的煤气化专有模块对煤气化过程的模拟结果准确可靠，具有重要的实用价值。

关键词: 煤气化, Rand法, 吉布斯自由能, 反应器

CLC Number:

TQ546

ZHAO Menglei, ZHAO Jun, LU Hongbin, TAO Shaohui, ZHAO Wenying, XIANG Shuguang. Development and application of coal gasification reactor model based on Gibbs free energy minimization method[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 4793-4799.

赵梦磊, 赵军, 鲁鸿滨, 陶少辉, 赵文英, 项曙光. 基于吉布斯自由能最小化法煤气化反应器模型开发及应用[J]. 化工进展, 2024, 43(9): 4793-4799.

Figures/Tables 9

References 25

1	张利合, 张凡, 李昌伦, 等. BGL煤气化动力学模型构建与验证[J]. 化工学报, 2022, 73(10): 4668-4678.
	ZHANG Lihe, ZHANG Fan, LI Changlun, et al. Construction and verification of BGL coal gasification kinetic model[J]. CIESC Journal, 2022, 73(10): 4668-4678.
2	郑志行, 张家元, 李谦, 等. 气流床煤气化的Aspen Plus建模: 平衡模型和动力学模型[J]. 化工进展, 2021, 40(8): 4165-4172.
	ZHENG Zhihang, ZHANG Jiayuan, LI Qian, et al. Aspen Plus modeling of the entrained bed coal gasification: Equilibrium model and kinetic model[J]. Chemical Industry and Engineering Progress, 2021, 40(8): 4165-4172.
3	WHITE W B, JOHNSON S M, DANTZIG G B. Chemical equilibrium in complex mixtures[J]. The Journal of Chemical Physics, 1958, 28(5): 751-755.
4	NICHITA Dan Vladimir, GOMEZ Susana, LUNA Eduardo. Multiphase equilibria calculation by direct minimization of Gibbs free energy with a global optimization method[J]. Computers & Chemical Engineering, 2002, 26(12): 1703-1724.
5	ROSSI C C R S, CARDOZO-FILHO L, GUIRARDELLO R. Gibbs free energy minimization for the calculation of chemical and phase equilibrium using linear programming[J]. Fluid Phase Equilibria, 2009, 278(1/2): 117-128.
6	YOSHIDA Hiroki, KIYONO Fumio, TAJIMA Hideo, et al. Two-stage equilibrium model for a coal gasifier to predict the accurate carbon conversion in hydrogen production[J]. Fuel, 2008, 87(10/11): 2186-2193.
7	朱有健, 王定标, 周俊杰. 固定床煤气化炉的模拟与优化[J]. 化工学报, 2011, 62(6): 1606-1611.
	ZHU Youjian, WANG Dingbiao, ZHOU Junjie. Simulation and optimization of fixed bed gasifier[J]. CIESC Journal, 2011, 62(6): 1606-1611.
8	KONG Xiangdong, ZHONG Weimin, DU Wenli, et al. Three stage equilibrium model for coal gasification in entrained flow gasifiers based on Aspen Plus[J]. Chinese Journal of Chemical Engineering, 2013, 21(1): 79-84.
9	Marek ŚCIĄŻKO, Leszek STĘPIEŃ. A modified Gibbs free energy minimisation model for fluid bed coal gasification[J]. Chemical and Process Engineering, 2015, 36(1): 73-87.
10	张志刚, 段明哲, 宋一鸣, 等. 基于Aspen Plus的热解粉焦气流床气化过程模拟与分析[J]. 煤化工, 2015, 43(6): 10-13.
	ZHANG Zhigang, DUAN Mingzhe, SONG Yiming, et al. Simulation and analysis of pyrolytic coke fine entrained flow gasification process based on aspen plus[J]. Coal Chemical Industry, 2015, 43(6): 10-13.
11	刘忠慧, 于旷世, 张海霞, 等. 基于Aspen Plus的循环流化床工业气化炉模拟[J]. 化工进展, 2018, 37(5): 1709-1717.
	LIU Zhonghui, YU Kuangshi, ZHANG Haixia, et al. Simulation of industrial circulating fluidized bed gasifier by Aspen Plus[J]. Chemical Industry and Engineering Progress, 2018, 37(5): 1709-1717.
12	姚源朝, 仇鹏, 许建良, 等. 基于混合模型的气流床气化炉建模[J]. 化工学报, 2021, 72(5): 2727-2734.
	YAO Yuanchao, QIU Peng, XU Jianliang, et al. Modeling of entrained-bed gasifier based on hybrid model[J]. CIESC Journal, 2021, 72(5): 2727-2734.
13	褚宏达, 唐升连. 灰熔聚流化床粉煤气化模拟[J]. 一重技术, 2014(4): 59-61.
	CHU Hongda, TANG Shenglian. Simulation of fluid-bed pulverized coal gasification with ash fusion agglomeration[J]. CFHI Technology, 2014(4): 59-61.
14	赵伟刚, 范飞, 李建仓, 等. ASPEN PLUS对循环流化床煤气化模拟研究[J]. 计算机与应用化学, 2018, 35(5): 400-406.
	ZHAO Weigang, FAN Fei, LI Jiancang, et al. Simulation of coal gasification in a circulatingfluidized bed using ASPEN PLUS[J]. Computers and Applied Chemistry, 2018, 35(5): 400-406.
15	王武谦, 方晨昭, 韩方煜. 多相多组份化学平衡模拟的研究(自由能最小法)[J]. 计算机与应用化学, 1990, 7(4): 259-267.
	WANG Wuqian, FANG Chenzhao, HAN Fangyu. Study on the equilibrium simulation of multicomponent and multiphase system (minimizating Gibbs free energy)[J]. Computers and Applied Chemistry, 1990, 7(4): 259-267.
16	林金清, 李浩然, 韩世钧. 应用遗传算法求解含化学反应体系的相平衡[J]. 化工学报, 2002, 53(6): 616-620.
	LIN Jinqing, LI Haoran, HAN Shijun. Computation algorithm for simultaneous chemical and phase equilibrium by using genetic algorithm[J]. Journal of Chemical Industry and Engineering (China), 2002, 53(6): 616-620.
17	郑小青, 魏江, 葛文锋, 等. 通用Gibbs反应器的机理建模和求解方法[J]. 计算机工程与应用, 2014, 50(19): 241-244.
	ZHENG Xiaoqing, WEI Jiang, GE Wenfeng, et al. First-principle modeling and solving method for universal Gibbs reactor[J]. Computer Engineering and Applications, 2014, 50(19): 241-244.
18	MCDONALD Conor M, FLOUDAS Christodoulos A. Global optimization and analysis for the Gibbs free energy function using the UNIFAC, Wilson, and ASOG equations[J]. Industrial & Engineering Chemistry Research, 1995, 34(5): 1674-1687.
19	OTTO Christopher, KEMPKA Thomas. Synthesis gas composition prediction for underground coal gasification using a thermochemical equilibrium modeling approach[J]. Energies, 2020, 13(5): 1171.
20	GAUTAM Rajeev, SEIDER Warren D. Computation of phase and chemical equilibrium: Part Ⅰ. Local and constrained minima in Gibbs free energy[J]. AIChE Journal, 1979, 25(6): 991-999.
21	ZHU Yi, OYEDUN Adetoyese Olajire, WANG Maojian, et al. Simultaneous optimization of a heat integrated coal gasification process[J]. Chemical Engineering Research and Design, 2015, 98: 136-146.
22	GAUTAM Rajeev, SEIDER Warren D. Computation of phase and chemical equilibrium: Part Ⅱ. Phase-splitting[J]. AIChE Journal, 1979, 25(6): 999-1006.
23	GAUTAM Rajeev, SEIDER Warren D. Computation of phase and chemical equilibrium: Part Ⅲ. Electrolytic solutions[J]. AIChE Journal, 1979, 25(6): 1006-1015.
24	WHITE Charles White Iii, SEIDER Warren D. Computation of phase and chemical equilibrium, part Ⅳ: Approach to chemical equilibrium[J]. AIChE Journal, 1981, 27(3): 466-471.
25	LI X, GRACE J R, WATKINSON A P, et al. Equilibrium modeling of gasification: A free energy minimization approach and its application to a circulating fluidized bed coal gasifier[J]. Fuel, 2001, 80(2): 195-207.

工业分析（质量分数，干基）/%					元素分析（质量分数，干基）/%
固定碳	挥发分	灰分	湿含量		碳	氢	氧	氮	硫
61.64	31.57	6.79	16		74.05	4.99	10.37	1.01	0.64

工业分析（质量分数，干基）/%					元素分析（质量分数，干基）/%
固定碳	挥发分	灰分	湿含量		碳	氢	氧	氮	硫
61.64	31.57	6.79	16		74.05	4.99	10.37	1.01	0.64

项目	H₂体积分数/%	CO体积分数/%	CO₂体积分数/%	CH₄含量/mg·L^-1	H₂S体积分数/%	(CO+H₂)体积分数/%
模拟值	37.14	40.57	21.52	435	0.19	77.72
实际值	37.79	41.47	20.29	398	0.17	79.26
绝对偏差	-0.65	-0.9	1.23	37	0.02	-1.54
相对偏差/%	1.72	2.17	6.06	9.30	11.76	1.94

项目	H₂体积分数/%	CO体积分数/%	CO₂体积分数/%	CH₄含量/mg·L^-1	H₂S体积分数/%	(CO+H₂)体积分数/%
模拟值	37.14	40.57	21.52	435	0.19	77.72
实际值	37.79	41.47	20.29	398	0.17	79.26
绝对偏差	-0.65	-0.9	1.23	37	0.02	-1.54
相对偏差/%	1.72	2.17	6.06	9.30	11.76	1.94

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