10MWth高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

doi:10.11949/j.issn.0438-1157.20181415

化工学报 ›› 2019, Vol. 70 ›› Issue (6): 2279-2288.DOI: 10.11949/j.issn.0438-1157.20181415

10MW_th高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

王璐璐¹(),宋涛²(),张将¹,段媛媛²,沈来宏¹

1. 能源热转换及其过程测控教育部重点实验室，东南大学能源与环境学院，江苏南京210096
2. 南京师范大学能源与机械工程学院，江苏南京210042

收稿日期:2018-11-27 修回日期:2019-02-27 出版日期:2019-06-05 发布日期:2019-06-05
通讯作者: 宋涛
作者简介:<named-content content-type="corresp-name">王璐璐</named-content>（1993—），女，博士研究生，<email>18251811255@163.com</email>
基金资助:
国家重点研发计划项目(2018YFB0605404);基金项目:国家自然科学基金项目(51761135119);江苏省研究生科研与实践创新计划项目(KYCX18_0082)

Simulation of chemical looping gasification of high-sulfur petroleum coke for syngas production coupled with recycling sulfur in 10 MW_th system

Lulu WANG¹(),Tao SONG²(),Jiang ZHANG¹,Yuanyuan DUAN²,Laihong SHEN¹

1. Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing 210096, Jiangsu, China
2. School of Energy and Mechanical Engineering, Nanjing Normal University, Nanjing 210042, Jiangsu, China

Received:2018-11-27 Revised:2019-02-27 Online:2019-06-05 Published:2019-06-05
Contact: Tao SONG

摘要/Abstract

摘要：

基于化学链气化技术依靠气固反应定向调控气化产物中H₂S和SO₂摩尔比为2的优势，将化学链气化与Claus工艺中的催化转化单元相结合，提出了高硫石油焦化学链气化制合成气和回收硫磺的新系统。针对系统核心单元，即化学链气化过程，基于Aspen Plus，开展热输入10 MW_th的高硫石油焦化学链气化过程模拟，以赤铁矿石为载氧体，水蒸气为气化介质，重点考察了氧碳比、气化温度对化学链气化过程及硫转化过程的影响。结果发现，氧碳比的增大导致合成气产率显著降低，但系统从需要外部提供能量逐渐转变为对外部放热，在氧碳比0.8669～0.9535区间内，系统可以达到热量自平衡。同时，气化温度的提高对合成气产率是有利的，在975℃时达到2.15 m³/kg，主要是由于CO体积分数随气化温度增加而增加。氧碳比和气化温度的提高都会导致H₂S浓度的降低和SO₂浓度的提高。并且研究了当H₂S和SO₂摩尔比为2的最佳工况时，氧碳比和气化温度为反相关，其中氧碳比为0.8669，气化温度为900℃时，冷煤气效率为64.09%。

关键词: 载氧体, 化学链气化, 石油焦, 硫磺, 模拟

Abstract:

The present work proposes a novel system which integrates high-sulfur petroleum coke chemical looping gasification (CLG) and sulfur recovery. Depending on the gas-solid reaction, CLG process has the ability to control the reaction pattern to obtain the mole ratio of H₂S and SO₂ as 2 in the syngas. The chemical chain gasification is combined with the catalytic conversion unit in the Claus process, and the high sulfur petroleum coke chemistry is proposed. Focusing on the core part of the system, CLG section, the simulation using the Aspen Plus was performed. The thermal input was designed as 10 MW_th with high-sulfur petroleum coke as fuel. Iron ore and steam were used as oxygen carrier and gasification agent respectively. Effects of O/C, gasification temperature on the thermal balance during CLG process, syngas yield, effective gas content and sulfur conversion were investigated. Results indicated that increasing O/C leads to a decrease in the production yield of syngas, but the system gradually shifts from the endothermic to exothermic. When O/C is between 0.8669 and 0.9535, the system can maintain the heat balance without extra energy. Further, the increase of temperature is beneficial to syngas production. The CO concentration increases with increasing temperature and reaches 2.15 m³/kg at a gasification temperature of 975℃. A high ratio of O/C and gasification temperature can enhance H₂S conversion during gasification process with a consequence of H₂S concentration decreasing and SO₂ concentration increasing. Furthermore, in the best case of the mole fraction of H₂S to SO₂ as 2, a negative correlation on the factors of O/C ratio and temperature was found. The cold gas efficiency is 64.09% at the conditions of the O/C ratio as 0.8669 and the gasification temperature of 900℃.

Key words: oxygen carrier, chemical looping gasification, petroleum coke, sulfur, simulation

中图分类号:

TK 16

王璐璐, 宋涛, 张将, 段媛媛, 沈来宏. 10MW_th高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究[J]. 化工学报, 2019, 70(6): 2279-2288.

Lulu WANG, Tao SONG, Jiang ZHANG, Yuanyuan DUAN, Laihong SHEN. Simulation of chemical looping gasification of high-sulfur petroleum coke for syngas production coupled with recycling sulfur in 10 MW_th system[J]. CIESC Journal, 2019, 70(6): 2279-2288.

图/表 15

图1 石油焦化学链气化制合成气耦合Claus催化转化回收硫磺新系统

Fig.1 Schematic diagram of system integrating high-sulfur petroleum coke CLG and sulfur recovery via Claus

图2 Aspen Plus模拟流程图

Fig.2 Flow chart of Aspen Plus simulation

表1 石油焦的工业分析、元素分析以及形态硫含量

Table 1 Proximate, ultimate and sulfur analysis of petroleum coke

工业分析/%

热值/

(MJ/kg)

表2 赤铁矿石的化学组成

Table 2 Chemical components of iron ore/%(mass)

Fe₂O₃	Al₂O₃	SiO₂	CaO	P₂O₅	MgO	Na₂O	K₂O	CaSO₄
83.21	5.13	7.06	0.24	0.38	1.25	1.26	1.26	0.21

图3 模拟结果与实验结果比较

Fig.3 Comparison of simulation and experiment results

图4 氧碳比对化学链气化中常规气体释放的影响

Fig.4 Effect of O/C ratio on conventional gas releasing during CLG

图5 氧碳比对化学链气化过程中合成气释放和能量平衡的影响

Fig.5 Effect of O/C ratio on syngas releasing and heat balance during CLG

图6 温度对化学链气化中常规气体释放的影响

Fig.6 Effect of gasification temperature on conventional gas releasing during CLG

图7 温度对化学链气化过程中合成气释放和能量平衡的影响

Fig.7 Effect of gasification temperature on syngas releasing and heat balance during CLG

图8 氧碳比对化学链气化中含硫气体释放的影响

Fig.8 Effect of O/C ratio on sulfur-containing gas releasing during CLG

图9 氧碳比对化学链气化中H2S/SO2摩尔比的影响

Fig.9 Effect of O/C ratio on molar ratio of H2S/SO2 during CLG

图10 温度对化学链气化中含硫气体释放的影响

Fig.10 Effect of gasification temperature on sulfur-containing gas releasing during CLG

图11 温度对化学链气化中H2S/SO2摩尔比的影响

Fig.11 Effect of gasification temperature on molar ratio of H2S/SO2 during CLG

图12 最佳工况中温度、氧碳比和冷煤气效率、能量平衡间的关系

Fig.12 Relationships among gasification temperature, ratio of O/C, cold gas efficiency and heat balance in best cases

图13 最佳工况下系统的最佳硫磺回收率

Fig.13 Optimal sulfur recovery rate in best cases

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10MW_th高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

Simulation of chemical looping gasification of high-sulfur petroleum coke for syngas production coupled with recycling sulfur in 10 MW_th system

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10MWth高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

Simulation of chemical looping gasification of high-sulfur petroleum coke for syngas production coupled with recycling sulfur in 10 MWth system

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10MW_th高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

Simulation of chemical looping gasification of high-sulfur petroleum coke for syngas production coupled with recycling sulfur in 10 MW_th system