化学链燃烧中煤灰原位改性对钙基载氧体炭沉积的影响

doi:10.16085/j.issn.1000-6613.2023-1027

化工进展 ›› 2024, Vol. 43 ›› Issue (8): 4253-4261.DOI: 10.16085/j.issn.1000-6613.2023-1027

• 化工过程与装备 • 上一篇

化学链燃烧中煤灰原位改性对钙基载氧体炭沉积的影响

梁国威¹^,²(), 金晶¹^,²(), 董波¹^,², 侯封校³

^1.上海理工大学能源与动力工程学院，上海 200093
^2.上海市动力工程多相流与传热重点实验室，上海 200093
^3.中北大学能源与动力工程学院，山西太原 030051

收稿日期:2023-06-21 修回日期:2023-07-29 出版日期:2024-08-15 发布日期:2024-09-02
通讯作者: 金晶
作者简介:梁国威（1999—），男，硕士研究生，研究方向为化学链燃烧。E-mail：484115282@qq.com。
基金资助:
国家自然科学基金(51976129);上海市科委项目(23010503500);山西省基础研究计划(202103021223197)

Effect of in-situ modification of coal ash on carbon deposition of Ca-based oxygen carrier in chemical looping combustion

LIANG Guowei¹^,²(), JIN Jing¹^,²(), DONG Bo¹^,², HOU Fengxiao³

^1.School of Energy and Power Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
^2.Shanghai Key Laboratory of Multiphase Flow and Heat Transfer in Power Engineering, Shanghai 200093, China
^3.School of Energy and Power Engineering, North University of China, Taiyuan 030051, Shanxi, China

Received:2023-06-21 Revised:2023-07-29 Online:2024-08-15 Published:2024-09-02
Contact: JIN Jing

摘要/Abstract

摘要：

在流化床中利用准东煤灰负载在钙基载氧体上，对钙基载氧体进行原位改性，从而制备改性的CaSO₄-Ash复合载氧体。借助TG-MS实验中的CO₂离子流量强度曲线，考察准东煤灰负载量对载氧体还原反应过程中炭沉积特性的影响规律，并通过固固反应与气固反应定量耦合实验，探究炭沉积的来源。结果表明：炭沉积量随原位改性制备过程中煤灰比例升高先减少后增加，添加质量分数为10%的准东煤灰制备的CaSO₄-10Ash复合载氧体能够最大程度降低炭沉积问题，减少了79.5%的炭沉积。固固反应中随煤灰负载比例升高，煤焦炭残留量减少，气固反应中煤灰负载比例大于5%时，复合载氧体性能开始呈下降趋势，积炭量开始增多；当煤灰负载比例大于10%时，随负载比例继续升高而增多的炭沉积的量主要来自于CO分解产生的积炭。

关键词: 化学链燃烧, 准东煤, 煤灰改性, CaSO₄载氧体

Abstract:

The modified CaSO₄-Ash composite oxygen carrier was prepared by in-situ modification of Ca-based oxygen carriers using Zhundong coal ash in a fluidized bed. With the help of CO₂ ion flow intensity curves in TG-MS experiments, the influence of the loading amount of Zhundong coal ash on the carbon deposition characteristics during the oxygen carrier reduction reaction process was investigated, and a quantitative coupling experiment of solid-solid reaction and gas-solid reaction was proposed to explore the source of carbon deposition. The results showed that the amount of carbon deposition decreased first and then increased with the increase of the proportion of coal ash in the process of in-situ modification. The CaSO₄-10Ash composite oxygen carrier prepared by adding 10% of Zhundong coal ash could minimize the problem of carbon deposition and reduce it by 79.5%. In the solid-solid reaction, with the increase of the coal ash loading ratio, the residual amount of coal coke decreased. When the coal ash loading ratio in the gas-solid reaction was greater than 5%, the performance of the composite oxygen carrier began to decline, and the carbon deposition began to increase; when the coal ash loading ratio was greater than 10%, the amount of carbon deposition that increased as the load ratio continued to increase mainly came from carbon deposit generated by CO decomposition.

Key words: chemical looping combustion, Zhundong coal, coal ash modification, CaSO₄ oxygen carrier

中图分类号:

TK16

梁国威, 金晶, 董波, 侯封校. 化学链燃烧中煤灰原位改性对钙基载氧体炭沉积的影响[J]. 化工进展, 2024, 43(8): 4253-4261.

LIANG Guowei, JIN Jing, DONG Bo, HOU Fengxiao. Effect of in-situ modification of coal ash on carbon deposition of Ca-based oxygen carrier in chemical looping combustion[J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4253-4261.

图/表 9

表1 准东煤煤质分析

工业分析w_ad/%					元素分析w_d/%
M	A	V	FC		C	H	O	N	S
5.64	5.09	27.24	62.03		63.78	4.42	19.21	1.00	0.87

图1 准东煤在氩气气氛下的热解TG曲线

图2 准东煤在氩气气氛下的热解MS曲线

表2 准东煤灰成分分析（质量分数，%）

Na₂O	K₂O	CaO	Fe₂O₃	MgO	Al₂O₃	SiO₂	SO₃
8.9	0.25	15.8	17.9	5.3	6.1	7.68	30.7

图3 准东原煤与CaSO4-Ash复合载氧体化学链燃烧CO2离子流强度图

图4 准东煤焦炭与CaSO4-Ash复合载氧体化学链燃烧CO2离子流强度图

图5 CO与CaSO4-Ash复合载氧体化学链燃烧CO2离子流强度图

表3 CaSO4载氧体和CaSO4-Ash复合载氧体BET测试数据

载氧体	BET比表面积A/m²·g^-1	BJH介孔平均孔径D/nm
CaSO₄	2.13	24.43
CaSO₄-5Ash	1.27	13.65
CaSO₄-10Ash	1.02	14.46
CaSO₄-20Ash	1.24	12.69

图6 CaSO4载氧体和CaSO4-Ash复合载氧体SEM-EDX谱图

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化学链燃烧中煤灰原位改性对钙基载氧体炭沉积的影响

Effect of in-situ modification of coal ash on carbon deposition of Ca-based oxygen carrier in chemical looping combustion

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