生物质气压烘焙技术研究进展

doi:10.16085/j.issn.1000-6613.2023-2126

化工进展 ›› 2024, Vol. 43 ›› Issue (5): 2494-2511.DOI: 10.16085/j.issn.1000-6613.2023-2126

• 新能源与可再生能源 • 上一篇

生物质气压烘焙技术研究进展

石鎏¹(), 胡振中¹, 李显¹(), 孙一鸣¹, 童珊¹, 刘显哲¹, 郭丽¹^,²^,³, 刘豪¹, 彭冰¹, 李硕¹, 罗光前¹, 姚洪¹

^1.华中科技大学能源与动力工程学院煤燃烧与低碳利用全国重点实验室，湖北武汉 430074
^2.新疆大学化工学院新疆煤炭清洁转化与化工自治区重点实验室，新疆乌鲁木齐 830002
^3.新疆维吾尔自治区计量测试研究院，新疆乌鲁木齐 830011

收稿日期:2023-12-01 修回日期:2024-02-04 出版日期:2024-05-15 发布日期:2024-06-15
通讯作者: 李显
作者简介:石鎏（1995—），男，博士研究生，研究方向为能源化工及固体燃料燃烧。E-mail：liu_shi@hust.edu.cn。
基金资助:
中国博士后科学基金(2023M731180);深圳华中科技大学研究院深圳科技计划(JSGG202011021534000001)

Gas-pressurized torrefaction of biomass: A review

SHI Liu¹(), HU Zhenzhong¹, LI Xian¹(), SUN Yiming¹, TONG Shan¹, LIU Xianzhe¹, GUO Li¹^,²^,³, LIU Hao¹, PENG Bing¹, LI Shuo¹, LUO Guangqian¹, YAO Hong¹

^1.State Key Laboratory of Coal Combustion, School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China
^2.Xinjiang Key Laboratory of Coal Clean Conversion & Chemical Engineering Process, School of Chemical Engineering and Technology, Xinjiang University, Urumqi 830002, Xinjiang, China
^3.Institute of Metrology and Testing of Xinjiang Uygur Autonomous Region, Urumqi 830011, Xinjiang, China

Received:2023-12-01 Revised:2024-02-04 Online:2024-05-15 Published:2024-06-15
Contact: LI Xian

摘要/Abstract

摘要：

气压烘焙技术具备反应条件温和、能耗低、脱氧效率高、能量回收率高、半焦燃料品质近似次烟煤等优势，是一种有希望替代传统烘焙的新型技术之一。本文介绍了气压烘焙的发展脉络，综述了气压烘焙工况优化（包括原料种类、温度、压力、时间）、产物组成与理化特性，阐述了气压烘焙宏观反应路径和微观反应机理，着重介绍了半焦的燃烧、热解、气化利用途径，回顾了气压烘焙的反应器设计及其在含氯固废、污泥等处置中的拓展。最后对气压烘焙技术可将生物质转化为高品质固体燃料，直接替代煤炭进行了总结和展望。

关键词: 生物质, 气压烘焙, 脱氧, 优化, 产物特性

Abstract:

Gas-pressurized (GP) torrefaction has the advantages of mild reaction conditions, low energy consumption, high deoxygenation efficiency, high energy recovery efficiency, and semi-coke fuel quality similar as subbitumiunous coal. It is one of the novel technologies promising to replace the traditional torrefaction. This review introduces the development of GP torrefaction, reviews the optimization of GP torrefaction conditions (including the raw biomass type, temperature, pressure and time) and product composition and physicochemical properties, explains the macroscopic reaction pathways and microscopic reaction mechanisms, focuses on the combustion, pyrolysis and gasification utilisation pathways of semi-coke, reviews the reactor design and expansion in solid waste treatment such as chlorinated solid waste, sludge, etc. Finally, the GP torrefaction technology converting biomass into high fuel quality solid fuel which can directly replace coal is summarised and prospected.

Key words: biomass, gas-pressurized torrefaction, deoxygenation, optimization, product characteristics

中图分类号:

石鎏, 胡振中, 李显, 孙一鸣, 童珊, 刘显哲, 郭丽, 刘豪, 彭冰, 李硕, 罗光前, 姚洪. 生物质气压烘焙技术研究进展[J]. 化工进展, 2024, 43(5): 2494-2511.

SHI Liu, HU Zhenzhong, LI Xian, SUN Yiming, TONG Shan, LIU Xianzhe, GUO Li, LIU Hao, PENG Bing, LI Shuo, LUO Guangqian, YAO Hong. Gas-pressurized torrefaction of biomass: A review[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2494-2511.

图/表 33

图1 密闭反应体系下的生物质气压烘焙示意图[28]

图2 稻秆常压和气压烘焙产物分布、氧分布及碳分布[37]（AP-200和GP-200分别表示200℃下的常压烘焙和气压烘焙，本图其余同类标注含义相同）

表1 气压烘焙与传统烘焙关键参数比较[10, 22, 29-35]

项目	常压烘焙	气压烘焙
条件	250~300℃	200~250℃
	常压	1~1.8MPa
	10~120min	15~60min
机制	热裂解反应	强化挥发分与生物质的二次反应
能耗	高	低
半焦品质	氧含量>30%；高位热值17~24MJ/kg	氧含量约20%；高位热值23~28MJ/kg
	能量回收率70%~95%	能量回收率85%~96%
	可磨性好	可磨性好
	燃料品质近似泥煤	燃料品质近似次烟煤

表2 农业和林业生物质烘焙半焦的工业分析、元素分析和高位热值

种类	样品	烘焙条件	工业分析（d.b.）/%			元素分析（d.a.f.）/%				高位热值（d.a.f.） /MJ·kg^-1
种类	样品	烘焙条件	挥发分	固定碳	灰分	C	H	N	O	高位热值（d.a.f.） /MJ·kg^-1
农业生物质	稻秆1^[36]		75.2	15.2	9.6	48.9	5.2	0.9	45.0	15.9
		250℃、15min常压烘焙	68.8	19.9	11.3	50.8	5.6	1.0	42.7	17.5
		250℃、2.5MPa、15min气压烘焙	40.8	40.5	18.7	68.4	5.2	1.5	24.9	26.2
	稻秆2^[28]		75.2	15.1	9.7	45.8	6.0	1.1	47.1	15.7
		250℃、60min常压烘焙	72.1	15.9	12.1	53.2	6.0	1.3	39.5	19.7
		250℃、1.8MPa、60min气压烘焙	45.9	36.0	18.2	70.8	5.5	1.9	21.8	28.0
	玉米秸秆^[37]		72.7	19.6	7.7	43.7	5.3	2.8	48.2	17.6
		250℃、30min常压烘焙	66.6	22.3	11.1	45.4	4.9	2.3	47.4	18.2
		250℃、2.5MPa N₂、30min气压烘焙	49.5	35.7	14.8	56.7	4.5	2.5	36.3	22.2
	芦苇^[38]		70.0	18.1	11.9	44.5	5.7	1.7	48.1	14.6
		270℃、30min常压烘焙	35.3	47.0	17.7	51.4	5.1	2.1	41.4	17.3
		270℃、2.5MPa N₂、30min气压烘焙	30.9	43.4	25.7	59.6	4.0	3.0	33.4	19.9
林业生物质	松木1^[39]		85.5	14.1	0.4	50.3	5.9	0.04	43.8	17.7
		250℃、15min常压烘焙	82.5	17.0	0.5	53.3	6.0	0.03	40.6	19.4
		250℃、2.5MPa N₂、15min气压烘焙	62.1	37.1	0.8	65.4	5.5	0.09	29.1	24.7
	松木2		80.6	16.9	2.5	47.9	5.6	0.2	46.3	16.9
		250℃、60min常压烘焙	75.0	21.0	3.1	51.9	5.5	0.2	42.4	18.7
		250℃、1.8MPa、60min气压烘焙	43.0	53.6	3.4	71.3	4.7	0.3	23.7	27.0
	银合欢^[21]		87.3	12.2	0.5	50.1	7.4	0.7	41.8	20.4
		250℃、30min常压烘焙	81.6	17.3	1.1	54.0	6.4	0.7	38.9	21.9
		250℃、4.0MPa、30min气压烘焙	60.0	38.2	1.8	62.3	5.6	1.0	31.1	25.8
	杨木^[37]		84.0	15.1	0.9	49.2	5.5	0.8	43.5	19.5
		250℃、30min常压烘焙	82.9	15.6	1.5	49.8	5.7	0.8	43.7	19.8
		250℃、2.5MPa N₂、30min气压烘焙	71.2	26.9	1.8	58.4	5.6	0.5	35.4	23.5

表3 稻秆原样、褐煤、次烟煤和稻秆烘焙半焦的工业分析、元素分析和高位发热量分析结果比较[37, 41-42]

样品	工业分析（d.b.）/%			元素分析（d.a.f.）/%				高位热值（d.a.f.） /MJ·kg^-1
样品	挥发分	固定碳（diff.）	灰分	C	H	N	O（diff.）	高位热值（d.a.f.） /MJ·kg^-1
稻秆	75.2	15.2	9.6	48.9	5.2	0.9	45.0	15.9
AP-200	74.3	15.5	10.2	47.5	6.0	0.9	45.6	16.5
AP-250	68.8	19.9	11.3	50.8	5.6	1.0	42.7	17.5
AP-300	43.0	35.5	21.5	65.3	5.0	1.3	28.4	24.1
GP-200	49.8	33.8	16.4	61.0	5.6	1.3	32.1	22.8
GP-250	40.8	40.5	18.7	68.4	5.2	1.5	24.9	26.2
GP-300	30.6	47.5	21.9	73.2	5.1	1.6	20.0	28.6
褐煤	45.3	34.2	20.5	65.3	4.9	1.1	28.7	24.0
次烟煤	33.2	44.3	22.5	74.9	5.7	1.5	17.9	31.7

图3 稻秆和稻秆烘焙半焦的范·克雷维伦图[37]

图4 不同终压下烘焙半焦的氧分布[43]（GP-250-1.3表示250℃、1.3MPa下的气压烘焙，本图其余同类标注含义相同）

图5 总压和挥发分分压与气压烘焙半焦的氧减量与碳增量的关系[29]

图6 稻秆常压、半封闭和气压烘焙氧分布及气压和二次反应对稻秆气压烘焙脱氧的贡献度指数[35, 43]（GP-200-0表示200℃、0min下的气压烘焙，本图其余同类标注含义相同）

图7 稻秆气压烘焙半焦收率、氧含量及碳含量[43]（稻秆在常压和气压烘焙下以5℃/min的速率从室温25℃升温到250℃，并在250℃保温60min）

图8 稻秆烘焙产物收率分布[28]（GP-200-0.55表示200℃、0.55MPa、60min条件下的气压烘焙，本图其余同类标注含义相同）

图9 烘焙半焦中单糖组成与收率[28]（GP-200-0.55表示200℃、0.55MPa、60min条件下的气压烘焙，本图其余同类标注含义相同）

图10 稻秆原样、常压烘焙半焦和气压烘焙半焦的热重曲线和热重微分曲线[43]（GP-250-1.3表示250℃、1.3MPa条件下的稻秆气压烘焙半焦，本图其余同类标注含义类似）

图11 稻秆常压和气压烘焙液体产物的组成和收率[28]（GP-200-0.55表示200℃、0.55MPa、60min条件下的气压烘焙，本图其余同类标注含义相同）

图12 烘焙过程液体产物中有机物的组成分类及其收率[28]（GP-200-0.55表示200℃、0.55MPa、60min条件下的气压烘焙，本图其余同类标注含义相同）

图13 稻秆烘焙过程液体产物中有机物的典型指纹分子[28]

图14 稻秆常压和气压烘焙气体产物的组成[46]（GP-200-0.55表示200℃、0.55MPa、60min条件下的气压烘焙，本图其余同类标注含义相同）

图15 稻秆原样，250℃、15min稻秆常压烘焙和250℃、1.5MPa、15min气压烘焙半焦的宏观和微观形貌[37]

表4 稻秆原样、烘焙半焦和褐煤的部分理化特性[46]

样品	体积密度（d.b.）/kg·m^-3	能量密度（d.b.）/MJ·m^-3	可磨性粒径的中位数/nm	平衡吸水率/%
稻秆原样	165	2163	88850	13.96
常压烘焙半焦^①	144	2010	416.1	9.42
气压烘焙半焦^②	180	3309	28.25	7.52
褐煤	560～600	10600～11400	20000～60000	21.50

图16 稻秆原样、烘焙半焦的XRD谱图[43]（GP-250-30表示250℃、30min气压烘焙半焦，本图其余同类标注含义相同）

图17 稻秆原样、烘焙半焦的红外谱图[43]（GP-250-30表示250℃、30min气压烘焙半焦，本图其余同类标注含义相同）

图18 气压和常压烘焙半焦的13C NMR谱图[28]（GP-200-0.55表示200℃、0.55MPa条件下的气压烘焙，本图其余同类标注含义类似）

图19 白杨在280℃、不同压力下烘焙的TG和DTG曲线[18]

图20 传统烘焙、半封闭烘焙和气压烘焙的动力学反应路径[43]

图21 250℃气压烘焙和常压烘焙半焦脱氧和结构演化示意图[28]

表5 稻秆原样、烘焙半焦的的燃烧行为参数[46]

样品	着火点 /℃	燃尽温度 /℃	最大失重温度 /℃	最大失重速率 /%·min^-1
稻秆原样	250	500	285	8.6
常压烘焙半焦^①	271	522	294	10.2
气压烘焙半焦^②	297	511	382	6.6
次烟煤	317	549	406	35.3

表6 稻秆和木屑原样、常压烘焙半焦和气压烘焙半焦热解制得生物油的元素组成与高位热值[31]

样品	元素分析/%				高位热值 /MJ·kg^-1
样品	C	H	N	O	高位热值 /MJ·kg^-1
稻秆
原样-热解生物油	34.0	8.7	0.8	56.5	13.9
常压烘焙-热解生物油	36.5	8.0	1.1	54.4	14.1
气压烘焙-热解生物油	59.6	4.0	1.4	31.1	20.3
木屑
原样-热解生物油	36.3	8.4	0.1	55.2	14.4
常压烘焙-热解生物油	42.0	7.8	0.6	49.6	16.5
气压烘焙-热解生物油	53.8	7.4	0.1	38.7	21.9

图22 稻秆和木屑原样、常压烘焙半焦和气压烘焙半焦热解制得生物油的产物组成与含量[31]（250℃、15min稻秆常压烘焙半焦和250℃、1.5MPa、15min稻秆气压烘焙半焦在500℃下热解10min）

图23 稻秆、常压和气压烘焙半焦的气化的气体产物分布和液体含量[37]（250℃、15min稻秆常压烘焙半焦和250℃、5.0MPa、15min稻秆气压烘焙半焦在900℃下0.25L/min CO2气化20min）

图24 稻秆-煤、常压烘焙半焦-煤和气压烘焙半焦-煤共气化气体产物分布[49]（RS-25%表示25%稻秆原料与75%褐煤混合气化，本图其余同类标注含义类似；250℃、15min稻秆常压烘焙半焦和250℃、5.1MPa、15min稻秆气压烘焙半焦在950℃下0.1L/min CO2气化20min）

图25 稻秆-煤、常压烘焙半焦-煤和气压烘焙半焦-煤气化与共气化的碳转化率[49]（RS表示稻秆气化的碳转化率；RS-褐煤表示50%稻秆原料与50%褐煤混合气化的碳转化率；RS-褐煤-理论表示50%稻秆原料与50%褐煤混合气化的理论碳转化率；本图其余同类标注含义类似）

图26 一种生物质热量自平衡气压烘焙系统[50-51]1—物料进口；2—螺杆进料器；3—气动蝶阀；4—烟气换热器；5—温度传感器；6—压力传感器；7—输送螺杆；8—控制器；9—卸料阀；10—物料出口；11—传送带；12—燃烧器；13—烟气分流器；14—烟气出口；15—烟气增压泵；16—换热器烟气出口；17—背压阀

图27 一种基于气压烘焙的高氯固废处置方法及装置[52]1—给料器；2—第一缩合组件；3—支撑杆；4—压力传感器；5—温度传感器；6—气体入口；7—固氯器；8—燃烧器；9—增压泵；10—气化炉；11—气体分离器；12—计算机；13—温度传感器；14—气体传感器；15—气锁组件；16—脱氯反应器

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生物质气压烘焙技术研究进展

Gas-pressurized torrefaction of biomass: A review

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