CO2水热处理对香蕉假茎理化性质及气化成灰行为影响

  温室效应是人类命运共同体需要面对的问题，为此我国提出“碳达峰碳中和”战略目标。生物质能的开发利用是减少CO₂等温室气体排放的有效手段，生物质气化技术能够高效利用生物质资源，但在气化过程中会遇到生物质能量密度低及沾污、结渣等灰化学问题。本工作采用富钾香蕉假茎为原料，利用CO₂水热方式脱除生物质中碱金属及碱土金属，同时提高生物质热值，为气化提供优质原料。

  基于以上目的，考察水热气氛、温度、压力、水相循环次数对水热固体产物影响。通过工业分析、元素分析、热值等基本特性选择最优实验条件，采用FTIR、XRD对理化性质的变化原因进行探究。研究表明240℃、5 MPa CO₂水热是最优实验条件。通过ICP-MS研究水热温度对碱金属及碱土金属迁移规律和赋存形态影响，Ca、Mg、K、Na最高脱除率分别为58.55%、29.58%、98.55%、68.25%。

  通过ICP-MS、TGA、SEM、XRD、XPS等考察水热关键因素（温度）对气化成灰的影响。碱金属的大量脱除有效改善了气化过程中的灰行为。随着水热温度的增加，降低了气化灰中残炭的含量、降低熔融颗粒的数量，避免灰渣团聚的现象。在CO₂水热温度为200℃的水热炭其气化灰中出现了较强的CaCO₃、MgO衍射峰；水热温度240℃以上时，气化灰中出现MgCa(CO₃)₂衍射峰。不同温度CO2水热炭对应气化灰表面Ca元素形态各不相同，仅在原料、120℃水热炭气化灰表面观察到K的存在，水热温度的增加使得含Al化合物相对含量增加，气化过程中矿物组成转变为硅铝化合物。

  考察了气化关键因素（气化温度）对气化成灰影响。原料、水热炭气化灰分别在1200、1300℃以熔融玻璃态粘附在瓷舟上。随着气化温度的增加，原料气化灰产率逐渐降低；水热炭气化灰产率先降低，在1000℃后基本不变，气化反应较为完全。随着气化温度的增加，水热炭气化灰中碱金属及碱土金属总量增加，K占据比例变化幅度小；原料气化灰中碱金属及碱土金属总含量先略微降低再增加，K占据比例变化幅度大；水热炭气化灰物质结构转变较为简单，而原料会转变为复杂的硅铝酸盐。CO₂水热处理可以有效改善香蕉假茎气化过程中的成灰行为，提高气化反应效率。探究CO₂水热处理对水热炭理化性质及气化成灰行为影响，为富钾生物质的高效气化提供理论支撑。

The greenhouse effect need all people on earth to face it. “Carbon peak carbon neutral” proposed by China. The utilization of biomass is an effective way to solve it. Biomass gasification could make use of biomass, with low energy density, fouling and slagging problem and so on. CO2 hydrothermal pretreatment was used to handle banana pseudostem with high alkali metals, for removing AAEMs, also increasing calorific value.

Hydrochar were prepared by different hydrothermal atmosphere, temperature, pressure, and aqueous phase cycle times. Choosed the optimal experimental conditions by comparing industrial analysis, elemental analysis, calorific value and so on. Also explored the reason of physicochemical properties changed by FTIR and XRD. The result showed that 240℃, 5 MPa were the optimal experimental conditions of CO2 hydrothermal. Meanwhile, assessed content and the chemical speciation of AAEMs in the hydrochar by ICP-MS and chemical fractionation analysis. The highest removal rate of Ca, Mg, K, and Na were 58.55%, 29.58%, 98.55% and 29.58%, respectively.

The key factor for physicochemical characteristics was temperature, the effects of hydrothermal temperature for gasification ash were investigated by ICP-MS, TGA, SEM, XRD and XPS. With the increased of hydrothermal temperature, left less char and less molten particles in ash after gasification. Ash agglomeration was avoided during hydrochar gasification. Strong CaCO3 and MgO diffraction peaks appeared in the gasification ash from hydrochar made at 200℃. MgCa(CO3)2 diffraction peaks appeared at 240℃ or higher. The bind energy of Ca were not same in gasification ash from different temperature hydrochar. Only observed the presence of K on surface of gasification ash from 120℃ hydrochar and banana pseudostem. As the hydrothermal temperature increased, the silica-aluminium compounds were observed on surface of gasification ash from hydrochar.

Also, the effects of gasification temperature on gasification ash were investigated. Molten glassy state gasification ash from hydrochar and banana pseudostem appeared at 1300℃ and 1200℃, respectively. With the gasification temperature increased, the banana pseudostem ash yield gradually decreased, hydrochar ash yield was first to decrease, unchanged after 1000℃. Which mean the gasification reaction of hydrochar was more complete than banana pseudostem. With the increased of gasification temperature, the content of AAEMs in the hydrochar gasification ash increased, and the proportion of K changed small. The content of AAEMs in banana pseudostem gasification ash slightly decreased and then increased, and the proportion of K changed large. The structure transformation of hydrochar gasification ash were not complicated, while the banana pseudostem gasification ash would be transformed into complex silica-alumina. The CO2 hydrothermal pretreatment could effectively alleviate the ash problem during gasification, and made the gasification react more completely. Explored the effect of CO2 hydrothermal pretreatment for physicochemical characteristics of banana pseudostem and ash characteristics during gasification, to increase effeciency of gasification of potassium-rich biomass.

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