不同反应条件对造纸黑液水热炭化产物特性的影响OA
Effects of different reaction conditions on the characteristics of hydrothermal carbonization products from black liquor
针对造纸黑液的传统碱回收炉法处理高耗能、燃烧效率低等问题,该研究采用水热炭化技术直接处理造纸黑液,系统分析了单因素条件下水热温度(240~320℃)、保温时间(0.5~8 h)、黑液浓度(5%~57.24%)、初始 pH(1~8.8)及添加玉米秸秆的共水热炭化对于黑液水热炭化产物的不同影响并首次提出了水热炭化耦合厌氧消化的黑液资源化处理新路径.结果表明,在不同水热温度下,水热炭产率变化并不显著,且普遍较低(15%左右),但通过提高水热温度可有效提升水热炭品质,320℃时水热炭碳含量及热值分别由 240℃的 63.11%、25.87 MJ/kg提升至 83.85%和31.26 MJ/kg;保温时间与水热温度的影响类似,但程度较弱;黑液浓度与水热炭产率成正相关,但过度提高则会造成水热炭灰分的累积(7.96%~17.44%)和水热液有机负荷(33.39~320.10 g/L)的增加.酸性条件下,可有效提高黑液水热炭产率(14.61%~22.72%),且通过降低初始 pH 至 1时得到了最大的碳回收率(65.71%)、能量回收率(54.66%)以及 SCOD(soluble chemical oxygen demand)降解率(56.06%);添加玉米秸秆的共水热炭化可弥补黑液水热炭产率低的问题,且当黑液浓度大于 10%时,二者具有明显的协同效应.该研究可为造纸黑液的资源化处置和高值化利用提供思路和理论支撑.
Black liquor,a primary waste product from pulping and paper making,contains substantial amounts of inorganic components such as free alkali and sulfides,along with organic substances like lignin and hemicellulose.As a result,black liquor presents both significant environmental challenges and considerable potential for resource recovery.Hydrothermal carbonization(HTC)offers an effective route to overcome the concentration limitations of traditional alkali recovery combustion technology,enabling the solidification of dissolved organic matter in black liquor and in-situ upgrading to produce high-value solid carbon materials.By simultaneously concentrating carbon components and controlling the migration of inorganic species from black liquor,HTC provides a promising pathway for the coupled resource valorization and pollution mitigation of black liquor.Accordingly,this study investigates the application of HTC for black liquor treatment and carbon recovery.The effects of hydrothermal temperature(240-320℃),holding time(0.5-8 h),black liquor concentration(5%-57.24%),initial pH(1-8.8),and co-HTC(co-hydrothermal carbonization)with corn straw on product characteristics were systematically investigated.The characteristics of the collected hydrochar(yield,proximate analysis,C content,and HHV)and the aqueous phase(SCOD)were thoroughly analyzed.And based on these measurements,quantitative calculations of carbon recovery rate,energy recovery rate,and SCOD degradation rate were performed to comprehensively evaluate the dual benefits in achieving both resource recovery and harmless disposal of black liquor.Results showed that the characteristics of the hydrothermal carbonization products were significantly affected by changes in hydrothermal temperature,time,black liquor concentration,initial pH,and co-HTC with corn straw.At different hydrothermal temperatures,the yield of hydrochar did not vary significantly and remains generally low(around 15%),but increasing hydrothermal temperature effectively improved the fuel quality of hydrochar.When the hrdrothermal temperature reached 320℃,the carbon content and HHV of hydrochar increased from 63.11%and 25.87 MJ/kg at 240℃to 83.85%and 31.26 MJ/kg,respectively.The effect of holding time was similar to that of hydrothermal temperature,but to a lesser extent.Black liquor concentration was positively correlated with hydrochar yield.However,excessively increasing the black liquor concentration lead to an accumulation of ash in the hydrochar(7.96%-17.44%)and an increase in the organic load of the aqueous phase(33.39-320.10 g/L).Lowering the initial pH to 1 significantly increased the hydrochar yield to 22.72%and reduced the ash content to 1.43%,representing an ash removal efficiency of 99.36%.Furthermore,the maximum carbon recovery rate(65.71%),energy recovery rate(54.66%),and SCOD degradation rate(56.06%)were achieved at a relatively low temperature(240℃),which mitigates the energy consumption issues associated with high-temperature hydrothermal treatment.In addition,co-HTC with corn straw effectively addressed the low yield issue of hydrochar derived from black liquor.When the black liquor concentration exceeded 10%,the process exhibited significant synergistic effects in terms of hydrochar yield,carbon recovery,energy recovery,and SCOD degradation rate.These results indicate that HTC enables simultaneous resource utilization and pollution mitigation for black liquor.Given that 40%-60%of carbon remains in the hydrothermal liquor,coupling HTC with anaerobic digestion(AD)in a closed-loop configuration represents a viable pathway for achieving deeper contaminant removal and diversified resource recovery from black liquor.
郑克领;陈博阳;姜烨;连淑娟;何涛;付善飞
中国石油大学(华东)石大山能新能源学院,青岛 266580||中国科学院青岛生物能源与过程研究所,青岛 266101中国科学院青岛生物能源与过程研究所,青岛 266101||山东能源研究院,青岛 266101中国石油大学(华东)石大山能新能源学院,青岛 266580中国科学院青岛生物能源与过程研究所,青岛 266101||山东能源研究院,青岛 266101中煤(深圳)研究院有限责任公司,深圳 518102中国科学院青岛生物能源与过程研究所,青岛 266101||山东能源研究院,青岛 266101
资源环境
造纸黑液水热炭化反应条件水热炭碳回收能量回收共水热
black liquorhydrothermal carbonizationreaction conditionhydrocharcarbon recoveryenergy recoveryco-hydrothermal carbonization
《农业工程学报》 2026 (15)
80-89,10
国家自然科学基金青年项目(42307180)山东省自然科学基金青年项目(ZR2023QD002)吉林省与中国科学院科技合作高新技术产业化专项(2024SYHZ0002)
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