生物质超临界水流化床气化制氢系统与方法研究

本文提出在生物质超临界水气化制氢过程中采用流化床反应器防止反应器结渣堵塞.首先,基于流化床内多相流动力学理论,通过分析获得了超临界水流化床的主要参数包括最小流化速度、终端速度、流化方式等的设计准则.应用此设计准则成功构建了一套超临界水流化床气化制氢系统,实验研究表明高浓度生物质浆料在长达5个小时的气化过程中反应器未见堵塞现象,并获得了与生物质在管流反应器中气化相似的气体产物.     

超临界水气化制氢耦合金属单质及其氧化物制备的技术探索

超临界水气化技术(Supercritical Water Gasification, SCWG)作为一种很有竞争力的制氢技术,在“双碳”目标愿景下,积极探索与氢冶金的结合路线具有重要的现实意义。本文提出一种新的技术路线：在同一个反应釜内,超临界水气化制氢的同时,完成金属氧化物的还原,简化冶金流程。从热力学及实验两方面验证了该技术的可行性,在甘油质量浓度2%、5%及10%的超临界水气化氛围下,均能迅速还原制取Fe₃O₄、Cu及MoO₂粉末;在甲酸质量浓度50%、60%及70%下气化均能实现蓝钨(WO_2.9)、紫钨(WO_2.72)的制取,且在50%质量浓度下,针状结构明显,较少结块。     

生物质超临界水制氢的数值模拟

本文对生物质在超临界水环境下气化制氢过程提出简化的两相流物理化学模型,并利用该模型进行数值模拟.着重讨论了温度、颗粒半径对生成气体摩尔百分比、气化率的影响.数值结果表明,颗粒的半径主要影响生物质颗粒气化分解的速率,而温度主要影响颗粒气化产物进一步生成氢气的过程.颗粒越小,气化分解的速率越快.温度的影响主要集中在气相反应上,使得CO进一步转化为H2.本文的理论和数值结果对实际的制氢过程中的参数控制具有实用价值.     

超临界水流化床反应器加料方式优化的数值模拟

超临界水流化床反应器是应用于生物质气化制氢工程中的一种新型反应器,它避免了以往管式反应器容易出现结渣、堵管的不足,而且还具有床内升温迅速、生物质气化充分以及产氢率高等优点。由于采用超临界水作为流化工质,传统流化床的设计方法已经不能满足设计要求。本文基于欧拉双流体模型对超临界水流化床加料方式进行了数值模拟研究,建立了最优加料口结构评价方法,分析了加料口结构、加料速度比以及初始床层高度对超临界水流化床颗粒分布的影响。本文研究进一步完善了超临界水流化床的设计理论。     

超临界水流化床内煤气化过程建模与仿真(2):气化反应动力学模型及气化规律

本文成功建立了煤超临界水气化动力学模型,其中包括煤在超临界水中热解、液化、固相残碳及液化产物的蒸汽重整等均相和非相反应。该动力学模型能准确反应煤在超临界水中气化特征。在前述第一部分工作的基础上,耦合该气化动力学模型,对煤在超临界水流化床中气化过程进行了建模。通过该模型研究了宽温度参数范围下反应器内典型反应速率、反应组分分布演变规律,揭示了反应器内部化学反应特征与气化规律。研究加深了对超临界水流化床内煤气化过程的认识,对超临界水流化床反应器的优化、放大以及实际运行具有指导意义。     

含碳能源直接制氢的热力学分析与实验研究

本文在对构建的含碳能源直接制氢体系进行热力学分析的基础上,建造了含碳能源直接制氢近零排放定容实验系统,并进行了不同参数下的实验研究。热力学分析表明本文构建的系统不仅存在合适的反应条件,而且在此反应条件下可以实现体系的热平衡。实验结果表明了该系统的可行性,实现了气态产物中氢含量大于80％,二氧化碳及一氧化碳含量均小于0.1％,达到了直接制氢和近零排放的目标。     

煤炭超临界水流化床制氢反应器内颗粒流动及传热特性的数值分析

煤炭超临界水气化是极具发展前景的高效洁净煤转化利用技术,深入研究反应器内流动和传热过程对反应器的设计及优化具有重要意义.本文基于欧拉-拉格朗日方法,耦合化学反应动力学模型,建立了煤炭超临界水流化床制氢反应器的三维瞬态CFD模型,研究了反应器内流动和传热特性、颗粒及产物组分的分布转化规律,得到了煤炭颗粒表面的对流和辐射换热系数,并从传热学的角度,揭示了颗粒粒径对煤炭转化速率的影响机理。     

煤炭超临界水气化复叠发电系统热力性能分析

为实现煤炭高效清洁低碳发电，本文基于超临界水气化构建了采用H₂O/CO₂混合工质循环、朗肯循环复叠的发电系统，建立系统热力性能分析模型，其净发电效率和?效率分别为51.1%和49.9%，可实现CO₂完全捕集和水的回收利用。分析了气化给水温度、水煤浆浓度对气化氧化单元以及系统不可逆性的影响规律，发现气化单元?效率随给水温度的升高而升高，气化氧化单元的?效率可提升至81%。当水煤浆浓度为19%时，系统净发电效率和?效率分别可达52.0%和50.7%。     

碳制氢过程的比较及直接制氢分析

本文对不同碳制氢过程进行了热力学分析,比较了相同进料条件下,采用不同过程进行碳制氢时,过程的冷煤气效率以及最终产物组成,并分析了“一步制氢”中温度、压力、不同进料比对最终产物组成的影响。结果表明,直接制氧适宜的气化温度为923-973 K;增加水蒸气分压力(气化压力随之增加),气体产物的量增加;吸收剂有一最佳的量。     

太阳能制氢腔式吸热器混合对流的数值模拟研究

混合对流热损失是影响太阳能与生物质超临界水气化耦合制氢腔式吸热器热效率的关键因素之一。本文以动力工程多相流实验室建成的生物质超临界水与太阳能聚集供热耦合制氢腔式吸热器为研究对象,对腔式吸热器混合对流换热进行了数值模拟研究。通过使用RNGkε湍流模型,研究了制氢吸热器在外界风吹掠环境下的混合对流热损失,获得了腔式吸热器在不同风速、风向吹掠下的混合对流换热准则Nusselt数。模拟结果表明,侧向风与侧迎向风对腔内对流热损失影响最大,当风速超过某一数值(Richardson数>1),外界风诱发的强制对流会在对流热损失中占主导作用,且随着风速增加,混合对流热损失随Re提高而增大。     

非预混燃烧模型模拟流化床生物质气化器中富氢气体的制备

对用流化床生物质气化器合成富氢气体,建立了基于非预混燃烧的模型对气化器中的生物质在空气-水蒸汽环境中的气化反应过程的模型,并采用流体力学软件 FLUENT 6.0对过程进行了模拟.通过模拟结果与实验结果的对比分析发现,水蒸汽与生物质的比、空氧比和生物质颗粒的粒径大小是决定产气中氢气含量的重要参数.同时,对气化器中氢气的分布进行了研究.     

生物油及生物质炭电催化制氢

报道了以生物质热裂解产物-生物油和生物质炭为原料,利用双固定床反应器和电催化水蒸气重整方法高效制氢过程研究．获得的最大绝对氢产率达到110.9 g H₂/1 kg干生物质,气相产物包括72%H₂、26%CO₂、1.9%CO和痕量的CH₄．研究了添加生物质炭对生物油制氢效果的影响,以及重整反应温度、通入催化床的电流等反应条件对生物油和生物质炭制氢效果的影响．结果表明,生物质炭的添加使绝对氢产率增加了大约20%～45%,提     

超声波光生物制氢反应器启动及产氢特性

实验研究了超声波光生物制氢反应器的启动工艺以及反应器的产氢特性,探讨了超声时间和超声功率对反应器产氢性能的影响。超声波光生物反应器的启动实验进行了96 h,此时反应器光合细菌生物量和反应液pH值趋于稳定,启动完成。在系统稳定运行后,随着超声时间、超声功率的增大,超声波光生物制氢反应器的产氢速率和产氢得率呈先增加后降低的趋势,然而葡萄糖去除率却随着超声时间的增加而增大。     

Sequential hydrothermal gasification of biomass to hydrogen

A new technology, in which a renewable biomass is used to produce hydrogen fuel, is described. This hydrogen can be used as a feed for fuel cells to generate electricity or in other energy-producing processes. Degradation and gasification of cellulose-based biomass in compressed water was studied in the 100–400 °C temperature range. Phase behavior of the cellulose in subcritical water was studied in a diamond-anvil cell, coupled with optical microscopy, at heating rates of 1 and 5 °C/s. Homogeneous conditions of a single water-cellulose phase were established. Complete dissolution of the cellulose was achieved at 333 °C. The evolution mechanism based on a rapid hydrolysis of the cellulose to oligomers and glucose is suggested. Glucose was then used as a model compound to characterize the chemistry of biomass gasification. A 0.1-M glucose solution was fed into a continuous-flow reactor at a pressure of 100 bar using an HPLC pump. Catalytic effects of Pt/Al₂O₃ on the gasification temperature were determined. Gas product composition was analyzed using online GC-TCD. A mixture of H₂, CO₂, and CH₄ gas was produced. Quantitative analysis of the total organic carbon in the liquid residue indicated 67% carbon gasification efficiency at 330 °C. Qualitative analyses of liquid residues showed that the main decomposition products in the liquid phase were alcohols and carboxylic acids. It was shown that the hydrogen fuel could be efficiently generated from biomass.     

Ultrasonic-assisted catalytic transfer hydrogenation for upgrading pyrolysis-oil

Recent interest in biomass-based fuel blendstocks and chemical compounds has stimulated research efforts on conversion and upgrading pathways, which are considered as critical commercialization drivers. Existing pre-/post-conversion pathways are energy intense (e.g., pyrolysis and hydrogenation) and economically unsustainable, thus, more efficient process solutions can result in supporting the renewable fuels and green chemicals industry. This study proposes a process, including biomass conversion and bio-oil upgrading, using mixed fast and slow pyrolysis conversion pathway, as well as sono-catalytic transfer hydrogenation (SCTH) treatment process. The proposed SCTH treatment employs ammonium formate as a hydrogen transfer additive and palladium supported on carbon as the catalyst. Utilizing SCTH, bio-oil molecular bonds were broken and restructured via the phenomena of cavitation, rarefaction, and hydrogenation, with the resulting product composition, investigated using ultimate analysis and spectroscopy. Additionally, an in-line characterization approach is proposed, using near-infrared spectroscopy, calibrated by multivariate analysis and modeling. The results indicate the potentiality of ultrasonic cavitation, catalytic transfer hydrogenation, and SCTH for incorporating hydrogen into the organic phase of bio-oil. It is concluded that the integration of pyrolysis with SCTH can improve bio-oil for enabling the production of fuel blendstocks and chemical compounds from lignocellulosic biomass.     

含氧有机物催化重整制备纯氢

研究了一种新的利用含氧化合物制备纯氢的催化变换过程,该过程耦合了含氧化合物的催化重整、水煤气变换反应和CO₂去除步骤. 详细研究了重整催化剂的筛选、反应条件以及不同的含氧化合物催化重整行为. 利用所述集成方法获得的最高氢气浓度为99.96vol%和最大转化率为97.1mol%. 此外,通过含氧化合物的解离、催化重整和水煤气变换反应研究,探讨了含氧化合物制备纯氢的相关反应路径.     

ATR-IR分析氢氧化钠对水及离子液体/水体系氢键作用的影响

利用衰减全反射红外光谱（ATR-IR）分析NaOH对水及1-乙基-3-甲基咪唑醋酸酯离子液体水溶液（EmimAc/水）氢键网络的影响,研究结果表明,NaOH的加入会影响水分子的氢键对称性和类型,对称性氢键谱带Ⅰ（3 218 cm-1）和Ⅱ（3 375 cm-1）随着NaOH浓度的提高而降低。NaOH使水溶液氢键发生极化,产生连续吸收带,连续吸收带随着NaOH浓度的提高而增强。水对EmimAc的阳离子和阴离子均有影响。水分子的OH和EmimAc的COO-产生强的相互作用,在3 400~3 200 cm-1产生宽的吸收谱带;而水分子的质子和COO-作用使得C═O吸收谱带红移。水的加入使得EmimAc指纹区的谱带蓝移或吸收强度下降,表明水可以破坏EmimAc原有的氢键网络,形成“阴离子…HOH…阴离子”团簇,减弱了离子液体阴、阳离子之间的相互作用。NaOH替代水与EmimAc混合,ATR-IR谱图的变化并不显著,主要表现在谱带的吸收强度上。与EmimAc/水相比,EmimAc/NaOH水溶液的ATR-IR谱的吸收强度更高,表明NaOH水溶液对EmimAc氢键网络的破坏不如水显著。由此可见,可利用EmimAc/NaOH体系降低离子液体体系黏度,并且降低离子液体使用成本,对木质纤维原料预处理有一定的指导意义。     

Removal of pharmaceuticals from wastewater by biological processes,hydrodynamic cavitation and UV treatment

To augment the removal of pharmaceuticals different conventional and alternative wastewater treatment processes and their combinations were investigated. We tested the efficiency of (1) two distinct laboratory scale biological processes: suspended activated sludge and attached-growth biomass, (2) a combined hydrodynamic cavitation–hydrogen peroxide process and (3) UV treatment. Five pharmaceuticals were chosen including ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac, and an active metabolite of the lipid regulating agent clofibric acid.Biological treatment efficiency was evaluated using lab-scale suspended activated sludge and moving bed biofilm flow-through reactors, which were operated under identical conditions in respect to hydraulic retention time, working volume, concentration of added pharmaceuticals and synthetic wastewater composition. The suspended activated sludge process showed poor and inconsistent removal of clofibric acid, carbamazepine and diclofenac, while ibuprofen, naproxen and ketoprofen yielded over 74% removal. Moving bed biofilm reactors were filled with two different types of carriers i.e. Kaldnes K1 and Mutag BioChip? and resulted in higher removal efficiencies for ibuprofen and diclofenac. Augmentation and consistency in the removal of diclofenac were observed in reactors using Mutag BioChip? carriers (85% ± 10%) compared to reactors using Kaldnes carriers and suspended activated sludge (74% ± 22% and 48% ± 19%, respectively). To enhance the removal of pharmaceuticals hydrodynamic cavitation with hydrogen peroxide process was evaluated and optimal conditions for removal were established regarding the duration of cavitation, amount of added hydrogen peroxide and initial pressure, all of which influence the efficiency of the process. Optimal parameters resulted in removal efficiencies between 3–70%. Coupling the attached-growth biomass biological treatment, hydrodynamic cavitation/hydrogen peroxide process and UV treatment resulted in removal efficiencies of >90% for clofibric acid and >98% for carbamazepine and diclofenac, while the remaining compounds were reduced to levels below the LOD. For ibuprofen, naproxen, ketoprofen and diclofenac the highest contribution to overall removal was attributed to biological treatment, for clofibric acid UV treatment was the most efficient, while for carbamazepine hydrodynamic cavitation/hydrogen peroxide process and UV treatment were equally efficient.