纤维素亚临界和超临界水液化实验研究

在温度为340～420℃、压力为30～40MPa的实验条件下，对亚临界和超临界水中纤维素液化进行实验研究，液化产物经GC—MS分析，得到其主要成分是糠醛、5-甲基糠醛、5-羟甲基糠醛和一些含甲基、羟基、羟甲基等官能团的酮类、苯酚类化合物，且反应温度变化时，液化产物成分和浓度有较大变化；对纤维素液化转化率有重要影响的两个因素——反应温度和纤维素与水质量比进行初步实验研究，结果表明：(1)反应温度为380℃左右。液化转化率最高；(2)纤维素与水的质量比为1：15左右，转化率达最大值。     

生物质在超临界水流化床反应系统中气化制氢实验研究

以生物质模型化合物葡萄糖为原料,在温度500～600℃,压力23～37胁范围内,利用新研制的超临界水流化床系统对其气化制氧特性进行研究,讨论了过程主要参数温度、压力、物料浓度以及催化剂添加对气化制氢的影响.实验结果表明:温度对气化影响最大,而压力对气化的影响较小,升高温度和压力都有利于产氢.随着物料浓度增加葡萄糖气化效果下降,在超临界水流化床气化制氢系统中实现30%葡萄糖的连续稳定气化.K_2CO_3提高气化率同时降低了产气中CO含量,ZnCl_2的加入虽对气化率影响不大,但大大提高了氢气的选择性.该文的实验研究验证了超临界水流化床气化制氢系统的有效性.     

超临界和超超临界发电机组

火电厂超临界和超超临界机组指的是锅炉内工质的压力。锅炉内的工质都是水,水的临界压力是22.115MPa,温度为347.15℃。在这个压力和温度时,水和蒸汽的密度是相同的,这就叫水的临界点,炉内工质压力低于这个压力就叫亚临界锅炉,大于这个压力就是超临界锅炉,炉内蒸汽温度不低于593℃或蒸汽压力不低于31MPa则称为超超临界。     

高效宽负荷率超超临界锅炉垂直管圈水冷壁在低质量流速下的传热特性

在压力p=21~29.8 MPa、质量流速G=600~1 100kg/(m~2·s)、热负荷q=330~793kW/m~2工况范围内,对低质量流速优化内螺纹管的传热特性进行了实验研究,并根据实验数据得到了近临界压力区和超临界压力区的传热实验关联式.结果表明:在近临界压力区,亚临界部分的传热特性好于超临界部分的传热特性,质量流速增大能推迟传热恶化,热负荷增大则使传热恶化提前发生,内螺纹管抑制膜态沸腾(DNB)的能力有所减弱;在超临界压力区,压力越低,大比热容区内强化传热作用越显著,在其他条件一定时,超临界水的热物性变化对管内传热的作用由质量流速和热负荷共同决定;质量流速不变,继续增大热负荷,大比热容区内的传热将由强化转变为恶化.     

二甲醚/液化石油气液滴超临界蒸发特性的数值模拟

引入相平衡理论建立了DME-LPG-N2三元气、液高压相平衡,获得了液滴表面各组分的物质的量分数.建立了混合液滴超临界蒸发的计算模型,计算了二甲醚(DME)/液化石油气(LPG)双燃料液滴的蒸发过程,考察了液滴的初始直径、初始组分、环境温度和环境压力对蒸发过程的影响.结果表明:环境压力、温度越大,环境介质(N2)在液滴中的溶解越明显;液滴初始直径越小,蒸发寿命越短;液滴中DME越多,亚临界蒸发过程中的液滴蒸发寿命越长,而超临界蒸发过程中液滴蒸发寿命越短;环境温度越高,液滴蒸发寿命越短;在研究的温度范围内,环境压力越高,在亚临界条件下液滴蒸发寿命越短,而在超临界条件下液滴蒸发寿命越长.     

亚/超临界压力下碳氢燃料液滴的燃烧特性

建立了一个适用于超临界压力下包括能够正确描述跨临界迁移现象的液滴燃烧模型,提出了跨临界迁移时刻液滴表面处燃料质量流束有限的新观点.利用开发的计算模型,以碳氢燃料液滴自燃着火为研究对象,研究了亚临界和超临界压力下单液滴的燃烧特性,并从传热传质过程出发,阐明了跨临界迁移前、后液滴燃烧过程的热质输运机理及物理控制因素.结果表明:在亚临界压力下,液滴燃烧不会发生跨临界迁移现象,燃烧过程始终受燃料在液滴表面处相变的控制,液滴的燃烧速度取决于传热过程,并且液滴温度受该压力下燃料沸点的限制而增长缓慢.而在超临界压力下,液滴着火之后很快发生跨临界迁移现象,此后燃料向燃烧反应区域的扩散不存在相变,液滴的燃烧速度取决于传质过程,并且液滴温度不再受燃料沸点的限制而持续升高.     

玉米芯在超临界水中气化制氢实验研究

以玉米芯为原料,羧甲基纤维素纳(CMC)为添加剂,利用连续管流反应器,在反应压力为22.5MPa~27.5MPa、反应器壁温为550℃~650℃、反应停留时间为0.33min~0.67min、物料浓度为3wt%~6wt%的条件下,对玉米芯超临界水气化制氢进行了实验研究。利用正交实验设计与分析方法,得到实验条件范围内玉米芯超临界水气化制氢的最佳反应参数,同时对气化过程主要操作参数的影响进行了分析。实验表明温度对气化影响最大,高温度有利于产氢,气化制氢的最佳压力为25MPa,反应停留时间越长气化越完全,低浓度生物质比高浓度生物质更容易气化。     

亚/超临界环境下燃料的喷雾燃烧特性研究

采用高温高压定容燃烧弹系统对亚/超临界环境下燃料在纯氧中的喷射燃烧现象进行试验研究,通过高速相机和阴影法进行燃烧图像信息的采集,研究在相同的超临界温度下,正己烷和乙醚两种燃料喷射燃烧火焰特性随环境压力和喷油脉宽的改变而呈现的差异性。试验结果表明:在亚临界压力下,两种燃料在不同喷油脉宽下的燃烧时间均随着环境压力的升高而升高,火焰发展后期基本保持较为稳定的形态和亮度,符合传统的喷射燃烧过程。正己烷在临界压力点下火焰长度最短,形态较为规则;超临界压力下,火焰形态有稳定趋势但仍有轻微波动,且火焰长度略短于亚临界;喷油脉宽改变时,燃烧时间在临界压力附近呈现出不同的趋势。乙醚的燃烧时间随压力的升高而增大,在临界压力处达到最大值,后随着压力的继续升高而下降,不同压力条件下火焰形态略有差别。燃烧现象存在差异性主要是由于亚/超临界坏境下燃料的物性参数和破碎蒸发机理不同。     

小桐子油脂肪酸在超临界甲醇中酯化反应动力学的研究

以小桐子油完全水解制取的脂肪酸为原料,对亚临界-超临界两步法制备生物柴油的第二步脂肪酸在超临界甲醇中酯化反应的影响因素进行了研究。试验结果表明:在脂肪酸与甲醇体积比为1:2,反应温度290℃,反应时间20min时,小桐子油脂肪酸酯化反应较为合适,转化率为98.49%。由试验数据采用数学规划求解进行动力学分析,得到小桐子油脂肪酸在超临界甲醇中酯化反应的平均反应级数为1.4467,活化能为66.79kJ/mol,动力学模型为-(dc_A)/(dt))=5.65×10~5e~(-(66.79)/(RT))c_A~(1.4467)。     

超临界水氧化技术处理2-萘酚废水的研究

2-萘酚是严重污染环境和危害人体健康的有害物质,目前采用传统废水处理方法,很难将其彻底去除.超临界水氧化技术是一种新兴废水处理技术,能够对许多传统方法难以去除的有机废水进行有效处理.对含2-萘酚废水的超临界水氧化降解进行了研究,主要讨论了温度、压力、停留时间等因素对反应的影响,2-萘酚的降解率随着这3个因素的升高而升高...     

Hydrogen production by biomass gasification in supercritical water: A parametric study

Hydrogen production by biomass gasification in supercritical water is a promising technology for utilizing high moisture content biomass, but reactor plugging is a critical problem when feedstocks with high biomass content are gasified. The objective of this paper is to prevent the plugging problem by studying the effects of the various parameters on biomass gasification in supercritical water. These parameters include pressure, temperature, residence time, reactor geometrical configuration, reactor types, heating rate, reactor wall properties, biomass types, biomass particle size, catalysts and solution concentration. Biomass model compounds (glucose, cellulose) and real biomass are used in this work. All the biomasses have been successfully gasified and the product gas is composed of hydrogen, carbon dioxide, methane, carbon monoxide and a small amount of ethane and ethylene. The results show that the gas yield of biomass gasification in supercritical water is sensitive to some of the parameters and the ways of reducing reactor plugging are obtained.     

Supercritical water gasification of glucose in fluidized bed reactor: A numerical study

Supercritical water fluidized bed (SCWFB) is a new reactor concept for gasification of biomass and coal in supercritical water. In this paper, physical fields, residence time and gas yield in a SCWFB reactor were investigated numerically based on the Eulerian two-fluid method with the kinetic theory of granular flow. A three-step reaction model including steam reforming, water-gas shift and methanation was used to describe the supercritical water gasification of glucose. Distributions of velocity and temperature were obtained, and the results show that the mixing of preheated water and cold glucose solution at the bottom in the bed leads to a region with low solid volume fraction and local swirl flow. In the freeboard, most of reactants flow near the wall and with a velocity much higher than the superficial velocity. The reaction rates and conversion ratio of glucose at different regions in the reactor were also obtained. Distribution of residence time was found to be non-uniform, and its effect on glucose gasification was analyzed. In addition, the effects of operation condition and reactor structure on gas yield and residence time were studied to explore best operation rules for increasing gas yield. The results from this work may be of interest to operators attempting to obtain more information in the reactor and provide instruction for the design of SCWFB reactor.     

Debye relaxation mechanisms of microwave heating of near-critical polar gases

In this work, the average time of slow dielectric relaxation in sub- and supercritical polar gases is considered in terms of a combination of two Debye relaxation mechanisms. Under the assumption of thermal equilibrium, the corresponding relaxation times are theoretically predicted to be proportional to the mean binary collision time and mean translational deceleration time of free molecules with the proportionality factor close to unity. The microwave heating rate for pressurized pure gases and gas mixtures in constant-pressure and constant-density conditions is found from the Poynting formula. Temperature-dependent frequency spectra of the isobaric and isochoric heating rates for sub- and supercritical water are obtained with an allowance for non-Debye high-frequency relaxations. Perceptible temperature effects in the supercritical water heating rates at relaxation frequency are predicted when pressures/densities are high enough and considerable reduction of the heating time for higher pressures/densities is expected.     

Performance analysis in near-critical conditions of organic Rankine cycle

According to fluid critical temperature and heat source temperature, organic Rankine cycle (ORC) is recognized in two categories: subcritical ORC and supercritical ORC. For a given heat source, some organic fluids not only can be used in subcritical ORC, but also can be used in supercritical ORC. For heat source with temperature of 90 °C, HFC125, HFC143a and HF218 can be used in both ORCs. Performance of the three substances in both cycles, especially in near-critical conditions is studied with expander inlet temperature of 85 °C and hot water mass flow rate of 1 kg/s. The results show that when fluids go in supercritical ORC from subcritical ORC, cycle thermal efficiency varies continuously, while mass flow rate and net power generation vary discontinuously. Maximum net power generation in near-critical conditions of subcritical ORC is higher than that of supercritical ORC. For HFC125 and HFC143a, outlet temperature of hot water decreases with the increase of heating pressure ratio. For HF218, outlet temperature of hot water increases firstly and decreases secondly with the increase of heating pressure ratio, which leads to an increase of net power generation with the increase of heating pressure ratio in high heating pressure ratio conditions.     

Continuous hydrogen production by biomass gasification in supercritical water heated by molten salt flow: System development and reactor assessment

Hydrogen production by biomass gasification using solar energy is a promising approach for overcoming the drawbacks of fossil fuel utilization, but the storage of discontinuous solar flux is a critical issue for continuous solar hydrogen production. A continuous hydrogen production system by biomass gasification in supercritical water using molten-salts-stored solar energy was proposed and constructed. A novel double tube helical heat exchanger was designed to be molten salts reactor for hydrogen production. Model compounds (glycerol/glucose) and real biomass (corn cob) were successfully gasified in this molten salts reactor for producing hydrogen-rich gas. The unique temperature profiles of biomass slurry in the reactor were observed and compared with that of conventional electrical heating and direct solar heating approaches. Product gases yield, gasification efficiency and exergy conversion efficiency of the reactor were analyzed. The results showed that the performances of reactor were determined by feedstock style, biomass concentration, residence time and biomass slurry temperature profiles.     

Supercritical water gasification of wastewater sludge for hydrogen production

The use of hydrogen as clean fuel gas in the power generation sector becomes essential to reduce the environmental issues related to conventional fuel usage. By avoiding biomass drying process, supercritical water gasification is considered the most efficient technology in hydrogen production from wastewater sludge. Wastewater sludge is difficult to disposal in its received form since it is often produced with high moisture content, contribute to numerous environmental issues and direct contact with this waste can result in health concerns. The assessment of the treatment and conversion of this material into fuel gas at condition beyond supercritical state (374°C and 22.1 MPa) is required. This paper is discussed the degradation routes of wastewater sludge in supercritical water. Furthermore, it is reviewed the influence of the main operation parameters role in the hydrogen production, which includes reaction temperature, pressure, residence time, feed concentration and catalysts. The development in reactor design and setup for maximum hydrogen production is highlighted. The technical challenges encountered during the conversion process and its solutions are also discussed. In addition, future prospective to optimal and standardization of the supercritical water gasification process is reviewed.     

Biodiesel from corn germ oil catalytic and non-catalytic supercritical methanol transesterification

Transesterifications of grain of corn oil samples in KOH catalytic and in supercritical methanol were studied without using any catalyst. Biodiesel, an alternative biodegradable diesel fuel, is derived from triglycerides by transesterification with methanol and ethanol. The transesterification reaction is affected by the molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids and water content of oils or fats. It was observed that increasing the reaction temperature, especially to supercritical temperatures, had a favorable influence on methyl ester (biodiesel) conversion. The molar ratio of methanol to corn germ oil is also one of the most important variables affecting the yield of methyl esters. Higher molar ratios result in greater ester production in a shorter time. In the transesterification, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalysts, and reduces catalyst effectiveness, all of which result in a low conversion.     

Supercritical water gasification of biomass for hydrogen production

Hydrogen from waste biomass is considered to be a clean gaseous fuel and efficient for heat and power generation due to its high energy content. Supercritical water gasification is found promising in hydrogen production by avoiding biomass drying and allowing maximum conversion. Waste biomass contains cellulose, hemicellulose and lignin; hence it is essential to understand their degradation mechanisms to engineer hydrogen production in high-pressure systems. Process conditions higher than 374 °C and 22.1 MPa are required for biomass conversion to gases. Reaction temperature, pressure, feed concentration, residence time and catalyst have prominent roles in gasification. This review focuses on the degradation routes of biomass model compounds such as cellulose and lignin at near and supercritical conditions. Some homogenous and heterogeneous catalysts leading to water–gas shift, methanation and other sub-reactions during supercritical water gasification are highlighted. The parametric impacts along with some reactor configurations for maximum hydrogen production and technical challenges encountered during hydrothermal gasification processes are also discussed.     

Transesterification of rapeseed and palm oils in supercritical methanol and ethanol

The results of the rapeseed and palm oils transesterification with supercritical methanol and ethanol were presented. The studies were performed using the experimental setups which are working in batch and continuous regimes. The effect of reaction conditions (temperature, pressure, oil to alcohol ratio, reaction time) on the biodiesel production (conversion yield) was studied. Also the effect of preliminary ultrasonic treatment (ultrasonic irradiation, emulsification of immiscible oil and alcohol mixture) of the initial reagents (emulsion preparation) on the stage before transesterification reaction conduction on the conversion yield was studied. We found that the preliminary ultrasonic treatment of the initial reagents increases considerably the conversion yield. Optimal technological conditions were determined to be as follows: pressure within 20-30 MPa, temperature within 573-623 K. The optimal values of the oil to alcohol ratio strongly depend on preliminary treatment of the reaction mixture. The study showed that the conversion yield at the same temperature with 96 wt.% of ethanol is higher than with 100 wt.% of methanol.     

Low-temperature alcohol-assisted methanol synthesis from CO2 and H2: The effect of alcohol type

Carbon dioxide (CO₂) conversion to higher-value products is a promising pathway to mitigate CO₂ emissions. Methanol is a high-value-chain chemical in industries that can be produced through CO₂ hydrogenation, which is an exothermic reaction. Due to thermodynamic limitations, a typical synthesis temperature between 250 °C and 300 °C results in a low conversion of CO₂ at equilibrium. To enhance the CO₂ conversion, high pressures of 50–100 bar are required, which inevitably causes the process to be energy-intensive. In this study, an alternative method called alcohol-assisted methanol synthesis is investigated. In this method, alcohol is used as a catalytic solvent and helps decrease the reaction temperature and pressure (150 °C and 50 bar) and significantly increases methanol yield. Ethanol is used as the alcohol due to its reactivity, providing a high methanol yield (47.80%) with 63.93% CO₂ conversion and 67.54% methanol selectivity. However, due to unwanted side reactions, ethanol generates ethyl acetate as a byproduct that forms an azeotrope with methanol, leading to difficulty in product purification. The effects of alcohol type (molecular weight and structure), including ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, tert-butanol and 1-pentanol, on CO₂ conversion, methanol yield and byproducts are investigated. It is found that smaller-molecule alcohols provide a higher methanol yield. Moreover, n-alcohols provide a higher methanol yield than branched alcohols, and the byproducts of the reaction with n-alcohols do not form an azeotrope with methanol. Therefore, 1-propanol is compared with ethanol providing 26.55% methanol yield, 69.02% CO₂ conversion and 70.82% methanol selectivity.