Supercritical water gasification of glycerol: Intermediates and kinetics

In this paper, the liquid products from supercritical water gasification (SCWG) of glycerol were analyzed and some intermediates were identified. A simplified reaction pathway for gases production from SCWG of glycerol was proposed. The first quantitative kinetics model for describing the gaseous products (H₂, CO, CH₄ and CO₂) of SCWG of glycerol was developed. The model comprises seven reactions to describe the typical reactions in SCWG, and the reaction rate constant of each reaction was obtained by using the nonlinear least-square fitting method. The reaction rate analysis showed that the main sources of hydrogen yield were glycerol pyrolysis and steam reforming of intermediates, while the hydrogen yield from water–gas shift reaction (WGSR) was very small. The temperature estimated by the kinetics model for completely SCWG of glycerol solution was given. In addition, the sensitivity analysis of rate constant of WGSR was done based on the model.     

Hydrothermal gasification of olive mill wastewater as a biomass source in supercritical water

In this study, the hydrothermal gasification of biomass in supercritical water is investigated. The work is of peculiar value since a real biomass, olive mill wastewater (OMW), is used instead of model biomass compounds. OMW is a by-product obtained during olive oil production, which has a complex nature characterized by a high content of organic compounds and polyphenols. The high content of organics makes OMW a desirable biomass candidate as an energy source. The hydrothermal gasification experiments for OMW were conducted with five different reaction temperatures (400, 450, 500, 550 and 600 °C) and five different reaction times (30, 60, 90, 120 and 150 s), under a pressure of 25 MPa. The gaseous products are mainly composed of hydrogen, carbon dioxide, carbon monoxide and C₁-C₄ hydrocarbons, such as methane, ethane, propane and propylene. Maximum amount of the gas product obtained is 7.71 mL per mL OMW at a reaction temperature of 550 °C, with a reaction time of 30 s. The gas product composition is 9.23% for hydrogen, 34.84% for methane, 4.04% for ethane, 0.84% for propane, 0.83% for propylene, 49.34% for carbon dioxide, and 0.88% for minor components such as n-butane, i-butane, 1-butene, i-butene, t-2-butene, 1,3-butadiene and nitrogen at this reaction conditions.     

超临界水氧化技术中有关设备腐蚀问题的研究进展

超临界水氧化技术是一种新兴的有机废物和废水处理技术。该技术是基于水的温度和压力均超过超临界值(673.3 K和22.12 MPa)时,水的物理性质发生迅速变化而得到的。此时超临界水拥有很强的溶解能力,是氧化分解难溶物质的一种理想均相介质。虽然目前该技术有很大的前景,但是腐蚀问题严重的阻碍了该技术的工业化应用。本文在对超临界水氧化技术的研究基础上着重对水溶液有关参数进行分析,希望通过调节有关参数来减小设备的腐蚀。其次,对超临界水氧化中耐腐蚀性的材料进行分析,以便研发出不同介质中的抗腐蚀性较好的设备。     

Kinetic analysis for decomposition of 2,4-dichlorophenol by supercritical water oxidation

2,4-Dichlorophenol (2,4-DCP), as a halogenated model pollutant, was decomposed by using supercritical water oxidation (SCWO) in a batch reactor made of Hastelloy C-276. SCWO experiments for 2,4-DCP decomposition were performed in the range of 380–420 °C, 230–280 bar and 0.074-0.221 mol/L H₂O₂. The effect of oxidant concentration on decomposition rate and efficiency was significant near the critical temperature of 380 °C. However, the role of the oxidant concentration in the SCWO process decreased with an increase in temperature; also, excess oxidant played a key role in quite significantly decreasing the activation energy of 2,4-DCP oxidation. Variation of the reaction rate by the change of pressure was negligible even at a near critical temperature. The kinetic rate for the decomposition of 2,4-DCP in the SCWO process was well described by a simple first-order kinetic and global reaction rate model. From the SCWO experiments, the various intermediates identified with a GC/MS implied that the first reaction pathway for 2,4-DCP decomposition led to dimers such as dichlorophenoxyphenols, and the second led to single-ring and ring-opening products.     

Transpiring wall reactor in supercritical water oxidation

Reactor corrosion and plugging problems have hindered the commercialization of supercritical water oxidation (SCWO) for wastewater purification. The use of transpiring wall reactor (TWR) is an effective means to overcome the above two problems by forming a protective water film on the internal surface of the reactor to aviod contacting corrosive species and precipitated organic salts. This work mainly aims to objectively review experimental investigations and numerical simulation results concerning TWR. Subsequent investigations for parameters optimizations of TWR are also proposed in order to ultimately build effective regulation methods of obtaining excellent water film properties. All this information is very important in guiding the structure design and operation parameters optimization of TWR.     

煤气化废水的超临界水氧化处理实验

对煤气化废水的超临界水氧化处理效果开展了探索性实验研究,以污水、污泥处理达标为目标,对过程中的工艺条件及有害物质的去除效果进行了研究和评价,结果表明,优化条件下无需经过预处理及后续深度处理,出水主要指标即可达到国家《污水综合排放标准》(GB 8978—1996)一级排放标准,并可实现废水的无害化处理和污泥的无害化减量。在此基础上,创新性地提出了碎煤加压气化-超临界水氧化组合工艺方案。     

Hydrothermal flames in supercritical water oxidation: investigation in a pilot scale continuous reactor

Hydrothermal flames at 25 MPa supercritical water environment were investigated using a 4800 ml reaction tower, in which the sapphire windows were fitted for optical access. Down flowing hydrothermal flames were observed for oxidation of 2-propanol when the reactor was fed with inlet organic concentration higher than 2 vol% and air ratio higher than 1.8. Flame temperature, as high as 1100 °C, was measured by means of a thermocouple and the temperature was found to be strongly influenced by air ratio. Effective and stable oxidation of organics with TOC removal rate of 99.9% was achieved. Dioxins were also decomposed with a ratio higher than 99.9%, within 1 min reaction time in this reactor configuration.     

Supercritical water gasification of hydrochar

Hydrochar is the product of the hydrothermal carbonization process, which is able to convert biomass into a carbon-rich material at mild hydrothermal conditions. This article is aimed at exploring a novel possibility, that is converting hydrochar into a valuable fuel gas by means of another hydrothermal technology: supercritical water gasification (SCWG), which operates at higher temperatures and pressures. Tests were performed in 5 ml micro-autoclaves with a hydrochar concentration of 15 wt.%. Residence times between 1 h and 16 h were adopted. The results showed that hydrochar derived from maize silage can still be gasified, producing a gas rich in CO₂ and CH₄. The data here obtained were also compared with literature data concerning the SCWG of glucose and beech sawdust, highlighting the main differences in terms of solid, liquid and gaseous yields. The solid material obtained after SCWG was observed by means of scanning electron microscopy after different residence times, highlighting the formation of coke spheres. Finally, the effect of the addition of an alkali catalyst (K₂CO₃) was tested and discussed.     

超临界水氧化技术与开发污染物资源的研究

阐述了超临界水氧化反应另一机理———有机物热力燃烧,介绍了超临界水氧化技术处理难降解有机污染物、固体废弃物及污泥等的研究动态,分析了超临界水氧化反应过程中的反应热值。对利用超临界水氧化技术开发污染物资源,促进循环经济发展进行了探讨。     

Biomass gasification in supercritical water: Part 1. Effect of the nature of biomass

In this study, biomass feedstocks, including lignocellulosic materials and the tannery wastes, were gasified in supercritical water. Gasification experiments were performed in a batch autoclave at 500 °C. The amount of gases, the gas compositions and the amount of water soluble compounds from gasification were determined. The hydrogen yields ranging between 4.05 and 4.65 mol H₂/kg biomass have been obtained. The results showed that the yields and composition of gases depend also on the organic materials other than cellulose and lignin in lignocellulosic material. In addition to this, it was concluded that the kind of lignin may also have an effect on gasification products. In the case of tannery wastes, the type of tannen agent used in leather production considerably effected the gasification results.     

Non-catalytic Oppenauer oxidation of alcohols in supercritical water

Non-catalytic Oppenauer oxidation was applied for alcohols, such as benzyl alcohol (4) and benzhydrol (1), in the presence of an excess amount of carbonyl compound, formaldehyde (5a), as an oxidant with and without water. Oppenauer oxidation took place in both reactions of 4 and 1 to afford the oxidation products, benzaldehyde (6) (95%) and benzophenone (2) (64%), concomitant with relatively small amounts of reduction products, toluene (7) (1%) and diphenylmethane (3) (13%), respectively, at 400 °C for 10 min without water in an SUS 316 batch-type tubular reactor. Lower yields of oxidation products 6 (68%) and 2 (30%) were obtained in supercritical water under the conditions of 400 °C, 10 min, and 0.35 g/mL water density, while the formation of the reduction products 7 and 3 was completely suppressed. Thus, water was indispensable for the clean and highly selective Oppenauer oxidation of 4 and 1 to yield 6 and 2.     

Hydrogen production by biomass gasification in supercritical water: A systematic experimental and analytical study

Hydrogen production from biomass gasification in supercritical water is a new technology, which was developed in last two decades. Biomass energy of low quality can be converted to hydrogen energy of high quality by supercritical water gasification. Particularly, supercritical water gasification is an elegant way of wet biomass utilization. Up to now, many important progresses have been made in supercritical water gasification technology by the studies of researchers around the world. Since 1997, supercritical water gasification, which include reaction system, rule of biomass gasification and theory, have been studied in State Key Laboratory of Multiphase Flow in Power Engineering of Xi’an Jiaotong University. In this paper, we summarize the results from systematic experimental and analytical study on biomass gasification in supercritical water in our laboratory. Also, the development status and future prospect on supercritical water gasification is evaluated.     

Catalytic denitrogenation of hydrocarbons through partial oxidation in supercritical water

In this work, the denitrogenation of hydrocarbons under supercritical water oxidation environment was investigated in a rotated bomb reactor at 623-723 K and 25-35 MPa over sulfided NiMo catalyst. Quinoline was used as a model nitrogen-containing compound. A high reduction of total nitrogen up to about 85% was obtained. The denitrogenation pathway is composed of two consecutive steps: in situ H₂ generation and the hydrogenation of quinoline. The hydrogenation mechanism of quinoline varies with reaction temperature because of the participation of supercritical water in HDN step. The strong adsorption of quinoline and its hydrogenation intermediates on catalyst surface has an adverse influence on total nitrogen reduction rate.     

生物质超临界水部分氧化气化的能量过程分析(英文)

Partial oxidation gasification in supercritical water could produce fuel gases (such as H2, CO and CH4) and signif-icantly reduce the energy consumption. In this work, an energetic model was developed to analyze the partial oxidative gasification of biomass (glucose and lignin) in supercritical water and the related key factors on which gasification under autothermal condition depended upon. The results indicated that the oxidant equiva-lent ratio (ER) should be over 0.3 as the concern about energy balance but less than 0.6 as the concern about fuel gas production. Feedstocks such as glucose and lignin also had different energy recovery efficiency. For ma-terials which can be efficiently gasified, the partial oxidation might be a way for energy based on the combustion of fuel gases. Aromatic materials such as lignin and coal are more potential since partial oxidation could produce similar amount of fuel gases as direct gasification and offer additional energy. Energy recovered pays a key role to achieve an autothermal process. Keeping heat exchanger efficiency above 80%and heat transfer coefficient below 15 kJ·s?1 is necessary to maintain the autothermal status. The results also indicated that the biomass loading should be above 15%but under 20%for an autothermal gasification, since the increase of biomass loading could improve the energy supplied but decrease the efficiency of gasification and gaseous yields. In general, some specific conditions exist among different materials.     

Energetic analysis of gasification of biomass by partial oxidation in supercritical water

Partial oxidation gasification in supercritical water could produce fuel gases (such as H2, CO and CH4) and signif-icantly reduce the energy consumption. In this work, an energetic model was developed ...     

Continuous salt precipitation and separation from supercritical water. Part 1: Type 1 salts

The precipitation and separation performance of various binary type 1 salt-water mixtures was systematically studied for the first time in a continuously operated laboratory plant. The aim was to find a field of operation for the salt separator where salts can be separated with high efficiency. Experiments with aqueous solutions of the salts NaNO₃, KNO₃, Ca(NO₃)₂, K₂CO₃, KHCO₃, (NH₄)₂CO₃, K₃PO₄, K₂HPO₄, KH₂PO₄, NaCl, KCl, NH₄Cl and (NH₄)₂SO₄ were carried out at 30 ± 0.5 MPa varying the salt separator temperature from sub-critical to supercritical. For most of these salts separation efficiencies ranging from 80 to 97% were obtained. For the nitrates the separation efficiency increased in the order NaNO₃ < KNO₃ < Ca(NO₃)₂, whereas for potassium salts the separation efficiency of the phosphates was significantly higher than that of KNO₃. Considerable hydrolysis of the phosphate and the hydrogen phosphate salts in supercritical water was found, although this had no negative influence on the phosphate separation efficiency. It was found that the ammonium salts decompose in supercritical water, probably to ammonia and the corresponding mineral acids, leading to reduced separation of the ammonia due to its high solubility in supercritical water.     

A process for generating power from the oxidation of coal in supercritical water

A theoretical study of power generation from oxidation of coal by supercritical water oxidation (SCWO) is presented. Two versions of SCWO power plant are compared to two of the most efficient conventional power plant processes: pulverised coal power plants and pressurised fluidised bed power plant. The effects of steam pressure and temperature on produced (W_p), consumed (W_c) and net work (W_N) are calculated in order to compare the efficiency of these power plants for the same steam conditions. Enthalpies have been calculated using residual enthalpies by Peng-Robinson equation of state. Calculated results show that net work in SCWO power plant is 5% higher than in other power plants, due to the fact that no air surplus is necessary for complete combustion and because steam is produced by direct heating. Energetic efficiency of SCWO increases more quickly with temperature than for the other power plants. The effect of steam pressure is different: until 30 MPa power plant efficiencies increase more quickly in SCWO power plants than in conventional plants, but when steam pressures increases beyond 30 MPa, efficiencies decrease in SCWO power plants.     

Reprint of: Application of subcritical water liquefaction as pretreatment for supercritical water gasification system in domestic waste water treatment plant

Applicability of pretreatment using subcritical water liquefaction (subCWL) for supercritical water gasification (SCWG) of sewage sludge was investigated. Effects of pretreatment conditions on liquefaction and viscosity were studied; the results revealed that treatment at 250 °C for 30 min was optimum in fluidizing the sewage sludge used herein. The pretreatment tended to enhance H₂ and CH₄ yields in the subsequent SCWG while suppressing CO₂ production. A continuous SCWG system assembled with a subCWL pretreatment process was designed. From energy balance and cost analysis on SCWG-installed municipal wastewater treatment plant (WWTP) with conventional activated sludge process, the system was capable of producing surplus energy by utilizing exhaust heat. Cost analyses indicated that the capital cost and treatment fees were cost competitive compared to conventional treatments.     

High-yield hydrogen production by supercritical water gasification of various feedstocks: Alcohols,glucose, glycerol and long-chain alkanes

Continuous supercritical water gasification (SCWG) of various feedstocks of C1–C16 was conducted to produce hydrogen-rich gas. These feedstocks represent model compounds of biomass such as methanol/ethanol (alcohol-type), glucose and glycerol (byproducts of biodiesel synthesis), and model compounds of petroleum fuels such as iso-octane/n-octane (gasoline), n-decane/n-dodecane (jet fuels) and n-hexadecane (diesel). Almost complete gasification of all the feedstocks was achieved at 25 MPa, 740 °C and 10 wt% with low total organic carbon values of their liquid effluents. The hydrogen gas yields of each feedstock were very similar to the theoretical equilibrium yields estimated by Gibbs free energy minimization. SCWG at different gasification temperatures (650 and 740 °C) and concentrations (10 and 20 wt%) revealed that methanol and ethanol (alcohols), the simple oxygenated hydrocarbons, were easier to be gasified, producing negligible amounts of liquid products, when compared with long-chain hydrocarbons (iso-octane and n-decane) under the identical conditions. When the feedstock concentration was increased from 10 to 20 wt%, the equilibrium hydrogen ratio from iso-octane gasification decreased from 1.02 to 0.79 while that of n-decane increased from 1.12 to 1.50, implying that a branched hydrocarbon may be more resistant to gasification in supercritical water.     

超临界水中氨基乙酸的气化产氢特性

鉴于湿生物质如食品加工工业残余物和城市污泥中含有大量蛋白质的情况,以氨基乙酸作为蛋白质的模型化合物进行超临界水气化实验,研究了反应温度和反应时间耦合条件下Na₂CO₃的催化特性以及氨基乙酸气化产物特性。结果表明：添加Na₂CO₃会增大氨基乙酸的气化效率、氢气的体积分数和产率以及反应后液体化学需氧量（COD）的去除率,且添加质量分数为0.1%时的催化效果优于0.2%;Na₂CO₃主要是对H₂产率产生影响,其催化机理与已有碱性化合物的催化机理不同,可能是通过促进氨基乙酸的水解产物（甲酸）的脱羧反应来提高H₂的产率;氨基乙酸气化效率可达99.4%,生成物包括H₂、CO₂、N₂、CH₄和C₂～C₃气体,其中H₂的体积分数可超过50%,产率可达1.8 L·g^-1,且超过一半的份额来源于水,反应后液体清澈透明,COD和pH值指标均可以达到《生活杂用水水质标准》,可以进行回收利用。