超临界水氧化布雷顿封闭循环系统反应热模拟计算

超临界水氧化技术(SCWO)主要应用于低浓度有机废水的研究。文中在超临界热力条件下对超临界水氧化过程进行模拟,力求实现能量的自补偿过程。通过应用Aspen P lus模拟软件建立模型对SCWO过程进行模拟,采用布雷顿封闭循环(CBC)系统来实现SCWO的能量自补偿过程。计算结果表明:SCWO能量自补偿过程损失的能量要远小于产生的能量(QR-QH>p),超临界水氧化CBC系统的能量自补偿过程是可以实现的,此过程环己烷的能量平衡点为2.4%。     

超临界水氧化技术工业化的瓶颈问题及解决方法

超临界水氧化技术作为一种绿色环保技术,在处理有毒、难降解和高浓度有害物质上有众多优势,且目前其应用基础已经形成,国外也有实际的工业应用之例。但是超临界水氧化反应器的腐蚀和结垢问题,以及超临界水氧化的高能耗、高费用的问题严重阻碍了该技术在工业生产中的推广和发展,成为制约其工业化的瓶颈问题。本文综述超临界水氧化过程中的反应器的腐蚀和结垢问题、反应热问题,同时指出当前解决这些问题的方法。此外还列举了目前采用超临界水氧化技术的单位以及其所采用的反应器类型。     

城市污泥超临界水氧化及反应热的实验研究

研究了间歇式反应器中城市污泥的超临界水氧化反应(SCWO).实验表明:污泥COD去除率可达到99.98%以上,随反应时间增加、温度升高,污泥COD去除率显著增大;压力对过程无显著的影响;氧化剂过量倍数小于一定程度时,对污泥的去除率影响显著,超过此值时则几乎没有影响.应用SCWO能快速实现污泥的减量减容和无害化处理,脱水污泥完全氧化后的残余固体质量仅为脱水污泥的8%;在450℃,经过95 s的反应时间后,反应液的化学需氧量即可小于40 mg·L-1.此外,藉反应介质焓值的变化探索了污泥SCWO的反应热,获得了反应过程中能量平衡时,污泥的最大含水率和最小有机物质量含量的方程.结果表明:污泥中有机物完全氧化释放的反应热为21319.15kJ·kg-1,在400℃、26 MPa条件下,当污泥中有机物质量含量超过3.0%时,SCWO反应即能实现能量的平衡--自热.     

超临界水氧化技术能量回收工艺

超临界水氧化技术具有高温、高压特点,高温产物的能量回收是实现超临界水氧化技术工业化的关键。设计2种超临界水能量回收工艺,以火用效率和能量效率为目标函数,研究预热温度400～600℃、体系压力21～29 MPa、透平压力0.1～23 MPa和乏汽温度160～200℃条件下能量回收情况。结果表明：其热能回收优先于压力能回收的工艺,预热温度600℃、反应压力23 MPa、透平出口压力0.1 MPa和换热器热流股出口温度为211.85℃时具有更高火用效率和能量效率,分别为87.7%和76.7%。优先回收热能有利于超临界水氧化技术发展。     

超临界水氧化能量回收系统的设计优化

超临界水氧化（SCWO）工艺非常适用于高浓度废液的处理。针对目前SCWO处理系统能耗大、能量回用方式单一的问题,介绍了传统工艺流程的能量回收方式,分析了系统能量利用效率,创新性地采用透平和有机朗肯循环（ORC）串联的方式分别对压力能和热能进行回收。利用Aspen Plus建立SCWO系统能量回收模型,研究不同工艺流程对系统能效、(火用)效及输出功率的影响,在此基础上探讨透平的入口温度和出口压力、ORC的蒸发温度对系统性能的影响。结果表明：对反应产物依次进行压力能和热能回收为系统最佳能量回收方式;提高透平的入口温度和出口压力均可提高系统的性能,并同时提高透平输出功率的稳定性;降低ORC的蒸发温度会提高系统蒸汽产量,但同时也减少了可直接利用电能的产生量。     

超临界水氧化法处理有机废水的研究进展

超临界水氧化技术是一种能彻底破坏有机污染物结构的新型氧化技术,它在废水处理方面有着独特的优势。作者对超临界水氧化技术的工艺流程、反应器类型及研究现状进行了综述,并对其应用前景进行了展望。     

有机危废超临界水氧化技术进展

超临界水氧化技术是一种高效的有机危废无害化处理技术。从机理、工艺、设备三个方面介绍了超临界水氧化技术的研究进展,并针对辽宁省危废处置市场进行了应用前景分析。     

超临界水氧化法降解葡萄糖的研究

实验研究了葡萄糖在超临界水中的氧化降解。结果表明 ,超临界水氧化技术能有效地降解废水中的葡萄糖 ,COD去除率可达 98%。随着反应温度的升高、压力的增大、停留时间的延长和初始废水浓度的增大 ,COD去除率也随之提高。葡萄糖在超临界水中氧化降解的动力学方程为- d[COD]dτ =2 4.2 exp - 3.0× 10 4RT [COD]1.0 3 [O2 ]0 .0 670     

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。     

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。     

Influence of process parameters on the hydrothermal decomposition and oxidation of glucose in sub- and supercritical water

Supercritical water oxidation (SCWO) of wet waste biomass for energy recovery could be an advantageous alternative to conventional combustion with preceding drying. Therefore the reactions of glucose as a model substance for cellulosic biomass were investigated in sub- and supercritical water. The results of hydrothermal and oxidative experiments carried out in a continuous high-pressure plant with a feed solution of 0.2-1.2% (g g⁻¹) glucose at 24-34 MPa, 250-480 °C and residence times of 2-35 s are presented. In the presence of a stoichiometric oxygen concentration (for total oxidation to carbon dioxide and water) glucose decomposes already at subcritical temperatures readily to carbon monoxide and low molecular liquid substances, chiefly organic acids like e.g. acetic acid and glycolic acid. In turn these are in general more stable and react only slowly with oxygen. The effect of temperature, residence time, pressure, reactant concentration and addition of zinc sulfate on the conversion and the yields of reaction products was demonstrated. Already at 350 °C (24 MPa and 30 s) 99% of the glucose are converted. With increasing temperature the production of CO₂ increases. However, even at 480 °C (34 MPa and 4 s) significant amounts of CO are formed and the reaction of glucose to CO₂ and H₂O is not complete. Higher temperatures or greatly longer residence times are needed for a total combustion of the glucose.     

Oxidation characteristics of phthalic and adipic acids by supercritical water

Supercritical water oxidation (SCWO) was carried out in a flow-type reactor for modeling of waste-water containing phthalic or adipic acid. For each acid, the reaction order and rate constant, k, were determined over a wide range of experimental conditions : temperatures from 633.15 to 713.15 K, pressures from 18 to 29 MPa, excess amounts of hydrogen peroxide from zero to 800 percent, and the mean residence time in the reactor from 1.1 to 49.1 seconds. The concentration of both acids in model wastewater was set by 500 ppm. For phthalic acid, we found that the orders of decomposition reaction with respect to the reactant concentrations were 0.56 for phthalic acid, 0.31 for hydrogen peroxide, and 0.53 for water. For adipic acid, the orders of oxidation were 0.78 for adipic acid, 0.53 for hydrogen peroxide, and 0.74 for water. Then measured activation energy for phthalic acid was 33.08 kcal/mol and that for adipic acid was 19.51 kcal/mol, respectively.     

Treatment of dyehouse waste‐water by supercritical water oxidation: a case study

BACKGROUND: Supercritical water oxidation (SCWO) of dyehouse waste‐water containing several organic pollutants has been studied. The removal of these organic components with unknown proportions is considered in terms of total organic carbon concentration (TOC), with an initial value of 856.9 mg L^?1. Oxidation reactions were performed using diluted hydrogen peroxide. The reaction conditions ranged between temperatures of 400–600 °C and residence times of 8–16 s under 25 MPa of pressure. RESULTS: TOC removal efficiencies using SCWO and hydrothermal decomposition were between 92.0 and 100% and 6.6 and 93.8%, respectively. An overall reaction rate, which consists of hydrothermal decomposition and the oxidation reaction, was determined for the hydrothermal decomposition of the waste‐water with an activation energy of 104.12 ( ± 2.6) kJ mol^?1 and a pre‐exponential factor of 1.59( ± 0.5) × 10⁵ s^?1. The oxidation reaction rate orders for the TOC and the oxidant were 1.169 ( ± 0.3) and 0.075 ( ± 0.04) with activation energies of 18.194 ( ± 1.09) kJ mol^?1, and pre‐exponential factor of 5.181 ( ± 1.3) L^0.244 mmol^?0.244 s^?1 at the 95% confidence level. CONCLUSION: Results demonstrate that the SCWO process decreased TOC content by up to 100% in residence times between 8 and 16 s under various reaction conditions. The treatment efficiency increased remarkably with increasing temperature and the presence of excess oxygen in the reaction medium. Color of the waste‐water was removed completely at temperatures of 450 °C and above. Copyright © 2010 Society of Chemical Industry     

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。     

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 ...     

Corrosion control methods in supercritical water oxidation and gasification processes

Use of supercritical water (SCW) as a medium for oxidation reactions, conversion of organic materials to gaseous or liquid products, and for organic and inorganic synthesis processes, has been the subject of extensive research, development, and some commercial activity for over 25 years. A key aspect of the technology concerns the identification of materials, component designs, and operating techniques suitable for handling the moderately high temperatures and pressures and aggressive environments present in many SCW processes. Depending upon the particular application, or upon the particular location within a single process, the SCW process environment may be oxidizing, reducing, acidic, basic, nonionic, or highly ionic. Thus, it is difficult to find any one material or design that can withstand the effects of all feed types under all conditions. Nevertheless, several approaches have been developed to allow successful continuous processing with sufficient corrosion resistance for an acceptable period of time. The present paper reviews the experience to date for methods of corrosion control in the two most prevalent SCW processing applications: supercritical water oxidation (SCWO) and supercritical water gasification (SCWG).     

Total organic carbon disappearance kinetics for supercritical water oxidation of dimethyl methylphospate used as a chemical agent simulant

Supercritical Water Oxidation (SCWO) has been proven to be a powerful technology to treat a wide range of wastes, but there are few references in the literature about the application of SCWO to chemical weapon agents. In this work, SCWO has been tested to treat a chemical agent stimulant, dimethyl methylphosphonate (DMMP), which is similar to the nerve agent VX and GB (Sarin) in its structure. The experiments were performed in an isothermal tubular reactor with H₂O₂ as an oxidant. The reaction temperatures ranged from 398 to 633 ‡C at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon (TOC) on the liquid effluent samples. It was found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 seconds at 555 ‡C. An assumed first-order global power-law rate expression was determined with activation energy of 32.35±2.21 kJ/mol and a pre-exponential factor of 54.63±1.45 s ’ to a 95% confidence level. By taking into account the dependence of the reaction rate on oxidant concentration, a global power-law rate expression was regressed from the complete set of data. The resulting activation energy was 42.00±0.41 kJ/ mol; the pre-exponential factor was 66.56±0.48l ^1.31 mmol^-0.31 s^-1; and the reaction orders for DMMP (based on TOC) and oxidant were 0.96±0.02 and 0.35±0.04, respectively.