超临界水氧化水膜反应器热动力特性研究
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摘要
随着我国工农业的的迅速发展,各类含有毒有害难降解有机物的高浓度废水相应增多,给环境造成了严重的污染。超临界水氧化(简称SCWO)技术作为一种新兴的绿色有机废水处理技术,能够完全氧化废水中的难于生物降解的有机物,处理后的气液相产物污染性极小,被视为是最有前途的废水处理技术。但是超临界水氧化反应器的腐蚀和堵塞问题严重影响了该技术的工业化推广。水膜反应器因其具有良好的抗腐蚀、抗盐沉积性能,成为超临界水氧化系统中反应器的首选型式。目前对于水膜反应器的研究主要集中在对有机物的处理效果以及长期运行状况下系统的稳定性。水膜反应器内多孔管内壁的亚临界水膜层是决定水膜反应器抗腐蚀和盐沉积性能的关键。而目前对于影响多孔管内壁面上亚临界水膜形成及厚度大小的因素的研究则很少,至今没有对该反应器形成一种比较精确的运行指导方法。
超临界水氧化反应是放热反应,当有机物浓度高于一定数值时,系统可以实现热量的自补偿,且余热可以回收利用。因此有必要对scwo系统的能量利用进行分析并探讨该技术处理废液的运行费用,寻找提高系统经济性的途径,从而推动该技术的工业化发展。
针对上述情况,本文首先建立了一套以水膜反应器为主体的超临界水氧化系统,同时兼顾了系统热能的回收利用。水膜反应器的设计和运行引入了蒸发水分层概念,最上层蒸发水以亚临界温度进入反应器内,在保证不影响反应区氧化效果的提前下在多孔管内壁面形成亚临界温度水膜层。最下层蒸发水以常温进入反应器进行冷却,以保证反应器出口温度低于水的临界温度,即在反应器下部形成亚临界溶盐区。为了回收利用反应产生的热量,反应器出口高温高压的反应产物首先分流后分别经过换热器预热有机废液和上层蒸发水,而后混合后通过换热器进行余热回收,实现热水的对外供应。
在上述试验系统中以甲醇溶液模拟为有机废液、以氧气为氧化剂进行了系统的试验研究。研究了各个运行参数(主要包括：反应器入口废液温度、废液流量、废液有机物浓度、蒸发水流量和不同层蒸发水温度)对有机物TOC去除率、气相产物成分、反应器内轴向温度分布、物料有效停留长度和有效停留时间的影响。从系统处理效果和能力、稳定运行及节能角度出发,确定了适宜的操作参数。试验研究结果表明：有机物TOC去除率依赖于反应最高温度和物料在反应器内的有效停留时间,为获得高于99%的TOC去除率,有效停留时间应保持在15s以上。反应器入口甲醇溶液温度是影响反应器内是否发生超临界水氧化的关键。本系统中只有在入口甲醇溶液温度高于369℃时,超临界水氧化反应才得以进行,此时TOC降解效率超过了99%。甲醇溶液浓度和反应最高温度存在线性的函数关系,随着浓度的升高,反应最高温度和TOC的去除率随之升高。浓度≤2%时,反应最高温度低于500℃,停留时间小于15s,甲醇不能完全降解。而浓度增加到8%时,反应最高温度迅速增加到700℃以上。浓度过高,反应器内顶端存在的过热现象不利用反应器的长期运行,最终选择试验系统比较适宜的甲醇溶液浓度应为4%-6%。甲醇溶液流量的升高,导致物料的有效停留时间显著下降,甲醇降解不完全。试验系统废液流量在小于14kg/h时,TOC降解效率均能达到99%。蒸发度和反应器入口中层蒸发水温度对反应器内轴向温度分布以及TOC的降解效率影响很小。本试验系统蒸发度在0.04-0.08范围内,中层蒸发水入口温度即使降至105℃,TOC去除率也达到了99%以上。随着上层蒸发水温度的升高,物料有效停留时间增加,上层蒸发水温度只有高于285℃时方能获得99%以上的TOC降解效率。
由于在试验过程中难于实现反应器内径向温度的精确测量,也没法实现水膜厚度的在线测量,本文根据水膜反应器内物质的流动和反应特点,确定了适合的物理模型和数学模型,利用FLUENT6.2软件对水膜反应器内的温度场分布和水膜厚度分布进行计算研究。
本文模拟中的流动模型采用RNG k-ε模型,化学反应采用单步的甲醇氧化反应,反应速率由薄层有限速率／涡耗散模型控制,多孔区域内的流动遵循达西定律。为了计算的收敛性,对临界点附近水的物性参数采用去峰线性化的方法进行计算。水膜反应器物理模型的结构尺寸完全按照试验系统中实际建造的反应器尺寸。由于水膜反应器为轴对称结构,为减小计算量,本文选取模型的一半进行计算分析。最终将模拟计算和试验所测得的反应器内轴向温度分布的结果进行了对比,变化趋势基本一致,误差小于8%。
通过对水膜反应器的数值模拟确定了各个运行参数对反应器内温度场分布和水膜厚度分布的影响规律,计算过程中参数的选择是参考试验结果确定的。计算结果表明：各个运行参数对反应器内轴向温度分布的影响规律与试验结论完全吻合。反应器内水膜厚度沿轴向经历先降低,甚至降至负值后,并逐渐升高的过程,存在负值的区域仅限于上层蒸发水区域。水膜厚度存在负值说明多孔管内的温度亦超过了水的临界温度。反应器入口有机溶液的温度对水膜厚度的变化影响很小,只要保证超临界水氧化反应的开始即可。有机溶液的浓度、流量以及中层蒸发水温度对处于负值区的水膜厚度的大小基本没有影响,在存在亚临界水膜层的区域内,随着浓度和流量的降低以及中层蒸发水温度的降低,水膜厚度随之增加,具体选择范围需要根据试验结果兼顾TOC去除率。随着上层蒸发水流量的升高,出现负值的水膜厚度的区域逐渐减少,而对反应器下部的水膜厚度影响不大。在诸多运行参数中,上层蒸发水温度对水膜厚度的影响最大,随着上层蒸发水温度的降低,水膜厚度出现负值的的区域明显减小,且反应器下部水膜厚度也明显增加。在蒸发度为0.06时,上层蒸发水温度降至约为250℃时,水膜厚度全部为正值,表明此时整个反应器多孔内壁上的水流均为亚临界温度。但是,根据试验结果,当其温度过低时,会影响TOC的去除效果。在确定反应器入口废液温度、流量、有机物浓度以及中下层蒸发水强度和温度后,水膜厚度出现临界值时,上层蒸发水温度和上层蒸发度呈线性关系。
明确了各个运行参数对水膜厚度的影响规律,还需要在各个参数以及反应器结构和水膜厚度之间建立起关联公式,确定具体的亚临界水膜层形成的条件,以指导水膜反应器的设计和系统运行参数的正确选择。本文根据水膜反应器内物质换热基本原理,推导出了物质之间换热的基本方程式。通过简化并结合数值计算结果,忽略了对水膜厚度影响甚小的参数,最终建立起了各参数之间的数学关系式,确定了亚临界水膜层形成的条件。多孔管内壁面上亚临界水膜层厚度的变化是由于蒸发水和主流物质之间的换热引起的,一方面是由于主流物质和蒸发水之间因蒸汽分压差导致的蒸发换热,另一方面是两者之间由于温差导致的接触换热。
水膜反应器出口温度是否低于水的临界温度374℃,取决于下层常温的蒸发水量,本文取水膜反应器为控制体,根据质量平衡和能量平衡确定了下层蒸发水量和系统其它运行参数之间的数学关联式,即确定了反应器内亚临界溶盐区形成的条件,从而可以指导下层蒸发水量的选择。
为了探讨基于水膜反应器的超临界水氧化能量回收系统的工业应用前景,本文对系统的能量有效利用率和处理成本作了计算分析,结果表明：在试验和模拟研究得到的优化参数下,系统的有效能量利用率可达到54.06%,系统通过背压阀降压引起的能量损失达20%左右。为提高系统的经济性,必须进一步研究系统压力能的利用途径。对废液处理量为300m3/d, COD含量为40000m/L的超临界水氧化系统进行的经济性分析表明：系统处理成本为33.05元/t,其中氧气的费用约占总运行费用的71.8%。为提高系统的经济性,需要寻找新的氧化剂使用方式来降低系统的运行费用。
在保持系统高的TOC去除率条件下,根据本文确定的亚临界水膜层形成条件以及亚临界溶盐区形成条件选择系统最佳运行参数后,水膜反应器可以有效缓解超临界水氧化系统中的腐蚀和盐沉积问题,对于处理高浓度难降解的有机废弃物,随着系统压力能利用方式的开发以及氧化剂使用方式的优化,超临界水氧化技术具有非常广阔的应用前景。
Along with the rapid development of agriculture and industry in China, all kinds of high-concentrated hard-degradation liquid waste containing toxic and harmful organic matters have correspondingly increased, which has do great harm to the environment. As an emerging green technology of water treatment, the technology of supercritical water oxidation (SCWO) can completely oxidize the hard-degraded organic matters in the liquid waste, and the post-treated gas-liquid product has little pollution, which is regarded as the most promising liquid waste treatment technology. However, the industrialization extension has been influenced severely by the corrosion and plugging in the SCWO reactor. Due to its benign anti-corrosion and anti-salt deposit performance, the transpiring wall reactor has become the primary type of reactor in the SCWO system. Currently, the study on the transpiring wall reactor mainly focuses on the treatment effect of the organic matters and the stability of the system in the long-term operation. It is crucial that whether the water film layer at sub-critical temperature exists at the internal face of the porous tube in the transpiring wall reactor, which determines the anti-corrosion and anti-deposit performance of transpiring wall reactor. Currently, there are few studies on the factors that influences the formation and thickness of water film layer with sub-critical temperature on the internal face with porous tube, and no precise operation guidance has been shaped to such a reactor.
SCWO reaction is an exothermic reaction. When the organic concentration is higher than a certain value, the system will realize the heat auto-compensation, and the excess heat can be recycled. Therefore, it is necessary to analyze the energy utilization in the SCWO reaction system, discuss the operation cost of the liquid waste treatment and seek for the approaches which improve the economic of the system so as to boost the development of industrialization of this technology.
Pointing to the above situation, the SCWO reaction system majoring in transpiring wall reactor has been firstly established, meanwhile, the energy recycling in the system has been taken into consideration. The definition of transpiring water layer has been introudced into the design and operation of the transpiring wall reactor, the top transpiring water has been injected into the reactor at sub-critical temperature and the water film layer forms at sub-critical temperature in the internal face of porous tube, which can ensure the oxidation effect in the reaction area. The bottom transpiring water enters the reactor for refrigeration with normal temperature, which is to ensure the outlet temperature of the reactor is lower than the sub-critical temperature of water, that is, the sub-critical soluble salt area forms at the bottom of the reactor. In order to recycle and utilize the heat generated by the reaction, the reaction products with high temperature and pressure in the outlet of reactors will primarily be split-flow to preheat the organic liquid waste and transpiration water respectively through two heat exchangers and then they mix and heat up the heating hot water through the third heat exchanger.
The systematic experiment has been performed with the way that simulates the organic liquid waste with methanol water solution and the oxidant with oxygen, which has researched on the items as follows, that is, the consequences of all the operation parameters for the strainaway rate of the organic matter, the element of gas phase product, the temperature distribution of the axial in the reactor, the effective remaining length and time of the supplies. (The parameters mainly include the liquid waste flow, the temperature of liquid waste in the reaction inlets, the organic matter concentration in the liquid waste, the water flow of the evaporation, and transpiration water temperature in different layers). From the perspective of treatment effect and capability of the system, the stable operation and energy conservation, the proper operation parameters have been determined. The experiment study result has proved that the TOC strainaway rate relies on the highest temperature and the effective residence time in the reactors, in order to acquire the TOC strainaway rate as high as 99%, the effective residence time should keep more than 15s. The methanol water solution in the reactor outlet is the key issue that influences whether the SCWO has reacted in the reactors. SCWO reaction will not work until the temperature of the methanol water solution in the reactor inlet is higher than 369℃, the degradation effectiveness of TOC will be over 99%. The concentration of the methanol water solution has a linear function relationship with the highest temperature of reaction, the higher the concentration is, the higher the reactive temperature and the strainaway rate of TOC is. When the concentration is less than or equal to 2%, the highest temperature of the reaction is less than 500℃, and the residence time is less than 15s, and the methanol cannot degrade completely. However, if the concentration increased to 8%, the highest temperature of reaction will increase rapidly to over 700℃. If the concentration is over-high, the overheat phenomenon existing in the top of the reactors will not do good to the long-term operation, finally, the proper concentration of the methanol water solution will be selected within 4%～6%. If the flow of the methanol water solution raises, the effective residence time of the materials will drop evidently, and the organic matters will not be degraded completely. If the flow of liquid waste in the experiment system is less than 14kg/h, the degraded effectiveness of the TOC will reach 99%, the evaporativity and the transpiration water temperature in the inlet of reactor will have little influence on the axial temperature distribution in the reactors and the degraded effectiveness of TOC. The evaporativity in the experiment system is within 0.04-0.08, and even if the temperature of the middle-layer evaporation water in the inlet of the reactor drops to 105℃, the strainaway rate of TOC will reach to more than 99%. Along with the rising temperature of the transpiration water in the top layer, the effective residence time of materials will increase, more than 99% of the TOC degrading efficiency will be gained only when the temperature of transpiration water in the top layer is higher than 285℃.
The precise measurement of the radial temperature in the reactor will be hard to achieve in the process of experiment, and the online measurement of the water film thickness cannot be achieved, therefore, the proper physical model and mathmatical model has been determined in accordance with the material flow and reaction characteristics in the transpiring wall reactor; the temperature field distribution and water film thickness distribution within the transpiring wall reactor have been calculated and studied with the help of FLUENT 6.2 commercial software.
The RNG k-εmodel has been applied into the flow model in simulation, and the oxidizing reaction with single step has been taken; the Arrhenius rate and mixed rate are calculated by the finite rate/vortex dissipative model with thin layer, and the smaller one of them has been applied, in addition, the Darcy law should be obeyed within the porous area. In order to gain the astringency of the calculation, the physical parameter of the water near the sub-critical points will be calculated with the peak linearization. The structure size of the physical model of transpiring wall reactor is completely in accordance with the actual reactor size in the experiment system. The transpiring wall reactor has a structure with axial symmetry; in order to reduce the calculated amount, the half of the model has been taken for calculation and analysis in the paper. Finally, the results of the axial temperature distribution in the reactors acquired from the simulation calculation and experiments have been compared, and the alteration trends is almost the same, and the error is less than 8%.
The influence law of all the operation parameters on the temperature filed distribution and water film thickness in the reactor has been determined by the numerical value simulation of the water film reactors, and the parameter selection in the process of calculation is determined by the reference to the experiment results. The calculation result has proved that the influence law of all the operation parameters on the axial temperature distribution within the reactors have completed identical to the experiment conclusions, the water film thickness of the reactors will go through the process that low firstly, even low to the minus value, then rise gradually, the areas that existing minus value is only in the transpiration water area in the top layer. The minus value existing in the water film thickness has proved that the temperature within the porous tube has surpassed the sub-critical temperature of the water. The temperature of the organic solution in the inlet of the reactor has little influence on the changes of water film thickness, as long as it can guarantee the starting performance of SCWO reaction. The organic solution's concentration, flow and the temperature of evaporation water in the middle layer has little influence on the size of the water film thickness in minus value areas; within the area of water film layer at sub-critical temperature, along with the lower of the concentration and flow as well as the drop of the transpiration temperature in the middle layer, the thickness of water film will increase correspondingly. And the specific selection boundary will be in accordance with the experiment results and the strainaway rate of TOC should be also taken into consideration. Along with the uprising of the transpiration water flow in the top layer, the areas of water film thickness with minus value have gradually decreased, which has little influence on the water film thickness at the bottom of the reactor. The transpiration water temperature has the most powerful influence on the water film thickness in the operation parameters; along with the drop of the transpiration water temperature in the top layer, the areas of water film thickness with minus value have decreased evidently, and the water film thickness at the bottom of reactors has rise evidently. When the transpiration intensity is 0.06 and the transpiration water temperature in the top layer drop to about 250℃, the thickness of water film is positive value, which suggests that the water flow of the porous wall of the whole reactor is sub-critical temperature. However, according to the experiment results, when the temperature is over-low, it will impact on the strainaway effectiveness of the TOC. After having determined the temperature, flow and organic concentration in the liquid waste inlet, and the intensity and temperature of the transpiration water in the middle and bottom layer, and when the water film thickness emerges the sub-critical value, a linear relationship will present between the transpiration water temperature and the transpiration intensity in the top layer.
After the influence law of all the operation parameters on the water film thickness has been determined, what should be done is to establish the relevance equation between all the parameters or between the reaction structure and the water film thickness, determine the conditions to form the specific sub-critical water film layers to guide the design and correct parameters selection of the transpiring wall reactor system. According to the basic principle of material heat exchange within the transpiring wall reactor, the basic equation for heat exchange between materials has been deduced. Through simplifying and combining the numerical value calculation, neglecting the parameters that has little influences on the water film thickness, then the mathematical relations between all the parameters is established and the conditions that form the sub-critical water film layers is determined. The change of sub-critical water film layer in the internal face of porous tube is caused by the exchange between the transpiration water and the mainstream materials, on the one hand, the transpiration heat exchange is caused by the partial pressure between mainstream materials and transpiration water; on the other hand, the touching heat exchange is caused by the temperature difference between mainstream materials and transpiration water.
Whether the temperature in the outlet of transpiring wall reactor is lower than 374℃of the critical temperature of water, which depends on the transpiration water with normal temperature in the low layer; the transpiring wall reactor has been selected as the controlling volume in the paper, according to the quality balance and energy balance, and the mathematical relevance between the transpiration water and other parameters in the systems have been determined, that is, the conditions that form the sub-critical salt-solutions areas within the reactors, so as to guide the selection of the transpiration water in the bottom layers.
In order to discuss the application outlook of the SCWO energy recycling system based on the transpiring wall reactor, the availability of the energy and treatment cost in the system has been calculated and analyzed, which has suggested t hat the availability of the system can reach 54.06% with the optimized parameter in the experiment and simulation research, and the energy loss caused by the depressurization of back pressure valve reaches about 20%. In order to improve the economy of the system, the further research should be done on the available approaches to using pressure energy of the system. The economic analysis on the liquid waste treatment with 300m3/d, the COD in liquid waste with 40000mg/L has proved that, the treatment cost of system is 33.05￥/t, in which the cost of oxygen has covered 71.8% of the total cost. In order to improve the economy of the system, it is necessary to seek for new oxidant application method to reduce the operation cost of the system.
Having kept the high TOC strainaway rate in the system, according to the determined conditions that form the sub-critical water film layers, after the best operation parameters have been selected for the conditions that form the sub-critical salt solutions areas, transpiring wall reactors can effectively relieve the corrosion and salt deposits of the SCWO system; along with the development of the application manner of system pressure energy and the optimization of the application manner of oxidant, SCWO technology has widely application for dealing with the organic waste with high concentration and tough degradation.
超临界水氧化反应是放热反应,当有机物浓度高于一定数值时,系统可以实现热量的自补偿,且余热可以回收利用。因此有必要对scwo系统的能量利用进行分析并探讨该技术处理废液的运行费用,寻找提高系统经济性的途径,从而推动该技术的工业化发展。
针对上述情况,本文首先建立了一套以水膜反应器为主体的超临界水氧化系统,同时兼顾了系统热能的回收利用。水膜反应器的设计和运行引入了蒸发水分层概念,最上层蒸发水以亚临界温度进入反应器内,在保证不影响反应区氧化效果的提前下在多孔管内壁面形成亚临界温度水膜层。最下层蒸发水以常温进入反应器进行冷却,以保证反应器出口温度低于水的临界温度,即在反应器下部形成亚临界溶盐区。为了回收利用反应产生的热量,反应器出口高温高压的反应产物首先分流后分别经过换热器预热有机废液和上层蒸发水,而后混合后通过换热器进行余热回收,实现热水的对外供应。
在上述试验系统中以甲醇溶液模拟为有机废液、以氧气为氧化剂进行了系统的试验研究。研究了各个运行参数(主要包括：反应器入口废液温度、废液流量、废液有机物浓度、蒸发水流量和不同层蒸发水温度)对有机物TOC去除率、气相产物成分、反应器内轴向温度分布、物料有效停留长度和有效停留时间的影响。从系统处理效果和能力、稳定运行及节能角度出发,确定了适宜的操作参数。试验研究结果表明：有机物TOC去除率依赖于反应最高温度和物料在反应器内的有效停留时间,为获得高于99%的TOC去除率,有效停留时间应保持在15s以上。反应器入口甲醇溶液温度是影响反应器内是否发生超临界水氧化的关键。本系统中只有在入口甲醇溶液温度高于369℃时,超临界水氧化反应才得以进行,此时TOC降解效率超过了99%。甲醇溶液浓度和反应最高温度存在线性的函数关系,随着浓度的升高,反应最高温度和TOC的去除率随之升高。浓度≤2%时,反应最高温度低于500℃,停留时间小于15s,甲醇不能完全降解。而浓度增加到8%时,反应最高温度迅速增加到700℃以上。浓度过高,反应器内顶端存在的过热现象不利用反应器的长期运行,最终选择试验系统比较适宜的甲醇溶液浓度应为4%-6%。甲醇溶液流量的升高,导致物料的有效停留时间显著下降,甲醇降解不完全。试验系统废液流量在小于14kg/h时,TOC降解效率均能达到99%。蒸发度和反应器入口中层蒸发水温度对反应器内轴向温度分布以及TOC的降解效率影响很小。本试验系统蒸发度在0.04-0.08范围内,中层蒸发水入口温度即使降至105℃,TOC去除率也达到了99%以上。随着上层蒸发水温度的升高,物料有效停留时间增加,上层蒸发水温度只有高于285℃时方能获得99%以上的TOC降解效率。
由于在试验过程中难于实现反应器内径向温度的精确测量,也没法实现水膜厚度的在线测量,本文根据水膜反应器内物质的流动和反应特点,确定了适合的物理模型和数学模型,利用FLUENT6.2软件对水膜反应器内的温度场分布和水膜厚度分布进行计算研究。
本文模拟中的流动模型采用RNG k-ε模型,化学反应采用单步的甲醇氧化反应,反应速率由薄层有限速率／涡耗散模型控制,多孔区域内的流动遵循达西定律。为了计算的收敛性,对临界点附近水的物性参数采用去峰线性化的方法进行计算。水膜反应器物理模型的结构尺寸完全按照试验系统中实际建造的反应器尺寸。由于水膜反应器为轴对称结构,为减小计算量,本文选取模型的一半进行计算分析。最终将模拟计算和试验所测得的反应器内轴向温度分布的结果进行了对比,变化趋势基本一致,误差小于8%。
通过对水膜反应器的数值模拟确定了各个运行参数对反应器内温度场分布和水膜厚度分布的影响规律,计算过程中参数的选择是参考试验结果确定的。计算结果表明：各个运行参数对反应器内轴向温度分布的影响规律与试验结论完全吻合。反应器内水膜厚度沿轴向经历先降低,甚至降至负值后,并逐渐升高的过程,存在负值的区域仅限于上层蒸发水区域。水膜厚度存在负值说明多孔管内的温度亦超过了水的临界温度。反应器入口有机溶液的温度对水膜厚度的变化影响很小,只要保证超临界水氧化反应的开始即可。有机溶液的浓度、流量以及中层蒸发水温度对处于负值区的水膜厚度的大小基本没有影响,在存在亚临界水膜层的区域内,随着浓度和流量的降低以及中层蒸发水温度的降低,水膜厚度随之增加,具体选择范围需要根据试验结果兼顾TOC去除率。随着上层蒸发水流量的升高,出现负值的水膜厚度的区域逐渐减少,而对反应器下部的水膜厚度影响不大。在诸多运行参数中,上层蒸发水温度对水膜厚度的影响最大,随着上层蒸发水温度的降低,水膜厚度出现负值的的区域明显减小,且反应器下部水膜厚度也明显增加。在蒸发度为0.06时,上层蒸发水温度降至约为250℃时,水膜厚度全部为正值,表明此时整个反应器多孔内壁上的水流均为亚临界温度。但是,根据试验结果,当其温度过低时,会影响TOC的去除效果。在确定反应器入口废液温度、流量、有机物浓度以及中下层蒸发水强度和温度后,水膜厚度出现临界值时,上层蒸发水温度和上层蒸发度呈线性关系。
明确了各个运行参数对水膜厚度的影响规律,还需要在各个参数以及反应器结构和水膜厚度之间建立起关联公式,确定具体的亚临界水膜层形成的条件,以指导水膜反应器的设计和系统运行参数的正确选择。本文根据水膜反应器内物质换热基本原理,推导出了物质之间换热的基本方程式。通过简化并结合数值计算结果,忽略了对水膜厚度影响甚小的参数,最终建立起了各参数之间的数学关系式,确定了亚临界水膜层形成的条件。多孔管内壁面上亚临界水膜层厚度的变化是由于蒸发水和主流物质之间的换热引起的,一方面是由于主流物质和蒸发水之间因蒸汽分压差导致的蒸发换热,另一方面是两者之间由于温差导致的接触换热。
水膜反应器出口温度是否低于水的临界温度374℃,取决于下层常温的蒸发水量,本文取水膜反应器为控制体,根据质量平衡和能量平衡确定了下层蒸发水量和系统其它运行参数之间的数学关联式,即确定了反应器内亚临界溶盐区形成的条件,从而可以指导下层蒸发水量的选择。
为了探讨基于水膜反应器的超临界水氧化能量回收系统的工业应用前景,本文对系统的能量有效利用率和处理成本作了计算分析,结果表明：在试验和模拟研究得到的优化参数下,系统的有效能量利用率可达到54.06%,系统通过背压阀降压引起的能量损失达20%左右。为提高系统的经济性,必须进一步研究系统压力能的利用途径。对废液处理量为300m3/d, COD含量为40000m/L的超临界水氧化系统进行的经济性分析表明：系统处理成本为33.05元/t,其中氧气的费用约占总运行费用的71.8%。为提高系统的经济性,需要寻找新的氧化剂使用方式来降低系统的运行费用。
在保持系统高的TOC去除率条件下,根据本文确定的亚临界水膜层形成条件以及亚临界溶盐区形成条件选择系统最佳运行参数后,水膜反应器可以有效缓解超临界水氧化系统中的腐蚀和盐沉积问题,对于处理高浓度难降解的有机废弃物,随着系统压力能利用方式的开发以及氧化剂使用方式的优化,超临界水氧化技术具有非常广阔的应用前景。
Along with the rapid development of agriculture and industry in China, all kinds of high-concentrated hard-degradation liquid waste containing toxic and harmful organic matters have correspondingly increased, which has do great harm to the environment. As an emerging green technology of water treatment, the technology of supercritical water oxidation (SCWO) can completely oxidize the hard-degraded organic matters in the liquid waste, and the post-treated gas-liquid product has little pollution, which is regarded as the most promising liquid waste treatment technology. However, the industrialization extension has been influenced severely by the corrosion and plugging in the SCWO reactor. Due to its benign anti-corrosion and anti-salt deposit performance, the transpiring wall reactor has become the primary type of reactor in the SCWO system. Currently, the study on the transpiring wall reactor mainly focuses on the treatment effect of the organic matters and the stability of the system in the long-term operation. It is crucial that whether the water film layer at sub-critical temperature exists at the internal face of the porous tube in the transpiring wall reactor, which determines the anti-corrosion and anti-deposit performance of transpiring wall reactor. Currently, there are few studies on the factors that influences the formation and thickness of water film layer with sub-critical temperature on the internal face with porous tube, and no precise operation guidance has been shaped to such a reactor.
SCWO reaction is an exothermic reaction. When the organic concentration is higher than a certain value, the system will realize the heat auto-compensation, and the excess heat can be recycled. Therefore, it is necessary to analyze the energy utilization in the SCWO reaction system, discuss the operation cost of the liquid waste treatment and seek for the approaches which improve the economic of the system so as to boost the development of industrialization of this technology.
Pointing to the above situation, the SCWO reaction system majoring in transpiring wall reactor has been firstly established, meanwhile, the energy recycling in the system has been taken into consideration. The definition of transpiring water layer has been introudced into the design and operation of the transpiring wall reactor, the top transpiring water has been injected into the reactor at sub-critical temperature and the water film layer forms at sub-critical temperature in the internal face of porous tube, which can ensure the oxidation effect in the reaction area. The bottom transpiring water enters the reactor for refrigeration with normal temperature, which is to ensure the outlet temperature of the reactor is lower than the sub-critical temperature of water, that is, the sub-critical soluble salt area forms at the bottom of the reactor. In order to recycle and utilize the heat generated by the reaction, the reaction products with high temperature and pressure in the outlet of reactors will primarily be split-flow to preheat the organic liquid waste and transpiration water respectively through two heat exchangers and then they mix and heat up the heating hot water through the third heat exchanger.
The systematic experiment has been performed with the way that simulates the organic liquid waste with methanol water solution and the oxidant with oxygen, which has researched on the items as follows, that is, the consequences of all the operation parameters for the strainaway rate of the organic matter, the element of gas phase product, the temperature distribution of the axial in the reactor, the effective remaining length and time of the supplies. (The parameters mainly include the liquid waste flow, the temperature of liquid waste in the reaction inlets, the organic matter concentration in the liquid waste, the water flow of the evaporation, and transpiration water temperature in different layers). From the perspective of treatment effect and capability of the system, the stable operation and energy conservation, the proper operation parameters have been determined. The experiment study result has proved that the TOC strainaway rate relies on the highest temperature and the effective residence time in the reactors, in order to acquire the TOC strainaway rate as high as 99%, the effective residence time should keep more than 15s. The methanol water solution in the reactor outlet is the key issue that influences whether the SCWO has reacted in the reactors. SCWO reaction will not work until the temperature of the methanol water solution in the reactor inlet is higher than 369℃, the degradation effectiveness of TOC will be over 99%. The concentration of the methanol water solution has a linear function relationship with the highest temperature of reaction, the higher the concentration is, the higher the reactive temperature and the strainaway rate of TOC is. When the concentration is less than or equal to 2%, the highest temperature of the reaction is less than 500℃, and the residence time is less than 15s, and the methanol cannot degrade completely. However, if the concentration increased to 8%, the highest temperature of reaction will increase rapidly to over 700℃. If the concentration is over-high, the overheat phenomenon existing in the top of the reactors will not do good to the long-term operation, finally, the proper concentration of the methanol water solution will be selected within 4%～6%. If the flow of the methanol water solution raises, the effective residence time of the materials will drop evidently, and the organic matters will not be degraded completely. If the flow of liquid waste in the experiment system is less than 14kg/h, the degraded effectiveness of the TOC will reach 99%, the evaporativity and the transpiration water temperature in the inlet of reactor will have little influence on the axial temperature distribution in the reactors and the degraded effectiveness of TOC. The evaporativity in the experiment system is within 0.04-0.08, and even if the temperature of the middle-layer evaporation water in the inlet of the reactor drops to 105℃, the strainaway rate of TOC will reach to more than 99%. Along with the rising temperature of the transpiration water in the top layer, the effective residence time of materials will increase, more than 99% of the TOC degrading efficiency will be gained only when the temperature of transpiration water in the top layer is higher than 285℃.
The precise measurement of the radial temperature in the reactor will be hard to achieve in the process of experiment, and the online measurement of the water film thickness cannot be achieved, therefore, the proper physical model and mathmatical model has been determined in accordance with the material flow and reaction characteristics in the transpiring wall reactor; the temperature field distribution and water film thickness distribution within the transpiring wall reactor have been calculated and studied with the help of FLUENT 6.2 commercial software.
The RNG k-εmodel has been applied into the flow model in simulation, and the oxidizing reaction with single step has been taken; the Arrhenius rate and mixed rate are calculated by the finite rate/vortex dissipative model with thin layer, and the smaller one of them has been applied, in addition, the Darcy law should be obeyed within the porous area. In order to gain the astringency of the calculation, the physical parameter of the water near the sub-critical points will be calculated with the peak linearization. The structure size of the physical model of transpiring wall reactor is completely in accordance with the actual reactor size in the experiment system. The transpiring wall reactor has a structure with axial symmetry; in order to reduce the calculated amount, the half of the model has been taken for calculation and analysis in the paper. Finally, the results of the axial temperature distribution in the reactors acquired from the simulation calculation and experiments have been compared, and the alteration trends is almost the same, and the error is less than 8%.
The influence law of all the operation parameters on the temperature filed distribution and water film thickness in the reactor has been determined by the numerical value simulation of the water film reactors, and the parameter selection in the process of calculation is determined by the reference to the experiment results. The calculation result has proved that the influence law of all the operation parameters on the axial temperature distribution within the reactors have completed identical to the experiment conclusions, the water film thickness of the reactors will go through the process that low firstly, even low to the minus value, then rise gradually, the areas that existing minus value is only in the transpiration water area in the top layer. The minus value existing in the water film thickness has proved that the temperature within the porous tube has surpassed the sub-critical temperature of the water. The temperature of the organic solution in the inlet of the reactor has little influence on the changes of water film thickness, as long as it can guarantee the starting performance of SCWO reaction. The organic solution's concentration, flow and the temperature of evaporation water in the middle layer has little influence on the size of the water film thickness in minus value areas; within the area of water film layer at sub-critical temperature, along with the lower of the concentration and flow as well as the drop of the transpiration temperature in the middle layer, the thickness of water film will increase correspondingly. And the specific selection boundary will be in accordance with the experiment results and the strainaway rate of TOC should be also taken into consideration. Along with the uprising of the transpiration water flow in the top layer, the areas of water film thickness with minus value have gradually decreased, which has little influence on the water film thickness at the bottom of the reactor. The transpiration water temperature has the most powerful influence on the water film thickness in the operation parameters; along with the drop of the transpiration water temperature in the top layer, the areas of water film thickness with minus value have decreased evidently, and the water film thickness at the bottom of reactors has rise evidently. When the transpiration intensity is 0.06 and the transpiration water temperature in the top layer drop to about 250℃, the thickness of water film is positive value, which suggests that the water flow of the porous wall of the whole reactor is sub-critical temperature. However, according to the experiment results, when the temperature is over-low, it will impact on the strainaway effectiveness of the TOC. After having determined the temperature, flow and organic concentration in the liquid waste inlet, and the intensity and temperature of the transpiration water in the middle and bottom layer, and when the water film thickness emerges the sub-critical value, a linear relationship will present between the transpiration water temperature and the transpiration intensity in the top layer.
After the influence law of all the operation parameters on the water film thickness has been determined, what should be done is to establish the relevance equation between all the parameters or between the reaction structure and the water film thickness, determine the conditions to form the specific sub-critical water film layers to guide the design and correct parameters selection of the transpiring wall reactor system. According to the basic principle of material heat exchange within the transpiring wall reactor, the basic equation for heat exchange between materials has been deduced. Through simplifying and combining the numerical value calculation, neglecting the parameters that has little influences on the water film thickness, then the mathematical relations between all the parameters is established and the conditions that form the sub-critical water film layers is determined. The change of sub-critical water film layer in the internal face of porous tube is caused by the exchange between the transpiration water and the mainstream materials, on the one hand, the transpiration heat exchange is caused by the partial pressure between mainstream materials and transpiration water; on the other hand, the touching heat exchange is caused by the temperature difference between mainstream materials and transpiration water.
Whether the temperature in the outlet of transpiring wall reactor is lower than 374℃of the critical temperature of water, which depends on the transpiration water with normal temperature in the low layer; the transpiring wall reactor has been selected as the controlling volume in the paper, according to the quality balance and energy balance, and the mathematical relevance between the transpiration water and other parameters in the systems have been determined, that is, the conditions that form the sub-critical salt-solutions areas within the reactors, so as to guide the selection of the transpiration water in the bottom layers.
In order to discuss the application outlook of the SCWO energy recycling system based on the transpiring wall reactor, the availability of the energy and treatment cost in the system has been calculated and analyzed, which has suggested t hat the availability of the system can reach 54.06% with the optimized parameter in the experiment and simulation research, and the energy loss caused by the depressurization of back pressure valve reaches about 20%. In order to improve the economy of the system, the further research should be done on the available approaches to using pressure energy of the system. The economic analysis on the liquid waste treatment with 300m3/d, the COD in liquid waste with 40000mg/L has proved that, the treatment cost of system is 33.05￥/t, in which the cost of oxygen has covered 71.8% of the total cost. In order to improve the economy of the system, it is necessary to seek for new oxidant application method to reduce the operation cost of the system.
Having kept the high TOC strainaway rate in the system, according to the determined conditions that form the sub-critical water film layers, after the best operation parameters have been selected for the conditions that form the sub-critical salt solutions areas, transpiring wall reactors can effectively relieve the corrosion and salt deposits of the SCWO system; along with the development of the application manner of system pressure energy and the optimization of the application manner of oxidant, SCWO technology has widely application for dealing with the organic waste with high concentration and tough degradation.
引文
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