城市生活垃圾中再生PVC富氧燃烧重金属迁移特性分析

文章采用化学热力平衡计算方法,研究富氧燃烧气氛下,再生PVC中重金属(Zn,Pb,Cd,Cr,Cu和Ni)的迁移特性,并利用高温管式炉进行实验验证。研究结果表明:燃烧温度对重金属的迁移有显著影响,高温条件下,Cl易于与重金属Zn,Pb生成易挥发的气体;燃烧温度为1 000℃时,20%O2/80%N2与20%O2/80%CO2气氛基本不影响重金属Zn,Pb和Cd的迁移,而在20%O2/80%CO2气氛下,挥发性较弱的重金属Cr,Cu和Ni在底灰中的富集程度更大。燃烧温度为1 000℃时,随着O2浓度的增加,富氧燃烧气氛能够抑制重金属的挥发。     

吸附剂对垃圾焚烧中重金属分布规律影响的热力学模拟研究

通过吉布斯自由能最小热力学平衡法模拟研究了垃圾焚烧过程中重金属As,Cr,Cd和Pb的迁移和转化规律;考察了焚烧温度、空气过量系数、吸附剂(CaO,Al2O3和SiO2)的添加等主要焚烧工艺参数对重金属迁移和转化的影响。研究结果表明,焚烧温度对As,Cr,Cd和Pb的迁移转化有较大的影响,当温度高于800℃,重金属主要以CrAsO4,AsO(g),CrO2,CdO,CdCl2(g)和PbCl2(g)等形态存在。空气过量系数对重金属迁移转化影响较小。吸附剂的添加对重金属有一定的捕集作用。CaO的添加有利于降低As,Cr,Cd的挥发性;Al2O3的添加对As的捕集有很好的效果,但对Cr,Cd和Pb的挥发性影响较小;SiO2的添加对Pb的捕集有很好的效果,但对As,Cr和Cd的挥发性影响较小。     

垃圾焚烧中吸附剂对镉进行脱除的热力学平衡研究

采用热力学平衡分析的方法研究了3种吸附剂CaO、SiO2、Al2O3在垃圾焚烧中对镉(Cd)进行脱除的影响.采用系统吉布斯自由能最小的方法进行计算,计算软件为CHEMKIN.结果表明,吸附剂CaO对Cd的化学吸附效果较差,SiO2和Al2O3对Cd的吸附效果较好,SiO2能在较大温度范围内对Cd进行高效的脱除.同时对垃圾中含有的S、Cl对吸附剂性能的影响进行了评价,结果表明,S、Cl与Cd有很强的亲合力,会抑制SiO2和Al2O3对Cd的吸附,但在1 200 ～1 300 K,SiO2对Cd的化学吸附效率在80%以上.研究发现,Cl能使Al2O3对Cd的脱除失效,但在S存在的情况下,Al2O3是一种很好的镉吸附剂;SiO2、Al2O3共存时,SiO2对Cd的脱除性能优于Al2O3.     

城市污泥流化床焚烧炉飞灰中重金属迁移特性

对120 t/d城市污泥循环流化床焚烧炉飞灰中重金属迁移富集特性进行试验研究,对污泥、飞灰及不同温度、取样点的飞灰中Cr、Mn、Ni、Cu、Zn、As、Cd和Pb 8种重金属迁移富集特性进行了分析。试验结果表明:飞灰、底渣及入炉污泥中主要化学成分为Si O_2、Fe_2O_3、Ca O、Al_2O_3和P_2O_5,"Si0_2-Ca O-Al_2O_3-金属氧化物"体系构成了重金属吸附的载体,也为不同形态重金属的吸附提供了活性空间。Cd、As为易挥发性重金属,在炉膛内挥发的Cd、As及其化合物蒸气在503℃和475℃时几乎全部富集于飞灰颗粒;Cr、Mn、Cu、Zn主要通过夹带富集于飞灰颗粒,它们在尾部烟道不同温度区域飞灰颗粒上的富集程度相当,为难挥发性重金属。     

氧-燃料燃烧气氛下木屑与聚氯乙烯焚烧时的重金属迁移特性

文章在管式炉中开展燃烧实验,采用ICP-OES技术测试灰渣中的重金属含量,研究在氧-燃料燃烧气氛下木屑与聚氯乙烯(PVC)单独燃烧和混合燃烧过程中重金属的迁移规律,以及在此燃烧条件下有机氯(PVC)与无机氯(NaCl)对重金属迁移特性的影响。研究结果表明:在氧-燃料燃烧气氛下,重金属熔沸点和燃烧温度决定了垃圾组分焚烧过程中重金属的迁移特性;与常规空气燃烧气氛相比,氧-燃料燃烧气氛提高了Pb和Zn的挥发率,降低了Cr的挥发率;木屑与PVC的混烧质量比为5∶5时,混烧对重金属挥发的促进作用要低于质量比例为7∶3和3∶7时;在氧-燃料燃烧气氛下,有机氯对Pb挥发的促进作用大于无机氯。     

污泥与高碱煤协同燃烧中碱金属与重金属竞争机制研究

在CFB锅炉燃烧温度下研究了低品质燃料(高碱煤)与生物质燃料(污泥)协同燃烧中重金属元素Pb、Ni和As的迁移特性。结果表明:燃烧温度对重金属元素热力学平衡分布起到重要的作用,温度越高,Pb、Ni和As在气相中的摩尔分数越高;当温度超过1 300℃时,Pb将全部以单质形态迁移至气相中,在CFB锅炉燃烧温度区间里大部分以PbCl2(g)、少量以PbCl的形态固集于飞灰颗粒上;当温度高于1 800℃时,系统中主要成分为Ni(g);在整个燃烧温度区间,As以单质的形态存在于系统中,其摩尔分数随着温度的升高而上升;碱金属Na主要竞争燃料中的Cl和O元素,实现重金属化合物形态的转化;与Na相比,K的竞争是微弱的,在700℃时K竞争Ni化合物中的CrO_4~(2-),导致NiO摩尔分数下降,而在850℃时,K与Ni竞争系统中的O元素,这与700℃的反应过程不同。     

垃圾和污泥共燃过程中重金属的赋存迁移规律

采用热力学平衡计算方法,研究了垃圾和污泥焚烧过程Cu、Mn、Zn重金属的迁移规律,考察了温度、HCL、S以及焚烧中污泥水分高低对重金属迁移特性的影响.研究结果表明:除焚烧温度外,HCl是影响重金属迁移的主要因素,HCl的存在会促进难挥发重金属(Cu、Zn)低温时就挥发出来;污泥含水率的降低会增加氯化锌的挥发量,但影响较小,含水率由72％降至12％,氯化锌百分含量增加不到5％.     

生物质热解燃烧过程Cl析出规律研究

用化学平衡软件“Factsage”计算了稻草秸秆在200～800℃温度范围内热解条件和500 ～900℃温度范围内燃烧条件下,与Cl相关的各种无机物质的热力学平衡分布.采用管式炉反应器,研究了秸秆在热解和燃烧条件下的Cl的析出规律.理论计算结果表明,当温度低于600℃时,Cl主要以固态KCl的形式存在；在温度超过600℃,热转化中Cl的气化析出随温度升高而增加,在氧化性气氛下该趋势加剧.管式炉实验与理论计算的生物质Cl析出率随温度升高的变化趋势总体吻合,但是析出份额上有显著差异.     

竹园污泥焚烧污染物排放特性的试验研究

选取上海竹园污泥,将原始污泥样品分为全干污泥、均匀干化污泥(含水率10%)和干湿混合污泥(含水率20%,干湿污泥质量比例为10∶3)三种样品,分别送入小型流化床焚烧炉中焚烧。试验研究了全干污泥在750℃、850℃、950℃三个工况下的燃烧特性,并研究了均匀干化污泥和干湿混合污泥在850℃工况下的燃烧特性。研究发现,上海竹园污泥在小型流化床焚烧炉中燃烧时,排放的主要常规污染物包括CO、SO2、NOx、HCl等以及二噁英和Cd、Hg、Pb等重金属。不同燃烧温度和含水率对污染物的排放有一定影响,提高燃烧温度,CO、SO2、NOx、HCl等的排放基本呈现出下降趋势,而烟气中Pb的排放随着温度上升而升高,相同燃烧温度下含水率升高能降低二噁英的排放总量,随着含水率的提高飞灰中重金属含量有所降低,而底渣中重金属含量呈上升趋势。     

城市垃圾焚烧过程中重金属释放行为的试验研究

以城市垃圾为研究对象，在流化床试验装置上进行焚烧试验，并采用电感耦合等离子体发射光谱仪在线测量烟气中的重金属浓度，研究不同气氛条件(空气、混合气和氮气)下Cd、Pb及Zn3种重金属的释放特性．试验发现，城市垃圾焚烧过程中，在还原气氛及HCl存在的情况下，Cd及Pb较易挥发释放，而Zn释放程度较低，且基本不受气氛条件的影响．研究结果对揭示城市垃圾流化床焚烧过程中重金属释放行为有一定的意义．     

Thermodynamically coupled heat and mass flows in a reaction-transport system with external resistances

Considerable work has been published on mathematically coupled nonlinear differential equations by neglecting thermodynamic coupling between heat and mass flows in reaction-transport systems. The thermodynamic coupling refers that a flow occurs without or against its primary thermodynamic driving force, which may be a gradient of temperature, or chemical potential, or reaction affinity. This study presents the modeling of thermodynamically coupled heat and mass flows of two components in a reaction-transport system with external heat and mass transfer resistances. The modeling equations are based on the linear nonequilibrium thermodynamics approach by assuming that the system is in the vicinity of global equilibrium. The modeling equations lead to unique definitions of thermodynamic coupling (cross) coefficients between heat and mass flows in terms of kinetic parameters and transport coefficients. These newly defined parameters need to be determined to describe coupled reaction-transport systems. Some representative numerical solutions obtained by MATLAB illustrate the effect of thermodynamic coupling coefficients on the change of temperature and mass concentrations in time and space.     

Decentralized drying-gasification scheme of sewage sludge with torrefied biomass as auxiliary feedstock

A drying-autothermal gasification scheme with torrefied biomass as auxiliary feedstock was proposed for the first time in order to realize the decentralized treatment of sewage sludge in wastewater treatment plant. Thermodynamic equilibrium and energy flow balance for the proposed system were evaluated. A non-stoichiometric thermodynamic equilibrium model was applied to evaluate the effect of adding ratio of torrefied biomass on the autothermal gasification performance. A novel dual-check algorithm was developed to determine the molar numbers of syngas components and the injected air. The energy utilization ratio for the whole process was introduced to measure the ratio of the energy used in the whole system to the total input energy. High adding ratio of torrefied biomass was favor of lifting the cold gas efficiency, but it would lead to low energy utilization ratio in terms of sewage sludge treatment.     

Reforming of vegetable oil for production of hydrogen: A thermodynamic analysis

The vegetable oils are one of the promising renewable feedstock for production of hydrogen suitable for application in hydrogen based fuel cells for electrical power generation. In the present work, a thermodynamic equilibrium analysis of steam reforming (SR) and autothermal steam reforming (ATSR) of vegetable oils to synthesis gas was investigated by Gibbs free energy minimization method. The thermodynamic equilibrium analysis was performed considering the vegetable oils as a mixture of triglycerides containing three same fatty acid groups in the structure. The property method used for equilibrium analysis was first regressed using available physical and chemical properties of the considered triglycerides. The regressed property method was then used to calculate the equilibrium products composition. The effects of various parameters of SR of vegetable oils, temperature and steam-to-carbon ratio (SCR), on hydrogen yield and selectivity of CO and methane was studied in a broad range of temperature (573-1273 K) and SCRs (1-6). The optimum conditions for SR of vegetable oils were then determined for maximum hydrogen yield with very low selectivity of methane. The thermodynamic equilibrium analysis of ATSR of vegetable oils was then performed at different oxygen-to-carbon ratios and thermoneutral conditions were then determined for various operating conditions.     

高碱灰渣烧结反应的化学热力学平衡计算

针对高碱灰渣烧结特性进行化学热力学平衡反应计算,并与试验结果进行了比较.计算采用FactSage 5.2计算软件中的Equilib模型.计算结果显示高碱灰渣的强烧结特性主要是由大量黝方石、蓝方石、霞石、无水芒硝等较低熔点的钠基复合盐造成.计算结果与试验分析物相基本一致,表明化学热力学反应平衡分析方法是研究灰渣烧结特性的有效手段.     

差压控制器在热水供热系统的实际应用

热力系统水力失调问题严重影响着供热系统正常运转。本文对自力式差压控制器原理进行分析和论述,通过地区热网的热平衡改造实际应用,有效解决了长期困扰热力系统水力失调的问题。     

Potential of molten lead oxide for liquid chemical looping gasification (LCLG): A thermochemical analysis

Molten lead oxide is revealed to have favourable thermodynamic performance for gasification in a new process employing chemical looping of a molten liquid metal oxide. In this process, the feedstock is partially oxidized with molten lead oxide in the fuel reactor, while the reduced molten lead is oxidized in the air reactor. As with other chemical looping processes, this avoids direct contact between air and fuel, which prevents the undesirable dilution of the gaseous product with nitrogen. The Gibbs minimization method was employed together with thermo-chemical equilibrium analysis to assess the feasibility of the gasification process using graphite as a surrogate for more realistic, but complex carbonaceous fuels, together with steam and/or carbon dioxide as the gasifying agent. It was found that both the reduction and oxidation reactions of molten lead oxide with carbonaceous fuel are spontaneous. Likewise, the ratio of H₂:CO can be as high as 2.5, while the carbon conversion can reach 94% based on the thermochemical analysis. An energetic performance analysis was also employed for the case of a supercritical steam turbine cycle to extract work from the hot gaseous co-products. On this basis, the first law efficiency of the power cycle was estimated to be up to 33.8%, while the syngas co-product stream for applications such as Fischer-Tropsch synthesis has a chemical exergy efficiency of 41%.     

用元素扩散方程和化学平衡热力计算的方法求解多组分反应流场

提出了一种新的方法来计算多组分化学反应流场。它首先引入了元素的分布方程，然后根据化学平衡的热力计算方法求解每一位置的组分及温度。这样，在计算低速流场时，就避免了处理化学反应源项引起的数值计算过程中的方程刚性问题，也减少了组分方程的数量。计算结果表明，这种方法的计算结果比EBU模型的计算结果更好的反应了物质热解离的情况。     

Thermodynamic equilibrium analysis of combined dry and steam reforming of propane for thermochemical waste-heat recuperation

The thermochemical waste-heat recuperation is one for perspective way of increasing the energy efficiency of the fuel-consuming equipment. In this paper, the thermochemical waste-heat recuperation (TCR) by combined steam-dry propane reforming is described. To understand the influence of technological parameter such as temperature and composition of inlet gas mixture on TCR efficiency, thermodynamic equilibrium analysis of combined steam-dry propane reforming was investigated by Gibbs free energy minimization method upon a wide range of temperature (600–1200 K) and different feed compositions at atmospheric pressure. The carbon and methane formation was also calculated and shown. From a thermodynamic perspective, the TCR can be used for increasing energy efficiency at temperatures above 950 K because in this range the maximum conversion rate is reached (from 1.22 to 1.30 for the different feed composition). Approximately 10 mol of synthesis gas can be generated per mole of propane at the temperatures greater than 1000 K. Furthermore, the propane conversion rate and yield of hydrogen are increased with the addition of extra steam to the feed stock. Also, undesirable carbon formation can be eliminated by adding steam to the feed. The thermodynamic equilibrium analysis was accomplished by IVTANTHERMO which is a process simulator for thermodynamic modeling of complex chemically reacting systems and several results were checked by Aspen-HYSYS.     

羧甲基纤维素钠对CH4水合物形成过程的影响

羧甲基纤维素钠（CMC-Na）是水基钻井液中的重要组分,为研究CMC-Na对天然气水合物热力学和动力学的影响,实验测量了质量浓度介于0.5% ~ 1.5%的CMC-Na溶液中甲烷水合物的相平衡条件,以及275.2 K、6 MPa的初始条件下CMC-Na溶液中甲烷水合物的形成过程。研究结果表明,CMC-Na对甲烷水合物的热力学稳定性具有微弱的抑制作用,相同压力下相平衡温度降低了0.1 ~ 0.2 K。CMC-Na溶液中形成的甲烷水合物为I型,水合物数为5.84 ~ 5.90。在CMC-Na溶液中,甲烷水合物形成所需的诱导时间大大缩短,表明CMC-Na对甲烷水合物的形成过程具有促进作用。在CMC-Na溶液中水合物生成所需气体消耗量呈阶段式增长。水合物转化率低于35%的情况下,已经生成的水合物没有对搅拌器叶片形成持续附着进而卡住搅拌器。因此,CMC-Na对甲烷水合物的热力学稳定性具有一定的负面影响,对水合物的形成具有一定的促进作用。另外,CMC-Na能够降低水合物生成过程中搅拌扭矩的波动,对维持搅拌的正常运行具有重要作用。     

汽轮机末级湿蒸汽凝结流动模型差异性研究

以汽轮机末级叶片为研究对象,采用计算流体力学方法对单流道几何模型进行数值计算,研究了湿蒸汽平衡与非平衡凝结流动模型之间的特性差异,并基于非平衡凝结探讨表面张力修正系数(NBTF)在定常分析中对湿蒸汽参数的影响。结果表明：非平衡凝结模型主要影响液滴数目及颗粒直径,速度场分布与平衡凝结模型有较大差异;基于非平衡凝结模型对表面张力进行修正的模型会降低级内热力学损失,总-静效率比未修正表面张力的原型增加0.16%,相较平衡凝结模型降低3.26%;在主频下,修正模型动叶所受轴向激励力相较于平衡凝结模型减少52.76%,切向激励力减少57.12%,但轴向力与切向力载荷均方根值分别增加1.59%和0.21%。