O2／CO2燃烧技术研究进展

O2／CO2燃烧技术不仅有效收集烟气中的CO2,还能减少NOx和SO2的排放,是一种新型的洁净煤燃烧技术。介绍了其应用、发展历程以及在燃烧、传热和污染物排放的研究进展,指出了这一技术领域中存在的问题,并对下一步的研究方向给出了建议。     

Coal combustion in O2/CO2 mixtures compared with air

As part of CO₂ abatement strategies for climate change, we are investigating coal combusion behaviour in various O₂/CO₂ mixtures and in air. The goal is to simulate conditions of coal combustion with flue gas recirculation in order to maximize the CO₂ concentration in the flue gas prior to its recovery. A western Canadian sub‐bituminous coal and a U.S. eastern bituminous coal were investigated. Thermal input was set at 0.21 MW with a flue gas oxygen concentration of 5 vol%. Experiments were done using various O₂/CO₂ mixtures and air. The oxygen concentration ranged from 21% to 42%. Up to 95% CO₂ concentrations were achieved in the flue gas. This paper describes experimental results in terms of flame temperatures and pollutant emissions (NO_x', SO₂ and CO).     

O2/CO2气氛下煤燃烧SO2/NO析出特性

在水平管式炉上研究了O₂浓度、CO₂浓度、温度及石灰石添加等各参数对O₂/CO₂气氛下徐州烟煤和龙岩无烟煤燃烧过程中SO₂/NO排放特性的影响。结果发现,O₂/CO₂气氛下,烟煤和无烟煤燃烧SO₂/NO的析出规律与空气气氛下不同,同等O₂浓度下析出量比空气气氛下小。O₂/CO₂气氛下,随着O₂浓度的提高,烟煤和无烟煤SO₂/NO排放量均增大;随着CO₂浓度的升高, SO₂/NO排放量均减小。O₂/CO₂气氛下,石灰石添加对SO₂排放的抑制作用低于空气气氛下;石灰石添加对NO的排放有一定减排作用。对煤灰的元素分析显示O₂/CO₂燃烧对SO₂的抑制主要是由于煤灰的自固硫能力增强,而对NO的减排作用则是促进燃料N向其他含N气体的转换。     

基于Langmuir-Hinshelwood动力学解析O2/CO2/H2O气氛下烟煤焦反应机理

流化床富氧燃烧湿烟气循环兼具经济与环保优势。湿烟气循环（O₂/CO₂/H₂O）条件下煤焦与O₂、CO₂及H₂O的反应同时发生。为探究O₂/CO₂/H₂O气氛下煤焦-O₂、煤焦-CO₂、煤焦-H₂O反应间的相互作用机制,在自制高精度热重实验装置上系统考察了O₂、CO₂、H₂O及其混合气氛下,典型烟煤焦在900℃的反应特性。基于吸附和脱附原理的Langmuir-Hinshelwood（L-H）机理性模型分别计算了烟煤焦与O₂、CO₂和H₂O反应的动力学参数。通过采用单独活性位点与竞争活性位点两种假设分析了O₂/CO₂、O₂/H₂O和CO₂/H₂O气氛下烟煤焦-O₂、烟煤焦-CO₂和烟煤焦-H₂O两两反应间的作用机制,揭示了H₂O分子优先吸附于烟煤焦表面活性位点,O₂分子次之,而CO₂分子相对滞后。O₂/CO₂/H₂O气氛下烟煤焦-O₂、烟煤焦-CO₂、烟煤焦-H₂O反应表现出部分竞争反应活性位点,传统的单独活性位点与竞争活性位点假设均无法准确描述其反应速率特性。基于H₂O分子优先,O₂分子次优先吸附的原理,建立了O₂、CO₂、H₂O混合气氛下煤焦反应速率L-H动力学方程,方程计算结果与实验值良好吻合。研究结果为深入分析煤焦颗粒流化床富氧燃烧特性及构建可靠、准确的燃烧反应模型提供了理论支撑。     

固体碱K2CO3/Al2O3催化酯交换法合成乙二醇甲醚乙酸酯

以固体碱K2CO3/Al2O3为催化剂,催化乙酸乙酯和乙二醇甲醚酯交换合成了乙二醇甲醚乙酸酯。考察了反应物摩尔比,催化剂用量,反应时间,催化剂重复使用等因素对反应的影响,结果表明:当n(乙酸乙酯)∶n(乙二醇甲醚)=4∶1,K2CO3/Al2O3用量为总反应物质量的1.0%,反应4.5h时,乙二醇甲醚的转化率为98.8%,选择性为100%;催化剂重复使用5次后,乙二醇甲醚的转化率仅下降3.7%。     

TiO2掺杂对Na2CO3/Al2O3吸收剂CO2捕捉性能的影响

钠基固体吸收剂脱除燃煤烟气CO₂技术具有反应温度低、能耗低等优点,日益受到学术界的关注。该技术的主要不足是吸收剂的活性成分碳酸钠与CO₂的反应（碳酸化反应）活性较低。针对这一问题,本文旨在研制一种新型改性钠基固体吸收剂,采用活性氧化铝作为载体、TiO₂作为掺杂剂进行改性,利用热重分析装置、XRD、SEM和氮吸附仪研究钠基固体吸收剂的CO₂捕捉性能。结果表明：掺杂TiO₂后,钠基固体吸收剂与CO₂的反应速率加快,CO₂捕捉量增加;反应前后除TiO₂外无其他含Ti化合物生成;碳酸化反应产物为NaHCO₃和Na₅H₃（CO₃）₄;然而TiO₂掺杂过多会堵塞吸收剂的微观孔道,不利于甚至阻碍碳酸化反应的进行,因此,TiO₂的掺杂量应控制在一定的范围内。     

负载型K2CO3/Al2O3二氧化碳吸收剂的碳酸化反应特性

引言 全球变暖已经成为一个备受关注的环境问题.据预测,如不采取积极的温室气体减排措施,从现在起到2100年,全球近地面平均气温将继续升高1.4～5.8℃[1].CO2是主要的温室气体,而我国燃煤电厂是CO2排放量最大、最集中的化石燃料燃烧场所.因此研究和开发适用于燃煤电厂的CO2减排技术至关重要.     

封存CO2的泄漏过程预测与泄漏速率的影响因素特性

地下封存CO₂泄漏的评估方法和风险控制是碳捕集和封存（CCS）技术亟待解决的核心问题。为了揭示封存CO₂泄漏过程的影响因素及其特性,本文建立两相流驱替过程数学模型描述封存CO₂的泄漏过程,采用COMSOL Multiphysics 3.5a软件进行数值模拟。通过对基准问题及其解的拓展,分别对注入井与泄漏通道之间距离、泄漏通道半径、泄漏通道渗透率、CO₂注入速率和CO2注入深度等因素对封存CO2泄漏过程的影响特性进行研究,通过过程模拟和数据分析得到了影响因素的定量函数关系。研究表明：封存CO₂的渐近泄漏速率与注入井与泄漏通道之间距离倒数呈对数线性关系,与泄漏通道半径呈抛物线型关系,与注入速率呈线性关系;泄漏通道的绝对渗透率是CO₂泄漏速率控制的关键因素,而CO₂注入深度的增加并不能有效地降低CO₂泄漏速率。本文的计算模型和数值模拟结果不仅揭示了地下封存CO₂泄漏过程的影响因素与泄漏速率之间的定量关联规律,还可为地下封存CO₂的封存地点选择、泄漏速率估计和泄漏风险评估提供工程分析方法和计算工具。     

Numerical Analysis on the Characteristics of Soot Particles in C2H4/CO2/O2/N2 Combustion

The purpose of this study is to investigate the characteristics of soot particles in C₂H₄/CO₂/O₂/N₂ combustion at equivalence ratio of 3.0-5.0. As the oxidant is switched from conventional air to CO₂/O₂/N₂ mixture, the key species C₂H₂, C₃H₃ responsible for formation of first aromatic ring, the typical aromatics and 4-ring aromatics total production rate all decrease greatly. In addition, with CO₂ mole fraction from 0.2 to 0.5 in the mixture, the soot particle number density, volume fraction, surface area density, which are three most important parameters to soot particle property, are suppressed obviously. Furthermore, the increasing content of CO₂ in the oxidizer influences mostly H, OH radical concentrations by two reactions: CO+OH=CO₂ H and H+O₂=O+OH, and the production rate of H, OH from the two reactions declined, which revealed that CO₂ in mixture has an inhibiting effect on soot particle generation.     

低湿CO2/H2O混合气体吸附特性实验

CO₂捕集、封存及利用是实现“双碳”目标的重要途径,为将碳捕集后的低湿CO₂/H₂O进行CO₂提纯和资源化利用,采用动态吸附实验研究了不同温度（303K、313K）、H₂O含量（0.7%~3.0%）的CO₂/H₂O在活性炭、活性氧化铝、分子筛3A和13X四种吸附剂上的动态吸附穿透曲线、吸附床温度分布、吸附量,分析了CO₂/H₂O分离系数和吸附热。结果表明,在CO₂/H₂O动态吸附过程中,吸附床温度与各组分浓度随时间变化趋势相同。H₂O饱和时间随进气温度升高而缩短;H₂O含量增加,抑制CO₂吸附;活性炭和氧化铝中H₂O的饱和时间随H₂O含量增加而增长,但分子筛3A和13X饱和时间缩短。H₂O吸附量随H₂O含量增加而增加,吸附热随吸附量增加而减小,CO₂则相反。分子筛3A对CO₂吸附量最小且CO₂/H₂O分离系数最大。H₂O含量小于1%时,CO₂吸附量最大的分子筛13X分离系数大于活性氧化铝,分子筛3A和13X适合分离低湿CO₂/H₂O。     

Cu2O/CuO/Cu电极光电催化还原CO2

利用表面氧化法在铜基底上制备CuO纳米带(CuO NRs),通过电化学法将Cu_2O沉积到CuO NRs上,得到复合电极Cu_2O/CuO/Cu。借助X射线衍射(XRD)、透射电子显微镜(TEM)对Cu_2O/CuO/Cu复合电极的结构进行了表征。通过线性扫描伏安法(LSV)、光电流-时间测试、电化学阻抗测试对Cu_2O/CuO/Cu复合电极光电催化CO_2性能进行了考察。借助变色酸分光光度法来测定CO_2光电还原产物。结果表明:氧化铜在铜基底上呈纳米带生长;复合电极Cu_2O/CuO/Cu对CO_2有较强的光响应性,表现出优异的光电催化性能;Cu_2O/CuO/Cu复合电极光电催化还原CO_2的主要产物是甲醇,在0.1 mol/L NaHCO_3溶液中光电催化6 h后,甲醇质量浓度为32.2mg/L。     

负载型K2CO3/Al2O3吸收剂吸收CO2反应机理

利用热重分析仪、扫描电镜和氮吸附仪对不同粒径的K₂CO₃颗粒和负载型K₂CO₃/Al₂O₃二氧化碳吸收剂的碳酸化特性进行研究。负载后的吸收剂比表面积和孔隙结构得到较大改善,使得碳酸化反应速率和转化率均提高,吸收剂碳酸化特性得到改善。纯K₂CO₃颗粒吸收剂的反应速率和转化率随着粒径的增加而减小,负载型吸收剂的反应速率和转化率随着粒径的增加略增大。研究了不同粒径和反应时间对K₂CO₃/Al₂O₃颗粒微观结构的影响,结果表明K₂CO₃/Al₂O₃颗粒具有较稳定的微观结构。采用负载型粒子模型对K₂CO₃/Al₂O₃吸收剂吸收CO₂碳酸化过程进行研究,所建立的粒子模型计算结果与试验值吻合较好。利用建立的模型对不同CO₂浓度下K₂CO₃/Al₂O₃吸收剂碳酸化反应特性进行模拟计算,模拟结果具备一定的合理性和准确性,为开展进一步研究提供了基础。     

尖晶石CoAl2O4光催化还原CO2的研究

采用无机盐溶胶-凝胶法制备了CoAl2O4纳米粉体,用紫外-可见分光光度计(UV-Vis)、X射线衍射光谱仪(XRD)和扫描电子显微镜(SEM)对其光电活性、晶体结构和形貌进行了表征。结果表明,所制备催化剂属尖晶石结构,颗粒呈近球形和不规则形状,粒子尺寸约4.39 nm,光吸收极限波长大于800 nm,计算得到禁带宽度Eg1.55 eV。在高压汞灯照射下,分别选用K2C2O4、NaHSO3和NaH2PO2为供电子试剂,进行了光催化还原CO2制取甲酸的研究。结果表明,在选用NaHSO3的情况下,CoAl2O4的催化效果最好,光照4 h,甲酸产量达到4004.16μmol/g-Cat。     

Progress in the Study on the Phase Equilibria of the CO2·H2O and CO2-HeO-NaCI Systems

To study the feasibility of CO2 geological sequestration,it is needed to understand the complicated mul- tiple-phase equilibrium and the densities of aqueous solution with CO2 and multi-ions under wide geological condi- tions（273.15—473.15K,0—60MPa）,which are also essential for designing separation equipments in chemical or oil-related industries.For this purpose,studies on the relevant phase equilibria and densities are reviewed and analyzed and the method to improve or modify the existing model is suggested in order to obtain more reliable predictions in a wide temperature and pressure range.Besides,three different models（the electrolyte non random two-liquid（ELECNRTL）,the electrolyte NRTL combining with Helgeson model（ENRTL-HG）,Pitzer activity coefficient model combining with Helgeson model（PITZ-HG））are used to calculate the vapor-liquid phase equilib- rium of CO2-H2O and CO2-H2O-NaCl systems.For CO2-H2O system,the calculation results agree with the experimental data very well at low and medium pressure（0—20MPa）,but there are great discrepancies above 20MPa.For the water content at 473.15K,the calculated results agree with the experimental data quite well.For the CO2-H2O-NaCl system,the PITZ-HG model show better results than ELECNRTL and ENRTL-HG models at the NaCl concentration of 0.52mol·L ^-1 .Bur for the NaCl concentration of 3.997mol·L ^-1 ,using the ELECNRTL and ENRTL-HG models gives better results than using the PITZ-HG model.It is shown that available experimental data and the thermodynamic calculations can satisfy the needs of the calculation of the sequestration capacity in the temperature and pressure range for disposal of CO2 in deep saline aquifers.More experimental data and more accurate thermodynamic calculations are needed in high temperature and pressure ranges（above 398.15K and 31.5MPa）.     

封存CO_2在泄漏通道中迁移及相变过程的模拟分析

预测相变位置对封存CO2泄漏过程的监控和风险评估具有重要意义。针对泄漏通道中CO2的非等温流动相变过程,提出了Span-Wagner状态方程与等效比热法的耦合计算方法描述CO2泄漏过程中相变过程,研究了焦耳-汤姆逊效应、黏性耗散效应以及地层传热效应对CO2泄漏相变过程的影响,阐明CO2泄漏过程中相变过程的影响因素及其作用。研究表明:虽然焦耳-汤姆逊效应和黏性耗散对泄漏通道温度的作用相反,但两者均使泄漏CO2液气相变位置向深层移动;增强泄漏通道与地层之间换热将使泄漏通道温度降低,焦耳-汤姆逊效应和地层换热的共同作用将进一步降低泄漏通道的温度,导致泄漏CO2液气相变位置向浅层移动,泄漏通道出口处CO2的泄漏流率增大。     

Co3O4-Bi2O2CO3催化剂的制备及其光催化性能

以Bi(NO₃)₃·5H₂O、Co(CH₃COO)₂·4H₂O为原料,采用化学沉淀-水热法制备了Co₃O₄-Bi₂O₂CO₃异质结构复合半导体光催化剂,并通过X射线衍射仪（XRD）、扫描电镜（SEM）、X射线光电子能谱（XPS）、紫外可见漫反射光谱（DRS）、荧光光谱（PL）等手段对所合成的复合型催化剂进行了理化性能表征。研究结果表明：引入Co₃O₄没有改变Bi₂O₂CO₃物相结构,但促进了Bi₂O₂CO₃ 对可见光的吸收能力,提高了Bi₂O₂CO₃表面吸附氧物种的数量,抑制了光生载流子复合。复合光催化剂对罗丹明B（RhB）的光催化脱色实验显示引入Co₃O₄能够明显提高Bi₂O₂CO₃催化剂的光催化脱色能力。尤其是Co₃O₄引入量为0.6%的Co₃O₄-Bi₂O₂CO₃样品对罗丹明B染料的光催化脱色率可达到97%（模拟日光照射30min）。本文为复合型光催化剂制备提供了简单易行的技术路线,制备的新型半导体复合光催化剂Co₃O₄-Bi₂O₂CO₃在环境净化方面表现出了较好的应用前景。     

Gas leakage recognition for CO2 geological sequestration based on the time series neural network

The leakage of stored and transported CO₂ is a risk for geological sequestration technology. One of the most challenging problems is to recognize and determine CO₂ leakage signal in the complex atmosphere background. In this work, a time series model was proposed to forecast the atmospheric CO₂ variation and the approximation error of the model was utilized to recognize the leakage. First, the fitting neural network trained with recently past CO₂ data was applied to predict the daily atmospheric CO₂. Further, the recurrent nonlinear autoregressive with exogenous input (NARX) model was adopted to get more accurate prediction. Compared with fitting neural network, the approximation errors of NARX have a clearer baseline, and the abnormal leakage signal can be seized more easily even in small release cases. Hence, the fitting approximation of time series prediction model is a potential excellent method to capture atmospheric abnormal signal for CO₂ storage and transportation technologies.     

Experimental and Modeling Study on de-NOx Characteristics of Selective Non-catalytic Reduction in O2/CO2 Atmosphere

An experimental study of thermal de-NOx using NH3 as reductant in O2/CO2 atmosphere with the effect of SO2 and different additives was performed in a drop tube furnace. Results show that the optimum te...     

DECOMPOSITION BEHAVIOR AND MECHANISM OF CALCIUM SULFATE UNDER THE CONDITION OF O2/CO2 PULVERIZED COAL COMBUSTION

The decomposition behavior and mechanism of calcium sulfate in O₂/CO₂ pulverized coal combustion were studied in an entrained flow reactor. A reaction rate expression correlating the influence of various factors was proposed for CaS0₄ decomposition and it is able to predict CaS0₄ decomposition satisfactorily. Under the conditions investigated, the decomposition of CaS0₄ was found to be a regime of chemically controlled shrinking core reaction. A CO₂-rich atmosphere enhances CaSO₄ decomposition in absence of oxygen. CaSO₄ particles have catalytic effect on formation of CO from CO₂. A high SO₂ concentration inhibits CaSO₄ decomposition. The kinetics of CaSO₄decomposition has obvious dependence on experimental facilities and conditions, whereas the activation energy has much lower dependence. The kinetics derived in this work is more appropriate for investigating desulfurization in O₂/CO₂ pulverized coal combustion because an entrained flow reactor has a much closer condition to that in O₂/CO₂ pulverized coal combustion than a TGA.