Effects of Steam Addition during Calcination on Carbonation Behavior in a Calcination/Carbonation Loop

The effects of steam addition during calcination on the carbonation behavior of calcium‐based sorbents in cyclic calcination/carbonation experiments were investigated. Variations in the CaO conversion rate during carbonation were measured to evaluate the influence of operating conditions and particle size on the carbonation reaction in kinetic‐ and diffusion‐controlled reaction regimes. Surface sintering and particle aggregation during cyclic calcination/carbonation affected the sorbent surface area, pore volume, and possibly the pore size, resulting in less sorbent recyclability and a trigger time retard in the fast kinetic‐controlled carbonation. Steam addition during calcination positively affected the recyclability of the sorbents and altered the carbonation behavior.     

Interaction of a porous carbon particle with steam and carbon dioxide

As part of a diffusion-kinetic model of gasification of a porous carbon particle in steam and carbon dioxide, this paper presents a study of heat- and mass-transfer processes both inside the porous particle and in the gas phase above its surface. The radiation heat transfer between the particle and the walls of the furnace is taken into account. Heterogeneous reactions of carbon with steam and carbon dioxide and the homogeneous reaction of carbon monoxide with steam. are considered. In addition, allowance is made for pressure variation in the porous particle due to an increase in gas mass during heterogeneous reactions. Dependences of the gasification rate on the composition of the reaction mixture, pressure, furnace temperature, and particle size, and the inner surface area of the porous carbon particle.     

水蒸气对煅烧石灰石碳酸化反应影响的实验与模型分析

利用热重分析仪,对比了不同反应温度、不同水蒸气浓度对煅烧石灰石碳酸化反应的影响。碳酸化反应温度在500℃时,反应初期水蒸气对碳酸化反应的影响并不明显,反应10 min之后,在含有1.5%、10%和20%(体积分数)水蒸气条件下碳酸化转化率比无水蒸气条件下转化率分别提高了19.8%、27.2%和30.5%。水蒸气的存在有助于提高碳酸化反应转化率,但随着水蒸气浓度的增加转化率增加幅度减小。利用随机孔隙模型,对产物层扩散阶段扩散系数及反应活化能进行了计算。高温条件下,气氛中含有1.5%的水蒸气使反应活化能从237.7 kJ·mol^-1降低到179.9 kJ·mol^-1,提高水蒸气浓度到10%和20%后,反应活化能从156.6 kJ·mol^-1降低到148.6 kJ·mol^-1。不同水蒸气浓度条件下,碳酸化反应存在两个明显特征:一是大约在550℃处存在一个明显扩散系数的斜率变化,这一温度与气氛中是否存在水蒸气无关;另一特征是随着反应温度的提高,水蒸气的促进作用减弱。依据实验和模型计算结果,推测了当反应处于产物层扩散阶段时水蒸气对碳酸化反应影响的作用机理。     

Thermal transport model of a sorbent particle undergoing calcination–carbonation cycling

A numerical model coupling transient radiative, convective, and conductive heat transfer, mass transfer, and chemical kinetics of heterogeneous solid–gas reactions has been developed for a semitransparent, nonuniform, and nonisothermal particle undergoing cyclic thermochemical transformations. The calcination–carbonation reaction pair for calcium oxide looping is selected as the model cycle because of its suitability for solar‐driven carbon dioxide capture. The analyzed system is a single, porous particle undergoing thermochemical cycling in an idealized, reactor‐like environment. The model is used to investigate two cases distinguished by the length of the calcination and carbonation periods. The calcination–carbonation process for a single particle is shown to become periodic after three cycles. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2647–2656, 2015     

红土镍矿有价元素高附加值利用的绿色冶金工艺（Ⅰ）熔融碱法提硅制备白炭黑

以红土镍矿为原料,采用碱熔融－碳酸化分解工艺制备出白炭黑产品。研究表明,SiO2的浸出率随反应时间、碱矿比的增加和红土镍矿粒度的减小而增加,随反应温度的升高而先增加后减少。经XRD分析,产品为无定型结构;经FT-IR检测产品为水合二氧化硅;经SEM检测产品颗粒均匀,粒度小于100nm。产品理化性能符合国家化工行业HG/T3065-1999标准。     

Absorption of carbon dioxide in ethylenediamine solutions i. absorption kinetics and equilibrium

The chemical absorption of carbon dioxide by a laminar jet of ethylenediamine has been studied at 25.5°C under pseudo-first-order kinetic conditions. The reaction was found to be second-order with a rate constant of 1.0 x 10⁵ 1/g. mole sec. Equilibrium calculations at 18°C indicate that the partial pressure of carbon dioxide is very low, even over highly carbonated ethylenediamine solutions. The effects of amine concentration and carbonation ratio on the physical solubility and diffusivity of carbon dioxide in solution were inferred from corresponding results for nitrous oxide     

甲烷二氧化碳重整制合成气中积炭效应的数值模拟

通过建立包含动量、质量传递以及化学反应动力学方程的多物理场耦合数值模型,对以Ni为催化剂的甲烷二氧化碳重整制合成气过程中的积炭效应展开了计算。计算结果阐明了包含多孔介质催化剂段的反应通道中的速度场及压力分布,以及在通道中随气体流动以及沉积在催化剂表面的碳颗粒的浓度分布,分析了积炭对 催化剂孔隙率和渗透率的影响,并进一步讨论了甲烷浓度以及温度对积炭产生的影响,最后提出了消减积炭的方法。本文的结论对于进一步研究Ni基催化剂在CH₄-CO₂重整制合成气反应中积炭效应的消减有一定的指导意义。     

Competition of several carbonation reactions in concrete: A parametric study

Carbonation caused by atmospheric carbon dioxide is one of the major physicochemical processes which can compromise the service life of reinforced concrete structures. While the bulk of the carbonation reaction is that of calcium hydroxide, other constituents of the porous matrix can also carbonate and compete with calcium hydroxide for carbon dioxide. Particularly the carbonation of calcium–silicate hydrates and unhydrated constituents are neglected by most authors in carbonation prediction models. In this paper, a mathematical model of carbonation is extended to include additional carbonation and hydration reactions. The competition of the several reactions and their effect on the carbonation depth is investigated by dimensional analysis and numerical simulations. A parameter study emphasises that multiple internal reaction layers appear. Their position and speed essentially depend on the strength of the different reactions. It is also observed that, for a wide range of parameters, the effect of some of the additional reactions on the carbonation depth is small. In particular, a comparison with data from laboratory experiments justifies the neglect of the carbonation of the unhydrated constituents in prediction models.     

Mechanisms of aqueous wollastonite carbonation as a possible CO2 sequestration process

The mechanisms of aqueous wollastonite carbonation as a possible carbon dioxide sequestration process were investigated experimentally by systematic variation of the reaction temperature, CO₂ pressure, particle size, reaction time, liquid to solid ratio and agitation power. The carbonation reaction was observed to occur via the aqueous phase in two steps: (1) Ca leaching from the CaSiO₃ matrix and (2) CaCO₃ nucleation and growth. Leaching is hindered by a Ca-depleted silicate rim resulting from incongruent Ca-dissolution. Two temperature regimes were identified in the overall carbonation process. At temperatures below an optimum reaction temperature, the overall reaction rate is probably limited by the leaching rate of Ca. At higher temperatures, nucleation and growth of calcium carbonate are probably limiting the conversion, due to a reduced (bi)carbonate activity. The mechanisms for the aqueous carbonation of wollastonite were shown to be similar to those reported previously for an industrial residue and a Mg-silicate. The carbonation of wollastonite proceeds rapidly relative to Mg-silicates, with a maximum conversion in 15 min of 70% at , 20 bar CO₂ partial pressure and particle size of . The obtained insight in the reaction mechanisms enables the energetic and economic assessment of CO₂ sequestration by wollastonite carbonation, which forms an essential next step in its further development.     

超细碳酸钙制备的研究

利用电导仪跟踪碳化反应历程，详细研究了反应温度、ＣＯ２浓度、Ｃａ（ＯＨ）２浓度、气体流量和活加剂用量等因素对反应时间及ＣａＣＯ３产品粒径的影响。     

Combustion of porous carbon particles in air

Combustion of a carbon particle in air is considered on the basis of a diffusion-kinetic model. Two regimes of combustion are shown to exist: high- and low-rate regimes. In the high-rate combustion regime, oxygen is totally consumed in a homogeneous reaction running above the particle surface and does not reach the particle, whereas carbon is consumed in a reaction with carbon dioxide. In the low-rate combustion regime, oxygen reaches the particle surface, and the reaction of carbon with oxygen producing carbon dioxide runs within the porous particle.     

自蔓延高温技术制备ZrC粉体(英文)

采用自蔓延高温合成(self-propagating high-temperature synthesis,SHS)技术,以 Zr+C 为反应体系合成了 ZrC 粉末。研究了实验参数对 SHS过程中点火电流、燃烧温度的影响。采用了 3 种碳源,研究了其对最终产物形貌及化学组成的影响。通过添加不同含量的 NaCl 作为 SHS 稀释剂,控制产物粒径及形貌。结果表明:炭黑是高温自蔓延法制备 ZrC 粉体的最佳碳源。由该体系制备的 ZrC 粉末粒径在 0.5～1 μm之间,氧含量为 0.38%。随稀释剂 NaCl 含量增加,体系燃烧温度降低,产物粒径减小。当 NaCl 含量为 30% (质量分数)时,体系燃烧温度下降至 1 810 K,产物 ZrC 粉末的粒径减小至 50 nm。     

螺旋通道型旋转床制备纳米拟薄水铝石的研究

以偏铝酸钠溶液和二氧化碳气体为原料,采用螺旋通道型旋转床超重力法制备纳米拟薄水铝石粉末。讨论了拟薄水铝石的碳分机理和合成工艺条件,考察了老化、添加表面活性剂、原料浓度及气液比对粉体粒径的影响;并进行了螺旋通道型旋转床超重力法与搅拌槽反应法的对比实验。用XRD和TEM等测试方法对产品进行了分析表征,结果表明RBHC碳分法可制得平均粒径为5～10nm的纤维状的纳米拟薄水铝石。     

The effect of oxygen and carbon dioxide concentration on soot formation in non-premixed flames

The influence of oxygen concentration and carbon dioxide as diluents in the oxidizer side on soot formation was studied by Time Resolved Laser Induced Incandescence (TIRE-LII) and TEM photography in non-premixed co-flowing flames. TIRE-LII method was used to measure the distribution of two-dimensional soot volume fraction and primary particle size. The soot was directly sampled by the thermophoretic method, and its diameter was examined by TEM photography. Two suitable delay times of the TIRE-LII method affecting measurable range and sensitivity were determined by comparing TEM photographs with the TIRE-LII signal. The effects of oxygen concentration and carbon dioxide as diluents in the oxidizer side on soot formation were investigated with these calibrated techniques. An O₂+(CO₂, N₂, and [Ar+CO₂]) mixtures in co-flow were used to isolate carbon dioxide effects systematically. The primary particle number concentration and soot volume fraction were abruptly decreased by the addition of carbon dioxide to co-flow. This suppression was resulted from the short residence time in inception region because of the late nucleation and the decrease of surface growth distance by the low flame temperature due to the higher thermal capacity and the chemical change of carbon dioxide. The increase of oxygen concentration in the co-flow caused an enhancement of soot nucleation and thus the residence time increase, but the specific growth rate showed almost the same value regardless of the co-flow mixture in the growth region. This result suggests that the specific growth rate has a weak dependence on the relative change of co-flow conditions in non-premixed co-flowing flames.     

电石渣制备轻质碳酸钙的研究

研究了以电石渣为原料,经浸取、碳化、过滤、洗涤、干燥制备轻质碳酸钙的工艺。用TEM、粒径分布测试对所合成的样品进行表征。重点考查了碳化反应温度、二氧化碳体积浓度、气体流速、搅拌速率等因素对反应速率及产品粒径的影响,确定了最佳的工艺条件。     

低温干馏煤气/富氧大当量比燃烧实验及数值模拟研究

在内热式低温煤干馏中,引入富氧燃烧,同时提高煤气当量比,是在维持炉内温度分布基本不变的前提下提高煤气质量的有效途径。通过不同富氧比及不同尺寸烧嘴下的大当量比煤气/富氧燃烧实验结合数值模拟分析,探究了富氧低温干馏中的内热火焰温度分布特性及其受工艺条件和烧嘴尺寸的影响。结果表明:增大富氧比的同时增大燃料当量比可以维持平均火焰温度与空气助燃工况基本一致,但火焰锋面温度受局部当量比及流动条件影响;减小燃料及氧化剂射流的初始速度差,可以减缓组分混合、延长火焰并降低火焰锋面温度;煤气中三种气体按参与反应的速率快慢排序依次为氢气、一氧化碳、甲烷,随着燃烧反应进入湍流混合速率控制模式,组分间的选择性燃烧特征相对减弱。     

Durability of concrete incorporating large volumes of low-quality fly ash

The carbonation, corrosion of steel reinforcement in concrete and corrosion resistance of concrete, incorporating large volumes of low-quality fly ash (LVLQFA), were studied. The effect of concentration of carbon dioxide used in the experiment on estimating the carbonation resistance of LVLQFA concrete were also investigated. Test results show that the LVLQFA concrete with an activator has good carbonation and corrosion resistances of steel reinforcement. The corrosion resistance of LVLQFA concrete is better than that of the control concrete. The concentration of carbon dioxide used in the experiment has considerable effect on estimating the carbonation resistance of LVLQFA concrete.     

The pore solution phase of carbonated cement pastes

Samples of hydrated cement pastes were exposed to atmospheres with various carbon dioxide concentrations at relative humidities controlled by different saturated salt solutions. When carbonated throughout their thickness, as indicated by the phenolphthalein test, they were resaturated with water and subjected to pore solution expression and analysis. The effects of the various carbonating environments on the pore solution composition and on aspects of the pore structure and mineralogy of the carbonated products are reported. Implications regarding the likely effects of different accelerated carbonation regimes on the corrosion behaviour of steel in concrete are discussed. In particular, it is shown that the use of saturated sodium nitrite solution to control the relative humidity of atmospheres with high concentrations of carbon dioxide may cause an evolution of gaseous oxides of nitrogen, which can result in the contamination of the pore solution with nitrite and nitrate salts.     

The effect of carbon dioxide during the desulfurization of flue gas with Mardin–Mazıdagı phosphate rock

The effects of temperature, CO₂ concentration and particle size on simultaneous calcination/sulfation of Mardin–Maz?dag? phosphate rock in fluidized-bed reactor were investigated. For this, a raw sample was exposed to calcination and sulfation processes in a fluidized-bed reactor to determine the effects of parameters by using a model gas mixture similar to the flue gas composition. The calcination ratio increased with increasing temperature and decreasing particle size, but decreased with increasing CO₂ concentration. In sulfation process, however, sulphate conversion ratio increased with increasing CO₂ ratio and decreased with decreasing particle size. The sulfation reaction is well represented by the shrinking core model and can be divided into two regions with different rate controlling step. For low conversions, the controlling step was found to be chemical reaction at the interface, but the diffusion through the product layer for high conversion. The activation energies for the chemical reaction at the interface and diffusion through the product layer cases were calculated as 100 and 296 kJ mol^?1, respectively.     

300 MW循环流化床锅炉大比例掺烧煤泥试验研究

循环流化床锅炉大比例掺烧煤泥是一种处理煤泥等低品质煤的有效手段。利用一维小室模型对掺混不同比例煤泥的CFB锅炉运行工况进行模拟,研究了掺混煤泥比例对CFB锅炉炉膛内物料平均粒径、颗粒停留时间以及炉膛上部物料浓度的影响,确定了大比例掺烧煤泥条件下的流态优化条件。模拟结果表明,增加煤泥比例可以提高物料循环流率和中间粒径档位(0.1~0.3 mm)颗粒在炉内的停留时间,改善燃料的燃尽率,提高煤泥比例还可以增加炉膛上部的颗粒浓度,有利于提高炉膛上部的传热,降低炉膛温度,便于污染物的控制。根据盘北电厂300 MW循环流化床锅炉机组大比例掺烧煤泥的运行数据,分析了掺烧煤泥比例对床温、排烟温度、底渣与飞灰含碳量的影响。当锅炉负荷为300 MW时,掺烧煤泥后床温明显降低,飞灰含碳量和排烟温度随着掺烧煤泥比例的增加而增大,底渣含碳量则随着掺烧煤泥比例的增加而降低。为了实现大比例掺烧,建议控制矸石的入炉煤粒径,且需要强化尾部吹灰或适当调整尾部受热面。