粉煤灰对制备钙基脱硫剂水热固相反应的自催化研究

文章利用扫描电子显微镜/能量色散谱研究了粉煤灰对水热固相反应及脱硫反应的自催化作用.粉煤灰表面纳米级的SiO<,2>、Al<,2>O<,3>、CaO微粒为形成硅铝酸钙的核心提供良好的原料;大量纳米级多余的SiO<,2>不断插入硅铝酸钙的结晶体中,在一定程度上控制了反应速度,形成了粗大纤维状的水合硅酸单钙((CaO)·S...     

Calcium-based sorbents behaviour during sulphation at oxy-fuel fluidised bed combustion conditions

Sulphur capture by calcium-based sorbents is a process highly dependent on the temperature and CO₂ concentration. In oxy-fuel combustion in fluidised beds (FB), CO₂ concentration in the flue gas may be enriched up to 95%. Under so high CO₂ concentration, different from that in conventional coal combustion with air, the calcination and sulphation behaviour of the sorbent must be defined to determine the optimum operating temperature in the FB combustors.In this work, the SO₂ retention capacity of two different limestones was tested by thermogravimetric analysis at typical oxy-fuel conditions in FB combustors. The effect of the main operating variables affecting calcination and sulphation reactions, like CO₂ and SO₂ concentrations, temperature, and sorbent particle size, was analysed.It was observed a clear difference in the sulphation conversion reached by the sorbent whether the sulphation takes place under indirect or direct sulphation, being much higher under indirect sulphation. But, in spite of this difference, for a given condition and temperature, the CO₂ concentration did not affect to the sulphation conversion, being its major effect to delay the CaCO₃ decomposition to a higher temperature.For the typical operating conditions and sorbent particle sizes used in oxy-fuel FB combustors, the maximum sorbent sulphation conversions were reached at temperatures of about 900 °C. At these conditions, limestone sulphation took place in two steps. The first one was controlled by diffusion through porous system of the particles until pore plugging, and the second controlled by the diffusion through product layer. As a consequence, the maximum sulphation conversion increased with decreasing the particle size and increasing the SO₂ concentration.     

THERMAL DEHYDRATION OF THE SODIUM CARBONATE HYDRATES

A thermal gravimetric method was employed to explore the course of dehydration of Na₂CO₃ · 10 H₂O, and Na₃CO₃ · H₂O particles. Experimental data were amassed both in the temperature-increasing and constant temperature mode. Very small sample masses were used in an effort to eliminate an effect of heat and mass transfer processes on the rate of reaction. Kinetic equations of Arrhenius type were proposed for two stages of the dehydration and tested against the results collected by experiment.     

“Chemical Heat Accumulators”: A new approach to accumulating low potential heat

The first presentation of new composite Chemical Heat Accumulation materials based on granulated open-porous matrix filled with a hygroscopic substance is given. At storing heat, the materials operate in a reversible hydration/dehydration mode. When crystalline hydrates of simple salts are used as the hygroscopic substance, the new materials allow to reach the heat storing capacity up to 2000 kJ kg⁻¹ even for accumulation of low temperature heat (of circa 20–40°C). The materials also possess improved properties for mass and heat transfer. All these make a serious advantage of these materials in comparison with those using a latent melting-solidification heat as well as with zeolites capable of reversible hydration/dehydration. The new materials can be widely used in energy efficient and freons-less air conditioning devices, for cooling the electronic units, fire-extinguishing and some other applications.     

新型钡基高温燃烧固硫剂的研究与应用

引　言燃烧脱硫技术是在高温燃烧过程中将煤中的硫转化为硫酸盐或硫化物 ,因而其固硫率与硫酸盐或硫化物的热力学形成过程密切相关 .据文献报道 ,ＣａＳＯ3和ＣａＳＯ4 分别在 10 0 4℃[1] 和 1195～ 12 14℃[2 ] 就已开始分解 .纯ＣａＳＯ4 在 12 5 0℃高温下的分解率为 85 % .纯ＢａＳＯ4 的分解温度为 15 80℃[3] ,大大高于ＣａＳＯ4 ,显示较高的热稳定性 .根据元素周期表递变规律 ,位于第 6周期的Ｂａ较位Ｆｉｇ .1　Ｓｃｈｅｍａｔｉｃｏｆｉｎｔｅｌｌｉｇｅｎｔｓｕｌｆｕｒｄｅｔｅｒｍｉｎａｔｉｏｎ1—ｍａｉｎｆｒａｍｅｏｆｉｎ…     

高活性吸收剂去除二氧化硫的实验研究

飞灰与消石灰可以制备高活性吸收剂去除烟气中的二氧化硫。在常温下进行固定床实验,研究了高活性吸收剂的脱硫机理。讨论了吸收剂的含水率、二氧化硫的初始浓度、氧气浓度对二氧化硫去除率的影响。根据穿透曲线得出了吸附容量。     

Sorptive Removal of Cesium-137 and Strontium-90 from Water by Unconventional Sorbents. I. Usage of Bauxite Wastes (Red Muds)

Bauxite wastes of alumina manufacture, i.e., red muds, have been tested for radiocesium and strontium removal from water. The red muds were water-washed, acid-, and heat-treated before usage to produce hydrous oxide like sorbents. Surface treatment of the sorbent was benefical for ¹³⁷s uptake, while heat-treatment was detrimental to the -SOH surface sites responsible for high ⁹⁰Sr affinity. Fractionation of the sorbent with respect to apparent grain size did not produce significant differences in the sorption efficiency. The distribution coefficients vs. equilibrium activity in solution showed a maximum with Cs, and a gradual decrease trend with Sr. The solution activity vs. adsorption data were fitted to B.E. T. (essentially types IV-V) isotherms for Cs and B.E. T.-Langmuir isotherms for Sr. Desorption, temperature-, pH-, and ionic strength-dependence tests revealed that the primary mode of sorption for both cations is specific adsorption while the secondary mode is ion exchange. A rise in pH favours the ion- exchange sorption of Sr while the specific adsorption of Cs is negatively affected. Competitive adsorption of an inert electrolyte, i.e., NaCl, severely hinders Cs sorption, while Sr sorption on water-washed red mud is not significantly affected.     

钙基固体碱催化酯交换反应制备生物柴油研究进展

综述了近期氧化钙、钙化合物、负载型氧化钙等钙基固体碱催化剂用于酯交换制备生物柴油的研究进展。钙基固体碱具有较高的酯交换制备生物柴油催化活性,且原料来源广、价格相对较低,是一类具有前景的用于生物柴油清洁生产的固体碱催化剂。钙基固体碱催化剂在存放过程中易碳酸盐化而失去催化活性,生物柴油原料含水含酸量不但降低催化剂催化活性,而且增加催化剂回收难度、增加生物柴油产品中钙离子含量,在研究钙基固体碱催化剂催化酯交换反应机制的基础上,解决以上一系列问题,有助于钙基固体碱催化剂的工业化应用。     

Synthetic Ca‐based solid sorbents suitable for capturing CO2 in a fluidized bed

Coprecipitation and hydrolysis of CaO have been employed to produce Ca‐based synthetic sorbents suitable for capturing CO₂ in a fluidized bed. Their composition, CO₂ uptake, volume in small pores (2–200 nm) and resistance to attrition were measured and compared to those of limestone and dolomite. Sorbents produced by hydrolysis showed the highest uptake and resistance to attrition. After 20 cycles of carbonation and calcination, two sorbents exceeded the uptake of both limestone and dolomite, when subjected to the same regimes of reaction. A sorbent's uptake of CO₂ was shown to be determined by the volume in pores narrower than ～200 nm.