不同钙基吸附剂捕集CO2后的硫酸化反应特性研究

钙基吸附剂进行多次CO₂捕集后,碳酸化效率会大幅衰减,此时的吸附剂能否高效脱硫利用是值得重点关注的问题。鉴于此,筛选了高性能合成钙基吸附剂和天然石灰石吸附剂,通过热重分析仪分析对比其在多循环CO₂捕集后的碳酸化和硫酸化反应性能,采用微粒模型研究其硫酸化反应动力学特征。结果发现,高性能合成钙基吸附剂的碳酸化反应速率和CO₂吸附能力明显高于石灰石吸附剂。在长达500循环的CO₂捕集试验后,高性能合成钙基吸附剂的CO₂吸附能力比石灰石高10倍以上,其SO₂吸附能力相较于石灰石提升约40%。经历多次CO₂捕集反应循环后,2种吸附剂的硫酸化能力均有提升:其中,石灰石吸附剂的提升幅度更大,硫酸化转化率从26%提升到35%,而高性能合成钙基吸附剂的硫酸化转化率则从38%提升到43%。通过微粒模型计算发现,2种吸附剂的硫酸化反应均是与SO₂浓度相关的一级反应,多循环捕集CO₂反应后,石灰石吸附剂的硫酸化反应活化能下降接近30%,而高性能合成钙基吸附剂的硫酸化反应活化能只下降了5%。研究结果说明2种不同钙基吸附剂在进行循环CO₂捕集后,脱硫能力得到了不同程度的提高,且均可以较好地应用于SO₂的脱除。     

Effects of rapid calcination on properties of calcium-based sorbents

The calcination process may influence subsequent fragmentation, sintering and swelling when CaO derived from limestone acts as a CO₂ or SO₂-sorbent in combustion, gasification and reforming. Sorbent properties are affected by CO₂ partial pressure, total pressure, temperature, heating rate, impurities and sample size. In this study, the effect of calcination heating rate was investigated based on an electrically heated platinum foil. The effects of heating rate (up to 800 °C/s), calcination temperature (700-950 °C), particle size (90-180 μm) and sweep gas velocity were investigated. Higher initial heating rates led to lower extents of limestone calcination, but the extents of carbonation of the resulting CaO were similar to each other. Calcium utilization declined markedly during carbonation or sulphation of CaO after calcination by rapid heating. Experimental results show that carbonation and calcium utilization were most effective for carbonation temperatures between 503 and 607 °C. Increasing the extent of calcination is not the best way to improve overall calcium utilization due to the vast increase in energy consumption.     

Properties and reactivity of reactivated calcium-based sorbents

Calcium-based sorbents used in the process of high temperature desulfurisation of flue gases are partly regenerable by hydration with steam; the best results are obtained for treatment temperatures of approximately 300 °C. The regeneration process, and the consequent increase in the sorbent consumption can be correlated to the surface characteristics (BET surface area, porosity and pore size distribution) of the sorbents themselves. In particular, the presence of suitable pore structure, also having pores large enough to let molecules easily penetrate the inner part of the sorbent particles, is very important.     

钙基吸收剂吸收CO_2的动力学分析

利用热天平在非等温条件下研究了在N2/CO2气氛下,升温速率、样品粒径及CO2浓度等因素对钙基吸收剂与CO2反应特性的影响,并利用活化能和频率因子进行表征。结果表明:在5种不同前体制备的吸收剂中,草酸钙和乙酸钙制备的钙基吸收剂的活化能最低,更容易与CO2发生反应;在其他条件相同的情况下,分析纯CaCO3制备的钙基吸收剂的活化能,随循环次数增加而逐渐变大,并且在第5次循环到第10次循环之间,活化能增加幅度较大;随着分析纯CaCO3颗粒粒径的增大,其活化能也随之增大;随着升温速率的增大和反应气氛中CO2质量分数的增大,分析纯CaCO3制备的钙基吸收剂的活化能逐渐减小,而频率因子逐渐增大;掺杂有MgO的碳酸钙制备的钙基吸收剂的活化能小于分析纯CaCO3,且MgO掺杂比例为0.05的钙基吸收剂的活化能小于MgO掺杂比例为0.1的钙基吸收剂。     

钙基CO2吸附剂的惰性掺杂和形貌调控研究进展

有效捕集CO₂对于缓解亟待解决的温室效应、气候变暖、环境污染和能源危机问题具有重大意义。钙基吸附材料因为CO₂吸附容量高及成本低廉而受到了广泛关注。本文介绍了钙基吸附剂的CO₂吸附机理,着重阐述了显著提高吸附性能的两种改性方法,包括惰性掺杂和形貌调控。归纳了利用Zr、Ce、Mn、Mg、Al等塔曼温度较高或富含氧空穴的金属氧化物对氧化钙进行单掺杂和复合掺杂改性,针对合成方法、吸脱附条件、惰性组分掺杂量、钙基前体等不同参数对掺杂改性钙基CO₂吸附剂性能的影响进行总结。同时指出,采用聚苯乙烯小球、碳凝胶、碳球、表面活性剂等制备得到的中空结构球形钙基吸附剂或实心结构球形钙基吸附剂,具有良好的CO₂吸附容量和吸附稳定性。提出两种改性方法距离工业化应用还有较大的差距,亟需深入探讨吸附剂的结构与性能之间的关系,从而为吸附剂的设计提供理论指导。     

Absorption of HCl by calcium-based sorbents during filtration combustion in a continuous reactor

Experimental data on hydrogen chloride absorption by calcium-containing sorbents in solid fuel gasification in a continuous filtration combustion reactor are presented. The addition of the sorbents to the stock allows up to 80% of the chlorine to be sorbed. The chlorine remains as calcium chloride in the solid combustion residue. The incompleteness of HCl sorption is due to the hydrolysis of the resulting calcium chloride in the high-temperature zone of combustion.     

钙基脱硫剂增压喷动流化床煤气化炉的炉内脱硫

用石灰石作为脱硫剂在热输入0.1 MW的加压喷动流化床试验台上进行了煤部分气化过程中的炉内脱硫试验研究。系统地考察了温度、压力、钙基脱硫剂粒径、钙硫摩尔比等参数对脱硫效率的影响。试验结果如下：随着温度的升高、压力的增加,脱硫效率均提高,但增长幅度减缓。随钙硫摩尔比的增加,脱硫效率提高,但当Ca/S（摩尔比）＝2后,继续增大Ca/S,脱硫效率提高有限。脱硫剂粒径减小,脱硫效率提高。     

CO2 uptake of modified calcium-based sorbents in a pressurized carbonation-calcination looping

This study focuses on enhancing CO₂ uptake by modifying limestone with acetate solutions under pressurized carbonation condition. The multicycle tests were carried out in an atmospheric calcination/pressurized carbonation reactor system at different temperatures and pressures. The pore structure characteristics (BET and BJH) were measured as a supplement to the reaction studies. Compared with the raw limestone, the modified sorbent showed a great improvement in CO₂ uptake at the same reaction condition. The highest CO₂ uptake was obtained at 700 °C and 0.5 MPa, by 88.5% increase over the limestone at 0.1 MPa after 10 cycles. The structure characteristics of the sorbents on N₂ absorption and SEM confirm that compared with the modified sorbent, the effective pores of limestone are greatly driven off by sintering, which hinders the easy access of CO₂ molecules to the unreacted-active sites of CaO. The morphological and structural properties of the modified sorbent did not reveal significant differences after multiple cycles. This would explain its superior performance of CO₂ uptake under pressurized carbonation. Even after 10 cycles, the modified sorbent still achieved a CO₂ uptake of 0.88.     

纳米钙基CO2吸附剂反应吸附与分解动力学

采用TGA测定纳米钙基CO₂吸附剂在500～650℃温度范围内,CO₂分压0.015～0.025 MPa氮气气氛中的吸附反应动力学。针对纳米钙基CO₂吸附剂吸附CO₂反应特征,提出以两倍最大吸附速率对应的时间点前后分别为快速反应段与慢速反应段。分别采用Boltzmann方程与Avrami-Erofeev方程拟合快速反应段与慢速反应段吸附反应动力学方程,得到纳米钙基CO₂吸附剂在快速反应段与慢速反应段的活化能分别为27.52、70.25 kJ·mol^-1。吸附率拟合与实验值平均相对误差分别为10.29％、4. 17%。研究测试了纳米钙基CO₂吸附剂在650～800℃温度范围内,N₂,0.02、0.04 MPa CO₂分压氮气气氛中的分解反应动力学。忽略反应过程中传热、传质影响,采用收缩核模型,分别求得吸附剂在N₂,0.02、0.04 MPa CO₂分压氮气气氛中的活化能为141.9、34.7、113.2 kJ·mol^-1。碳酸钙分解率与实验值比较平均相对误差分别小于5.66% 、7.82%、5.01%。     

流化床中钙基吸收剂与HCl的反应机理

在500~800 ℃的温度范围内, 在流化床反应器床料中添加 CaO吸收剂, 进行含氯有机废液 (含三氯乙醛) 的焚烧脱氯实验. 实验表明, 600 ℃脱氯效果最佳, 温度升高脱氯效果下降. 通过对产物层进行扫描电子显微镜 (SEM) 分析表明, 在温度大于600 ℃的条件下, CaO与HCl之间的反应在相当长的一段时间内受化学反应和产物层扩散共同控制, 不存在产物层扩散的单独控制. 考虑粒子的体积膨胀率, 利用缩核模型对反应处于产物层扩散控制阶段进行动力学分析, 得出产物层扩散活化能为9 95 kJ·mol-1.     

Cl含量对钙基吸收剂微观结构以及动力学性能的影响

通过浸渍法向分析纯CaCO₃中添加Cl,在双固定床反应器系统和热重分析仪上研究了其对钙基吸收剂循环捕集CO₂性能的影响,利用离子反应模型对添加Cl后吸收剂化学反应控制阶段进行动力学分析。结果显示：Cl对钙基吸收剂循环捕集CO₂性能具有不利影响。当Cl/Ca摩尔比大于0.25%后,随Cl/Ca摩尔比增加,化学反应控制阶段反应速率和持续时间均减小,导致在该阶段最终碳酸化转化率降低。对添加Cl前后吸收剂孔隙分布特性进行分析发现,添加Cl导致煅烧后吸收剂烧结加剧,比表面积降低,10~120nm范围内孔分布减少,导致CO₂在吸收剂内部扩散阻力增加,同时能与CO₂反应的CaO量减少,这是导致吸收剂化学反应控制阶段碳酸化反应速度较慢、最终碳酸化转化率较低的主要原因。鉴于Cl的不利影响,在选择钙基材料作为CO₂吸收剂或合成高活性复合吸收剂时,应避免吸收剂中Cl含量过高。     

金属氧化物掺杂对钙基吸附剂吸附CO_2性能的影响

化石燃料火电厂排放的CO2约占全球CO2总排放量的1/3,采用化学吸附法直接脱除高温烟气中的CO2既可以减少系统的能量损失又可以保护环境。文中采用机械混合法制备金属氧化物掺杂的钙基吸附剂,并以静吸附量和CO2吸附率为评价指标,气相色谱为检测手段,在自制吸附剂评价装置上,研究不同金属氧化物的掺杂对钙基吸附剂吸附性性能的影响。实验表明,掺杂金属氧化物对钙基吸附剂的吸附性能有一定影响,其中质量分数为1%的Li2CO3掺杂的钙基吸附剂的静吸附容量与钙基吸附剂的理论吸附量比较接近,并且优于其他金属氧化物掺杂的钙基吸附剂。     

An investigation on the rheological and sulfur-retention characteristics of desulfurizing coal water slurry with calcium-based additives

Desulphurizing coal water slurry is a kind of new clean coal water slurry(CWS), which has good performance on SO₂ emission during combustion and gasification process. But, the addition of sulfur-retention agents have some effects on the stability and fluid characters of the coal water slurry. In this paper, the viscosity, stability and rheology of Xinwen coal water slurry have been studied by adding different kinds of calcium-based sulfur-retention agents and different dosage. The results show that the sulfur-retention agents have little effect on rheological nature of CWS, which still presents pseudoplastic fluid. The addition of sulfur-retention agents will increase the viscosity of CWS, but the stability will decrease a little. The results also show that inorganic calcium has less negative effect on the performance of CWS than the organic calcium. The viscosity of the CWS with organic calcium agent keeps 1000–1200 mPa s when Ca/S molar ratio is 2. Sulfur release of the CWS with CaCO₃ reduces to 52% at Ca/S = 2 compared to original of 98%.     

Desulfurization characteristics of CuO-Fe2O3 sorbents

A series of CuO-Fe₂O₃ sorbents with 25 wt% SiO₂ as a support were prepared based on a simple mixing method in order to evaluate the effects of Fe₂O₃ on their desulfurization reactivities. The initial reactivities of sorbents were tested by using a TGA and their cyclic performance was investigated in a GC/microreactor system. The activation energy calculated by the Chatterjee-Conrad method based on the TGA experiment decreased as the content of Fe₂O₃ increased. Sulfur loading in the cyclic reactions increased with increase of Fe₂O₃ content, and its maximum value was 8.9 g sulfur per 100 g sorbent. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8–10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

流化床锅炉内石灰石同时煅烧/硫化反应中煅烧动力学特性

采用恒温热重实验台研究了循环流化床内石灰石同时煅烧硫化反应中煅烧反应与硫化反应的相互作用。当煅烧环境中存在SO₂时,煅烧反应与硫化反应同时发生,并在颗粒中生成CaSO₄。与纯煅烧工况相比,在含有SO₂的气氛中煅烧石灰石时,颗粒的质量下降速率降低,而煅烧终质量升高。SO₂的存在能够降低石灰石的煅烧速率,而且在0～0.3%的范围内,SO₂浓度越高,煅烧越慢。对该现象提出以下机理：当煅烧过程中存在SO₂时,SO₂会与正在煅烧的石灰石颗粒的CaO层发生硫化反应生成CaSO₄,所生成的CaSO₄会堵塞颗粒的孔隙,增加CO₂的扩散阻力,进而减慢煅烧反应速率。对煅烧产物孔结构的测试和计算表明在同时煅烧硫化中部分孔隙被堵塞、封闭,孔内CO₂有效扩散系数下降,证明所提出的机理能够合理解释SO₂对石灰石煅烧的减缓作用。随着粒径由0.4～0.45 mm减小到0.2～0.25 mm,无论反应环境是否存在SO₂,石灰石的煅烧速率均加快。温度对煅烧速率有明显的影响,850℃下SO₂对石灰石煅烧速率的减缓程度大于880℃,这可能是由于880℃下CaSO₄对颗粒孔隙的堵塞作用下降导致的。     

Blackened calcium-based composite particles and their apparent kinetics features for solar thermochemical energy storage

The calcium looping (CaL) thermochemical thermal energy storage is one of the best high-temperature heat storage schemes for 3th concentrating solar power (CSP) photothermal power. However, the application of this technology is greatly hindered by the low solar absorption capability and the poor cyclic stability of CaCO₃/CaO-based material. In this article, the solar absorbing capability of CaCO₃ particles is enhanced by doping Mn-Fe oxides, meanwhile, awns of setaria faberis (ASF) and microcrystalline cellulose (MCC) are used as bio-templates to generate pores inside the particles. The pore-making process promotes the cyclic stability and carbonation kinetic features of the composite particles simultaneously. The test results show that the proposed particles possess adequate anti-crushing strength, high cyclic stability, high solar absorption, and high carbonation rate. In addition, the apparent carbonation kinetic features of the composite porous particles are studied with the influencing factors such as CO₂ partial pressure, reaction temperature, and particle morphology taken into consideration. A kinetic equation involving these parameters is developed with the thermogravimetry data of the prepared samples. By employing this kinetic function, the carbonation reaction of the prepared particles inside the carbonator becomes predictable, which is of great significance for the design and regulation of the carbonator achieving highly stable thermal output from the CaL thermochemical heat storage system.     

纳米钙基CO2吸附剂反应吸附与分解动力学

采用TGA测定纳米钙基CO₂吸附剂在500～650℃温度范围内,CO₂分压0.015～0.025 MPa氮气气氛中的吸附反应动力学。针对纳米钙基CO₂吸附剂吸附CO₂反应特征,提出以两倍最大吸附速率对应的时间点前后分别为快速反应段与慢速反应段。分别采用Boltzmann方程与Avrami-Erofeev方程拟合快速反应段与慢速反应段吸附反应动力学方程,得到纳米钙基CO₂吸附剂在快速反应段与慢速反应段的活化能分别为27.52、70.25 kJ·mol^-1。吸附率拟合与实验值平均相对误差分别为10.29％、4. 17%。研究测试了纳米钙基CO₂吸附剂在650～800℃温度范围内,N₂,0.02、0.04 MPa CO₂分压氮气气氛中的分解反应动力学。忽略反应过程中传热、传质影响,采用收缩核模型,分别求得吸附剂在N₂,0.02、0.04 MPa CO₂分压氮气气氛中的活化能为141.9、34.7、113.2 kJ·mol^-1。碳酸钙分解率与实验值比较平均相对误差分别小于5.66% 、7.82%、5.01%。     

Internal diffusion kinetics of caprolactam in adsorption from aqueous solutions by carbon sorbents

The internal diffusion kinetics of liquid-phase adsorption of caprolactam by carbon sorbents were investigated. The effective internal diffusion coefficients were determined. A method of evaluating the correctness of the experimentally found values of the effective internal diffusion coefficient was developed for microporous sorbents. Translated from Khimicheskie Volokna, No. 3, pp. 38–41, May–June, 1998.