基于钙基吸收剂循环煅烧/碳酸化反应捕集CO2的试验

利用钙基吸收剂循环煅烧/碳酸化反应(CCCR)吸收CO2是一种新型、廉价、有效的CO2捕集方法.采用热重分析仪研究了吸收剂的矿物组成、颗粒粒径、煅烧温度和碳酸化温度对CCCR快速反应阶段吸收剂循环碳酸化率(XN)的影响.结果表明:吸收剂的碳酸化反应由快速化学反应控制阶段、过渡阶段和缓慢产物层扩散控制阶段组成;白云石具有良好的抗烧结能力,白云石的XN高于石灰石;随着颗粒粒径的增大,吸收剂的XN逐渐降低;当煅烧温度超过950℃时,随着循环反应次数的增加,吸收剂的XN严重降低;吸收剂在725℃碳酸化温度时的XN最高.     

Development of a Scalable Method for Manufacturing High‐Temperature CO2 Capture Sorbents

An engineered process for scalable manufacture of a calcium aluminum carbonate CO₂ sorbent with production amounts of about 1000 g per hour has been developed. The process includes mixing and heating, solid‐liquid separation, drying and extrusion, crushing and conveying, and calcined molding steps. The sorbent preparation involves the coprecipitation of Ca²⁺, Al³⁺, and CO₃^2– under alkaline conditions. By adjusting the Ca:Al molar ratio, a series of Ca‐rich materials could be synthesized for use as CO₂ sorbents at 750 °C. A calcium acetate‐derived sorbent exhibited better cyclic stability than sorbents originating from CaCl₂ and Ca(NO₃)₂. The initial sorption capacity increased with CaO concentration. High stability of more than 90 % was maintained by the Ca:Al sorbents after 40 looping tests.     

Natural Calcium‐Based Sorbents Doped with Sea Salt for Cyclic CO2 Capture

The calcium‐looping process for post‐combustion carbon dioxide capture, an economically and technically feasible method suitable for large‐scale use, has recently gained much attention. However, the capture capacity of calcium‐based sorbents rapidly decreases after only a few cycles. Herein, calcium‐based sorbents with enhanced cyclic CO₂‐capture capacity have been derived from cheap, natural raw materials by using a simple impregnation method. Limestone and shells were used as the calcium‐based raw materials, with sea salt as dopant. Modified limestone had the highest CO₂‐capture capacity after multiple carbonation‐calcination cycles. Sea‐salt‐doped sorbent showed a relatively stable porous surface during cycles, which resulted in a higher CO₂‐capture capacity.     

CO2 Capture Performance of Calcium‐Based Sorbents in the Presence of SO2 under Pressurized Carbonation

In order to understand the effect of SO₂ on the CO₂ capture performance under pressurized carbonation conditions, tests by orthogonal design were carried out in a calcination/pressurized carbonation reactor system. The effects of variables such as carbonation temperature, carbonation pressure, SO₂ concentration, CO₂ concentration, and the number of cycles on carbonation and sulfation were investigated. A range method was employed for analysis. Phase structure and scanning electron microscopy images were measured as supplement for a reaction study. Temperature increase enhanced the SO₂ capture, leading to a rapid decay in CO₂ uptake. The carbonation pressure had a stronger effect on the CO₂ uptake than the temperature. SO₂ uptake increased rapidly with increasing pressure while CO₂ uptake decreased.     

Increasing Porosity of Molded Calcium‐Based Sorbents by Glucose Templating for Cyclic CO2 Capture

With the aim to enhance the CO₂ capture capacity and anti‐attrition property of CaO‐based sorbents simultaneously, a novel CaO‐based sphere was prepared by extrusion‐spheronization using Ca(OH)₂ powder with glucose templating. The CO₂ capture characteristics and attrition resistance property of the sorbent were examined and the microstructure of the sorbents was analyzed. The results demonstrate that the obtained spherical sorbents exhibit an outstanding anti‐attrition performance compared to limestone sorbent. After 100 cycles, all of the templated sorbents hold a CO₂ capture capacity of more than one time higher than that of limestone. The optimum templating rate of glucose in the sorbent was 1–5 wt %.     

Competition for Sodium and Toxic Metals Capture on Sorbents

The removal of toxic heavy metals by sorbents has been the focus of much recent research. In single metal/single sorbent systems, laboratory experiments have demonstrated capture of lead and cadmium by kaolinite and lime at high temperatures. However, practical systems (i.e., pulverized coal fired boilers) generally involve sodium as well as toxic metals and the amount of sodium usually exceeds that of the toxic metals. The purpose of this paper is to explore the effect of sodium on the capture of lead and cadmium by sorbents. Experiments were conducted in a 16 kW, 0.15 m ID, 6 m tall laboratory downflow furnace. Aqueous solutions of toxic metals and metal/sodium pairs were introduced into the furnace through a natural gas flame via atomization and subse quent vaporization. For all experiments, the total metal/sorbent equivalence ratio was maintained at 0.7. Approximately 0.5g/min of lime or kaolinite powder (mean particle diameter congruent 1.4 mu m) was injected along the furnace centerline in the post flame at a temperature of 1500 K. Further downstream, at 1200 K, particulate samples were isokinetically extracted and size segregated in a Berner low pressure impactor. Experimental results showed that cadmium and sodium were captured by lime. Furthermore, cadmium was captured by lime preferentially over sodium. Lead capture by lime occurred at a much slower rate than that for cadmium or sodium. Kaolinite, on the other hand, showed a preference for lead and sodium capture over cadmium. Consequently, for capture of multiple metals, a sorbent mixture of lime and kaolinite might be more effective than a single sorbent.     

TiO2载体制备条件及结构对MnOx/TiO2催化剂性能的影响

采用水热法一步反应制备锐钛矿结构TiO2晶体,通过浸渍法负载活性组分MnOx得到MnOx/TiO2低温脱硝催化剂.利用X射线衍射仪(XRD)、比表面积分析仪(BET)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等手段,研究制备过程中水热温度、水热时间以及硫酸钠用量对TiO2载体和MnOx/TiO2催化剂性能的影响.结果表明,水热温度为120℃,水热时间为22 h以及硫酸钠与尿素摩尔比为0.12的条件下,得到的TiO2结晶度高,分散性好,最大比表面积为234.54 m2·g-1.由其制备的MnOx/TiO2低温脱硝催化剂具有最佳的低温脱硝活性,在空速为20000 h-1,反应温度为200℃时,催化剂脱硝率可达90％以上.     

二氧化碳捕集技术研究进展

随着全球工业的快速发展,二氧化碳的大量排放被认为是造成气候变暖最主要原因,二氧化碳的捕集和封存已经成为研究的热点,本文综述了近年来CO2捕集技术的研究进展,主要有燃烧后捕集、燃烧前捕集和富氧燃烧三条技术路线,最后提出了可以提高二氧化碳捕集能力的策略与展望。     

对苯醌电化学捕获CO2机理研究及捕获产物的结构分析

利用循环伏安法(CV)、现场红外光谱法、恒电位电解法开展了BQ在乙腈溶液中的电化学捕获CO2的研究.结果显示,CO2在BQ还原过程中被一价阴离子自由基BQ·-所捕获,表明BQ·-是可以当作亲核试剂来捕获CO2.采用恒电位电解的方法,得到了BQ电化学捕获CO2后的终产物.1H-NMR、IR、13C-NMR以及元素分析的结果表明,捕获CO2后的终产物为BQ与CO2进行化学反应的加合物,其化学计量比为1:2,且亲核进攻CO2的是BQ羰基上的氧,形成较为稳定的羧酸式结构.产物酸化处理生成对苯酚,进一步证明BQ电化学捕获CO2产物结构.     

Structure sensitivity of CO oxidation over model Au/TiO2 2 catalysts

Model catalysts of Au clusters supported on TiO₂ thin films were prepared under ultra-high vacuum (UHV) conditions with average metal cluster sizes that varied from ~2.5 to ~6.0 nm. The reactivities of these Au/TiO₂ catalysts were measured for CO oxidation at a total pressure of 40 Torr in a reactor contiguous to the surface analysis chamber. Catalyst structure and composition were monitored with Auger electron spectroscopy (AES) and scanning tunneling microscopy and spectroscopy (STM/STS). The apparent activation energy for the reaction between 350 and 450 K varied from 1.7 to 5 kcal/mol as the Au coverage was increased from 0.25 to 5 monolayers, corresponding to average cluster diameters of 2.5–6.0 nm. The specific rates of reaction ((product molecules) × (surface site)^-1 × s^-1 were dependent on the Au cluster size with a maximum occurring at 3.2 nm suggesting that CO oxidation over Au/TiO₂(001)/Mo(100) is structure sensitive. This revised version was published online in July 2006 with corrections to the Cover Date.     

TiO2对铝硼硅酸盐玻璃结构和性能的影响

采用熔融法制备不同TiO2含量的RO(包括CaO、MgO)-Al2O3-SiO2-B2O3系玻璃。利用红外光谱技术研究TiO2对玻璃结构的影响,分别探讨了玻璃密度、化学稳定性和介电性能的变化规律。结果表明:少量TiO2的加入能够增大玻璃结构聚合度,过多的TiO2将使玻璃结构变得相对疏松;随着TiO2含量的增加,介电常数和介电损耗在1MHz频率下先减小后增大,玻璃析晶倾向和密度呈现增大的趋势,耐酸和耐碱失重比呈现先减小后增大的变化。     

聚苯胺基多孔炭制备及 CO 捕集性能研究

以聚苯胺为原料,采用NaOH活化法,在原料与活化剂质量比为1砄4的情况下,研究了不同的活化时间（0.5 h、1 h、2 h）对多孔炭孔隙结构和CO2吸附性能的影响。通过N2吸附脱附、扫描电子显微镜（SEM）、透射电子显微镜（TEM）,对样品的孔隙结构和形貌进行了表征。采用变压吸附法在常温常压下测试了样品对CO2的吸附性能。结果表明：当活化时间为1 h时,比表面积达到最大值2024 m2／g,微孔孔容达到最大值0.926 cm3／g。然而,当活化时间为0.5 h时, CO2吸附量达到了最大值159 mg／g,表明了CO2吸附量与窄微孔孔径分布有直接关系。     

火电厂CO2捕获方式

随着社会经济的迅速发展,人类对于化石燃料的需求量越来越大,燃料燃烧后排放的有害物质也越来越多,全球环境污染问题严峻,温室效应尤为严重。CO2是主要温室气体,CO2总排放量的75%是由石化燃料燃烧产生的,我国CO2排放总量的一半来自电力工业[1]。中国作为负责任的国家,到2020年,中国要实现单位国内生产总值CO2排放量比2005年下降40%～45%这一目标。因此,火电厂CO2减排任务重大,采用CO2捕集与封存技术能减少电厂80%~95%排放量,理论上具有巨大的减排潜力,是当今世界公认的CO2减排的重要途径。目前电厂捕集技术大体上分作三种:燃烧前捕集、燃烧后捕集和富氧燃烧捕集。     

The Effects of Water on CO Oxidation over TiO2 Supported Au Catalysts

Polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) was used to investigate the effects of water on CO oxidation catalyzed by TiO₂ supported Au. The introduction of water into the reactant mixture caused two effects: (1) a decrease in the CO coverage; and (2) the appearance of a carbonate species. Since both effects inhibit CO oxidation, the promotional effects of water found by previous researchers can only be rationalized by its effects on molecular oxygen adsorption and activation. Although this argument is not confirmed by the PM-IRAS data alone, this conclusion is consistent with previous studies. It is further inferred from this study that carbonate species first form on TiO₂ sites and then migrate to Au sites. Surface hydroxyl species may play the same promotional role as adsorbed water.     

在TiO2上CO的光催化氧化

最近在“氧化的”ＴｉＯ２（即表面无氧空位和Ｔｉ＾３＋）上进行的ＣＯ光催化氧化研究发现：室温下,以黑光灯（峰值λ＝３６５ｎｍ）光照时,“氧化的”ＴｉＯ２无ＣＯ催化氧化的活性,但以杀菌灯（峰值λ＝２５３．７ｎｍ）光照时,则对ＣＯ产生显著的催化活性。参照ＣＯ在过渡金属表面的催化氧化机理,对本现象进行了解释：黑光灯照时,Ｏ２在ＴｉＯ２表面只生成Ｏ＾－２（ａ）,而Ｏ＾－２（ａ）不能使ＣＯ氧化,只有以杀菌灯照     

High‐Temperature Capture of CO2 on Lithium‐Based Sorbents Prepared by a Water‐Based Sol‐Gel Technique

A convenient water‐based sol‐gel technique was used to prepare a highly efficient lithium orthosilicate‐based sorbent (Li₄SiO₄‐G) for CO₂ capture at high temperature. The Li₄SiO₄‐G sorbent was systematically studied and compared with the Li₄SiO₄‐S sorbent prepared by solid‐state reaction. Both sorbents were characterized by X‐ray diffraction, scanning electron microscopy, nitrogen adsorption, and thermogravimetry. The CO₂ sorption stability was investigated in a dual fixed‐bed reactor. Li₄SiO₄‐G exhibited a special Li₄SiO₄ structure with smaller crystalline nanoparticles, larger surface area, and higher CO₂ adsorption properties as compared with Li₄SiO₄‐S. The Li₄SiO₄‐G sorbent also maintained higher capacities during multiple cycles.     

固废源CaO基CO2捕集材料的制备与捕集性能研究进展

CO₂捕集技术是当前应对全球气候变化、缓解温室效应的重要途径。利用含钙固体废弃物制备高效CaO基CO₂捕集材料有利于实现固废资源高值化利用、以废治废和清洁生产,具有重要的环境效益、经济效益和社会效益。基于固废源高效廉价CaO基CO₂捕集材料的良好应用前景,本文介绍了工业废渣、生物质和其他含钙固体废弃物的产生与资源化利用现状,综述了CaO基吸附剂的捕集原理、碳酸化动力学过程和CO₂捕集性能,对比了以不同含钙固体废弃物为前驱体制备CaO基吸附剂的吸附-脱附循环性能和不同改性方法对其吸附稳定性的影响,从经济角度分析了固废源CaO基吸附剂在钢铁厂、燃煤电厂和生物制氢中的应用潜力,展望了固废源CaO基CO₂捕集材料的应用前景和发展方向。该文旨在为固废源CaO基吸附剂前驱体的选择、吸附性能的提高和固废吸附材料的工业应用提供帮助。     

The influence of Si-modified TiO2 on the activity of Ag/TiO2 in CO oxidation

Nanocrystalline TiO₂ and Si-modified TiO₂ with Si/Ti ratios 0.01, 0.05, 0.1, and 0.3 were prepared by the solvothermal method and employed as the supports for Ag/TiO₂ catalysts for CO oxidation reaction. The incorporation of Si into the TiO₂ lattice in the form of Ti–O–Si as revealed by FT-IR results could inhibit the agglomeration of TiO₂ crystallites, resulting in an increase of both surface area and metal dispersion. However, there existed an optimum content of Si/Ti at ca. 0.05–0.1 which resulted in an improved catalytic activity of Ag/TiO₂ in CO oxidation. Based on the O₂-temperature program desorption (O₂-TPD) results, the catalysts with appropriate amounts of Si/Ti exhibited higher amount of O₂ adsorption and much lower desorption temperature. It is suggested that the presence of Ti–O–Si promoted the formation of active oxygen species and increased the mobility of lattice oxygen so that the catalytic activity was enhanced. There was no improvement in CO oxidation activity of the Ag/TiO₂ catalyst when the Si/Ti was further increased to 0.3 due probably to the formation of amorphous SiO₂ instead of the Ti–O–Si bond.     

Characterization of Porous Carbonaceous Sorbents Using High Pressure CO2 Adsorption Data

In this paper we present adsorption isotherms of carbon dioxide on five different activated carbons from CHEMVIRON CARBON Belgium (Centaur HSV, BPL 410, F30-470, WS 42, Reactivated) and on a carbon molecular sieve from BERGBAU FORSCHUNG Gmbh (CMS II). The temperature is 303 K and the pressure ranges from 100 kPa up to 4000 kPa. Such conditions correspond to relative pressures ranging from 0.01 to 0.5. We also provide, for the same six sorbents, the nitrogen isotherms at 77 K (pressure: 0.001 to 100 kPa, relative pressure: 10^-5 to 1). A theoretical treatment based on the Dubinin-Radushkevich and Stoeckli concept is presented and applied to the experimental results in order to obtain the micropore size distribution function (considered as Gaussian) of each sorbent. Using the CO₂ data, it is possible to point out important structural differences between the six carbons. The theoretical treatment provides micropore size distribution functions in agreement with what is physically expected. Using N₂ data, the structural differences are not so well marked. As a consequence, the structural parameters provided by the theoretical treatment are not reliable: except for the total micropore volume, they fluctuate strongly when changing the relative pressure domain of the used data.     

Na2CO3-Based Sorbents Coated on Metal Foil: Post Testing Analysis

Worldwide increase in energy demand coupled with a continued reliance on fossil fuel resources have contributed to a significant increase in atmospheric levels of carbon dioxide. According to the International Energy Agency’s (IEA’s) World Energy Outlook 2010 main scenario, the projected growth in energy demand will translate into a 21 % rise in energy related CO₂ emissions between 2008 and 2035, mostly due to robust economic growth in developing countries. This quantity of greenhouse gas emissions would make it next to impossible to meet a 2 ºC goal thought to avoid the worst consequences of global climate change without additional actions. Scenarios for stabilizing climate-forcing emissions suggest atmospheric CO₂ stabilization can only be accomplished through the development and deployment of a robust portfolio of solutions, of which carbon capture and sequestration represent one component. In previous work [1], Na₂CO₃/Al₂O₃ distributed on metal foil was shown to be effective for CO₂ capture. In the current work, Na₂CO₃/Al₂O₃ prepared in the powder-form and foil-form were tested in a fixed-bed reactor and characterized by X-ray diffraction, BET surface area, Raman spectroscopy and scanning electron microscopy, before and after testing, to better understand the performance of the sorbents. The powder sorbents exhibited higher performance, in general, but one of the foil samples showed the highest performance out of all the power and foil sorbents. The same sorbent was also tested for 500 cycles to understand the long-term stability.