采用纳米Al203和碳纳米管颗粒强化CO2吸收的理论及实验研究（英文）

The influence of nano-particles on CO2 absorption was studied experimentally in a stirred thermostatic reactor. Nano-A1203 and carbon nanotube （CNT） particles which showed different hydrophobic properties were chosen for the investigation. The experimental results were compared with that of micron-size activated carbon （AC） and Al2O3 particles. From the results, no enhancement by micron-size A1203 was found, and with the increase of A1203 concentration, the enhancement factor decreased. However, nano-Al203 showed a weak enlaancement tor me COz absorption. AC and CNT particles all intensified the gas-liquid mass transfer effectively, yet the trend of the enhancement factor with stirring speed for the two particles was different. With increasing stirring speed, the enhancement factor of AC particles was decreased, wl＇iereas in CNT suspensions it was increased. The experimental phenomena demonstrated a difference in enhancement mechanism for different size particles. For nano-particles, besides the influence of adsorbability and hydrophobicity, the micro-convection caused by Brownian motion should be also taken into account. Considering the micro-convection effect, a theoretical model was developed to shed light on the absorption enhancement bv nano-oarticles.     

CO2 absorption and regeneration of alkali metal-based solid sorbents

Potassium-based sorbents were prepared by impregnation with potassium carbonate on supports such as activated carbon (AC), TiO₂, Al₂O₃, MgO, SiO₂ and various zeolites. The CO₂ capture capacity and regeneration property were measured in the presence of H₂O in a fixed-bed reactor, during multiple cycles at various temperature conditions (CO₂ capture at 60 °C and regeneration at 130–400 °C). Sorbents such as K₂CO₃/AC, K₂CO₃/TiO₂, K₂CO₃/MgO, and K₂CO₃/Al₂O₃, which showed excellent CO₂ capture capacity, could be completely regenerated above 130, 130, 350, and 400 °C, respectively. The decrease in the CO₂ capture capacity of K₂CO₃/Al₂O₃ and K₂CO₃/MgO, after regeneration at temperatures of less than 200 °C, could be explained through the formation of KAl(CO₃)₂(OH)₂, K₂Mg(CO₃)₂, and K₂Mg(CO₃)₂·4(H₂O), which did not completely converted to the original K₂CO₃ phase. In the case of K₂CO₃/AC and K₂CO₃/TiO₂, a KHCO₃ crystal structure was formed during CO₂ absorption, unlike K₂CO₃/Al₂O₃ and K₂CO₃/MgO. This phase could be easily converted into the original phase during regeneration, even at a low temperature (130 °C). Therefore, the formation of the KHCO₃ crystal structure after CO₂ absorption is an important factor for regeneration, even at the low temperature. The nature of support plays an important role for CO₂ absorption and regeneration capacities. In particular, the K₂CO₃/TiO₂ sorbent showed excellent characteristics in CO₂ absorption and regeneration in that it satisfies the requirements of a large amount of CO₂ absorption (mg CO₂/g sorbent) and fast and complete regeneration at a low temperature condition (1 atm, 150 °C).     

Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。     

固载氨基化离子液体的制备及其对CO2的吸附性能

利用浸渍法将[NH₃P-mim][BF₄]和[MEA]L两种离子液体负载到AC、Al₂O₃和MCM-41上,考察了对CO₂的吸附性能,确定了[NH₃P-mim][BF₄]/AC对CO₂的吸附性能最优。并对[NH₃P-mim][BF₄]/AC考察了不同负载量、不同温度下对CO₂的吸附性能,确定了固载离子液体对CO₂的吸附容量随着负载量的增加而增加,且30℃是固载离子液体吸附CO₂的最佳温度,吸附容量达到0.063 mmol CO₂·(g SILP)^-1。对[NH₃P-mim][BF₄]/AC进行红外和热重两种表征,确定了负载离子液体的结构以及在50℃以下优良的热稳定性。     

Enhanced cycling stability of LiMn2O4 by surface modification with melting impregnation method

The surface of as-prepared LiMn₂O₄ was modified with Al₂O₃ by a melting impregnation method. X-ray diffraction, field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) studies indicated that Al₂O₃ nano-particles are distributed around the spinel. X ray absorption fine structure analysis (XAFS) further demonstrated that Al atoms were also doped to the surface of LiMn₂O₄ particles. The nano-Al₂O₃ particle coating improves the capacity retention of spinel LiMn₂O₄ efficiently at both room temperature and 55 °C. The mechanism of improvement for surface modified LiMn₂O₄ can be attributed to the inhibition of a surface Jahn-Teller distortion and the decrease of manganese dissolution, leading to good electric contact among particles.     

活性炭粒子对K2CO3溶液中CO2化学吸收的强化

The enhancement of chemical absorption of CO2 by K2CO3/H2O absorbents in the presence of activated carbon (AC) particles was investigated. The results show that the gas absorption rates can be enhanced significantly in the presence of AC particles,and the maximum enhancement factor 3.7 was observed at low stirring intensities.The enhancement factor increased rapidly with the solid loading during the initial period of absorption and then became mild gradually to a maximum value. Both the liquid-solid contact area and the probability of solid particles residing at the gas-liquid interface decreased with the increase of the particle size,leading to a negative effect on the enhancement of mass transfer. The influence of the particles on gas absorption decreased with the reaction rate. The stirring speed changed the interfacial coverage and mass transfer rate on the liquid side and consequently affected the mass transfer between the gas and liquid phases; the enhancement factor decreased with the stirring intensity. A heterogeneous two-zone model was proposed for predicting the enhancement factor and the calculated results agreed well with the experimental data.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

活性炭粒子对K2CO3溶液中CO2化学吸收的强化

The enhancement of chemical absorption of CO2 by K2CO3/H2O absorbents in the presence of activated carbon （AC） particles was investigated. The results show that the gas absorption rates can be enhanced significantly in the presence of AC particles, and the maximum enhancement factor 3.7 was observed at low stirring intensities. The enhancement factor increased rapidly with the solid loading during the initial period of absorption and then be- came mild gradually to a maximum value. Both the liquid-solid contact area and the probability of solid particles residing at the gas-liquid interface decreased with the increase of the particle size, leading to a negative effect on the enhancement of mass transfer. The influence of the particles on gas absorption decreased with the reaction rate. The stirring speed changed the interfacial coverage and mass transfer rate on the liquid side and consequently affected the mass transfer between the gas and liquid phases; the enhancement factor decreased with the stirring intensity. A heterogeneous two-zone model was proposed for predicting the enhancement factor and the calculated results agreed well with the experimental data.     

碱/碱土金属修饰Ni基催化剂的CO2吸附与甲烷化性能

采用分步浸渍法制备了碱/碱土金属修饰Ni基催化剂Ni-M/Al₂O₃ (M=K₂CO₃, Na₂CO₃, MgO, CaO)。探究了碱/碱土金属的添加对改性Ni基催化剂CO₂吸附和甲烷化性能的影响。研究发现,碱/碱土金属的添加提高了Ni/Al₂O₃催化剂表面的碱性活性位点密度,强化了其CO₂吸附性能。碱/碱土金属类型影响Ni-M/Al₂O₃催化剂碱性活性位点的分布、NiO物相的转化及Ni的分散度,进而影响其甲烷化性能。MgO添加使NiO物相转化为与载体呈强相互作用的β型和γ型NiO,降低了催化剂表面的强碱性活性位点比例,有利于CO₂吸附活化。Ni-MgO/Al₂O₃的CO₂吸附容量最高为0.68mmolCO₂/g,其CO₂转化率和CH₄选择性分别高达58.4%和95.4%,其在烟气CO₂捕集与原位甲烷化中极具应用前景。     

Na2CO3基吸附剂颗粒制备及其脱碳性能

采用挤压-滚圆法制备Na₂CO₃基CO₂吸附剂微球颗粒,在自行设计的CO₂吸收系统中对制备的样品进行脱碳性能测试。结合相关表征测试,探明不同载体、不同负载量的Na₂CO₃基吸附剂的微观结构、脱碳性能以及机械性能的变化规律和内在原因。研究表明：不同载体的Na₂CO₃基吸附剂颗粒脱碳性能存在明显差异,其中氧化铝负载的吸附剂（Na₂CO₃/Al₂O₃）的脱碳性能最好,可达1.14mmol/g。铝酸钙水泥负载的吸附剂（Na₂CO₃/CA）机械性能较好,但其脱碳性能最差。结合吸附剂脱碳和机械性能的综合考量,Na₂CO₃/Al₂O₃是最为合适的CO₂吸附剂,并进一步研究不同Na₂CO₃负载量的影响。研究发现随着Na₂CO₃负载量的变化,吸附剂的微观结构、脱碳性能以及机械性能都存在明显的差异。虽然60%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒的机械性能和脱碳效果较好,但其成球度较差,影响其实际应用。质量分数40%负载量的Na₂CO₃/Al₂O₃吸附剂颗粒具有良好的脱碳性能、机械性能以及成球度,CO₂脱除量为1.36mmol/g。总体而言,利用挤压-滚圆法制备的Na₂CO₃基吸附剂颗粒具有良好的流动特性、脱碳性能和机械性能,适用于电厂烟气中的CO₂脱除。     

纳米粒子对CO2水合物导热性能的影响

试验研究了不同种类（Al₂O₃、Cu、SiO₂）、不同质量分数（0.05%、0.1%、0.15%）及不同粒径（10、30、50 nm）的纳米粒子对CO₂水合物热导率的影响。结果表明温度为-5~5℃时,纯CO₂水合物热导率为0.553~0.5861 W·m^-1·K^-1,具有玻璃体的变化特性。分散剂SDBS的加入,可改善CO₂水合物-纳米粒子体系的导热性能。在相同的质量分数和粒径下,纳米Cu粒子对CO₂水合物热导率的增强作用最好,但综合考虑水合物生成特性和溶液悬浮稳定性,选用纳米Al₂O₃粒子较合适。Al₂O₃粒子粒径越小,水合物热导率越大,15 nm比50 nm纳米粒子体系中CO₂水合物热导率的增长率平均提高了12.7%。此外,CO₂水合物热导率随Al₂O₃粒子质量分数的增大而增大,质量分数由0.05%增加到0.15%时,水合物热导率的增长率由4.2%提高到8.2%。     

Control of the product ratio of CO2/(CO+CO2) and inhibition of catalyst deactivation for steam reforming of gasoline to produce hydrogen

Factors controlling the product ratio of CO₂/(CO+CO₂) and methods for inhibiting deactivation of catalyst for steam reforming of gasoline were studied. Syngas (H₂+CO) as major product was produced on Ni-Mo/Al₂O₃ and the major product on Ni-Re/Al₂O₃ was H₂ and CO₂ at the same reaction conditions. Hydrogen with a high CO₂/(CO+CO₂) ratio of about 92% was produced by coupling reaction of steam reforming and water gas shift on Ni-Re/Al₂O₃ catalyst at 805 K. The multifunctional activity of the bimetallic catalyst of Ni-Re/Al₂O₃ and the suitable reaction temperature were of crucial significance for the coupling reaction. Although no deactivation could be observed on both Ni-Mo/Al₂O₃ and Ni-Re/Al₂O₃ catalysts for steam reforming of sulfur-free fuels in about 200 h of time on stream, the activity and sulfur-tolerance of Ni-Re/Al₂O₃ was much better than the values of Ni-Mo/Al₂O₃ for steam reforming of sulfur-containing fuels because of the unique role of rhenium in the Ni-Re catalyst. The unique role of rhenium in Ni-Re catalyst was mainly because of alloying of rhenium with nickel to form bimetallic Ni-Re sites and interaction of rhenium with sulfur to form S-Re binds. The sulfur-tolerance of Ni-Re/Al₂O₃ for steam reforming of sulfur-containing gasoline was improved further by addition of a small amount of ZSM-5. The activity and sulfur-tolerance of Ni-Mo/Al₂O₃ was also enhanced by the addition of ZSM-5.     

Transient studies of carbon dioxide reforming of methane over Pt/ZrO2 and Pt/Al2O3

The mechanism of the CO₂ reforming of methane reaction over the Pt/ZrO₂ catalyst was investigated using a temporal analysis of products (TAP) reactor system. For comparative purposes, the reaction pathway using a Pt/Al₂O₃ catalyst was also examined. A reaction sequence is suggested for both catalysts. Over both catalysts, methane decomposition takes place over platinum. The main difference between the two catalysts concerns the carbon dioxide dissociation. Over Pt/Al₂O₃ this step is assisted by hydrogen. Over Pt/ZrO₂ this step takes place over the zirconia support and involves surface vacancies. Moreover, large pools of formate and carbonate species are present on the zirconia. Transient studies conducted to determine the origin of carbon species accumulated during CO₂ reforming revealed that more than 99% of the carbon was derived from the methane molecule over both catalysts. Over the Pt/ZrO₂ catalyst, only a single very reactive carbon species was detected, while over the Pt/Al₂O₃ a second less active species was also formed.     

钙基碳载体造粒的捕集CO特性及力学性能

采用挤出滚圆法对钙基碳载体Ca（OH）₂进行造粒。在双固定床反应器上研究了黏结剂、支撑体和造孔剂对造粒后钙基碳载体循环捕集CO₂性能的影响,并提出采用多孔Al₂O₃球粉作为新型支撑体。结果表明,选择聚乙烯吡咯烷酮为颗粒黏结剂时最佳添加量为2%。高铝水泥和多孔Al₂O₃球粉均可作为支撑体造粒。多孔Al₂O₃球粉作为支撑体造粒后碳载体的循环捕集CO₂性能更高,其10次循环后CO₂吸收量为0.23g/g,是添加高铝水泥造粒碳载体的1.35倍。微晶纤维素作为造孔剂显著提高了造粒碳载体的循环捕集CO₂性能。多孔Al₂O₃球粉作为支撑体造粒后碳载体的抗压强度略高于高铝水泥作为支撑体。多孔Al₂O₃球粉造粒钙基碳载体拥有大量30~100nm孔隙,其比孔容高于高铝水泥造粒碳载体,这有利于CO₂捕集。     

CO_2 methanation over TiO_2–Al_2O_3 binary oxides supported Ru catalysts

TiO_2 modified Al_2O_3 binary oxide was prepared by a wet-impregnation method and used as the support for ruthenium catalyst. The catalytic performance of Ru/TiO_2–Al_2O_3catalyst in CO_2 methanation reaction was investigated. Compared with Ru/Al_2O_3 catalyst, the Ru/TiO_2–Al_2O_3catalytic system exhibited a much higher activity in CO_2 methanation reaction. The reaction rate over Ru/TiO_2–Al_2O_3 was 0.59 mol CO_2·(g Ru)1·h-1, 3.1 times higher than that on Ru/Al_2O_3[0.19 mol CO_2·(gRu)-1·h-1]. The effect of TiO_2 content and TiO_2–Al_2O_3calcination temperature on catalytic performance was addressed. The corresponding structures of each catalyst were characterized by means of H_2-TPR, XRD, and TEM. Results indicated that the averaged particle size of the Ru on TiO_2–Al_2O_3support is 2.8 nm, smaller than that on Al_2O_3 support of 4.3 nm. Therefore, we conclude that the improved activity over Ru/TiO_2–Al_2O_3catalyst is originated from the smaller particle size of ruthenium resulting from a strong interaction between Ru and the rutile-TiO_2 support, which hindered the aggregation of Ru nanoparticles.     

Al2O3/AC正极选择性电容吸附水中氟离子

氟是人类生命活动必需的微量元素之一,但人体摄入过多的氟元素会引发氟斑牙、骨骼变形等氟中毒现象。本文以活性炭 （AC） 为载体,在多孔Al₂O₃纳米分散液中采用简单超声处理,得到Al₂O₃/AC复合材料。场发射扫描电镜证明Al₂O₃成功负载在AC表面,5% Al₂O₃在AC表面分布均匀。N₂吸-脱附测试结果表明Al₂O₃/AC复合材料的比表面积比AC有明显增加。循环伏安、恒流充放电及电化学阻抗测试结果表明Al₂O₃的掺杂可以改善AC的离子导电性,提高比电容;5% Al₂O₃/AC导电性最佳,比电容最高,在7 mmol·L^-1 NaF溶液中为92 F·g^-1,是AC比电容 （62 F·g^-1） 的1.5倍。以Al₂O₃/AC为正极的电容去离子 （CDI） 脱氟测试,结果表明5% Al₂O₃/AC电极脱氟量最大,达234 μmol·g^-1,远高于纯AC的脱氟量 （115 μmol·g^-1）。此外,5% Al₂O₃/AC电极对F^-的选择性吸附性能良好,在含F^-、Cl^-和SO₄^2-的模拟高氟地下水中采用5% Al₂O₃/AC电极对应的三组CDI池串联,可脱除80%的F^-、25%的Cl^-和56%的SO₄^2-,同时经过十次F^-吸脱附循环后,氟去除率仍可保持81%,证明5% Al₂O₃/AC电极对F^-具有良好的选择吸附性和循环稳定性。该电极材料制备简单,脱氟选择性好,在CDI过程中有望用于高氟地区地下水的净化脱氟。     

Total oxidation of propene and propane over gold–copper oxide on alumina catalysts: Comparison with Pt/Al2O3

Oxidation of propene and propane to CO₂ and H₂O has been studied over Au/Al₂O₃ and two different Au/CuO/Al₂O₃ (4 wt.% Au and 7.4 wt.% Au) catalysts and compared with the catalytic behaviour of Au/Co₃O₄/Al₂O₃ (4.1 wt.% Au) and Pt/Al₂O₃ (4.8 wt.% Pt) catalysts. The various characterization techniques employed (XRD, HRTEM, TPR and DR-UV–vis) revealed the presence of metallic gold, along with a highly dispersed CuO (6 wt.% CuO), or more crystalline CuO phase (12 wt.% CuO).

A higher CuO loading does not significantly influence the catalytic performance of the catalyst in propene oxidation, the gold loading appears to be more important. Moreover, it was found that 7.4Au/CuO/Al₂O₃ is almost as active as Pt/Al₂O₃, whereas Au/Co₃O₄/Al₂O₃ performs less than any of the CuO-containing gold-based catalysts.

The light-off temperature for C₃H₈ oxidation is significantly higher than for C₃H₆. For this reaction the particle size effect appears to prevail over the effect of gold loading. The most active catalysts are 4Au/CuO/Al₂O₃ (gold particles less than 3 nm) and 4Au/Co₃O₄/Al₂O₃ (gold particles less than 5 nm).     

Effect of fine solid particles on absorption rate of gaseous CO

The influence of the properties of solid particles in slurry on the absorption of CO₂ in the slurry was investigated in a stirred thermostatic reactor. The absorption experiments were carried out in three different slurries consisting of water, cyclohexane and soybean oil, respectively, and three kinds of solid particles (active carbon, active alumina and silica gel) were incorporated into each of the above mentioned slurries separately. The experimental results show that the active carbon particles could enhance the absorption rate of gaseous CO₂ in the aqueous slurry, while in the cyclohexane slurry, active carbon particles indicated no the absorption enhancement effect. However, it was observed that the active alumina and silica gel particles could enhance the absorption rate of CO₂ in the cyclohexane slurry. These phenomena indicate that the solid particles, which could enhance the gaseous CO₂ absorption rate, should possess two properties simultaneously, i.e. they rejected the solvent and had higher adsorption capacity for the solute. The experimental results also show that, as for those solid particles which could enhance the gas absorption rate, the enhancement increased quickly with the increase of solid concentration in slurry at first, and then reached a constant value gradually. It was also found that the enhancement factor was related to the coverage fraction of solid particles on the gas-liquid interface, and due to the reduction of surface fraction with increasing stirred speed, the enhancement factor decreased.     

磷石膏强化氨法CO2捕集机理与模型

基于化学活性颗粒强化气液吸收机理,建立了磷石膏悬浮液强化氨法烟气CO₂捕集模型。以液膜内量纲一传质距离λ^*为特征参数,增强因子E=1/λ^*+qβλ^*/2。用恒温反应器在不同搅拌转速及磷石膏颗粒固含量下实验测定CO₂吸收增强因子对模型进行检验,结果表明:随颗粒固含量由5%增加到30%(质量分数),增强因子由1.69增加到2.10;而随搅拌转速从150 r·min^-1增加到300 r·min^-1,增强因子仅由1.75略增到1.80,表明磷石膏颗粒固含量及溶解速率是影响增强因子的控制性因素。实验结果与模型预测值吻合良好, 偏差小于10%。     

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。