Comparison of the surface and catalytic properties of rare earth‐promoted CaO catalysts in the oxidative coupling of methane

Rare earth (viz. La, Ce, Sm, Nd and Yb) promoted CaO catalysts have been investigated, comparing their surface properties (viz. surface area and basicity/base strength distribution) and catalytic activity/selectivity in the oxidative coupling of methane at different reaction conditions (temperatures, 650–800 °C, CH₄/O₂ ratios, 2.0–8.0 and space velocity, 51 360 cm³ g^?1 h^?1). The surface properties and catalytic activity/selectivity are strongly influenced by the rare earth promoter and its concentration. Apart from the Sm‐promoted CaO catalyst, both the total and strong basic sites (measured in terms of CO₂ chemisorbed at 50° and 500 °C respectively) are decreased due to the promotion of CaO by rare earth metals (viz. La, Ce, Nd and Yb). The catalytic activity/selectivity is strongly influenced by the temperature, particularly below ?700 °C, whereas at higher temperature no further effect is seen. The La₂O₃? CaO, Nd₂O₃? CaO and Yb₂O₃? CaO catalysts showed high activity and selectivity, and also their results are comparable. Among the catalysts, Nd‐promoted CaO (with Nd/Ca = 0.05) showed the best performance (19.5% CH₄ conversion with 70.8% C₂₊ selectivity) in the oxidative coupling of methane. A close relationship between the surface density of total and strong basic sites (measured in terms of CO₂ chemisorbed at 50° and 500 °C respectively) and the C₂₊ selectivity and/or C₂₊ yield has been observed. Copyright © 2005 Society of Chemical Industry     

Silica removal from Mokai, New Zealand, geothermal brine by treatment with lime and a cationic precipitant

Preliminary experiments using two chemicals (CaO, a quicklime, and a cationic nitrogen-bearing precipitant, EC-004) to remove silica from geothermal brine were undertaken at the Mokai geothermal plant, New Zealand. The brine was mixed with the reagent (CaO or EC-004). The reaction was studied from the start of the experiment (NRT, 0 min, no retaining time) and after 15 min (15RT) at 90 °C. The concentration of silica in the brine was initially 954 mg/l, and decreased linearly with increasing reagent concentration. When CaO is added, the silica concentration at 15RT was 200 mg/l lower than at NRT and became almost zero on addition of 1.5 g/l. In contrast, when EC-004 is added, the total silica concentration nearly reaches the solubility of amorphous silica at 90 °C. In order to prevent silica scaling in Mokai brines cooled to 90 °C, the CaO and EC-004 added should be individually adjusted to 0.5 g/l and 80 mg/l, respectively.     

镍基高温合金真空感应熔炼脱氧

研究了使用CaO坩埚真空感应熔炼Ni-6Cr-2MO-6W-5Co合金时C与Al的脱氧作用.从热力学上计算了Al-O反应的平衡值,计算结果表明,Al-O反应在1773 K能使氧的质量分数降至6×10-6以下.计算了Ni-Al-C-O平衡,结果表明,C与Al2O3的反应在真空感应熔炼条件下可以进行,从而导致合金液精炼期C含量下降值大于脱氧所需值.     

纳米晶CaO稳定化ZrO2粉体的制备及其烧结

本文采用胶体 超临界流体干燥法合成CaO稳定化ZrO2 纳米粉体 ,并对粉体的烧结性能进行研究。研究结果表明 ,该法合成的粉体具有粒径小、粒径分布范围窄、比表面积大等特点 ;将粉体作为ZrO2 基陶瓷起始粉料 ,具有很高的烧结活性 ,可以有效地降低烧结温度 ,缩短烧结时间。此外 ,粉体中稳定剂的含量会很大程度上影响其性能。     

以DRE系列ICP发射光谱仪测定液碱中的CaO及SiO2含量

介绍以DRE系列ICP发射光谱仪测定液碱中CaO及SiO2含量的方法及其产生过程，验证了该方法的灵敏度和准确性。     

Improved hydration resistance of CaO granules via sol-processed metal oxide protective layers

Well-sintered CaO granules with hydration resistance are very important for the manufacturing and application of CaO-containing refractories. CaO granules with sol-processed metal oxide protective layers were prepared by granulation and surface treatment. The obtained results indicated that the usage of nano sol greatly improved the hydration resistance of CaO granules, especially when the CaO granules were treated by alumina sol. The promoting effect of nano sols in the sintering processes improved the density of CaO granules. Nanoparticles reacted with lime at lower temperature and a new phase was formed uniformly in the treated layer, which promoted densification of the treated layer. The grain size of CaO granules in the treated layer was increased obviously with the promotion of sintering. Moreover, nanoparticles were favorable for the formation of direct bonding between CaO grains by decreasing the dihedral angle.     

等速升温流态化下CaO/生物质焦的SO2/NO联合脱除特性

燃煤锅炉污染物超低排放标准对电厂脱硫和脱硝系统提出了更高的要求。CaO作为脱硫剂可以实现循环流化床锅炉烟气中SO₂的高效脱除,焦炭作为还原剂直接还原NO,同时CaO的存在对焦炭还原NO起催化作用,可以实现燃煤烟气中SO₂/NO的联合脱除。为了探究连续温度变化对CaO/生物质焦联合脱硫脱硝性能的影响,在钙循环捕集CO₂技术背景下,研究了等速升温流态化下CaO/生物质焦的SO₂/NO联合脱除特性。探究了烟气中O₂和CO₂对CaO/椰壳焦脱除SO₂/NO的影响。结果表明,O₂通过对椰壳焦表面碳原子的活化作用降低了异相还原NO温度,在300~950℃等速升温过程中CaO/椰壳焦的NO脱除效率逐渐增加,780℃以上能实现100%脱硝。O₂也提高了CaO/椰壳焦的脱硫效率。CO₂与CaO的碳酸化反应以及与椰壳焦的气化反应对同时脱除SO₂/NO有明显抑制作用。O₂和CO₂共同作用下,在500~800℃内CaO/椰壳焦的脱硝效率随温度升高而增加,脱硫效率先降低后升高。NO促进了CaO/椰壳焦脱除SO₂,而SO₂对脱硝有抑制作用。800℃时CaO/椰壳焦同时脱除SO₂和NO的效率分别为97.7%和93.9%。     

Efficient MgO-doped CaO sorbent pellets for high temperature CO2 capture

Novel MgO-doped CaO sorbent pellets were prepared by gel-casting and wet impregnation. The effect of Na⁺ and MgO on the structure and CO₂ adsorption performance of CaO sorbent pellets was elucidated. MgO-doped CaO sorbent pellets with the diameter range of 0.5-1.5 mm exhibited an excellent capacity for CO₂ adsorption and adsorption rate due to the homogeneous dispersion of MgO in the sorbent pellets and its effects on the physical structure of sorbents. The results show that MgO can effectively inhibit the sintering of CaO and retain the adsorption capacity of sorbents during multiple adsorption-desorption cycles. The presence of mesopores and macropores resulted in appreciable change of volume from CaO (16.7 cm³∙mol⁻¹) to CaCO₃ (36.9 cm³∙mol⁻¹) over repeated operation cycles. Ca2Mg1 sorbent pellets exhibited favorable CO₂ capture capacity (9.49 mmol∙g⁻¹), average adsorption rate (0.32 mmol∙g⁻¹∙min⁻¹) and conversion rate of CaO (74.83%) after 30 cycles.     

添加剂CaO对含金、银硫精矿氧化焙烧过程的影响

云南某含金、银硫精矿硫品位 44.24%,金、银品位分别为 3.07g/t、36.3g/t,金主要以裸露金的形式存在,银主要以硫化银和硫化物包裹银的形式存在。氧化焙烧预处理后,金、银浸出率分别为 79.66%、68.13%,高温下氧化铁会出现熔融状态,对金、银进行二次包裹。加入焙烧添加剂 CaO,金浸出率提高至86.56%,银浸出率提高至 68.43%。CaO 与 Fe2O3、SiO2 的亲和力大于 ZnO,焙烧过程加入 CaO 与 ZnO·SiO2、PbO·SiO2 与 FeO·SiO2 反应,形成 CaO·SiO2,阻碍致密 ZnO·SiO2、PbO·SiO2 和 FeO·SiO2 形成,减少其对金、银的包裹,焙砂硅酸盐包裹金由 0.52g/t 降低至 0.13g/t。     

残留CO2对石灰在转炉初渣中溶解的影响

 在转炉炼钢过程中,石灰快速溶解对转炉高效脱磷具有十分重要的意义,石灰溶解过程中熔渣/石灰界面处形成的2CaO·SiO₂产物层被认为是阻碍石灰溶解的关键因素。制备了具有两种不同CO₂含量的部分煅烧石灰石,采用浸泡法研究了部分煅烧石灰石在转炉初渣中的溶解行为,并与纯石灰、石灰石的溶解行为进行比较。结果表明,石灰石溶解时在液态熔渣中CaO的传质系数为石灰的2.1倍,残留CO₂质量分数为10%的部分煅烧石灰石的传质系数高达石灰石的6.7倍。在CO₂质量分数为0～43.5%时,石灰的溶解速率先增大后减小。石灰溶解过程中形成的2CaO·SiO₂层严重阻碍了FeO_x的扩散,从而减缓了石灰的溶解。与石灰不同,石灰石分解产生的CO₂能够破坏2CaO·SiO₂层并破坏自身结构,有利于熔渣的渗透,这也适用于残留CO₂的部分煅烧石灰石。制备纯石灰的过程中为了确保石灰芯部完全煅烧,因此极易导致石灰外表面发生过烧,而制备部分煅烧石灰石能在一定程度上解决表面过烧的问题。此外,与石灰石相比,部分煅烧石灰石由于表面是石灰外壳,溶解初期其表面附近的炉渣温降相对更低,能够避免溶解初期出现停滞阶段。在转炉富余热量有限的情况下,部分煅烧石灰石的石灰替换比高于石灰石,这取决于部分煅烧石灰石中的CO₂残留量。