电石水解制备复合钙基吸附剂及其循环吸附CO2的特性

利用电石水解制乙炔工艺制备新型电石渣CaO/Ca12Al14O33复合钙基吸附剂,考察了Ca12Al14O33含量、碳酸化和煅烧再生温度对CaO转化率和多循环吸附CO2的影响,并与分析纯CaCO3和传统电石渣进行了比较,对其表面形貌、比表面积和孔结构进行了分析. 结果表明,新型复合钙基吸附剂在多循环煅烧/碳酸化过程中具有较好的多循环吸附CO2的性能. Ca12Al14O33有效减缓了吸附剂烧结现象. 20次循环后,自制电石渣吸附剂的CaO转化率仍保持在48%以上.     

CaO含量对纳米CaO/Al2O3吸附剂性能的影响

研究了纳米CaO含量对CO2吸附剂微观结构和吸附性能的影响。以纳米CaCO3和铝溶胶为前驱体配制混合浆料,采用挤条方法制备CaO含量为6%～100%的CO2吸附剂颗粒,微观结构性能测试结果表明:CaO含量从6%提高到46%,比表面积从151.3 m2.g.1下降到8.1 m2.g.1,孔容从0.41 cm3.g.1下降到0.07 cm3.g.1,孔径从6.05 nm提高到12.39 nm。提高到CaO含量46%以上,吸附剂比表面积和孔结构没有变化,接近纯纳米CaO。当CaO含量超过27%后,氧化铝呈非晶形。吸附性能测试结果表明:随着CaO含量从12%提高到83%,吸附容量从1.02 mol CO2.kg.1增加到7.05 mol CO2.kg.1,吸附速率提高。研究结果还表明:CaO含量对纳米CaO基CO2吸附剂的微观结构和吸附性能的影响呈非线性关系。与纯CaO相比,加入少量氧化铝能提高吸附剂对CO2的吸附容量稳定性和吸附速率。     

不同结构活性炭对CO_2、CH_4、N_2及O_2的吸附分离性能

制备了比表面积为1943 m2/g的纯微孔活性炭AC-1和比表面积为1567 m2/g,中孔比例为47.18%的活性炭AC-2.分别以AC-1及AC-2为吸附剂测定CO2、CH4、N2和O2的298 K吸附等温线,考察了两种活性炭对CO2/N2、CO2/CH4及CH4/N2气体混合物的吸附分离性能.实验结果表明,孔结构是影响吸附剂吸附分离性能的主要因素.富中孔活性炭AC-2较AC-1更适用于CO2/N2、CO2/CH4气体混和物的吸附分离,而微孔活性炭AC-1对CH4/N2混合体系的吸附分离性能优于AC-2.     

混合气组分对CO在稀土复合吸附剂上吸附的影响

采用吸附柱动态实验装置,分别考察了混合气组分H2O、CO2、CH4对稀土复合吸附剂变压吸附CO的影响。实验结果表明,原料气中微量的H2O的存在对稀土复合吸附剂的吸附性能有较大影响,当水质量浓度仅为250mg/L时,CO的变压吸附量下降约35％;与CO相比,CO2在稀土复合吸附剂上为弱吸附组分,但对CO的吸附性能有一定影响,当CO2体积分数为1％时,CO的变压吸附量可维持在12.5 ml/g左右;而CH4的存在对CO在稀土复合吸附剂上的吸附量影响不大。     

化学吸附制冷用氯化锶复合吸附剂的制冷性能

对以SrCl₂、活性炭为吸附剂,NH₃为制冷剂所组成的吸附式制冷工质对的吸附性能进行了研究。拟解决SrCl₂吸附剂颗粒强度不高、长期使用后易出现膨胀粉化、吸附床传热传质性能下降等问题,将SrCl₂分别与活性炭、CaSO₄按质量比4∶1复配,进行吸附制冷性能实验。并对SrCl₂的吸附机理及CaSO₄的胶凝作用进行了探讨。实验结果表明：温度是过程的控制因素,在100℃时,SrCl₂/活性炭、SrCl₂/CaSO₄复合吸附剂的单位脱胶凝剂基吸附剂制冷量分别是SrCl₂的2.1倍和1.4倍。对吸附剂比表面积及孔结构进行表征,结果显示：SrCl₂/CaSO₄复合吸附剂的比表面积和孔结构保持良好;SrCl₂/活性炭复合吸附剂的比表面积和孔容明显增大,孔结构得到了改善。     

4A分子筛的吸附性能与孔结构研究

多孔材料的吸附性能与其独特、复杂的孔结构有关.为探究低温低压下4A分子筛的吸附性能,采用静态膨胀法获得了其在77 K下对N2、O2、空气的吸附曲线,分析了分子筛对不同吸附质的吸附量存在差异的原因.以N2、CO2、Ar为吸附质,利用气体吸附法来表征4A分子筛的微孔结构.研究结果表明:4A分子筛对O2的吸附量达到1 ×104Pa·L/g,高出N2、空气两个数量级;对于4A分子筛,273 K时,CO2是气体吸附法表征其微孔结构的理想吸附质;采用D-R法计算4A分子筛的比表面积更为合理,其比表面积为533.148 m2/g;基于最大吸附量计算的4A分子筛微孔孔容与文献值较为接近;与DFT法相比,H-K法更能准确表征具有微孔的4A分子筛的孔径分布,孔径在1 nm以下的孔体积比例占85.42％.     

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。     

石墨烯-13X/LiCl复合吸附剂开式吸附-解吸性能

利用不同质量分数的石墨烯（MLG）与13X/LiCl合成新型复合吸附剂。通过扫描电镜（SEM）和N₂吸附表征复合吸附剂的微观形貌和孔隙特性,测试了复合吸附剂开式环境下的水蒸气吸附及解吸性能,并探究复合吸附剂中石墨烯质量分数对吸附解吸性能的影响。通过80%相对湿度（RH）的高湿工况进一步筛选出盐的质量分数为18.4%的13X/LiCl为最佳盐含量的吸附剂（MZ）作为合成复合吸附剂的基质。实验结果表明：石墨烯增加了复合吸附剂的结构性参数（比表面积,孔体积及孔径）,其中比表面积由未添加石墨烯的MZ [(262±3)g/m²],最大可提升至12G-MZ [(304±4)g/m²];复合吸附剂表现出优异的水蒸气吸附性能,所有复合吸附剂的相对吸附量均高于MZ（0.554g/g）,3G-MZ吸附性能最佳,水蒸气吸附量高达0.587g/g,是13X的2.7倍;除12G-MZ外,随着吸附剂中石墨烯质量分数的增加,水蒸气解吸率随之增加,其中9G-MZ的解吸率接近90%,较MZ（81.8%）提升了9.7%。该研究可为复合吸附剂应用于吸附空气取水提供基础研究数据。     

汽油脱硫吸附剂的制备及性能评价

以微孔-介孔复合分子筛ZSM-5-MCM-41为载体,采用等体积浸渍法制备复合型吸附剂Ni-Co/MCM-41-ZSM-5.结果表明复合型吸附剂的活性组分为Co3O4和NiO,比表面积为545m2/g.最佳制备条件为：Ni、Co的负载量10％,浸渍时间12h,450℃焙烧4h;在上述制备条件下,吸附剂的饱和吸附量为37.08mgS/g吸附剂.     

部分脱除模板剂对MCM-41修饰负载有机胺吸附CO_2的影响

介孔分子筛MCM-41具有单一的孔道结构和较大的比表面积。通过负载有机胺形成的介孔有机胺二氧化碳固体吸附剂比常见的固体吸附剂具有高选择性、高吸附量等特点。利用化学方法部分脱除模板剂,负载PEI制备固体吸附剂,研究了模板剂脱除率PEI负载和对二氧化碳吸附性能的影响。用XRD、FT-IR、TEM、BET等方法对吸附剂结构进行表征,利用TG/DTA方法测定了CO2吸附量。研究结果表明,使用MCM-41原粉负载50%PEI吸附量达到131.0 mg/g(即262.0 mg/gPEI),比相同负载量除去模板剂的分子筛提高了12.6%;比单一的PEI分子吸附量(80.3 mg/g)提高了3.26倍,这说明在MCM-41原粉孔道内部由于存在丝状胶束而形成的亚纳米空间结构提高了有机胺的分散和利用率,增加了对CO2的吸附量。     

CaO/FA吸收剂高温吸收CO2及穿透特性

利用完全煅烧后的CaO和粉煤灰（Fly Ash）为材料制备了CaO/FA吸收剂。在350~650℃温度范围内对其碳酸化反应特性进行了研究。考察了不同质量比的CaO/FA吸收剂吸收CO2的性能。利用XRD、N2吸附等表征手段对吸收剂反应前后产物进行了表征。结果表明：通过水合反应过程,吸收剂比表面积增大,孔径在5~40nm范围内属于中孔,有利于减小CO2向颗粒内部的扩散阻力。CaO/FA吸收剂CO2吸收量随温度的升高而增加。当CaO与粉煤灰的质量比为3:1时制备的吸收剂具有最好的CO2吸收能力,在650℃时其最大CO2吸收量达到了227.13mg/g。通过多次循环试验后,吸附剂仍保持较高的CO2吸收量与稳定吸收性能。失活模型可以很好地预测CaO/FA吸收剂吸收CO2的过程,并得到了理想的吸收速率常数和失活速率常数。     

水蒸气催化活化半焦制活性炭和氢气的研究

以神府半焦为原料,通过水蒸气催化活化法制备了活性炭和氢气。考察了不同金属氧化物对活性炭吸附性能、活化过程中氢气产量的影响。结果表明,氧化物对活性炭吸附性能以及氢气产量影响很大。当氧化铁和氧化钙共同催化时,所制得的活性炭性能较好,氢气产量较大;活性炭碘吸附值为678 mg/g,亚甲基蓝值为55 mg/g,BET比表面积为775 m2/g,总孔容达0.414 8 cm3/g,平均孔径为3.902 nm,活化阶段氢气的产量为535 mmol/g半焦,约占活化过程释放气体总量的73.90%。     

Effect of different organic compounds on the preparation of CaO-based CO2 sorbents derived from wet mixing combustion synthesis

CaO based sorbents have great potential for commercial use to capture CO_2 of power plants. In the demand of producing sorbents with better cyclic performance, CaO-based sorbents derived from different kinds of calcium precursors, containing calcium carbonate(CC-CaO), calcium gluconate monohydrate(CG-CaO), calcium citrate(CCi-CaO) and calcium acetate monohydrate(CA-CaO), were tested cyclically and compared using simultaneous thermal analyzer(STA). And further study was conducted on the sorbents modified with citric acid monohydrate and 50% gluconic acid solution by wet mixing combustion synthesis. The modified sorbents showed better performance and higher pore parameters as well as porous microstructure with more organic acid added. After 20 cycles of carbonation and calcination, the C2CCi8(CaO: citric acid = 2:8 by mass ratio) and C2G8(CaO: gluconic acid = 2:8 by mass ratio) sorbent possess CO_2 capture capacity of 0.45 g·g~(-1)(g CO_2 per g sorbents) and 0.52 g·g~(-1) respectively. The citric acid was more effective for modification than gluconic acid for extended 50 cycles. Furthermore, good linear relationship between CaO conversion and specific surface area as well as pore volume were determined, of which the specific surface area showed closer correlation with CaO conversion.     

EtOH-H2O对钙基吸收剂分离CO2的影响

采用不同体积浓度的乙醇溶液分别对石灰石和石灰石的煅烧产物CaO进行调质处理,研究它们的碳酸化反应,并与水合调质CaO的碳酸化进行比较。通过SEM和N2吸附法考察吸收剂多次煅烧的微观结构特性,进一步揭示了乙醇溶液促进CaO碳酸化的机理。结果表明：随着循环反应次数的增加,乙醇溶液调质后CaO的碳酸化转化率明显高于石灰石和水合调质的CaO,对于石灰石,乙醇溶液则没有明显的调质效果。CaO经乙醇溶液调质后在650～700℃内有利于碳酸化的进行。乙醇浓度越高,则经调质后CaO的转化率越高,抗烧结性能越好。经乙醇溶液调质的CaO煅烧后比表面积和比孔容均比单纯水合大,远高于煅烧后的石灰石;比孔容分布和孔比表面积分布明显优于煅烧后的水合CaO和石灰石。乙醇溶液调质对CaO的孔有明显的增扩效应。     

Enhanced CO2 adsorption capacity and stability using CaO‐based adsorbents treated by hydration

The synthesis of highly efficient CaO‐based sorbents using Ca(Ac)₂ as a precursor and ethanol as a modification agent for CO₂ capture is described. This adsorbent has several characteristics such as large surface area and pore volume and small particle size. The influence of ratio of ethanol and water on CO₂ adsorption capacity was evaluated considering that the ethanol concentration could affect the pore structure of sorbents. The results showed that CaO modified by ethanol solution had a higher carbonization and better stability. Particularly, when the volume ratio of ethanol and water was 3, a performance of adsorption capacity of 74% and conversion of 94% was observed. CaO modified by ethanol solution had a superior performance due to the decrease of grain size and the formation of loose porous structure. The influence of steam on stability of adsorbents at high temperatures was examined, and it was found that with the existence of steam diffusion, the capacity of the sorbent could remain at a higher level and the stability was evidently improved. After 18 cycles of adsorption/desorption process, the capacity remained as high as 65%. It was proposed that dynamic and cyclic steam injection was favorable for preventing the sintering of sorbents and facilitating the diffusion of CO₂. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3586–3593, 2013     

KOH负载的不同催化剂催化合成生物柴油

采用湿法浸渍法研究了五种KOH负载的催化剂催化合成生物柴油反应,并采用XRD﹑SEM﹑CO2-TPD等方法对其进行结构和性能表征。结果表明,15%(质量分数,下同)KOH负载的CaO催化酯化活性最高,在醇油摩尔比16∶1,反应温度65℃,催化剂加入量为4%条件下,反应1h,脂肪酸甲酯收率达到97.1%。KOH负载的CaO催化剂中出现了K2O的晶相,15%CaO/KOH催化剂有更多的活性位点,有利于生物柴油酯交换反应。     

Modification of CaO-based sorbents prepared from calcium acetate for CO2 capture at high temperature

CaO-based sorbent is considered to be a promising candidate for capturing CO_2 at high temperature. However,the adsorption capacity of CaO decreases sharply with the increase of the carbonation/calcination cycles. In this study, CaO was derived from calcium acetate(CaAc_2), which was doped with different elements(Mg, Al,Ce, Zr and La) to improve the cyclic stability. The carbonation conversion and cyclic stability of sorbents were tested by thermogravimetric analyzer(TGA). The sorbents were characterized by N_2 isothermal adsorption measurements, scanning electron microscopy(SEM) and X-ray diffraction(XRD). The results showed that the cyclic stabilities of all modified sorbents were improved by doping elements, while the carbonation conversions of sorbents in the 1st cycle were not increased by doping different elements. After 22 cycles, the cyclic stabilities of CaO–Al, CaO–Ce and CaO–La were above 96.2%. After 110 cycles, the cyclic stability of CaO–Al was still as high as 87.1%. Furthermore, the carbonation conversion was closely related to the critical time and specific surface area.     

高温抗烧结吸附剂对SeO2捕集性能

使用气固瞬时反应装置在700~1100℃下对不同氧化物（氧化镁、氧化铁、氧化铝、氧化钙）的硒捕集性能进行研究,确定吸附产物性质。基于此选取相应的典型矿物及双组分抗烧结吸附剂改善硒高温吸附能力。结果表明：900℃前氧化钙捕集效果最好,但1100℃时其吸附量迅速降低到167.59μg/g;γ-氧化铝在高温下捕集效果较好,1100℃时吸附量可达415.04μg/g,这与其优异的孔隙结构有关。钙基矿物方解石因其具有一定的抗烧结能力和发达的孔隙结构,表现出更好的高温捕集能力,1100℃时吸附量可提高到1064.97μg/g。双组分吸附剂高温捕集能力展现出不同程度的提高。钙-铝基吸附剂高温捕集性能提高相对较小;而钙-硅基吸附剂在高温下效果远高于单组分吸附剂,与氧化钙相比,1100℃时可提高1787.21μg/g。     

Sulphur dioxide removal using South African limestone/siliceous materials

This study presents an investigation into the desulfurization effect of sorbent derived from South African calcined limestone conditioned with fly ash. The main aim was to examine the effect of chemical composition and structural properties of the sorbent with regard to SO₂ removal in dry-type flue gas desulfurization (FGD) process. South African fly ash and CaO obtained from calcination of limestone in a laboratory kiln at a temperature of 900 °C were used to synthesize CaO/ash sorbent by atmospheric hydration process. The sorbent was prepared under different hydration conditions: CaO/fly ash weight ratio, hydration temperature (55-75 °C) and hydration period (4-10 h). Desulfurization experiments were done in the fixed bed reactor at 87 °C and relative humidity of 50%. The chemical composition of both the fly ash and calcined limestone had relatively high Fe₂O₃ and oxides of other transitional elements which provided catalytic ability during the sorbent sorption process. Generally the sorbents had higher SO₂ absorption capacity in terms of mol of SO₂ per mol of sorbent (0.1403-0.3336) compared to hydrated lime alone (maximum 0.1823). The sorbents were also found to consist of mesoporous structure with larger pore volume and BET specific surface area than both CaO and fly ash. X-ray diffraction (XRD) analysis showed the presence of complex compounds containing calcium silicate hydrate in the sorbents.