甲烷催化燃烧用LaMn/Al_2O_3催化剂研究

为获得具有优良低温活性的甲烷燃烧用催化剂,采用稀土La作为助剂制备了系列Mn基催化剂,借助X射线衍射(XRD)、X射线光电子能谱(XPS)和程序升温还原(TPR)技术对催化剂的结构进行了表征,并评价了其对甲烷燃烧的低温催化性能。结果表明,La助剂的添加显著促进了活性组分MnO2的分散,使其更易于还原,且使Mn4+和晶格氧富集于催化剂表面,因而显著提高了催化剂对甲烷催化燃烧的低温活性。当La质量分数为5%时,催化活性最高,甲烷50%转化率对应的温度较未加助剂时降低了70℃,且完全转化的温度低至480℃。     

CO2 capture performance of calcium-based sorbent doped with manganese salts during calcium looping cycle

The effects of manganese salts including Mn(NO₃)₂ and MnCO₃ on CO₂ capture performance of calcium-based sorbent during cyclic calcination/carbonation reactions were investigated. Mn(NO₃)₂ and MnCO₃ were added by wet impregnation method. The cyclic CO₂ capture capacities of Mn(NO₃)₂-doped CaCO₃, MnCO₃-doped CaCO₃ and original CaCO₃ were studied in a twin fixed-bed reactor and a thermo-gravimetric analyzer (TGA), respectively. The results show that the addition of manganese salts improves the cyclic carbonation conversions of CaCO₃ except the previous cycles. When the Mn/Ca molar ratios are 1/100 for Mn(NO₃)₂-doped CaCO₃ and 1.5/100 for MnCO₃-doped CaCO₃, the highest carbonation conversions are achieved respectively. The carbonation temperature of 700-720 °C is beneficial to CO₂ capture of Mn-doped CaCO₃. The residual carbonation conversions of Mn(NO₃)₂-doped and MnCO₃-doped CaCO₃ are 0.27 and 0.24 respectively after 100 cycles, compared with the conversion of 0.16 for original one after the same number of cycles. Compared with calcined original CaCO₃, better pore structure is kept for calcined Mn-doped CaCO₃ during calcium looping cycle. The pore volume of calcined MnCO₃-doped CaCO₃ is 2.4 times as high as that of calcined original CaCO₃ after 20 cycles. The pores of calcined MnCO₃-doped CaCO₃ in the pore size range of 27-142 nm are more abundant relative to clacined original one. That is why modification by manganese salts can improve cyclic CO₂ capture capacity of CaCO₃.     

Coal gasification with in situ CO2 capture by the synthetic CaO sorbent in a 1 kWth dual fluidised-bed reactor

Coal gasification with in situ CO₂ capture is believed to be able to produce highly concentrated H₂ with little or no CO₂ compared with the conventional process. This has been demonstrated by other researchers working on a single fluidised bed by continuously feeding the CaO sorbent. This work presents the results of coal gasification with in situ CO₂ capture by a synthetic CaO sorbent in a 1 kW_th dual fluidised-bed reactor at atmospheric pressure, which has not been reported in the literature. The synthetic CaO sorbent is cyclically used by going through multiple carbonation/calcination cycles during coal gasification.     

氨基磷酸树脂负载镧化合物杂化吸附剂的制备与性能

制备了水合氧化镧(LaH)并将水合氧化镧负载于氨基磷酸树脂(APAR)上制得杂化吸附剂LaH-APAR,用红外光谱(FT-IR)、热重(TGA)对LaH-APAR的结构和热学性能进行了测试,并研究了pH值、温度对LaH及LaH-APAR吸附氟离子性能的影响。结果表明,La3+与APAR以配位键结合,LaH-APAR吸附剂在300℃以下比较稳定,它与LaH吸附性能基本相同,受pH值影响不大,可以在较宽的pH范围内使用;在pH不变的情况下,LaH-APAR随着温度的升高吸附速率也相应提高,属于温度控制吸附,且为化学吸附。     

High capacity potassium-promoted hydrotalcite for CO2 capture in H2 production

This paper presents an experimental study for a newly modified K₂CO₃-promoted hydrotalcite material as a novel high capacity sorbent for in-situ CO₂ capture. The sorbent is employed in the sorption enhanced steam reforming process for an efficient H₂ production at low temperature (400–500 ^°C). A new set of adsorption data is reported for CO₂ adsorption over K-hydrotalcite at 400 °C. The equilibrium sorption data obtained from a column apparatus can be adequately described by a Freundlich isotherm. The sorbent shows fast adsorption rates and attains a relatively high sorption capacity of 0.95 mol/kg on the fresh sorbent. CO₂ desorption experiments are conducted to examine the effect of humidity content in the gas purge and the regeneration time on CO₂ desorption rates. A large portion of CO₂ is easily recovered in the first few minutes of a desorption cycle due to a fast desorption step, which is associated with a physi/chemisorption step on the monolayer surface of the fresh sorbent. The complete recovery of CO₂ was then achieved in a slower desorption step associated with a reversible chemisorption in a multi-layer surface of the sorbent. The sorbent shows a loss of 8% of its fresh capacity due to an irreversible chemisorption, however, it preserves a stable working capacity of about 0.89 mol/kg, suggesting a reversible chemisorption process. The sorbent also presents a good cyclic thermal stability in the temperature range of 400–500 °C.     

A novel catalyst–sorbent system for an efficient H2 production with in-situ CO2 capture

This paper presents an experimental investigation for an improved process of sorption-enhanced steam reforming of methane in an admixture fixed bed reactor. A highly active Rh/Ce_αZr_1−αO₂ catalyst and K₂CO₃-promoted hydrotalcite are utilized as novel catalyst/sorbent materials for an efficient H₂ production with in situ CO₂ capture at low temperature (450–500 °C). The process performance is demonstrated in response to temperature (400–500 °C), pressure (1.5–6.0 bar), and steam/carbon ratio (3–6). Thus, direct production of high H₂ purity and fuel conversion >99% is achieved with low level of carbon oxides impurities (<100 ppm). A maximum enhancement of 162% in CH₄ conversion is obtained at a temperature of 450 °C and a pressure of 6 bar using a steam/carbon molar ratio of 4. The high catalyst activity of Rh yields an enhanced CH₄ conversion using much lower catalyst/sorbent bed composition and much smaller reactor size than Ni-based sorption enhanced processes at low temperature. The cyclic stability of the process is demonstrated over a series of 30 sorption/desorption cycles. The sorbent exhibited a stable performance in terms of the CO₂ working sorption capacity and the corresponding CH₄ conversion obtained in the sorption enhanced process. The process showed a good thermal stability in the temperature range of 400–500 °C. The effects of the sorbent regeneration time and the purge stream humidity on the achieved CH₄ conversion are also studied. Using steam purge is beneficial for high degree of CO₂ recovery from the sorbent.     

化成制度对富锂锰基/硅碳体系电池产气及电化学性能影响

针对富锂锰基正极材料独特的首周充电特性, 设计了一种脉冲化成制度, 通过优化化成制度减少富锂锰基/硅碳体系电池化成过程中的产气量, 提高电池的循环电化学性能。通过GC-MS, SEM, XPS和电化学测试表明, 对比传统的化成制度, 采用脉冲化成制度后电池的产气量降低了37%左右。此外, 脉冲化成制度能在正、负极活性物质表面形成一层致密的膜结构, 同时可以缓解化成过程中电芯结构的应力, 稳定电极结构。脉冲化成制度还可以有效地节省化成时间, 将时间从102.6 h缩短至81.5 h。提升了长循环过程中的电化学稳定性, 500周次循环后, 容量保持率和中值电压均得到了显著的提升。     

燃煤炉预混-喷钙二段脱硫技术研究

文章指出煤燃烧高温脱硫3方面难点：（1）石灰石分解速率低于煤燃烧时硫析出速率；（2）脱硫产物在CaSO41200℃以上再分解；（3）CaO颗粒高温严重烧结，对此，提出二段脱硫工艺，即一部分添加剂与煤预混进行料层脱硫，另一部分喷入炉内捕捉烟气中硫，建立了10t/h链条炉二段脱硫示范装置，试验和运行结果表明锅炉除尘器前脱硫率达到70％以上，除尘器后，烟气经半干法处理可达到80－90％。     

活性炭吸附剂控制Hg排放的研究进展

活性炭吸附剂表现出较好的物理与化学性能,经催化处理得到的较高O、N含量的活性炭可提高其吸附能力。利用活性炭吸附剂控制烟气Hg排放,必须考虑SO2、NOx和Hg之间的相互影响。     

管道喷射烟气脱硫性能及其脱硫产物分析

利用扫描电镜，分析了不同消化制备条件下消石灰的结构特性，在管道喷射试验装置上进行烟气脱硫的试验研究。结果表明，加NaCl加压消化所生成消石灰的颗粒粒度最小，比表面积最大；加压、加NaCl的脱硫产物的颗粒粒径较大，表面极不规则，有大量纤维状细颗粒附着，具有较高的粗糙度，为扩散和化学反应的最佳匹配创造了有利条件。在试验工况下，添加NaCl加压消化喷浆脱硫的脱硫效率最高。在Ca/S比为2．5的情况下，脱硫效率可以达到70％。