三元复合钙基材料CaO-Ca3Al2O6-MgO的合成及其CO2吸附性能

采用Al₂O₃和MgO同时掺杂改性的方法制备了CaO-Ca₃Al₂O₆-MgO复合钙基高温吸附CO₂材料。复合钙基材料孔隙发达,活性物相为CaO,惰性骨架物相为Ca₃Al₂O₆和MgO。Ca₃Al₂O₆/MgO质量比偏小的材料,表面微粒粒径较小。在10%（体积分数,下同）CO₂和90% N₂的混合气气氛下,采用热重分析仪测量了复合钙基材料吸附CO₂容量、碳化反应速率以及循环碳化（670℃）/煅烧（900℃）过程的稳定性。结果发现,复合钙基材料CaO-Ca₃Al₂O₆-MgO具有较好的吸附CO₂性能,提高Ca₃Al₂O₆/MgO质量比,合成材料的循环稳定性较好;降低Ca₃Al₂O₆/MgO质量比,合成材料的碳化反应速率加快,CaO转化率提高。最后,通过对不同循环次数下复合钙材料的比表面积、孔径分布、微观形貌、表面元素分布,晶相、晶粒大小进行研究分析,对合成材料的失活以及掺杂物质对烧结的抑制机理进行了讨论。     

H2S对铝基固态胺吸附剂吸附CO2性能的干扰机制

H₂S杂质对固态胺吸附剂吸附CO₂性能的干扰机制还缺少全面研究。以Al₂O₃为载体负载聚乙烯亚胺(PEI)制备铝基固态胺吸附剂(PEI@Al₂O₃),系统探究了H₂S对其CO₂吸附容量、吸附速率和循环吸附性能的影响规律。结果表明：H₂S与CO₂共存时,会相互抢占吸附剂上的胺基活性位点,从而发生竞争性吸附,但在模拟沼气条件(40%CO₂+59.5%CH₄+0.5%H₂S)下,H₂S的吸附竞争力远小于CO₂,H₂S吸附被抑制,且二者的最佳吸附温度不一致,在CO₂最佳吸附温度下,PEI@Al₂O₃的CO₂吸附容量和循环稳定性均不受H₂S干...     

钙循环捕集CO2后CaO的水合/脱水热化学储热性能

提出了基于CaO的钙循环捕集CO₂与CaO/Ca(OH)₂体系热化学储热耦合新工艺，在双固定床反应器上，研究了循环捕集CO₂中煅烧条件和碳酸化条件对CaO储热性能的影响，探究CaO循环捕集CO₂过程和循环水合/脱水储热过程的相互作用。研究表明，多次循环碳酸化/煅烧捕集CO₂后CaO仍具有较高储热性能，10次循环捕集CO₂后再经10次储热循环，CaO水合转化率可达0.66mol/mol。与苛刻煅烧条件相比，温和煅烧条件下经历多次循环捕集CO₂后CaO的储热性能更高。在碳酸化气氛中加入水蒸气对经历多次循环捕集CO₂后CaO储热性能的影响不大。钙循环捕集CO₂过程和水合/脱水循环储热过程能够相互促进。该工艺有望同时实现CO₂捕集和储热，具有一定的应用前景。     

钙基吸附剂循环吸附性能对增强式生物质气化制氢的影响研究

钙基吸附剂循环CO₂吸附性能对增强式生物质气化连续高效制氢起重要作用。采用将CaO颗粒分散在惰性载体中的方法并结合挤压成型技术制备了合成吸附剂颗粒。为了筛选循环吸附性能较好的吸附剂，在热重分析仪上进行了循环吸附性能测试。基于热重测试结果开展了吸附剂循环利用条件下的增强式生物质气化制氢实验。结果表明：添加惰性载体能延缓CaO烧结，提高吸附剂的循环吸附能力；挤压成型过程会破坏吸附剂原有孔隙结构，导致吸附剂颗粒吸附性能不同程度降低，其中CaSi75p、CaAl75p和CaY75p三种吸附剂循环性能较好；添加以上三种吸附剂颗粒均可显著提高生物质气化合成气中H₂浓度及产率，5次循环过程中气体成分和产率变化不大，表明吸附剂循环吸附能力和稳定性较好。     

掺杂Ce、Zr对CO2钙基吸附剂循环特性的影响

利用湿法混合-煅烧法将元素Ce、Zr掺杂到CO₂钙基吸附剂中,利用热重分析仪(TGA)研究了24种改性钙基吸附剂吸附CO₂的循环特性。研究发现:CeO₂散布在CaO晶粒之间可抑制晶粒融合,对吸附剂烧结有一定的阻碍作用;CeO₂可明显提高吸附剂在扩散控制阶段对CO₂的吸附速率,原因在于CeO₂中丰富的氧空位可促进CO₂以离子迁移的方式穿过表面产物层到达内部与CaO反应;吸附剂中CeO₂含量越高,稳定性越强;ZrO₂与CaO高温化合成具有高塔曼温度的CaZrO₃,均匀分散在CaO晶粒间,构成稳固的支撑骨架,有效抑制了吸附剂烧结。     

不同钙基吸附剂捕集CO2后的硫酸化反应特性研究

钙基吸附剂进行多次CO₂捕集后,碳酸化效率会大幅衰减,此时的吸附剂能否高效脱硫利用是值得重点关注的问题。鉴于此,筛选了高性能合成钙基吸附剂和天然石灰石吸附剂,通过热重分析仪分析对比其在多循环CO₂捕集后的碳酸化和硫酸化反应性能,采用微粒模型研究其硫酸化反应动力学特征。结果发现,高性能合成钙基吸附剂的碳酸化反应速率和CO₂吸附能力明显高于石灰石吸附剂。在长达500循环的CO₂捕集试验后,高性能合成钙基吸附剂的CO₂吸附能力比石灰石高10倍以上,其SO₂吸附能力相较于石灰石提升约40%。经历多次CO₂捕集反应循环后,2种吸附剂的硫酸化能力均有提升:其中,石灰石吸附剂的提升幅度更大,硫酸化转化率从26%提升到35%,而高性能合成钙基吸附剂的硫酸化转化率则从38%提升到43%。通过微粒模型计算发现,2种吸附剂的硫酸化反应均是与SO₂浓度相关的一级反应,多循环捕集CO₂反应后,石灰石吸附剂的硫酸化反应活化能下降接近30%,而高性能合成钙基吸附剂的硫酸化反应活化能只下降了5%。研究结果说明2种不同钙基吸附剂在进行循环CO₂捕集后,脱硫能力得到了不同程度的提高,且均可以较好地应用于SO₂的脱除。     

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。     

循环捕集CO2后煅烧石灰石的硫化特性

ZEC(zero emission coal)系统中,粗煤气进入碳酸化/重整炉前需先脱除H₂S,提出利用经过多次碳酸化/煅烧捕集CO₂循环的煅烧石灰石(CaO)脱除H₂S,并研究循环碳酸化/煅烧次数、硫化温度、H₂S浓度和微观结构对循环CaO硫化特性的影响。结果表明,多次循环碳酸化/煅烧捕集CO₂后CaO仍具有较高H₂S吸收性能。前20次循环,CaO硫化转化率随循环次数增加迅速降低;20次循环后,CaO硫化转化率缓慢下降。硫化120 min后,未循环CaO的硫化转化率接近100%,而经历1、20和100次循环后CaO的硫化转化率分别为94%、81%和74%。H₂S浓度对循环CaO硫化性能影响较大。硫化温度(800～1000℃)对循环CaO的硫化性能影响较小,最佳硫化温度为900℃。随循环次数增加,CaO颗粒发生高温烧结,导致比表面积降低和20～150 nm内孔隙减少,而这是与H₂S吸收密切相关的孔隙,导致CaO硫化转化率降低。     

钙基吸收剂循环吸收CO2技术的研究进展

阐述了对钙基吸收剂循环吸收CO₂技术的研究现状,包括各个可能因素对CaO碳酸化反应的影响,如吸收剂成分、颗粒特性、反应温度、反应时间、CO₂浓度等,并总结了各种CaO吸收CO₂反应动力学模型。同时对钙基吸收剂循环吸收CO₂技术未来的研究方向作了简述。     

烟气中水蒸气对钙基吸收剂碳酸化的影响特性

在循环煅烧/碳酸化反应系统上考察煅烧气氛和碳酸化气氛中水蒸气含量以及CO₂分压对钙基吸收剂成型颗粒碳酸化的影响,通过对钙基吸收剂微观结构分析(扫描电镜、氮吸附分析)以理解水蒸气影响碳酸化特性的机理。结果表明,煅烧气氛和碳酸化气氛中的水蒸气均可提高钙基吸收剂的碳酸化转化率,水蒸气含量分别为10%和5%时,吸收剂的碳酸化性能较好;水蒸气在碳酸化气氛中对高铝水泥改性吸收剂的改善作用较石灰石显著。煅烧气氛中的CO₂分压越高,烧结现象越严重,降低钙基吸收剂的捕集效率;碳酸化气氛CO₂分压提高,有利于提高钙基吸收剂的碳酸化转化率。烟气中水蒸气丰富了吸收剂的微观孔隙,使得吸收剂捕集CO₂性能得到改善。     

CO2 capture by double metal modified CaO-based sorbents from pyrolysis gases

High-temperature pyrolysis technology can effectively solve the problem of municipal solid waste pollution. However, the pyrolysis gas contains a large amount of CO₂, which would adversely affect the subsequent utilization. To address this problem, a novel method of co-precipitation modification with Ca, Mg and Zr metals was proposed to improve the CO₂ capture performance. X-ray diffraction (XRD) patterns and energy dispersive X-ray spectroscopy analysis showed that the two inert supports MgO and CaZrO₃ were uniformly distributed in the modified calcium-based sorbents. In addition, the XRD results indicated that CaZrO₃ was produced by the reaction of ZrO₂ and CaO at high temperatures. The effects of doping ratios, adsorption temperature, calcination temperature, CO₂ concentration and calcination atmosphere on the adsorption capacity and cycle stability of the modified calcium-based sorbent were studied. The modified calcium-based sorbent achieved the best CO₂ capture performance when the doping ratio was 10:1:1 with carbonation at 700 ℃ under 20% CO₂/80% N₂ atmosphere and calcination at 900 ℃ under 100% N₂ atmosphere. After ten cycles, the average carbonation conversion rate of Ca-10 sorbent was 72%. Finally, the modified calcium-based sorbents successfully reduced the CO₂ concentration of the pyrolysis gas from 37% to 5%.     

Performance characteristics of fluidized bed syngas methanation over Ni-Mg/Al2O3 catalyst

The performance characteristics of isothermal fluidized bed syngas methanation for substitute natural gas are investigated over a self-made Ni–Mg/Al2O3 catalyst. Via atmospheric methanation in a laboratory fluidized bed reactor it was clarified that the CO conversion varied in 5% when changing the space velocity in 40–120 L·g?1·h?1 but the conversion increased obviously by raising the superficial gas velocity from 4 to 12.4 cm·s?1. The temperature at 823 K is suitable for syngas methanation while obvious deposition of uneasy-oxidizing Cγoccurs on the catalyst at temperatures around 873 K. From a kinetic aspect, the lowest reaction temperature is suggested to be 750 K when the space velocity is 60 L·g?1·h?1. Raising the H2/CO ratio of the syngas increased proportionally the CO conversion and CH4 selectivity, showing that at enough high H2/CO ratios the active sites on the catalyst are sufficient for CO adsorption and in turn the reaction with H2 for forming CH4. Introducing CO2 into the syngas feed suppresses the water gas shift and Boudouard reactions and thus increased H2 consumption. The ratio of CO2/CO in syngas should be better below 0.52 because varying the ratio from 0.52 to 0.92 resulted in negligible increases in the H2 conversion and CH4 selectivity but decreased the CH4 yield. Introducing steam into the feed gas affected little the CO conversion but decreased the selectivity to CH4. The tested Ni–Mg/Al2O3 catalyst manifested good stability in structure and activity even in syngas containing water vapor.     

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。     

Preparation and Application of the Sol-Gel Combustion Synthesis-Made CaO/CaZrO3 Sorbent for Cyclic CO2 Capture Through the Severe Calcination Condition

abstract Calcium looping method has been considered as one of the efficient options to capture CO2 in the combustion flue gas. CaO-based sorbent is the basis for application of calcium looping and shou...     

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.     

化学链干重整联合制氢热力学分析及实验

提出了一种化学链甲烷干重整联合制氢工艺。该工艺由还原反应器、干重整反应器、蒸汽反应器和空气反应器组成，在实现制氢的同时获得可变H₂/CO比的合成气。借助ASPEN plus软件和小型流化床实验台，在等温条件下，温度900℃，采用Fe₂O₃/Al₂O₃载氧体，对该工艺进行热力学分析和实验验证。结果显示，当铁氧化物被还原至FeO/Fe时，干重整反应器内甲烷转化率可以达到98%，CO产率可以达到94%。干重整反应器中同时发生甲烷干重整和部分氧化反应，载氧体内部晶格氧可以有效降低积炭并提高合成气H₂/CO比。积炭发生于晶格氧消耗殆尽时。积炭进入蒸汽反应器，发生气化反应，降低氢气纯度。