CO2气氛下准东煤化学链燃烧特性研究

我国准东煤储量丰富,钠含量高。以高钠准东煤为燃料,CO₂为气化介质,铁矿石为载氧体,基于鼓泡流化床反应器开展准东煤化学链燃烧特性的实验研究,考察了煤粒径、温度、流化风速和煤焦粒径对煤及煤焦化学链燃烧过程中可燃气体逃逸规律的影响;同时研究了煤中矿物质对煤焦气化过程的影响。结果表明,在基于鼓泡流化床实施的煤化学链燃烧过程中,由于煤颗粒和载氧体床料流化特性差异大,存在离析现象;离析影响煤化学链燃烧过程中挥发分和焦炭的转化;较高流化风速可显著增强载氧体与煤/焦炭颗粒的混合,有效改善离析对可燃气体转化的影响,降低可燃气体逃逸,并加快焦炭气化速率;煤焦中的矿物质能够维持煤焦较快的气化速率。     

以CO_2和H_2O为气化剂的煤焦气化模拟

基于整体煤气化联合循环和燃料电池发电技术,利用固体氧化物燃料电池产生的高温、高纯度CO2与H2O作为煤焦气化的气化剂,运用Aspen Plus模拟软件平台基于Gibbs自由能最小化方法对煤焦的H2O-CO2共气化反应进行了模拟计算。考察了O2流量、H2O流量、CO2流量、预热温度、操作压力、反应温度对气化反应合成气组成和煤气低位发热量的影响。结果显示:通过调节O2流量,得出O2的最佳流量为20 kg/h,此时反应温度和合成气低位热值处于最高值;分别增加水蒸气流量和CO2流量都使反应温度降低,且使反应活性降低导致合成气低位热值降低,所以合理控制水蒸气和CO2流量至关重要;降低操作压力会降低合成气的低位热值,但相对于物料流量改变,影响较小;CO2预热对煤气低位发热量的影响要小于O2的预热效果。     

Migration of sulfur in in-situ gasification chemical looping combustion of Beisu coal with iron-and copper-based oxygen carriers

Chemical looping combustion (CLC) is an energy conversion technology with high efficiency and inherent separation of CO2.The existence of sulfur in coal may affect the CO2 purity and the performance of oxygen carrier due to the interactions between sulfur contaminants and oxygen carrier.The migration of sulfur in Beisu coal during the in-situ gasification chemical looping combustion (iG-CLC) process using two oxygen carriers (iron ore and CuO/SiO2) was investigated respectively.The thermodynamic analysis results showed the formation of metal sulfides was thermodynamically favored at low temperatures and low oxygen excess coefficients,while they were obviously inhibited and the production of SO2 was signifi-cantly promoted with an increase in temperature and oxygen excess coefficient.Moreover,part of sulfur was captured and fixed in the forms of alkali/alkaline earth metal sulfate due to the high amount of alkali/alkaline earth metal oxides in the coal ash or/and oxygen carrier.The experimental results showed that the sulfur in coal mainly released in the form of SO2,and the sulfur conversion efficiency (Xs) in the reduction stage were 51.04％ and 48.24％ when using iron ore and CuO/SiO2 respectively.The existence of metal sulfides was observed in the reduced oxygen carriers.The values of Xs in the reoxidation process reached 3.80％ and 7.64％ when using iron ore and CuO/SiO2 respectively.The residue and accumulation of sulfur were also found on the surfaces of two oxygen carriers.     

Co-Fe2O3纳米载氧体作用下CO化学链燃烧富集CO2

制备了不同量级Co掺杂Fe₂O₃载氧体Co-Fe₂O₃,利用BET和TEM对载氧体结构进行表征。通过在不同温度下Co-Fe₂O₃与气体燃料CO的还原反应,考察Co-Fe₂O₃对CO化学链燃烧特性。结果表明,同一温度条件下,掺杂量越高,还原反应转化率越高;掺杂量不变的情况下,温度升高促使还原程度加深,缩短了载氧体完全还原转化的时间。根据TGA曲线进行了化学动力学分析,发现Co_0.2Fe还原反应过程在344.7～391.0℃和414.7～472.5℃温度范围反应动力学对应扩散控制的Jander方程模型,607.6～681.5℃温度范围对应二维扩散反应模型,并分别计算出相应模型的表观活化能和频率因子。结果可为化学链燃烧技术应用提供理论指导。     

Wastepaper gasification with CO2 or steam using catalysts of molten carbonates

In this paper, wastepaper gasification with carbon dioxide or steam has been investigated in the presence of molten carbonate catalysts. The reactions of wastepaper with steam or carbon dioxide have been compared. Hydrogen was the main product on the condition of steam used as reactant gas, but in the case where carbon dioxide was used, the amount of carbon monoxide generated from wastepaper gasification greatly increased via the Boudouard reaction. Different ratios of mixtures of lithium, sodium and potassium carbonates as the catalysts have been tested; the lithium carbonate was found to play a critical role. The reaction rate of carbon conversion was approximately first order for low carbon conversions. Both the rate constants and the activation energies have been calculated at different temperatures (923–1023 K). In additions, the flexibility of this technique was examined with three different types of wastepaper. The results suggest that this process can promote effective use of wastepaper and recovery of carbon dioxide. At 1023 K, a high value of cold gas efficiency of about 95% was acquired.     

基于CoFe2O4载氧体的生物质化学链气化反应特性

在热重分析仪和固定床反应器上对基于CoFe₂O₄载氧体的生物质化学链气化反应特性进行了研究，考察了载氧体与生物质质量比、水蒸气、反应温度对生物质化学链气化反应特性的影响，同时也对载氧体的循环反应性能进行了研究。通过XRD及SEM对新制备的和反应后的载氧体进行了表征。热重结果表明：CoFe₂O₄能够提供晶格氧，有效促进生物质气化。当CoFe₂O₄与生物质质量比为0.8，水蒸气体积分数为50%，温度为900 ℃时，气化反应效果最好。5次循环反应后，仍能获得较高品质的合成气，载氧体能够循环再生且未出现明显烧结团聚。     

Development of Ni catalysts for tar removal by steam gasification of biomass

Catalytic performance of Ni/CeO₂/Al₂O₃ catalysts prepared by a co-impregnation and a sequential impregnation method in steam gasification of real biomass (cedar wood) was investigated. Especially, Ni/CeO₂/Al₂O₃ catalysts prepared by the co-impregnation method exhibited higher performance than Ni/Al₂O₃ and Ni/CeO₂/Al₂O₃ prepared by the sequential impregnation method, and the catalysts gave lower yields of coke and tar, and higher yields of gaseous products. The Ni/CeO₂/Al₂O₃ catalysts were characterized by thermogravimetric analysis, temperature-programmed reduction with H₂, transmission electron microscopy and extended X-ray absorption fine structure, and the results suggested that the interaction between Ni and CeO₂ became stronger by the co-impregnation method than that by sequential method. Judging from both results of catalytic performance and catalyst characterization, it is found that the intimate interaction between Ni and CeO₂ can play very important role on the steam gasification of biomass.     

Theoretical study of reduction mechanism of Fe2O3 by H2 during chemical looping combustion

An atomic-level insight into the H2 adsorption and oxidation on the Fe2O3 surface during chemical-looping combustion was provided on the basis of density functional theory calculations in this study.The results indicated that H2 molecule most likely chemisorbs on the Fe2O3 surface in a dissociative mode.The decomposed H atoms then could adsorb on the Fe and O atoms or on the two neighboring O atoms of the surface.In particular,the H2 molecule adsorbed on an O top site could directly form H2O precursor on the O3-terminated surface.Further,the newly formed H-O bond was activated,and the H atom could migrate from one O site to another,consequently forming the H2O precursor.In the H2 oxidation process,the decomposition of H2 molecule was the rate-determining step for the O3-terminated surface with an activation energy of 1.53 eV.However,the formation of H2O was the rate-determining step for the Fe-terminated surface with an activation energy of 1.64 eV.The Fe-terminated surface is less energetically favorable for H2 oxidation than that the O3-terminated surface owing to the steric hindrance of Fe atom.These results provide a fundamental understanding about the reaction mechanism of Fe2O3 with H2,which is helpful for the rational design of Fe-based oxygen car-rier and the usage of green energy resource such as H2.     

Effectiveness of K2CO3 and Ni as catalysts in steam gasification

The catalytic steam gasification of 34 coals ranging from anthracite to peat was conducted in a thermobalance at 1023 K. When the difference in the reactivities of coals with and without catalyst is taken as a measure of the catalyst efficacy, that of K₂CO₃ was found to be extremely large and almost independent of coal rank. The effectiveness of Ni depends on the coal type to a great extent and it was very large for several low rank coals. SEM observation and EDAX analysis showed that the K₂CO₃ catalyst was finely dispersed over the char and such a good dispersion was common for all the coals examined. The dispersion state of Ni catalysts depends on the coal type, Ni catalysts were well dispersed over low rank coal chars which showed high reactivity in the Ni-catalysed gasification.     

Isotopic steam investigations of hematite (Fe2O3) for chemical looping combustion of methane

The effect of steam on the chemical looping combustion of methane over hematite (Fe₂O₃) is studied by the isotopic exchange method coupled with mass spectroscopy. Traditional steam was replaced with deuterium-oxide providing interesting mechanistic information not previously reported. The rapid kinetics of steam reforming were established before complete combustion reaction, and adsorption of deuterium into the iron structure was observed. Additionally, the presence of deuterium-oxide drastically reduced the combustion conversion of methane to carbon dioxide.     

CO2取代光气合成氨基甲酸酯研究进展

介绍了近几十年来利用CO2活化进行含氮化合物羰化反应合成氨基甲酸酯的研究进展。评述分析了各种金属盐催化、氨基甲酸盐阴离子作为亲核试剂、电解制备离子液体亲核试剂及超临界CO2条件下合成氨基甲酸酯反应过程的优点及不足,阐述了其反应机理,并对非光气法CO2合成氨基甲酸酯的前景做了展望。     

Mechanism analysis and simulation of methyl methacrylate production coupled chemical looping gasification system

Nowadays,the efficient and cleaner utilization of coal have attracted wide attention due to the rich coal and rare oil/gas resources structure in China.Coal chemical looping gasification (CCLG) is a promising coal utilization technology to achieve energy conservation and emission reduction targets for highly pure synthesis gas.As a downstream product of synthesis gas,methyl methacrylate (MMA),is widely used as raw material for synthesizing polymethyl methacrylate and resin products with excellent properties.So this paper proposes a novel system integrating MMA production and CCLG (CCLG-MMA) processes aim-ing at energy saving and low emission,in which the synthesis gas produced by CCLG and purified by dry methane reforming (DMR) reaction and Rectisol process reacts with ethylene for synthesizing MMA.Firstly,the reaction mechanism of CCLG is investigated by using Reactive force field (ReaxFF)MD simulation based on atomic models of char and oxygen carrier (Fe2O3) for obtaining optimum reac-tion temperature of fuel reactor (FR).Secondly,the steady-state simulation of CCLG-MMA system is car-ried out to verify the feasibility of MMA production.The amount of CO2 emitted by CCLG process and DMR reaction is 0.0028 (kg CO2)-1·(kg MMA)-1.The total energy consumption of the CCLG-MMA system is 45521 kJ·(kg MMA)-1,among which the consumption of MMA production part is 25293 kJ·(kg MMA)-1.The results show that the CCLG-MMA system meets CO2 emission standard and has lower energy con-sumption compared to conventional MMA production process.Finally,one control scheme is designed to verify the stability of CCLG-MMA system.The CCLG-MMA integration strategy aims to obtain highly pure MMA from multi-scale simulation perspectives,so this is an optimal design regarding all factors influencing cleaner MMA production.     

蒸汽活化钙基吸收剂联合脱碳脱硫特性

利用管式炉（TF）、蒸汽发生器和热重分析仪（TGA）研究了钙基吸收剂联合脱碳脱硫以及水合特性,并通过N2吸附实验对不同烧结程度以及水合前后样品的孔隙结构进行了测量。结果表明,无水合时,40次碳化循环后的样品碳化活性降至18%,但仍具有44%的硫化活性,比新鲜剂仅低4%,说明脱碳失效剂仍是良好的脱硫剂。碳循环失效剂经蒸汽活化后其碳化活性可提高至68%左右,且具有与新鲜剂类似的活性下降规律。每两次碳化循环后进行一次蒸汽活化,可使样品保持65%的平均转化率。蒸汽活化后吸收剂硫化率可提高至80%,远高于新鲜剂,由电镜扫描实验发现这是由于水合时颗粒产生了大的裂缝和破碎,提供了大量产物可自由生长的外表面积。不考虑颗粒磨损,利用钙基吸收剂先循环脱碳再蒸汽活化最后脱硫是一项联合脱除烟气中CO₂和SO₂的新方法。     

Hydrogen production through chemical looping using NiO/NiAl2O4 as oxygen carrier

A new autothermal route to produce hydrogen from natural gas via chemical looping technology was investigated. Tests were conducted in a micro-fixed bed reactor loaded with 200 mg of NiO/NiAl₂O₄ as oxygen carrier. Methane reacts with a nickel oxide in the absence of molecular oxygen at 800 °C for a period of time as high as 10 min. The NiO is subsequently contacted with a synthetic air stream (21% O₂ in argon) to reconstitute the surface and combust carbon deposited on the surface. Methane conversion nears completion but to minimize combustion of the hydrogen produced, the oxidation state of the carrier was maintained below 30% (where 100% represents a fully oxidized surface). Co-feeding water together with methane resulted in stable hydrogen production. Although the carbon deposition increased with time during the reduction cycle, the production rate of hydrogen remained virtually constant. A new concept is also presented where hydrogen is obtained from methane with inherent CO₂ capture in an energy neutral 3-reactors CFB process. This process combines a methane combustion step where oxygen is provided via an oxygen carrier, a steam methane reforming step catalyzed by the reduced oxygen carrier and an oxidizing step where the O-carrier is reconstituted to its original state.     

MnFeO3和MnFe2O4氧载体在稻草化学链气化中的应用

通过溶胶凝胶燃烧法合成了MnFeO₃和MnFe₂O₄两种锰铁复合氧载体。通过原位红外实验探究其与稻草的化学链气化过程,发现其加速了稻草热解产物的析出,并通过气化反应促进CO和CO₂的产生,提高了碳转化率。固定床实验结果表明MnFeO₃和MnFe₂O₄在与水蒸气耦合气化的条件下大幅提高了合成气中H₂和CO的产率,气化效率分别达到94.49%和92.76%。并通过XRD分析,发现MnFeO₃和MnFe₂O₄在气化过程主要还原为(Fe,Mn)O,且在氧化反应后能回到初始晶相。在固定床的10次循环实验以及SEM的结果表明,MnFeO₃在循环反应中逐渐形成的颗粒状多孔结构有利于维持稳定的气化效率,而MnFe₂O₄由于团聚和烧结作用形成了块状结构,气化效率呈缓慢下降趋势。因此,认为MnFeO₃在生物质化学链气化中具有更好的适用性。     

Comparison of nickel- and iron-based oxygen carriers in chemical looping combustion for CO2 capture in power generation

In chemical looping combustion (CLC), a solid oxygen carrier circulates between two fluidised bed reactors and transports oxygen from the combustion air to the fuel; thus, the fuel is not mixed with air and an inherent CO₂ separation occurs. In this paper, CLC is integrated in a natural gas fired combined cycle (NGCC). In this system, nickel- and iron-based oxygen carriers are compared regarding the system's electrical and exergy efficiencies. Furthermore, the feasibility of CLC in two interconnected pressurised fluidised bed reactors (IPFBR) is studied for both oxygen carriers. The hypothetical layout plus dimensions of the IPFBR is presented for a capacity of 800 MW input of natural gas. Finally, top-firing is proposed as an option to overcome the apparent limitation in operating temperature of the reactor equipment and/or the oxygen carriers. The results indicate that there is no significant difference in the system's efficiency if both oxygen carriers could operate at the same temperature. However, CLC seems easier to be technically realised in an IPFBR with a nickel-based oxygen carrier.     

Hydrogen enrichment of fuels using a novel miniaturised chemical looping steam reformer

Experiments were conducted on the Fe₃O₄/FeO metal oxide system under pure methane and pure steam environments in a thermogravimetric analyser (TGA) and a prototype-miniaturised micro-reactor. Experimental results show that during a typical fuel oxidation step the concentration of methane in the product gas stream gradually decreases while Fe₃O₄ is being reduced to FeO. However, on or about a fractional conversion of 60% the slope of the CH₄ plot sharply increases due to catalytic effects of FeO on methane decomposition. Similarly, the H₂ plot associated with steam reforming step picks up rapidly and reaches a maximum of 98% at a fractional conversion of 30%. The conversion times of steam and fuel in the micro-reactor were generally shorter than conversion times obtained in the TGA system. The experimental results provided two vital pieces of information: (i) the chemical looping steam reforming cycle is technically viable, and (ii) the performance of the process at micro-scales needs to be further understood before high throughput miniaturised reformers could be designed and built.     

Synthesis gas production using steam hydrogasification and steam reforming

Experimental work has been carried out on the mixed reforming reaction, i.e., simultaneous steam and CO₂ reforming of methane under a wide range of feed compositions and four different reaction temperatures from 700 °C to 850 °C using a commercial steam reforming catalyst. The experiments were conducted for a CO₂/CH₄ ratio from 0 to 2 and a steam to methane ratio from 3 to 5. The effect of CO₂/CH₄ ratio on the exit H₂/CO ratio and the conversions of the reactants indicate that the dry reforming reaction is dominant under increased carbon dioxide in the feed. Steam reforming of typical steam hydrogasification product gas consisting of CO, H₂ and CO₂ in addition to steam and methane has also been investigated. The H₂/CO ratio of the product synthesis gas varies from 4.3 to 3.7 and from 4.8 to 4.1 depending on the feed composition and reaction temperature. The CO/CO₂ ratios of the synthesis gas varied from 1.9 to 2.9 and 2.0 to 3.3. The results are compared with simulation results obtained through the Aspen Plus process simulation tool. The results demonstrate that a coupled steam hydrogasification and reforming process can generate a synthesis gas with a flexible H₂/CO ratio from carbon-containing feedstocks.