甲烷空气部分氧化制合成气喷动床反应器的研究

On the basis of hydrodynamic and scaling-up studies, a pilot-plant-scale thermal spouted bed reactor (50 mm in ID and 1500 mm in height) was designed and fabricated by scaling-down cold simulators. It was tested for making syngas via catalytic partial oxidation (CPO) of methane by air. The effects of various operating conditions such as operating pressure and temperature, feed composition, and gas flowrate etc. on the CPO process were investigated. CH4 conversion of 92.20％ and selectivity of 92.3% and 83.30/0 to CO and H2, respectively, were achieved at the pressure of 2.1 MPa. It was found that when the spouted bed reactor was operated within the stable spouting flow regime, the temperature profiles along the bed axis were much more uniform than those operated within the fixed-bed regime. The CH4 conversion and syngas selectivity were found to be close to thermodynamic equilibrium limits. The results of the present investigation showed that spouted bed could be considered as a potential type of chemical reactor for the CPO process of methane.     

Enhancement of acetylene and ethylene yields in partially decoupled oxidation of ethane by changing the composition of heat carrier

In our previous work, a partially decoupled process(PDP) was proposed for efficient conversion of ethane to increase the ethylene yield and a new structural reactor called forward-impinging-back reactor(FIB)was proposed for scale-up. In this work, the influence of changing the composition and temperature of the heat carrier was investigated by simulations with detailed chemistry to further increase of the C₂(C₂ H₂+ C₂ H₄) yield in the PDP of...     

钙钛矿型混合导体透氧膜SrFe0.6Cu0.3Ti0.1O3－δ的制备与表征

Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ （SFCTO） was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5 mm thick SFCTO membrane was 0.35-0.96 ml·min ^-1·cm^-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2 kJ·mol^-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5 ml·min^-1·cm^- 2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.     

催化部分氧化甲烷制合成气的平衡热力学研究

The catalytic partial oxidation of methane to syngas (CO H2) has been simulated thermodynamically with the advanced process simulator PRO/Ⅱ. The influences of temperature,pressure,CH4/O2 ratio and steam addition in feed gas on the conversion of CH4 selectively to syngas and heat duty required were investigated, and their effects on carbon formation were also discussed. The simulation results were in good agreement with the literature data taken from a spouted bed reactor.     

钙钛矿型混合导体透氧膜SrFe0.6Cu0.3Ti0.1O3-δ的制备与表征

Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ (SFCTO) was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5mm thick SFCTO membrane was 0.35-0.96ml·min1·cm-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2kJ·mol-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5ml·min-1·cm2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.     

新型惰性膜反应器中丁烷氧化脱氢制丁二烯和丁烯

The oxidative dehydrogenation of butane to butadiene and butene was studied using a conventional fixed-bed ractor (FBR), inert membrane reactor (IMR) and mixed inert membrane reactor (MIMR). When IMR and MIMR were employed, a ceramic membrane modified by partially coating with glaze was used to distribute oxygen to a fixed-bed of 24-V-Mg-O catalyst. The oxygen partial pressure in the catalyst bed could be decreased. The effect of feeding modes and operation conditions were investigated. The selectivity of C4 dehydrogenation products (bntene and bntadiene) was found to be higher in IMR than in FBR. The feeding mode with 20% of air mixing with butane in MIMR was found to be more efficient than the feeding mode with all air permeating through ceramic membrane. The MIMR gave the most smooth temperature profile along the bed.     

用于PEMFC的丙烷自热重整制氢操作条件优化研究

Autothermal reforming （ATR） is one of the leading methods for hydrogen production from hydrocarbons. Liquefied petroleum gas, with propane as the main component, is a promising fuel for on-board hydrogen producing systems in fuel cell vehicles and for domestic fuel cell power generation devices. In this article, propane ATR process is studied and operation conditions are optimized with PRO/Ⅱ from SIMSCI for proton exchange membrane fuel cell application. In the ATR system including water gas shift and preferential oxidation, heat in the hot streams and cold streams is controlled to be in balance. Different operation conditions are studied and drawn in contour plots. The region for ATR reforming with the highest efficiency can thus be identified. One operation point was chosen with the following process parameters： feed temperature for the ATR reactor is 425℃, steam to carbon ratio S/C is 2.08, air stoichiometry is 0.256. Thermal efficiency for the integrated system is calculated to be as high as 84.0 % with 38.27 % H2 and 3.2μl·L^-1 CO in the product gas.     

Molar volume of eutectic solvents as a function of molar composition and temperature☆

The conventional Rackett model for predicting liquid molar volume has been modified to cater for the effect of molar composition of the Deep Eutectic Solvents (DES). The experimental molar volume data for a group of commonly used DES has been used for optimizing the improved model. The data involved different molar compositions of each DES. The validation of the new model was performed on another set of DESs. The average relative deviation of the model on the training and validation datasets was approximately 0.1%while the Rackett model gave a relative deviation of more than 1.6%. The modified model deals with variations in DES molar com-position and temperature in a more consistent way than the original Rackett model which exhibits monotonic performance degradation as temperature moves away from reference conditions. Having the composition of the DES as a model variable enhances the practical utilization of the predicting model in diverse design and process simulation applications.     

Leaching Gold Using Oxidation Products of Elemental Sulfur in Ca(OH)2 Solution Under Oxygen Pressure

A gold leaching process by using in situ oxidation products of added elemental sulfur in Ca(OH)2 solution was investigated. A gold concentrate containing 45 g/t Au was tested and 85%~87% of gold were leached. The leached gold depends mainly on the initial molar ratio of elemental sulfur to the hydroxyl ion, the consumption of oxygen and the reaction temperature. Adding some surfactants, such as lignosulfonic calcium, at lower concentration increased the leached Au but at higher concentration decreased it. Both of thermodynamic analysis and experimental results show that thiosulfate is the major complexing agent for gold in the process.     

Hydrolysis of Olive Oil with Immobilized Lipase in a Tapered Column Reactor

Lipase was immobilized in ion exchange resin and then used in the hydrolysis of olive oil to produce fatty acids and glycerol. The time course of hydrolysis of olive oil was investigated in a stirred tank reactor using both of the free and immobilized lipases to find the yield of activity of immobilized enzyme. Continuous hydrolysis of olive oil was also carried out in a tapered column reactor and a cylindrical column reactor with a bottom ID of 10 mm at different upward flow rates. It can be known from experimental results that the degree of hydrolysis of olive oil in the tapered column reactor is moderately better than that in the cylindrical column reactor, the pressure drop in the tapered column reactor is much smaller than that in the cylindrical column reactor.     

铁基载氧体对煤中汞释放行为的影响

采用Ontario-Hydro方法,在管式炉中考察了煤化学链燃烧/气化过程中Fe₄Al₆载氧体对煤中汞释放率、气态汞形态分布及汞在两反应器内释放行为的影响。结果表明,载氧体对煤中汞释放率具有显著的影响,在500~700℃,与无载氧体相比,化学链燃烧过程煤中汞释放率减少,化学链气化过程煤中汞释放率增大,而在900℃时,无论化学链燃烧过程还是化学链气化过程,煤中汞释放率均减小。Fe₄Al₆载氧体能够显著增加燃料反应器出口气态Hg²⁺的相对含量,其含量随温度的升高而逐渐升高。燃料反应器的温度也是影响煤中汞在两反应器中的分布以及空气反应器中不同价态汞百分含量的重要因素。此外,相同条件下不同煤种的汞释放率不同,主要与煤的组成不同有关。该研究对揭示载氧体对煤中汞迁移的影响机理以及煤化学链转化过程汞的控制提供了实验依据。     

10MWth高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

基于化学链气化技术依靠气固反应定向调控气化产物中H₂S和SO₂摩尔比为2的优势，将化学链气化与Claus工艺中的催化转化单元相结合，提出了高硫石油焦化学链气化制合成气和回收硫磺的新系统。针对系统核心单元，即化学链气化过程，基于Aspen Plus，开展热输入10 MW_th的高硫石油焦化学链气化过程模拟，以赤铁矿石为载氧体，水蒸气为气化介质，重点考察了氧碳比、气化温度对化学链气化过程及硫转化过程的影响。结果发现，氧碳比的增大导致合成气产率显著降低，但系统从需要外部提供能量逐渐转变为对外部放热，在氧碳比0.8669～0.9535区间内，系统可以达到热量自平衡。同时，气化温度的提高对合成气产率是有利的，在975℃时达到2.15 m³/kg，主要是由于CO体积分数随气化温度增加而增加。氧碳比和气化温度的提高都会导致H₂S浓度的降低和SO₂浓度的提高。并且研究了当H₂S和SO₂摩尔比为2的最佳工况时，氧碳比和气化温度为反相关，其中氧碳比为0.8669，气化温度为900℃时，冷煤气效率为64.09%。     

酸改性复合氧载体CaSO4-CaO的反应性能

将CaO添加到经不同酸改性后的CaSO₄氧载体中来制备CaSO₄-CaO复合氧载体。采用XRD、H₂-TPR、CO小型卧式管式炉开展恒温反应和循环实验,对氧载体进行表征和评价。主要研究了酸的种类对CO₂生成、气体硫化物的释放及复合氧载体循环反应性能的影响。结果表明：酸化的复合氧载体的氢气还原活性均明显优于未经改性过的CaSO₄,相比无酸化处理的CaSO₄氧载体,酸化后的CaSO₄-CaO复合氧载体,特别是HCl酸化,主要是提高了CaSO₄竞争还原副反应的选择性,导致主要气体硫化物SO₂释放显著增加,而COS释放略有降低。以CaCO₃煅烧得到的CaO与经HNO₃改性的CaSO₄进行机械混合制得的复合氧载体具有较好的反应活性,但是经过6次循环反应后,还原反应活性下降;循环反应中,气体硫化物主要来自于CaSO₄在还原阶段释放出的SO₂。     

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。     

化学链燃烧过程Fe2O3/Al2O3载氧体表面CH4反应：ReaxFF-MD模拟

借助ReaxFF-MD方法,对化学链燃烧过程Al₂O₃负载Fe₂O₃载氧体（Fe₂O₃/Al₂O₃）表面CH₄反应过程模拟,探究Al₂O₃惰性载体对Fe₂O₃-CH₄体系燃烧过程的调控机制。研究发现添加Al₂O₃惰性载体改变了化学链燃烧过程中Fe₂O₃载氧体反应性和Fe₂O₃/Al₂O₃-CH₄反应体系的热力学和动力学行为。主要是促进了Fe₂O₃载氧体表面CH₄氧化,并对CH₄反应过程、中间体、产物及其反应速率和放热量等均具有显著促进和调控作用。原因在于Al₂O₃惰性载体对Fe₂O₃活性相中晶格氧的活化作用促进了晶格氧的迁移-扩散-释放。添加惰性载体增强了Fe₂O₃载氧体在化学链燃烧过程晶格氧释放速率和释放量,有利于CH₄氧化燃烧向合成气的高效、清洁转化,强化了化学链燃烧过程,满足当前能源高效转化和碳减排目标。     

化学链燃烧过程Fe2O3/Al2O3载氧体表面CH4反应：ReaxFF-MD模拟

借助ReaxFF-MD方法,对化学链燃烧过程Al₂O₃负载Fe₂O₃载氧体（Fe₂O₃/Al₂O₃）表面CH₄反应过程模拟,探究Al₂O₃惰性载体对Fe₂O₃-CH₄体系燃烧过程的调控机制。研究发现添加Al₂O₃惰性载体改变了化学链燃烧过程中Fe₂O₃载氧体反应性和Fe₂O₃/Al₂O₃-CH₄反应体系的热力学和动力学行为。主要是促进了Fe₂O₃载氧体表面CH₄氧化,并对CH₄反应过程、中间体、产物及其反应速率和放热量等均具有显著促进和调控作用。原因在于Al₂O₃惰性载体对Fe₂O₃活性相中晶格氧的活化作用促进了晶格氧的迁移-扩散-释放。添加惰性载体增强了Fe₂O₃载氧体在化学链燃烧过程晶格氧释放速率和释放量,有利于CH₄氧化燃烧向合成气的高效、清洁转化,强化了化学链燃烧过程,满足当前能源高效转化和碳减排目标。     

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。     

废弃咖啡渣化学链气化反应特性

利用溶胶-凝胶法制备了以Fe₂O₃为活性组分,天然凹凸棒土(ATP)为惰性载体,KNO₃修饰的Fe4ATP6K1铁基复合载氧体。在高温流化床中考察了反应温度、水蒸气流量和O/C摩尔比对咖啡渣化学链气化过程的影响。结果表明,与以石英砂为床料的咖啡渣气化相比,以Fe4ATP6K1载氧体为床料的咖啡渣化学链气化对应的碳转化率由71.38%提高到86.25%。咖啡渣化学链气化的较优操作条件为:反应温度900℃、水蒸气量0.23 g·min^-1、O/C摩尔比1;在此操作条件下,合成气产量达到1.30 m³·kg^-1,氢气产量达到83.79 g·kg^-1,氢气的平均浓度达到52.75%。通过X射线衍射(XRD)、扫描电镜-能谱(SEM-EDS)对900℃反应前后的Fe4ATP6K1进行表征,发现Fe相、K相、Si相可以发生相互作用,K以KFeSi₃O₈的形式存在于载氧体中,并且K在反应过程中有少量流失。20次氧化/还原过程中,铁基复合载氧体Fe4ATP6K1表现出较好的循环性能,碳转化率和冷煤气效率均保持在75%以上,各气体的平均浓度较稳定。     

Reaction characteristics investigation of CeO2-enhanced CaSO4 oxygen carrier with lignite

Calcium sulfate (CaSO₄) has been verified as a promising oxygen carrier (OC) in the chemical looping combustion (CLC) for its high oxygen capacity, abundant reserve and low cost, but its low reactivity and deleterious sulfur species emission from the side reactions of CaSO₄ should be well considered for its wide application in CLC. In order to promote the reactivity of CaSO₄ and increase its potential to inhibit the gaseous sulfur emission, a CeO₂-enhanced CaSO₄ OC mixed OC of core-shell structure was prepared using the combined template synthesis method. Reaction characteristics of the prepared CaSO₄-CeO₂ mixed OC with a typical lignite was first conducted and systematically investigated, and an improved reactivity of the prepared CaSO₄-CeO₂ mixed OC was demonstrated than its single component CaSO₄ or CeO₂ due to the fast transfer and exchange of oxygen from the CaSO₄ substrate to coal via the doped CeO₂. Furthermore, the solid products formed from the mixed CaSO₄-CeO₂ OC with the selected coal were collected and analyzed. Especially, evolution and redistribution of the sulfur species of different forms were focused. At the latter reaction stage of YN reaction with the CaSO₄-CeO₂ mixed OC, the SO₂ emitted from the side reactions of CaSO₄ was greatly diminished and the doped CeO₂ was proven effective to directionally fix the SO₂ released to turn into different solid sulfur compounds, which were determined as Ce₂O₂S, Ce₂S₃ and Ce₂(SO₄)₃·5H₂O and formed through the different pathways. In addition, good regeneration of the reduced CaSO₄-CeO₂ mixed OC could be reached in spite of the unavoidable interaction between the included minerals in coal and the reduced mixed OC. Overall, the combined template method-made CaSO₄-CeO₂ mixed OC reported herein was not only endowed with enhanced reactivity for coal conversion, but also owned the potential to directionally fix the gaseous sulfur emission, which is quite applicable as OC for simultaneous decarbonatization and desulfurization in the real CLC process.     

钠修饰铁矿石载氧体的串行流化床煤化学链燃烧试验

利用1 kW_th串行流化床反应器对钠修饰铁矿石载氧体进行试验研究,考察燃料反应器温度对煤化学链催化燃烧特性的影响。结果表明,钠在820～920℃温度下显著促进了煤气化反应的进行,随着燃料反应器温度的提高,使用Na-铁矿石时燃料反应器出口CO₂浓度明显增大,CO浓度明显降低,在920℃时CO₂捕集效率和碳捕集效率分别达到78.60%和80.54%,而使用纯铁矿石时CO₂捕集效率和碳捕集效率仅为40.27%和45.65%。在高温950℃时Na-铁矿石活性下降,出现烧结和团聚现象,燃料反应器出现滞流态化现象,这可能是钠的化合物熔点较低和载氧体过度还原所导致的。XRD和SEM分析结果显示钠修饰铁矿石促使更多的Fe₂O₃被还原为Fe₃O₄。