带氧分布器的固定床反应器中甲烷-空气-水-二氧化碳制合成气

在带氧分布器的固定床反应器(FR-OD)中进行了Ni基催化剂上CH4-air-H2O-CO2三重整制合成气的研究。在分氧比为80%的条件下,考察了反应条件(压力、炉温、空速以及原料气CO2/CH4体积比)对催化剂床层温度分布和反应性能的影响,并进行了200h的寿命实验。结果表明,在压力为0.8MPa,出口温度为850℃,GHSV为13800h-1,原料气组成为V(CH4)/V(air)/V(H2O)/V(CO2)=1/2.4/0.8/0.4,分氧比为80%的条件下,催化剂床层入口处未出现热点,连续运行200h期间催化剂活性未见下降,以上结果初步表明采用氧分布器后的Ni基催化剂上可以较安全地进行甲烷三重整制合成气的操作。     

MgO改性Ni/γ-Al_2O_3催化剂用于甲烷重整制取合成气研究

采用分步浸渍法制备了不同MgO含量改性的γ-Al2O3载体Ni基催化剂,并利用XRD、H2-TPR对催化剂进行表征。在γ-Al2O3中添加适量的MgO,使得γ-Al2O3表面形成MgAl2O4尖晶石,改善催化剂的反应性能。考察了催化剂MgO添加量,反应温度和压力对甲烷蒸汽重整以及甲烷二氧化碳重整反应的影响,以及原料气CO2/CH4比对甲烷-二氧化碳-水蒸汽三重整制得的合成气的H2/CO比的影响。催化剂最佳的MgO添加量为10%质量分数。在甲烷-水蒸汽-二氧化碳混合重整反应中,当n(H2O)/n(CH4)为1时,n(CO2)/n(CH4)在0.4~0.5之间能得到n(H2)/n(CO)约为2的合成气。     

Tri-reformer with O2 side-stream distribution for syngas production

Methane tri-reforming combines steam reforming, dry reforming and partial oxidation of methane in a single reactor. The heat generated by the exothermic partial oxidation of methane can be used to supply the energy for the other two endothermic reactions (dry and steam reforming of methane). The thermoneutral condition allows the use of a tri-reformer with a simpler reactor structure since no external heat supply is necessary. Thermodynamic analysis of the thermoneutral reactor was performed using Gibbs free energy minimization approach. Conventional tri-reformers have heat and mass management problems. We developed a novel tri-reformer concept that utilizes proper distribution of O₂ gas to the reactor to address the problems. The optimization of the proposed reactor was performed with the objective function of minimizing total annual cost. Maintaining the peak temperatures by adjusting the O₂ flow rate at the distribution point along the reactor was shown to provide good load flexibility for the change in methane flow rate.     

反应条件对介孔Ni-CaO-ZrO_2催化剂上CH_4耦合重整反应性能的影响

利用并流沉淀法制备了介孔Ni-CaO-ZrO2催化剂,在该催化剂上考察了水蒸气重整(SRM)、CH4部分氧化(POM)和CO2重整(CDR)反应的不同耦合方式对CH4重整反应的影响,以及反应温度和气态空速对CH4三重整反应制合成气过程的影响。实验结果表明,与单纯的CDR反应相比,SRM-CDR耦合反应与CDR-POM耦合反应均具有明显的优势,前者侧重于产物分布的调节,而后者则对增强催化剂的活性和稳定性有重要意义。CH4三重整条件下催化剂失活的主要原因是复杂气氛条件下的晶相烧结;在反应温度为973 K、气态空速35.0 L/(h.g)、n(CH4)∶n(CO2)∶n(O2)∶n(H2O)=2∶1∶0.875∶0.50的条件下,催化剂上CH4转化率约为83%,产物合成气中n(H2)∶n(CO)约为2.00,且在反应10 h内催化剂活性稳定。     

新型可回收烟道气二氧化碳的能源系统的概念探讨

通过天然气和烟气三重整反应的原理分析,提出了新型的可回收二氧化碳生产二甲醚的多联产能源系统的概念性流程,从而为解决回收电站烟道气中的二氧化碳提供了新的思路。该能源系统中需要解决的关键性问题是开发耐二氧化硫的催化剂、高温除尘、多联产系统流程分析等。     

Tri-reforming of surrogate biogas over Ni/Mg/ceria–zirconia/alumina pellet catalysts

The performance of catalytic tri-reforming under industrially relevant situations (e.g., pellet catalysts, pressurized reactor) was investigated using surrogate biogas as the feedstock. Tri-reforming using Ni/Mg/Ce_0.6Zr_0.4O₂/Al₂O₃ pellet catalysts was studied in a bench scale fixed-bed reactor. The feed molar ratio for CH₄:CO₂:air was fixed as 1.0:0.70:0.95. The effects of temperature (800–860°C), pressure (1–6?bar), and H₂O/CH₄ molar feed ratio (0.23–0.65) were examined. Pressure has substantial impact on the reaction and transport rates and equilibrium conversions, making it a key variable. At 860°C, CO₂ conversion increased from 4 to 61% and H₂/CO molar ratio decreased from 2.0 to 1.1 as the pressure changed from 1 to 6?bar. CO₂ conversion and H₂/CO molar ratio were also influenced by the temperature and H₂O/CH₄ molar ratio. At 3?bar, CO₂ conversion varied between 4 and 43% and the H₂/CO molar ratio varied between 1.2 and 1.9 as the temperature changed from 800 to 860°C. At 3?bar and 860°C, CO₂ conversion decreased from 35 to 8% and H₂/CO molar ratio increased from 1.7 to 2.4 when the H₂O/CH₄ molar ratio was increased from 0.23 to 0.65. This work demonstrates that the tri-reforming technology is feasible for converting biogas under scaled-up conditions in a fixed-bed reactor.     

Optimal design of methane tri-reforming reactor to produce proper syngas for Fischer-Tropsch and methanol synthesis processes: A comparative analysis between different side-feeding strategies

Assessment of the recent research on the side-feeding strategy in the methane tri-reforming reactor, suggests that this procedure can be a beneficial method for producing syngas. In the present study, special attention is given to the length of methane tri-reformer due to its significant effect on the residence time of distributed components, reaction pathways, synthesis gas production, and reactor performance in side-feeding procedures. The optimal design of three types of membrane tri-reforming reactor, containing O-MTR, H-MTR, and C-MTR, in which O₂, H₂O, and CO₂ permeate as the distributed reactants through the micro-porous membrane, respectively, as well as the conventional tri-reformer (MTR) was carried out to produce proper syngas for methanol and gas-to-liquid (GTL) units. The results show that the O-MTR offers the most advantages in terms of CH₄ conversion (i.e., 99.98%), H₂ yield (i.e., 1.91), and catalyst lifetime due to no formation of hot spot temperature. Additionally, the CH₄ conversion and H₂ yield in the O-MTR increased by 5% compared to the MTR. However, the length of these reactor structures to produce appropriate syngas for Fischer-Tropsch and methanol synthesis processes was in the following order: MTR < C-MTR $?$ O-MTR < H-MTR.     

Use of a micro-porous membrane multi-tubular fixed-bed reactor for tri-reforming of methane to syngas: CO2, H2O or O2 side-feeding

A one-dimensional heterogeneous model for four configurations of a reactor, three micro-porous membrane reactors with O₂ (O-MMTR), CO₂ (C-MMTR) or H₂O (H-MMTR) side-feeding strategy and one traditional reactor (i.e., multi-tubular fixed-bed reactor (MTR)), was developed to explain tri-reforming of methane to produce syngas. Effect of various side-feeding strategies on reactor performance containing CH₄ and CO₂ conversion, H₂/CO ratio, and H₂ yield was investigated under the same condition and then described by chemical species and temperature profiles. It was found that use of side-feeding strategies could be feasible, beneficial, and flexible in terms of change in membrane thickness and shell-side pressure for syngas production with H₂/CO = 2 which is proper for methanol and Fischer-Tropsch process, and = 1.2 which is suitable for DME direct synthesis. However, the syngas produced by the MTR is only appropriate for the methanol and Fischer-Tropsch synthesis under the base case conditions. Also, the results show that the micro-porous membrane reactors have higher CO₂ conversion, based on the H₂/CO = 1.2; so these strategies are more environmentally friendly compared to the traditional reactor.     

Effect of ionic liquid in Ni/ZrO2 catalysts applied to syngas production by methane tri-reforming

This study investigates the influence of ionic liquid in morphology, acid-base properties, metal dispersion and performance of 5%Ni/ZrO₂ catalysts in the methane tri-reforming reaction. Zirconia was prepared by precipitation and the catalysts by wet impregnation. The ionic liquid modified the acid and basic character of the catalysts and positively influenced the methane tri-reforming reaction efficiency. The reaction was evaluated with synthetic biogas and with stoichiometric feed molar ratio (CH₄: CO₂: H₂O: O₂ = 1:0.5:0.5:0.1 and CH₄: CO₂: H₂O: O₂ = 1:0.33:0.33:0.16). The Ni/ZrO₂ prepared with ionic liquid exhibits promising catalytic activity and stability in methane tri-reforming at 800 °C in 4 h run, without coke formation. An increase in the reaction temperature results in an increase of hydrogen yield and the methane conversion, reaching ∼85% at 850 °C. The presented results demonstrate that the tri-reforming reaction could be used for production of syngas with H₂/CO ratio appropriate for methanol synthesis.     

O2, H2O or CO2 side-feeding policy in methane tri-reforming reactor: The role of influencing parameters

Methane tri-reforming is an efficient route to produce syngas. Distributing one component through a micro-porous membrane, namely side-feeding procedure, is an effective method for controlling reactions pathway and achieving the higher performance in membrane reactors. More recently, Alipour-Dehkordi and Khademi (2019) suggested a feasible and beneficial membrane multi-tubular reactor with O₂, H₂O or CO₂ side-feeding policy to describe the methane tri-reforming for producing a suitable syngas for the methanol and dimethyl ether direct synthesis processes. To complete the previous research, a theoretical study was presented to detect the role of effective parameters, including molar flow rate of feed components, membrane thickness, shell-side pressure, and inlet gas temperature on the H₂/CO ratio, CH₄ conversion, H₂ yield, and CO₂ conversion. Several results were observed, however one of the most attractive results was to achieve CO₂ conversion up to 40% in these configurations by controlling the influencing parameters (compared to CO₂ conversion in the conventional tri-reformer (i.e., 11.5%)); that would be favorable for the environment.