基于热负荷自动调节的延迟焦化加热炉三点注汽量智能优化

针对国内某炼油厂延迟焦化加热炉三点注汽问题，采用热负荷自动调节的算法进行了研究。运用该模型方法，分析了三点注汽量对加热炉热负荷和炉管结焦系数的影响，发现三点注汽量的改变均会对热负荷和炉管结焦系数产生影响，主要表现为提高注汽量将会提高热负荷，同时降低结焦系数；第1点注汽量和第2点注汽量对热负荷和结焦系数的影响较强，第3点注汽量对热负荷和结焦系数的影响较弱。在实际操作中，加热炉中的结焦程度既不能太强也不能太弱，合适的结焦系数能够保证正常开工周期里炉管不结焦，也能保证瓦斯、注汽量等参数的合理分配。通过对热负荷、注汽量的智能分配，可得到不同原料油加工负荷条件下更加合理的装置运行方案。     

甲基氯硅烷精馏流程的模拟与优化

采用Aspen plus软件对工业七塔精馏过程进行全流程建模与模拟，优化工艺参数，研究了新的精馏节能工艺。对一甲塔等7个精馏塔采用双因素水平的灵敏度分析，考察了塔釜采出率、回流比、进料位置和塔顶压力对产品浓度和热负荷的影响，确定一甲塔最优的工艺参数：塔釜摩尔采出率为0.92，摩尔回流比为130，塔顶压力为0.18 MPa，总理论板数为400，在210块理论板位置进料。在此基础上，针对高能耗的脱高塔/脱低塔，模拟研究了双效精馏新工艺，新工艺可节省39.70%的年总成本；针对一甲塔模拟研究了热泵精馏新工艺，新工艺可降低41.42%的年总成本。     

含不凝性气体蒸汽浸没射流冷凝压力振荡实验研究

实验研究了不凝性气体（空气）含量、水温和蒸汽质量流速对蒸汽浸没射流冷凝压力振荡特性的影响，实验工况横跨冷凝振荡（CO）区和稳定冷凝（SC）区。结果表明：对于纯蒸汽射流，压力振荡主频随水温的升高而降低，振荡强度随水温的升高而升高；在CO区，振荡主频和振荡强度均随蒸汽质量流速的升高而升高；在SC区，振荡主频随蒸汽质量流速的升高而降低，振荡强度基本上不随蒸汽质量流速的变化而发生改变；对于含空气射流，随空气质量分数的增加，振荡主频总体呈下降趋势，振荡强度先迅速下降后小幅上升，在空气质量分数为0.05～0.1区域内振荡主频和振荡强度均存在极小值。     

Production of calcium nitrate crystals via membrane distillation crystallization using polyvinylidene fluoride/sorbitan trioleate membranes

As an alternative to the energy-intensive evaporation-crystallization method, membrane distillation crystallization (MDC) was applied for the first time to obtain calcium nitrate crystals from its aqueous solution. Calcium nitrate solution was obtained through the reaction between calcium carbonate and nitric acid, and then it was concentrated in the membrane distillation (MD) process and further crystallized. The MD step was conducted using hydrophobic polyvinylidene fluoride (PVDF)/sorbitan trioleate (Span 85) membranes. Span 85 was incorporated into the membrane structure in various concentrations to improve the hydrophobicity of membranes, and the resultant membranes were characterized via different methods. In addition, the resultant calcium nitrate crystals were characterized by X-ray fluorescence (XRF) spectroscopy. The MDC results showed that the optimum amount of Span 85 in the polymeric solution was 4%, which led to the formation of a membrane with higher porosity (67.2%) and water contact angle (95.7°) compared to the neat PVDF membrane. The mentioned membrane exhibited the highest water flux in the MD process compared to the other membranes, and also it produced the highest amount of crystals due to its remarkably better performance in the MD step in terms of feed concentration.     

A generalized CFD model for evaluating catalytic separation process in structured porous materials

A hybrid multiphase model is developed to simulate the simultaneous momentum, heat and mass transfer and heterogeneous catalyzed reaction in structured catalytic porous materials. The approach relies on the combination of the volume of fluid (VOF) and Eulerian–Eulerian models, and several plug-in field functions. The VOF method is used to capture the gas–liquid interface motion, and the Eulerian–Eulerian framework solves the temperature and chemical species concentration equations for each phase. The self-defined field functions utilize a single-domain approach to overcome convergence difficulty when applying the hybrid multiphase for a multi-domain problem. The method is then applied to investigate selective removal of specific species in multicomponent reactive evaporation process. The results show that the coupling of catalytic reaction and interface species mass transfer at the phase interface is conditional, and the coupling of catalytic reaction and momentum transfer across fluid–porous interface significantly affects the conversion rate of reactants. Based on the numerical results, a strategy is proposed for matching solid catalyst with operating condition in catalytic distillation application.     

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming in a tubular fixed-bed reactor

The effect of non-uniform temperature on the sorption-enhanced steam methane reforming (SE-SMR) in a tubular fixed-bed reactor with a constant wall temperature of 600 °C is investigated numerically by an experimentally verified unsteady two-dimensional model. The reactor uses Ni/Al₂O₃ as the reforming catalyst and CaO as the sorbent. The reaction of SMR is enhanced by removing the CO₂ through the reaction of CaO + CO₂ → CaCO₃ based on the Le Chatelier's principle. A non-uniform temperature distribution instead of a uniform temperature in the reactor appears due to the rapid endothermic reaction of SMR followed by an exothermic reaction of CO₂ sorption. For a small weight hourly space velocity (WHSV) of 0.67 h^?1 before the CO₂ breakthrough, both a low and a high temperature regions exist simultaneously in the catalyst/sorbent bed, and their sizes are enlarged and the temperature distribution is more non-uniform for a larger tube diameter (D). Both the CH₄ conversion and the H₂ molar fraction are slightly increased with the increase of D. Based on the parameters adopted in this work, the CH₄ conversion, the H₂ and CO molar fractions at D = 60 mm are 84.6%, 94.4%, and 0.63%, respectively. After CO₂ breakthrough, the reaction of SMR dominates, and the reactor performance is remarkably reduced due to low reactor temperature.For a higher value of WHSV (4.03 h^?1) before CO₂ breakthrough, both the reaction times for SMR and CO₂ sorption become much shorter. The size of low temperature region becomes larger, and the high temperature region inside the catalyst/sorbent bed doesn't exist for D ≥ 30 mm. The maximum temperature difference inside the catalyst/sorbent bed is greater than 67 °C. Both the CH₄ conversion and H₂ molar fraction are slightly decreased with the increase of D. However, this phenomenon is qualitatively opposite to that for small WHSV of 0.67 h^?1. The CH₄ conversion and H₂ molar fraction at D = 60 mm are 52.6% and 78.7%, respectively, which are much lower than those for WHSV = 0.67 h^?1.     

Ultracompact methane steam reforming reactor based on microwaves susceptible structured catalysts for distributed hydrogen production

Hydrogen is a potential green energy vector. Since the heating of the reforming processes commonly used for its production is obtained by burning hydrocarbons, it has a substantial CO₂ footprint. One of the most critical aspects in the methane steam reforming (MSR) reaction is the heat transfer to the catalytic volume, due to the high heat fluxes required to obtain high methane conversions. Consequently, the reactor has complex geometries, along with the heating medium being characterized by temperatures higher than 1000 °C; expensive construction materials and high reaction volumes are therefore needed, resulting in slow thermal transients. These aspects increase the costs (both operative and fixed) as well as cause a decrease in the whole process efficiency. The heat transfer limitations due to the endothermicity of methane steam reforming reaction could be effectively overcome by microwave (MW) heating. This heating technique, that depends only on the dielectric properties of the materials, can result in an efficient and faster method for transferring heat directly to the catalyst, thus generating the heat directly inside the catalytic volume. In this work, Ni-based catalysts, differing from each other by the Ni loading (7 and 15 wt% with respect to the washcoat) were prepared. The catalysts were characterized by means of several techniques and tested in the MW-assisted methane steam reforming reaction. Furthermore, the energy balance of the entire process was performed to calculate the energy efficiency, making a preliminary evaluation of its feasibility in distributed hydrogen production also possible. The results of the preliminary tests showed that the prepared structured catalysts are very susceptible to the MW radiation, and that in the presence of the MSR reaction, it is possible to make the system reach a temperature of 900 °C. In the same tests, the CH₄ conversion showed a good approach to the thermodynamic equilibrium values starting at temperatures of about 800 °C at a value of gas hourly space velocity (GHSV) of about 5000 h^?1. The energy efficiency of the lab-scale system, calculated as the ratio among the energy absorbed by the system and the energy supplied by the microwaves, was about 50%. Future studies will deal with the microwave reactor optimization, aiming at the increase of the energy efficiency of the system, as well as to obtain a higher CH₄ conversion at lower temperatures and increase the H₂ yield and selectivity.     

A comparative study on the performance of M (Rh,Ru, Ni)-promoted metallurgical waste driven catalysts for H2 production by glycerol steam reforming

A comprehensive study was conducted on the performance of M-promoted (M = 1%Ru, 1%Rh, 5%Ni) upgraded slag oxide metallurgical waste catalysts (M-UGSO) for hydrogen production by glycerol steam reforming (GSR). The results confirmed that the tendency of the incorporated metal to interact with Mg/Fe containing species within UGSO plays a key role in the surface availability of the corresponding metal, structural changes after reduction, and catalyst stability. Aside its best stability, 5% Ni-UGSO showed a performance (glycerol conversion to gaseous products of 100% and H₂ yield of 74%) comparable with 1% Rh-UGSO (100% and 78%, respectively) or even surpassing that of 1% Ru-UGSO (94% and 71%, respectively), as noble metal-based catalysts. Synergistic cooperation was achieved by incorporated metals (M) and Fe/Mg containing species within UGSO, resulting in enhanced glycerol and water activation. The weakest results of Ru-UGSO could be justified by lack of propensity for MgO–RuO₂ interaction on UGSO surface.