Robust optimal operation of continuous catalytic reforming process under feedstock uncertainty

The continuous catalytic regenerative (CCR) reforming process is one of the most significant sources of hydrogen production in the petroleum refining process. However, the fluctuations in feedstock composition and flow rate could significantly affect both product distribution and energy consumption. In this study, a robust deviation criterion based multi-objective optimization approach is proposed to perform the optimal operation of CCR reformer under feedstock uncertainty, with simultaneous maximization of product yields and minimization of energy consumption. Minimax approach is adopted to handle these uncertain objectives, and the Latin hypercube sampling method is then used to calculate these robust deviation criteria. Multi-objective surrogate-based optimization methods are next introduced to effectively solve the robust operational problem with high computational cost. The level diagram method is finally utilized to assist in multi-criteria decision-making. Two robust operational optimization problems with different objectives are solved to demonstrate the effectiveness of the proposed method for robust optimal operation of the CCR reforming process under feedstock uncertainty.     

Ternary Blends of Renewable Fast Pyrolysis Bio-Oil,Advanced Bioethanol,and Marine Gasoil as Potential Marine Biofuel

An alternative for reducing emissions from marine fuel is to blend bio-oil from lignocellulose non-edible feedstocks to diesel fossil fuels. Phase diagrams of the ternary systems were built to represent the transition from heterogeneous regions to homogeneous regions. Four homogeneous blends of bio-oil of eucalyptus-bioethanol-marine gasoil were experimentally characterized with respect to the most important fuel parameters for marine engines: water content, flash point, low heating value, viscosity, and acidity. Blends with closer properties to marine gasoil replacement, lower costs, and environmental impacts should be tested for large engines.     

NNI-1型C_5/C_6烷烃异构化催化剂长周期运行分析及建议

中国石化海南炼油化工有限公司0.2 Mt/a C5/C6烷烃异构化装置以连续重整装置的拔头油为原料,使用NNI-1催化剂,采用一次通过流程,不设脱异戊烷塔和稳定塔,经设在连续重整装置内的脱丁烷塔稳定处理后作为汽油调合组分。该装置于2006年9月开工投产,截至2015年3月已连续运行3个周期。长周期运行分析结果表明:前两个周期中NNI-1催化剂具有较高的异构化活性及选择性,C5异构化率为60%左右,C6异构化率为80%左右,C6选择性为15%左右,产品辛烷值基本达到技术指标要求(RON≥78);而在第三周期运行中,催化剂积炭增加等原因导致其异构化活性及选择性降低,异构化产品辛烷值提升能力呈现逐步衰减的趋势,提高反应苛刻度已不能弥补催化剂活性下降造成的产品辛烷值降低。为保证装置长周期运行,建议择机停工对催化剂进行再生,或是直接换用与装置原料性质匹配的异构化催化剂。     

Dispersive optical constants and electrical properties of nanocrystalline CuInS2 thin films prepared by chemical spray pyrolysis

Nanocrystalline CuInS₂ thin films were deposited on borosilicate glass substrates via chemical spray pyrolysis method. The structural, morphological, optical, and electrical properties were studied as a function of increasing annealing temperature from 250 to 350 ̊C. XRD analysis showed mixed phases at lower temperatures with the preferred orientation shifting towards the (112) chalcopyrite CuInS₂ plane at higher substrate temperature. The crystallite size increased slightly between 13 and 18 nm with increase in annealing temperature. The optical band gap was determined on basis of Tauc extrapolation method and the Wemple–Di-Domenico single oscillator model. Possible structural and quantum confinement effect may have resulted in relatively larger band gaps of 1.67–2.04 eV, relative to the bulk value of 1.5 eV. The presence of Cu_xS in the as-deposited and wurtzite peaks after annealing at 350 ^̊C play a role in influencing the optical and electrical properties of CuInS₂ thin films.     

A novel combination of precursor pyrolysis assisted sintering and rapid sintering for construction of multi-composition coatings to improve ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites

A double-layer coating composed of MoSi₂–SiO₂–SiC/ZrB₂–MoSi₂–SiC was designed and successfully constructed by a novel combination of precursor pyrolysis assisted sintering and rapid sintering to improve the ablation resistance of SiOC ceramic modified carbon fiber needled felt preform composites (CSs). The ZrB₂–MoSi₂–SiC inner layer coating was in relatively uniform distribution in the zone of 0–3 mm from the surface of CSs through the slurry/precursor infiltration in vacuum and SiOC precursor pyrolysis assisted sintering, which played a predominant role in improving oxidation and ablation resistance and maintaining the morphology of CSs. The MoSi₂–SiO₂–SiC outer layer coating was prepared by the spray and rapid sintering to further protect CSs from high-temperature oxidation. The ablation resistance of CSs coated with double-layer coating was evaluated by an oxygen-acetylene ablation test under the temperature of 1600–1800 °C with different ablation time of 1000 and 1500 s. The results revealed that the mass recession rates increased with the rise of ablation temperature and extension of ablation time, ranging from 0.47 g/(m²·s) to 0.98 g/(m²·s) at 1600–1800 °C for 1000 s and from 0.72 g/(m²·s) to 0.86 g/(m²·s) for 1000–1500 s at 1700 °C, while the linear recession rates showed negative values at 1700 °C due to the formation of oxides, such as SiO₂ and ZrO₂. The ablation mechanism of the double-layer coating was analyzed and found that a SiO₂–ZrO₂–Mo_4.8Si₃C_0.6 oxidation protection barrier would be formed during the ablation process to prevent the oxygen diffusion into the interior CSs, and this study provided a novel and effective way to fabricate high-temperature oxidation protective and ablation resistant coating.     

渣油催化临氢热转化钼铁双金属催化剂的研究

Replacement of precious single metal catalysts with cost-effective, highly-dispersed composite catalysts for catalytic hydrothermal conversion of residue holds tremendous promise for the residue upgrading technologies. Organic metals were added to the feed as the oil-soluble precursors, and transformed into the catalytic active phases in this work. Physical properties and structures of the composite catalysts had been investigated by X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscope and transmission electron microscopy. The composite catalysts were found to be highly efficient in the catalytic hydrothermal conversion of both model compound and residue. Increased metal dispersion and synergistic effects of two metals played indispensable roles in such catalytic system. Results showed that under the test conditions in the article, the catalyst had the best catalytic performance when the mass ratio of molybdenum to iron was 1.5.     

生物质源多孔碳制备及其对废水中药物吸附研究进展

城市现代化与工业化的快速发展给环境造成的污染日趋严重，尤其以水体污染最为明显。近年来，工业废水中药物的含量逐年上升，污染程度已经不容忽视。因此，开发新型多孔材料用于废水中药物分子的吸附分离，已经成为了当前的研究热点。综述了近年来生物质源多孔碳（生物炭）在废水中污染物吸附分离方面的研究，首先简单介绍了废水中污染物的治理方法，在此基础上重点探讨了生物炭的制备与修饰，并结合碳材料表面化学性质与孔道结构，总结并展望了生物炭对药物的吸附性能。     

β-环糊精修饰Ni/SFCC强化C9石油树脂催化加氢性能

以废弃的流化催化裂化催化剂（简称SFCC）为载体、β-环糊精为金属络合剂、硝酸镍为镍源，采用湿法浸渍法制备β-环糊精修饰的Ni/SFCC催化剂（简称Ni/SFCC-CD催化剂），考察其对C9石油树脂的催化加氢性能。通过BET比表面积测试、H2程序升温还原、X射线光电子能谱等手段对催化剂的物相结构进行表征，研究β-环糊精的作用机理及其对催化剂加氢性能的影响。研究结果表明：在反应温度为260 ℃、反应压力为7 MPa、反应时间为2.0 h的最优条件下，采用Ni/SFCC-CD催化C9石油树脂加氢，可制得溴值为1.45 gBr/（100 g）、色号（加纳德）小于1的水白色氢化C9石油树脂，催化剂循环使用4次后仍保持良好活性；β-环糊精的作用机理是：β-环糊精与硝酸镍产生络合作用，抑制硝酸镍的分解、控制NiO的结晶过程和增强活性组分Ni与载体之间的相互作用力，从而提高了Ni/SFCC-CD的催化活性和稳定性。     

Investigation of flame spray synthesized La1-xSrxCoO3 perovskites with promotional catalytic performances on CO oxidation

To enhance the activity of catalysts for CO removal, the perovskite-type catalysts La_1-xSr_xCoO₃ (x = 0, 0.2, 0.4, 0.6, and 0.8) with different Sr²⁺ doping amount were synthesized by flame spray synthesis (FSS) method. The perovskite-type catalyst synthesized by FSS has a much larger specific surface area (SSA) than that prepared by other conventional methods. The SSA of catalyst increases with the increase of Sr²⁺ doping amount and the SSA of La_0.2Sr_0.8CoO₃ reaches 31.65 m²/g. Compared with other conventional methods, FSS method significantly improves the activity of catalyst and makes it close to the performances of catalysts with surface modification. The substitution of La³⁺ by Sr²⁺ promotes the generation of secondary phase Co₃O₄ and SrCO₃. The catalytic activity of La_1-xSr_xCoO₃ increases with the addition of Sr²⁺, which results from the increasing active sites and oxygen vacancies. Interestingly, La_0.4Sr_0.6CoO₃ performs the highest activity for CO oxidation and the CO conversion reaches 50% at 148.6 °C and 90% at 165.9 °C. The oxidation of CO over La_1-xSr_xCoO₃ catalyst may follow a combination of MvK and L-H mechanisms according to the experimental results of H₂-TPR. Moreover, the catalyst exhibits good catalytic activity in consecutive oxidation cycles. In consecutive oxidation experiments with La_0.4Sr_0.6CoO₃, the CO conversion reaches 50% at 168.8 °C and 90% at 197.8 °C in the eighth oxidation cycle. These results prove that FSS method can further improve the activity of catalysts and is suitable for the preparation of efficient catalysts.     

Kinetic,thermodynamic parameters and in vitro digestion of tannase from Aspergillus tamarii URM 7115

Tannase is an enzyme used in various industries and produced by a large number of microorganisms. The aim of this study was to evaluate tannase production to determine the biochemical, kinetic, and thermodynamic properties and to simulate tannase in vitro digestion. The tannase-producing fungal strain was isolated from “jamun” leaves and identified as Aspergillus tamarii. Temperature at 26°C for 67?h was the best combination for maximum tannase activity (6.35-fold; initial activity in Plackett–Burman design—15.53?U/mL and average final activity in Doehlert design—98.68?U/mL). The crude extract of tannase was optimally active at 40°C, pH 5.5 and 6.5. Moreover, tannase was stimulated by Na⁺, Ca²⁺, Mg²⁺, and Mn²⁺. The half-life at 40°C lasted 247.55?min. The free energy of Gibbs, enthalpy, and entropy, at 40°C, was 81.47, 16.85, and ?0.21?kJ/mol?·?K, respectively. After total digestion, 123.95% of the original activity was retained. Results suggested that tannase from A. tamarii URM 7115 is an enzyme of interest for industrial applications, such as gallic acid production, additive for feed industry, and for beverage manufacturing, due to its catalytic and thermodynamic properties.