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.     

煤基高能量密度燃料的合成及表征

高能量密度燃料是为新型高性能飞行器提供动力保障的关键,其合成及应用研究具有重要的前瞻性和重大战略意义。煤炭是我国的主体能源和重要原料,通过煤直接转化获取的煤基油,充分保留了煤中特有的环状分子化学结构,具有良好的热安定性和较高的能量密度,被认为是高超音速飞行器的优选燃料。以煤直接液化工艺生产的煤液化石脑油馏分为起始原料,通过富集轻质芳烃、化学合成、催化加氢稳定和产物分离提纯等方法制备煤基高能量密度燃料,并对其产物进行分子结构表征和性能评价。结果表明,煤直接液化生产的石脑油馏分是一种优异的催化重整原料,经催化重整富集轻质芳烃后,其轻质芳烃质量分数高达71.05%。Diels-Alder化学合成主产物是由多个封闭环平面组成且具有空间立体构型的二环或三环烃类物质,质量分数为46.18%,因分子内存在较大的张力能,结构紧凑,其拥有更大的密度和体积热值。煤基高能量密度燃料的密度和体积热值分别为0.8990 g/cm3与38.06 MJ/L,均大大超过现行的国内石油基喷气燃料(RP-3和RP-6)、煤基大比重喷气燃料、美国和俄罗斯军用标准。与单一纯物质合成高能量密度燃料(JP-10和T-10)比较,其密度与体积热值偏小。究其原因主要是轻质芳烃的富集度仅为71.05%,需进一步提高其轻质芳烃质量分数。另外,制备的煤基高能量密度燃料种类复杂,其主产物质量分数仅46.18%,下一步可重点调控合成产物的分子构型和纯化分离。     

Advanced Understanding of the Electron Transfer Pathway of Cytochrome P450s

Cytochrome P450s are heme-thiolate enzymes that participate in carbon source assimilation, natural compound biosynthesis and xenobiotic metabolism in all kingdoms of life. P450s can catalyze various reactions by using a wide range of organic compounds, thus exhibiting great potential in biotechnological applications. The catalytic reactions of P450s are driven by electron equivalents that are sourced from pyridine nucleotides and delivered by cognate or matching redox partners (RPs). The electron transfer (ET) route from RPs to P450s involves one or more redox center-containing domains. As the rate of ET is one of the main determinants of P450 efficacy, an in-depth understanding of the P450 ET pathway should increase our knowledge of these important enzymes and benefit their further applications. Here, the various P450 RP systems along with current understanding of their ET routes will be reviewed. Notably, state-of-the-art structural studies of the two main types of self-sufficient P450 will also be summarized.     

催化共振光散射法测定空气中痕量甲醛的研究

吖啶橙分子聚集体微粒可在513nm波长处出现最大的共振光散射强度(RLS)。在稀硫酸介质中,甲醛能催化溴酸钾氧化吖啶橙的反应,促使其RLS强度减弱。在最佳实验条件下,甲醛质量浓度ρ在0.020～0.25μg/mL的范围内与△I值呈良好的线性关系,线性回归方程为△I=1113.99ρ+49.23,线性相关系数r为0.9986。本法与国标法进行对照,在置信度等于95%时,用Cochran检验,两种方法间不存在显著性差异,方法操作简单、灵敏度高,用于室内外空气中甲醛测定,结果满意。     

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.     

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.     

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。     

核壳结构Fe3O4纳米催化剂催化降解酸性废水的研究

利用静电自组装法,将羧甲基纤维素(CMC)组装到Fe3O4上得到Fe3O4@CMC,再通过自由基聚合反应将丙烯酸(AA)和丙烯酰胺(AM)接枝交联到Fe3O4@CMC上,制备出F e3O4@CMC-g-p(AA-co-AM)(Fe3O4@hydrogel)微球。利用TEM、XRD、FTIR、TGA、XPS、BET等技术对Fe3O4hydrogel微球进行了表征,并将其作为催化剂应用于类芬顿高级氧化反应中催化降解酸性红73。结果表明:Fe3O4@hydrogel仍为反尖晶石型结构,共聚物CMC-g-p(AA-c o-AM)成功包覆在Fe3O4表面,且含量为17.7%,复合微球平均粒径在10n m左右,饱和磁化强度为44.8 emu/g,BET表面积为73.5m2/g,平均孔直径为8.3nm,为介孔结构。Fe3O4@hydrogel微球对酸性染料废水有良好的催化降解性能,通过调节芬顿反应体系中初始pH值、催化剂用量以及H2O2浓度,得到反应最适条件为pH3.5、H2O210mmol/l、催化剂用量200mg/l。在此条件下3h内能达到对酸性红7399.83%以上的降解。     

水热法制备Sr_2FeNiO_6催化剂及其催化性能研究

采用水热法制备双钙钛矿催化剂Sr_2FeNiO_6,考察不同浓度KOH溶液(4 mol·L~(-1)、6 mol·L~(-1)、8 mol·L~(-1)、10 mol·L~(-1)、12 mol·L~(-1)、14 mol·L~(-1))对催化剂性能的影响,利用X射线衍射、比表面积测定、程序升温还原和扫描电镜等对样品进行性能表征,并以催化甲烷燃烧为目标,考察催化剂催化性能。结果表明,矿化剂KOH浓度对样品性能影响较大,当浓度为10 mol·L~(-1)时,起燃温度最低,T_(10%)为430℃;浓度为8 mol·L~(-1)时,样品比表面积最大,为19.0 m~2·g~(-1),完全燃烧温度最低,T_(90%)为610℃。     

阴离子种类及浓度对RCT催化剂催化湿式氧化处理头孢废水的影响

采用催化湿式氧化法处理头孢类废水,以RCT为催化剂,考察了阴离子对污染物降解效果的影响。结果表明,不加阴离子时,RCT催化剂能有效催化污染物的降解,TOC和TN去除率分别为78.3%和85.9%;投加不同阴离子对反应的影响不同。RCT催化剂可将头孢氨苄废水中的有机N转化为$N_{2}$,少部分以$NO_{3}-N$形式存在;阴离子F^-、Cl^-、Br^-、I-及$S^{2-}_{4}$对TN的降解影响不大,而$N^{-}_{3}$、$P^{3-}_4$、$CO^{2-}_{3}$、$Si^{2-}_{3}$及$B_{4}O^{2-}_{7}$则明显抑制了对TN的去除。投加F^-、Cl^-、Br^-、I-及$NO^{-}_{3}$对TOC的降解有促进作用(I^-> F^-> Cl^-> Br^-> $NO^{-}_{3}$),TOC的降解率提高了3.1~18.6个百分点;而投加$S^{2-}_{4}$、P,$P^{3-}_4$、$CO^{2-}_{3}$、$SiO^{2-}_{3}$及$B_{4}O^{2-}_{7}$对TOC的降解有抑制作用($SiO^{2-}_{3}$> ,$P^{3-}_4$> $CO^{2-}_{3}$> $B_{4}O^{2-}_{7}$> $S^{2-}_{4}$),TOC的降解率降低了2.0~46.9个百分点。研究Cl-浓度对RCT催化剂降解效果的影响,当Cl-为0.1 mol·L-1时,对TOC的去除有抑制作用,而较高的Cl-浓度(≥0.3 mol·L-1)对TOC的去除却有促进作用,投加Cl-对TN的去除有促进作用,但随着Cl-浓度的增加[(0.1~0.8) mol·L-1],TN的去除率变化不明显(约为88%)。