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。     

Size-controlled synthesis of Mo powders via hydrogen reduction of MoO2 powders with the assistance of Mo nuclei

The size-controlled preparation of Mo powders is always a challenge and important task in the molybdenum metallurgy. In the current study, Mo powders with controllable sizes are synthesized by hydrogen reduction of MoO₂ powders with the assistance of Mo nuclei in the range of 900–1100 °C. The influences of the particle sizes of Mo nuclei, the additive amount as well as reaction temperature on the morphology and particle sizes of the final products are studied. For the hydrogen reduction of MoO₂ without any additive, the obtained Mo powders always have large particle sizes. However, the addition of small amounts of nuclei in MoO₂ can help Mo nucleate dispersedly, and the growth of Mo could be also controlled by adjusting the sizes of added nuclei, amount of addition and the reaction temperature. With the addition of Mo nuclei, the different sizes of Mo powders with the good dispersity can be prepared. As adding commercial Mo powders with the particle size of about 2.03 μm, the micron-sized Mo powders ranged from 2.11 μm to 3.25 μm could be prepared. While for the case of adding ultrafine Mo nuclei of about 170 nm, Mo powders from 0.28 μm to 0.88 μm can be obtained. Moreover, the more the amounts of nuclei added and the lower the reaction temperature (in the range of 900–1100 °C) is, the smaller the particle size of the prepared Mo powder will be. The current method is a facile and feasible method, and is potential to be used for industrial production of Mo powder with controllable particle sizes.     

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.     

Selective Analysis of Sulfur-Containing Species in a Heavy Crude Oil by Deuterium Labeling Reactions and Ultrahigh Resolution Mass Spectrometry

A heavy crude oil has been treated with deuterated alkylating reagents (CD₃I and C₂D₅I) and directly analyzed without any prior fractionation and chromatographic separation by high-field Orbitrap Fourier Transform Mass Spectrometry (FTMS) and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) using electrospray ionization (ESI). The reaction of a polycyclic aromatic sulfur heterocycles (PASHs) dibenzothiophene (DBT), in the presence of silver tetrafluoroborate (AgBF₄) with ethyl iodide (C₂H₅I) in anhydrous dichloroethane (DCE) was optimized as a sample reaction to study heavy crude oil mixtures, and the reaction yield was monitored and determined by proton nuclear magnetic resonance spectroscopy (¹H-NMR). The obtained conditions were then applied to a mixture of standard aromatic CH-, N-, O- and S-containing compounds and then a heavy crude oil, and only sulfur-containing compounds were selectively alkylated. The deuterium labeled alkylating reagents, iodomethane-d₃ (CD₃I) and iodoethane-d₅ (C₂D₅I), were employed to the alkylation of heavy crude oil to selectively differentiate the tagged sulfur species from the original crude oil.     

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.     

提高催化裂化装置(FCCU)柴汽比措施

为了满足市场的需要,中石化天津分公司炼油厂根据FCCU自身特点采取了一系列提高柴汽比的措施,包括:调节反应系统和分馏的操作条件及采用MGD技术,以提高柴油产率。实施后,FCCU的柴汽比从0.5提高到0.9,创造了良好的经济效益。     

SO4^2-／ZrO2固体超强酸的制备及其催化合成ETBE的研究

采用沉淀一浸渍法制备了负载型SO4^2-／ZrO2固体超强酸催化剂，运用IR、XRD等方法表征所制备催化剂的物化性质。结果表明，所制备的催化剂具有固体超强酸催化剂的特征，酸性与焙烧温度有关，适当提高焙烧温度有利于样品酸强度的提高，但焙烧温度过高会导致脱硫；浸渍液H2SO4浓度高有利于提高催化剂的硫含量，但是浓度过高，会在催化剂上形成硫酸盐，从而降低催化剂的比表面积和酸性。采用制备的催化剂气相催化乙醇与叔丁醇合成乙基叔丁基醚反应，乙基叔丁基醚的选择性为54．71％。     

基于中压加氢改质方案的炼油流程协同优化

中国石化北京燕山分公司(简称燕山分公司）为增产高附加值产品、提升效益，对炼油系统进行了流程协同优化。中压加氢裂化装置掺炼催化裂化柴油，由加氢裂化方案改为加氢改质方案运行，将改质柴油送入三号催化裂化装置（简称三催化装置）的提升管进行回炼；同时，将焦化蜡油改入加氢裂化装置进行加工，而蜡油加氢装置不再加工焦化蜡油以改善催化裂化原料。协同优化后，中压加氢改质装置的柴油产品十六烷值提高7个单位；三催化装置的液化气收率提高1.96百分点，汽油收率增加0.88百分点，总液体收率增加2.28百分点；高压加氢裂化装置喷气燃料产品的密度（20 ℃）降低至806 kg/m3，烟点为23.8 mm，尾油BMCI由11.8降低至10.8；蜡油加氢装置精制蜡油的饱和分质量分数提高4.68百分点，芳香分质量分数降低5.96百分点，氮质量分数降低0.06百分点，使催化裂化原料性质得以改善。通过将中压加氢改质装置的喷气燃料馏分抽出送催化裂化装置回炼，与回炼改质柴油相比，催化裂化汽油的研究法辛烷值（RON）增加1.0个单位，改质柴油十六烷值提高4.8个单位。通过全炼油板块系统性优化，燕山分公司车用柴油产品的十六烷值由53.5降低至51.5，解决了质量过剩问题。     

林达大型低压甲醇合成塔在内蒙天野20万吨/年装置上的应用

简要介绍了林达均温型甲醇塔在内蒙天野20万t/a甲醇装置开车及初步运行情况。运行情况验证了该反应器的先进性,其催化剂床层测温点多、温度分布均匀、运行稳定。     

催化裂解多产丙烯新技术

介绍了国内外利用蜡油或常压渣油等重质原料的增产丙烯技术CPP,ARGG FDFCC和TSRMP;还介绍了利用富含烯烃的混合碳四和催化裂化汽油等轻质原料的增产丙烯技术OCP,Propylur,Superflex,OCT,Meta-4和BASF公司的丁烯歧化工艺技术.