裂解汽油加氢一段催化剂失活原因分析

介绍了中国石油辽阳石化分公司烯烃厂裂解汽油加氢装置一段全馏分镍系加氢催化剂失活情况及原因分析。通过对酸性硫来源的分析及酸性硫对催化剂影响的评价，总结了处理酸性硫的对策及方法。     

有芯工频炉酸性炉衬对生产欧元材料的影响

通过对有芯工频炉酸性炉衬生产欧元材料出现的问题进行分析，发现在使用有芯工频炉酸性耐火材料时，炉衬寿命大大缩短，并使铜液Si含量超标，造成材料报废。而炉衬材料换成中性耐火材料时，基本上控制了Si含量，达到了欧元材料标准，并使炉衬寿命大大提高。     

SO_4~(2-)-TiO_2/Al_2O_3固体超强酸催化合成苹果酯-A和苹果酯-B的研究

通过浸渍法制备了SO42--TiO2/Al2O3固体超强酸催化剂,用Hammett指示剂法测定了其酸强度;以乙酰乙酸乙酯和乙二醇、1,2-丙二醇为原料,合成了苹果酯-A和苹果酯-B,考察了催化剂的焙烧温度、TiO2的负载量、反应温度、反应物配比、催化剂用量等因素对反应的影响以及催化剂的重复使用性。结果表明,在425～575℃温度范围内,SO42--TiO2/Al2O3体系可以形成超强酸;在苹果酯-A和苹果酯-B合成中具有催化活性高、催化速率快、化学稳定性好,重复使用性佳、无环境污染;在最佳条件下,苹果酯-A和苹果酯-B的收率分别可达89.3％和91.5％,质量分数为97％～99％。     

Marvelous self-assembly of hierarchically nanostructured porous zirconium phosphate solid acids with high thermal stability

A hierarchical structure of thermally stable macroporous zirconium phosphate solid acids with supermicroporous walls was prepared by a simple self-assembly process from the precursors of zirconium propoxide and orthophosphoric acid solution. The macroporous structures are uniform with the diameters ranging from 300 to 800 nm, one-dimensional channel-like. The effect of surfactant Brij 56 on the formation of macroporous structures has been studied. The frameworks of the synthesized hierarchical zirconium phosphates are amorphous with Zr–O–P bonding, exhibiting remarkably high thermal stability (at least 800 °C), on the basis of the X-ray diffraction (XRD), N₂ adsorption, X-ray photoelectron spectroscopy (XPS) analysis, Fourier transform infrared (FT-IR) and ³¹P nuclear magnetic resonance (NMR) spectra. Larger quantities of Zr–OH and P–OH groups are observed besides surface hydroxyl groups, suggesting the presence of acidity and the possibility of surface functionalization for practical applications including catalysis. The macroporous zirconium phosphates with hierarchical structures could also be the potential and efficient catalyst supports for the design of the structured catalysts and reactors.     

MTBE装置甲醇回收系统腐蚀原因分析及对策

分析了甲醇回收系统的腐蚀原因,分析结果表明,甲醇回收系统的腐蚀是电化学腐蚀,既存在析氢腐蚀也存在吸氧腐蚀,同时还存在机械磨损,分析结果有助于在工艺上采取减轻设备腐蚀方法的选择。     

Cesium salt of a heteropolyacid in nanotubular channels and on the external surface of SBA-15 crystals: preparation and performance as acidic catalysts

The Cs-salt of heteropolyacid with stoichiometry Cs_2.5H_0.5PW₁₂O₄₀ (CsHPW) was deposited selectively at the external surface of the SBA-15 silica microcrystals, inside its mesoporous channels and simultaneously at both location modes. The structure, texture and performance of these CsHPW/SBA-15 composites were compared with that of a reference bulk salt of the same composition. Location of CsHPW salt on the external surface of SBA-15 microcrystals leads to disintegration of its agglomerates increasing acidity of the catalytic phase. A novel preparation strategy consisting of grafting the basic Cs-species at the internal pores surface of SBA-15 stabilized the CsHPW phase inside the channels in form of 5–8 nm nanocrystals at 30–70 wt.% loadings. The catalytic tests demonstrated that insertion of the CsHPW catalytic phase inside the nanotubular channels of SBA-15 in combination with location of an additional amount of this phase at the external surface of SBA-15 microcrystals allows to increase the specific activity of this phase in MTBE synthesis, propionylation of anisole and alkylation of catechol with t-butanol by a factor of 1.5–3. This level of specific activity in combination with high total loading of catalytic phase >60 wt.% permit to get composite catalytic materials with catalytic activity higher by a factor of 1.2–1.5 with respect to the bulk CsHPW catalyst and stabilizing the catalytic phase against colloidization in polar media.     

Manipulation of gasification coal feed in order to increase the ash fusion temperature of the coal enabling the gasifiers to operate at higher temperatures

Coal is a crucial feedstock for South Africa’s unique synfuels and petrochemicals industry and used by Sasol as a feedstock to produce synthesis gas via the Sasol-Lurgi Fixed Bed Dry Bottom (FBDB) gasification process. The ash fusion temperature (AFT) gives detail information on the suitability of a coal source for gasification purposes, and specifically to which extent ash agglomeration or clinkering is likely to occur within the gasifier. Ash clinkering inside the gasifier can cause channel burning and unstable operation.Sasol-Lurgi FBDB gasifiers are currently operated with the philosophy of adding an excess of steam to the process to control the H₂/CO ratio of the syngas produced, but indirectly also to control the maximum gasifier temperature below the AFT of the coal. An opportunity exists to increase the AFT of the coal fed to the gasifiers by adding AFT increasing minerals to the coal blend before it is fed into the gasification process. For the aim of this study a South African coal source was investigated, as being used by the gasification operations in Secunda.With the specific aim of this study, to increase the AFT, the determination of the AFT of the coal blends where acidic components such as silica (SiO₂), alumina (Al₂O₃) and titania (TiO₂) were added was conducted. The Al₂O₃ had the biggest and most significant effect on the AFT with the least addition to the coal blend. The effect of SiO₂ and TiO₂ were very similar, but the effect was much smaller and further Al₂O₃ was needed to increase the AFT to a similar AFT level in comparison to the SiO₂ used. Kaolinite, roof and floor components (containing mainly Al₂O₃ and SiO₂) were also added, also showing an increase in the AFT with up to 4 mass% addition. Another observation was that the AFT was non-additive (not a linear weighted calculated average) and not the weighted average AFT as was expected for the other coal properties such as the ash content, for example. The ash slagging characteristics is a non-additive property of individual coal sources in the blend and therefore difficult to predict.In general it can be concluded that the unique opportunity exists to increase the AFT, was tested, proven and mechanistically outlined in this study on the coal source fed to the Sasol-Lurgi FBDB gasifiers. The AFT can be increased to >1350 °C by adding AFT increasing minerals or species to the coal blend before it is fed into the gasification process. By increasing the AFT, the direct effect will be that steam consumption can be decreased, which in turn will improve carbon utilization.     

DD3单晶高温合金的热腐蚀行为

用涂９０Ｎａ２ＳＯ４（ｗｔ％）和１０ＮａＣｌ（ｗｔ％）的混合盐膜法研究了单晶高温合金ＤＤ３在９００℃空气中的热腐蚀行为。结果表明，ＤＤ３单晶合金的高温热腐蚀是灾难性的；其动力学曲线无明显孕育期，但有明显的阶段性。文中对各阶段的腐蚀机理进行了简要的讨论。     

The isoxazolidines: the effects of steric factor and hydrophobic chain length on the corrosion inhibition of mild steel in acidic medium

Several new isoxazolidines having varying degree of steric environment and hydrophobic chain length, prepared efficiently using single-step nitrone cycloaddition reactions, are tested for corrosion inhibition of mild steel in 1 M and 5 M HCl at 50-70 °C range by gravimetric and electrochemical methods. All compounds have shown very good corrosion inhibition efficiency (IE%) in acidic solution. Steric crowding around the nitrogen centres and hydrophobic chain lengths as well as increase in temperature (in the presence of the inhibitor in the higher concentration range 100-400 ppm) are found to increase the inhibition efficiency of the isoxazolidines. Thermodynamic parameters (ΔG°_ads, ΔH°_ads, ΔS°_ads) for the adsorption process and kinetic parameters for the metal dissolution (or hydrogen evolution) reaction in the presence of one of the isoxazolidines were determined. Experimental results agree with the Temkin adsorption isotherm. The inhibition of corrosion in 1 M HCl, influenced by both physi- and chemi-sorption, was found to be under mixed control, but predominantly under cathodic control.     

制备条件对铜铬催化剂酸性质的影响

为了研究制备条件对铜铬催化剂酸性质的影响,建立了铜铬催化剂酸性质的检测方法,并采用共沉淀方法研制了不同制备条件的铜铬催化剂,通过SEM 对晶貌的分析得出,催化剂的酸性质与催化剂晶貌有关。通过Thanable假说和Seiyama假说建立了铜铬二元氧化物模型,分析得出,处于无定形状态的铜铬催化剂,其酸中心主要由一元氧化物氧化铜和氧化铬本身带来的,而处于结晶态的铜铬催化剂,其酸中心除了由一元氧化物本身带来的之外,还由于氧化铜和氧化铬混合的不均匀引起的B酸中心的增加。从而表明,铜铬二元氧化物的晶粒越小,晶粒越均匀,催化剂的酸性质越弱,B酸比例越小,相反则越强。