渣油加氢失活催化剂有效利用的新途径

论述了将渣油加氢失活催化剂制备成加氢型和非加氢型新催化剂的工艺和方法,着重探讨了钒含量较高的失活催化剂加工为新型渣油加氢催化剂的方法和思路,并对渣油加氢过程中钒的作用机理进行归纳。     

Reactivation and Reuse of a Hydrotreating Spent Catalyst for Cyclohexene Conversion

A comparative study has been made on the efficiency of leaching, using different concentrations of oxidized oxalic acid, and thermally treating techniques to reactivate a Ni‐Mo‐spent hydrotreating catalyst. The reactivation of the treated catalysts was performed in a pulse microcatalytic reactor under atmospheric pressure of hydrogen and reaction temperatures ranging from 250 °C to 450 °C using cyclohexene as model hydrocarbon. The studies revealed that a decoking spent catalyst after leaching using a low concentration (2 %) enhanced its physical characteristics (surface area and average pore diameter) and catalytic activity towards maximum cyclohexene hydrogenation and hydroisomerization reactions at 300 °C and 350 °C, respectively.     

脂肪酸甲酯加氢制脂肪醇Cu/Zn催化剂失活研究进展

脂肪醇是表面活性剂工业的重要基础原料。综述了脂肪酸甲酯加氢制脂肪醇Cu/Zn催化剂的失活研究进展,介绍了Cu/Zn催化剂的烧结、中毒、结焦等主要失活形式的机理,分析了硫、氯、氮、磷、钠的化合物和水、皂、游离脂肪酸、甘油、甘油酯等具有代表性的杂质对Cu/Zn催化剂活性的影响,讨论了Cu/Zn催化剂失活的控制方法。     

Deactivation of VMgO x Catalysts by Coke in the Process of Isobutane Dehydrogenation with Carbon Dioxide

The process of isobutane dehydrogenation in the presence or absence of carbon dioxide was carried out over VMgO _x catalysts with different vanadium loading. The performed tests show that both the reaction atmosphere and physicochemical properties of the catalysts (related to vanadium content) have a great influence on the activity decrease and the carbonaceous deposit formation. Despite small ability of carbon dioxide to remove coke in the Boudouard reaction, the amounts of carbonaceous species deposited on the catalysts after the isobutane dehydrogenation under CO₂ atmosphere were even twice greater in comparison to those deposited in helium stream. Moreover, the rate of coke deposition during the dehydrogenation in the inert gas flow was only slightly dependent on the reaction time, in contrast to the process in carbon dioxide atmosphere. The results show that the coke formation on VMgO _x is enhanced predominantly by surface acidity of the catalysts, which grows with the vanadium content and the presence of CO₂ in the feed.     

Simplex Lattice Approach to Optimize Yields of Light Oil Products from Catalytic Cracking of Bio-Oil with Mixed Catalysts

Bio-oil is a potential product from the fast pyrolysis of biomass. However, it should be upgraded before being used in subsequent applications and corrosion prevention. In this work, crude bio-oil from fast pyrolysis of Jatropha curcas residues, which has many long-chain compounds, and a high content of carboxylic acid, was catalytically upgraded over mechanically mixed catalysts (normal ZSM-5 and Y-Re-16) in a fixed-bed reactor. The effects of the key parameters on the yields of light oil products were analyzed, including cracking temperature (350–500°C), reaction time (15–60?min), catalyst loading (10–25%), and mixture ratio between Y-Re-16 and ZSM-5 (10–70%). Experimental test cases were based on a simplex lattice design. The gas chromatograph-mass spectrometer (GC-MS) analysis showed that the catalytic cracking of crude bio-oil using mixed catalysts resulted in the successful formation of short-chain acid methyls. The employed analytical fit of the experimental data gave R² and the adjusted R² of 0.902 and 0.843, respectively. The optimized operation conditions to produce aliphatic hydrocarbons from mechanically mixed catalysts were found to be at 400°C, 15?min of reaction time, 15% of catalyst loading, and a mixture ratio of about 1:5.     

炔烃及二烯烃选择加氢催化剂的研究进展

综述了在炔烃和二烯烃选择加氢制烯烃过程中的催化剂的应用研究进展。     

非晶态合金催化剂用于葡萄糖加氢制山梨醇的研究

采用石油化工科学院研制的非晶态合金催化剂进行葡萄糖加氢,考察了温度、压力、ｐＨ 值、剂糖比和反应时间等因素对加氢反应的影响,并与其它Ｒａｎｅｙ Ｎｉ 类催化剂进行了对比。结果表明,使用ＳＲＮＡ－３ 非晶态合金催化剂进行葡萄糖加氢,当反应温度为１３０ ～１４０℃、压力为５ ～９ＭＰａ、ｐＨ值为８．３５、剂糖质量比为１％ 、反应时间为７０～１２０ｍｉｎ 时,转化率可达１００％ ,产品色度好。ＳＲＮＡ－３ 催化剂的葡萄糖加氢活性好于Ｒａｎｅｙ Ｎｉ 催化剂,重复使用时,也可保持较高活性。     

Deactivation of CeO2 catalyst in the hydrogenation of benzoic acid to benzaldehyde

The CeO₂ catalyst has been investigated for hydrogenation of benzoic acid to benzaldehyde and shows little deactivation in stability test. BET results indicate that no significant sinter was observed on the used catalyst. SEM images show few changes taking place in surface feature of the used catalyst. Element analysis confirms that some coke is formed which leads to catalyst deactivation. XRD analysis reveals that crystalline size of catalyst is not relevant to the catalytic behavior in the range from 14.3 nm to 18.4 nm.     

加氢催化剂 fv－10在工业装置的应用分析

介绍了RN－10、 fv－10两种催化剂在润滑油加氢补充精制装置使用情况,通过比较两种催化剂工艺操作条件的变化、产品质量的变化、投用反应器数量变化等对比分析,说明了石蜡加氢催化剂fv－10在本装置表现出良好的加氢活性、稳定性、较强的脱色性能力,尤其在较低温度下对加氢原料的加氢性能较好,通过投用fv－10催化剂产生了新的节能和良好的经济效益。     

Use of Water as a Solvent in Directing Hydrogenation Reactions of Aromatic Acids over Pd/carbon Nanofibre Catalysts

By conducting the catalytic hydrogenation over water miscible Pd/carbon nanofibre catalysts, selective ring hydrogenation of aromatic acids can be performed in aqueous solution without the need to provide protection for the external acid function.     

国产钨基催化剂在烯烃歧化制丙烯工业侧线装置上的性能研究

针对丁烯和乙烯歧化增产丙烯技术(OCT技术)所用进口BASF催化剂价格昂贵、运输条件苛刻等情况,自主研发了钨基歧化催化剂,并在实验室小试装置和OCT工业侧线固定床反应器上,考察了该催化剂在OCT技术制备丙烯过程中的催化性能。结果表明,1-丁烯的异构化率和丙烯的选择性均随反应温度的升高和乙烯、丁烯摩尔比的增加而逐渐增加,自主研发催化剂的催化活性和进口催化剂相当,且催化剂稳定性良好,可连续运行400 h以上。     

Hydrogenation of Citral using Monometallic Pt and Bimetallic Pt‐Ru Catalysts on a Mesoporous Support in Supercritical Carbon Dioxide Medium

Supercritical carbon dioxide was shown to be a suitable reaction medium for the highly efficient hydrogenation of citral using monometallic Pt and bimetallic Pt‐Ru supported on a mesoporous material, MCM‐48, as catalyst. A remarkable change in the product distribution was observed after the addition of Ru to the monometallic Pt catalyst in supercritical carbon dioxide. The monometallic Pt catalyst was found to be highly selective to the unsaturated alcohol (geraniol+nerol) at a temperature of 323 K within 2 h whereas the bimetallic catalyst becomes selective to the partially saturated aldehyde (citronellal) under the same reaction conditions. Phase behavior plays an important role in the product distribution. Highest conversion and high selectivity to citronellal were achieved in the homogeneous phase for the Pt‐Ru catalyst while on the other hand the unsaturated alcohol (geraniol+nerol) was produced in the heterogeneous phase for the monometallic Pt catalyst. An XPS study offers strong evidence of the electronic modification of Pt after the addition of Ru in the bimetallic catalyst. The change in product distribution on the Pt‐Ru bimetallic catalyst may be explained by the appreciable interaction between the medium and the metal particles promoted by the presence of metallic Ru.     

Selective Hydrogenation of Ethyne in Ethene-Rich Streams on Palladium Catalysts. Part 1. Effect of Changes to the Catalyst During Reaction

The effect of various changes to the palladium catalyst during its stabilization in the course of the selective hydrogenation of ethyne-ethene mixtures (formation of hydride and carbide phases and of carbonaceous deposits) was reviewed. The deposits in the form of a carbonaceous overlayer on the palladium surface create sites at which selective ethyne hydrogenation to ethene can occur. The carbonaceous deposit on the support increases the selectivity to ethane formation by increasing the rate of ethene hydrogenation on support sites (spillover of hydrogen from metal to the support surface) and by decreasing the effective diffusivity of ethyne in the pores.     

Reliable Laboratory Reactor Data Analysis: Evaluation of Commercial FCC Catalysts in a Batch Fluidized Bed Reactor

Statistical techniques for the treatment and analysis of experimental data from laboratory reactors were considered, as applied to a CREC Riser Simulator reactor for the example of fluid catalytic cracking catalyst evaluation. Deviations in mass balances were reconciliated considering the variance in each product mass. After reconciliations, simple optimum performance envelope curves were used to fit the data due to their simplicity and proper representation of the yield curves. In the data fitting step, errors in both dependent and independent variables were considered by using information obtained in the reconciliation procedure. The impact of different levels of confidence bands in the models on the discrimination of experimental results was discussed. Significant improvements in catalyst evaluation could be achieved either in the CREC Riser Simulator or other types of laboratory reactors with the help of the statistical procedures described here without increasing substantially the number of experiments.     

Experimental and Kinetics Studies of Aromatic Hydrogenation in a Two‐Stage Hydrotreating Process using NiMo/Al2O3 and NiW/Al2O3 Catalysts

In this work, hydrogenation of aromatic compounds in light gas oil derived from Athabasca bitumen was carried out using a single‐ and two‐stage hydrotreating processes. Experiments were performed in a trickle‐bed reactor using two catalysts namely NiMo/Al₂O₃ and NiW/Al₂O₃. NiMo/Al₂O₃ was used in the first stage for nitrogen and sulphur containing heteroatoms removal whereas NiW/Al₂O₃ was used in the second stage for saturation of the aromatic rings in the hydrocarbon species. Temperature and liquid hourly space velocity (LHSV) were varied from 350‐390°C and 1.0‐1.5 h^?1, respectively, while pressure was maintained constant at 11.0 MPa for all experiments. Results from single‐stage were compared with those from two‐stage process on the basis of reaction time. Kinetic analysis of the single‐stage hydrotreating process showed that HDA and HDS activities were retarded by the presence of hydrogen sulphide that is produced as a by‐product of the HDS process. However, with inter‐stage removal of hydrogen sulphide in the two‐stage process, significant improvement of the HDA and HDS activities were observed.     

A Model for the Phosphorus Dynamics of VPO Catalysts during the Selective Oxidation of n‐Butane to Maleic Anhydride in a Tubular Reactor

A model for the phosphorus dynamics in vanadium‐phosphorus oxide (VPO) catalysts for the oxidation of n‐butane to maleic anhydride was developed. According to the model, reversible sorption processes determine the phosphorus content of the catalyst. Simulations reveal that several phenomena can be successfully described. If no phosphorus is added to the reactant feed, the catalytic activity increases until runaway occurs. With addition of a proper amount of phosphorus, the loss can be compensated while excessive phosphorus addition results in complete catalyst deactivation. Adjusting the model parameters to experimental data may result in a model that can be used to optimize the performance of maleic anhydride reactors.     

某化工园区污水处理厂的提标改造及其运行分析

为确保鄱阳湖生态经济区水资源安全,提高江西某化工园区污水处理厂的主要出水指标,采用"上流式厌氧污泥床(UASB)+A/O+臭氧氧化+缺氧+生物接触氧化+曝气生物滤池(BAF)"工艺进行提标改造。实际运行结果表明,COD、NH₃^-N去除率能分别达到80.2%、78.6%,出水TN、TP的质量浓度分别小于20、1 mg/L,各水质指标能够到达DB 36/852-2015中的"高效集约发展区"标准,废水的处理成本为4.43元/m³。     

N2循环升温延长大型合成氨装置催化剂使用期限

介绍引进国外30万t/a合成氨装置中，增设氮气循环管路，取消转化系统升温时的“干烧”，以避免催化剂及炉管在升温过程里受到热冲击影响，从而延长了催化剂及炉管的使用期限。     

Modelling of the Hydrolysis of Benzylpenicillin to 6-Aminopenicillanic Acid and Phenyl Acetic Acid by an Immobilised Penicillin Amidase in a Small Pilot Plant Batch Recirculated Reactor

This paper deals with the modelling of the hydrolysis of benzylpenicillin to 6-aminopenicillanic acid (6-APA) and phenyl acetic acid (PAA) in a small pilot plant batch recirculated reactor by an immobilised penicillin amidase preparation. By using the following linearised form for an integrated Michaelis-Menten equation Et/V₀X=α+β| In (1-X)/X| where α and β are reaction kinetic parameters, good correlations are obtained of α and β with linear velocity across the reactor, substrate concentration and temperature of operation. A process to determine α and β from initial velocity measurements is outlined. The applicability of the above equation to published data is also analysed.