植物油加氢制备高十六烷值柴油组分研究进展

介绍了植物油加氢制备柴油的主要化学反应、工艺方法以及该项技术的工业化状况,分析了植物油直接加氢、先加氢后异构、直接脱羧工艺以及植物油与矿物柴油掺炼工艺的特点,阐述了各工艺采用的催化剂类型、工艺条件以及产品属性。指出了该领域存在的问题和研究方向。     

Kinetics of the hydrotreatment of rapeseed oil fatty acid triglycerides under mild conditions

To establish principal regularities of the hydrotreatment of rapeseed oil fatty acid triglycerides (FATs), the kinetics of this process has been studied at temperatures of 300–380°C, contact times of 0.38–0.10 h, and a hydrogen pressure of 1.0 MPa in a flow fixed-bed reactor. The process is performed over nonsulfided nickel catalysts, which are of great practical interest for the production of green diesel. The kinetic scheme of the process with consideration for target products (alkanes) and all oxygen-containing by-products has been proposed. The quantitative estimate, which enables the prediction of the composition of products for other process conditions, has been obtained for the principal paths of the hydrotreatment of rapeseed oil FATs.     

FH-98加氢催化剂在石油三厂120万 t/a 中压加氢装置的应用

抚顺石化公司石油三厂120万 t/a 柴油中压加氢装置于2002年7月建成投产,并开车一次成功.2010年装置换用 FH-98加氢精制催化剂,工业应用表明,FH-98催化剂具有优异的加氢性能和高的加氢脱硫活性,加氢处理焦化汽油、柴油混合油,生产清洁柴油和合格的乙烯裂解原料.     

影响催化裂化柴油十六烷值的因素与MCI技术

对影响催化裂化柴油十六烷值的因素进行了工艺研究,结果表明,用加氢精制的方法不能大幅度提高柴油的十六烷值,而高压脱芳在工业生产上也受到限制,中国石化抚顺石油化工研究院(FRIPP)开发的MCI技术很好的解决了这一矛盾,为清洁燃料的生产开避了广阔前景.     

Reactivation of an industrial batch of CoMo/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst for the deep hydrotreatment of oil fractions

The results from industrial tests of technology developed earlier for the reactivation of CoMo/Al₂O₃ catalyst for the deep hydrotreating of diesel fuel, including the oxidative regeneration of the catalyst with subsequent treatment using organic complexing agents, are presented. Samples of the catalyst, fresh and at different stages of its reactivation, are investigated using a set of analytical and physicochemical methods. The chemical composition, textural characteristics, mechanical strength, structure of the active sulfide component (TEM, XPS) are determined. Catalytic tests are performed that include lifetime tests (360 h) in the hydrotreatment of a straight-run diesel fraction. The restoration of the physicochemical and catalytic properties is observed for a sample subjected to oxidative regeneration with subsequent treatment using organic complexing agents. An industrial batch of deep hydrotreatment catalyst reactivated by this technology is loaded into an L-24-6 industrial plant facility and ensures stable purification of straight-run diesel fuel containing up to 10% of light catalytic cracking gas oil to a residual sulfur content of less than 10 ppm. Comparison of the obtained results and data on the industrial operation of fresh catalysts shows that the technology developed by the Institute of Catalysis and PAO Gazprom Neft ensures almost complete restoration of the properties of the deactivated catalysts.     

Catalytic hydroprocessing of cottonseed oil in petroleum diesel mixtures for production of renewable diesel

The conversion of the esters included in refined cottonseed oil into hydrocarbon molecules compatible with petroleum diesel, which are named renewable diesel, has been studied at conventional hydrotreatment conditions. The vegetable oil was fed in mixture with desulphurized petroleum diesel to the hydrotreater containing a conventional CoMo/Al₂O₃ hydrotreatment catalyst. Conversion of esters was determined in the temperature range of 305-345 °C, at 30 bar and for 5 h⁻¹ < WHSV < 25 h⁻¹. Catalyst deactivation was followed for a period of 450 h in operation. A simple kinetic model of ester conversion suitable for scale-up and simulation studies has been tested.     

Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha I. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha has been evaluated over unsupported transition metal sulfide catalysts of the second row in the Periodic Table. The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enabled the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide (RuS₂) is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha.     

Second row transition metal sulfides for the hydrotreatment of coal derived naphtha III. Removal of individual nitrogen compounds

The disappearance of individual nitrogen compounds is followed during the hydrotreatment of a coal-derived naphtha containing a mixture of nitrogen-, sulfur- and oxygen-containing heteroatom compounds over bulk second row transition metal sulfides. The naphtha contains mainly three types of nitrogen compounds: pyridines, anilines and quinolines. While quinoline is the least reactive of the three simplest compounds in these compound classes, substituted anilines are the compounds most difficult to remove from the naphtha. The presence or absence of an alkyl substituent exerts a strong influence on the reactivity of individual compounds and can over-shadow the differences between compound types. The reactivity patterns of the methyl-substituted pyridines indicate a steric hindrance about the nitrogen atom. The order of reactivity between alkyl-substituted anilines is different over the various sulfides with steric hindrance about the nitrogen atom indicated for only the higher activity catalysts. Except for molybdenum sulfide, the reactivity of quinoline is less than or equal to that of methyl-substituted quinolines. The individual nitrogen compounds do not disappear according to a first order rate expression but indicate strong product inhibition of the reaction rate. The overall removal of nitrogen does not follow simple first, zero or second order kinetics and shows similar kinetic behavior as for the disappearance of individual nitrogen compounds.     

Catalytic processes for the production of hydrocarbon biofuels from oil and fatty raw materials: Contemporary approaches

The scientific and technical achievements made during the last 15 years in the deoxygenation processes for the production of hydrocarbon biofuels from oil and fatty raw materials are reviewed. The most advanced methods for the processing of triglycerides into hydrocarbons are associated with the use of pyrolysis, catalytic cracking, and hydrotreatment processes similar to those already used at petrochemical plants and oil refineries. The hydrotreatment technologies, which have already been adopted or ready for industrial application, are considered in more details. Nonsulphide catalysts for the single-stage production of waxy diesel fractions from vegetable oils and combined technologies are promising for reducing the consumption of hydrogen and increasing the yield of hydrocarbon products and the flexibility in obtaining different types of fuel.     

Inhibiting HDS and HYD reactions with quinoline on Co(Ni)–PMo(W)/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts: Effect of active phase composition on stability in the hydrotreatment of a model petroleum raw material

Со(Ni)–PMo(W)/Al₂O₃ catalysts are prepared using Keggin heteropoly acids H₃PMo(W)₁₂O₄₀ and cobalt (nickel) citrate. The physicochemical properties of the catalysts are studied via low-temperature nitrogen adsorption, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Their catalytic properties are determined in the hydrotreatment of a model raw material containing dibenzothiophene, naphthalene, and different amounts of quinoline (up to 1000 ppm of nitrogen), and in the hydrotreatment of a straight-run diesel fraction and vacuum gas oil. The composition of Со(Ni)–PMo(W)/Al₂O₃ catalysts plays an important role in the hydrotreatment of a complex hydrocarbon raw material. Ni–PW/Al₂O₃ catalyst is more resistant to organonitrogen inhibitors than Ni(Co)–PMo/Al₂O₃ samples with more reactive active sites. Ni–PW/Al₂O₃ catalyst provides the greatest depth of conversion for sulfur- and nitrogen-containing compounds and polycyclic aromatic hydrocarbons in the hydrotreatment of vacuum gas oil.     

柴油电催化加氢与氧化脱硫的系统集成

柴油中硫和多环芳烃含量要求越来越严,由于二苯并噻吩类硫化物的空间位阻导致传统的催化加氢难以实现以上目标。本文以泡沫铅为阴极,以石墨为阳极,在CH₃CN+EtOH+H₂O+Bu₄NBr电解体系中可以将柴油中多环芳烃的电解加氢和含硫化合物的电解氧化脱除集成。在该电解体系中泡沫铅电极上柴油电解加氢主要是温和的加氢,电解加氢后氢含量增加了1.1%,三环芳烃蒽类和菲类减少3.3%,但是总芳烃含量变化不大,十六烷值增加3.9。在石墨阳极上柴油中硫化物容易电解氧化,氧化产物砜类不能完全由电解体系萃取脱除,进一步通过活性炭吸附可以将柴油硫含量由884 μg·g^-1降低至44 μg·g^-1。     

Upgrading coal-derived liquids to diesel fuel

Distilled fractions of a coal-derived liquid from the H-Coal process were upgraded to diesel fuel by catalytic hydrotreatment. The total hydrotreated products were distilled into naphtha (<180°C) and diesel fuel fractions (>180°C) and the diesel fractions were analysed for hydrocarbon-type composition, hydrogen content and some diesel fuel properties. GC—MS-analyses were carried out on the hydrocarbon-type fractions to identify individual chemical compounds. To investigate the effect of different distillation cut points on diesel fuel yield and properties, cut points for one hydrotreated product were varied. The diesel fuel cetane numbers were correlated with percentage hydrogen, total aromatics and saturates. Cetane numbers above 40 were obtained for diesel fuels containing (i) more than 75% saturates, (ii) less than 15% total aromatics and (iii) a hydrogen content above 12.8%. Compounds identified by GC—MS-analyses (in the diesel fractions) were typical aromatic and cycloparaffin compounds. Normal-and iso-paraffin compounds were not detected. By varying the distillation cut point from 135 to 180°C, the cetane number of the residual diesel fraction improved from 37 to 44. This increase is ascribed to the removal of aromatic compounds in the 135–180°C boiling point range.     

减粘裂化装置的现状及发展

对减粘裂化装置的现状及发展进行了分析,对下流式反应塔减粘裂化、加热炉（无反应塔）减粘裂化、上流式反应塔减粘裂化等工艺的流程特点进行了对比,指出在上流式反应塔减粘裂化工业装置上结合减压渣油掺炼沥青可取得良好的经济效益,是减粘裂化装置可以考虑的发展方向。     

Comprehensive two-dimensional gas chromatography for basic and neutral nitrogen speciation in middle distillates

The molecular knowledge of nitrogen compounds in diesel feedstocks has become a key issue in the development of hydrotreatment processes, especially for ultra-low sulfur diesel production. Indeed, nitrogen species have a strong impact on the hydrodesulfurization (HDS) pathway, since basic nitrogen is known to poison acidic sites of HDS catalysts.Since conventional methods only allow a poor degree of information, the increased separation power of comprehensive two-dimensional gas chromatography (GC × GC-NCD) was used in this study to obtain a detailed overview of nitrogen compounds by type (basic/neutral), by family and by carbon breakdown in diesel and liquefied coal samples. Partially hydrogenated compounds such as tetrahydrocarbazole and tetrahydroquinoline derivatives could even be detected in liquefied coal samples as well as diesel from ebullated bed conversion units. Comparison of GC-NCD with GC × GC-NCD for quantitative determination of nitrogen compounds by family was achieved in a first step. These results demonstrate the superiority of GC × GC to allow for a comprehensive characterization of nitrogen compounds in diesel and related samples in one injection. Furthermore, nitrogen speciation by GC × GC-NCD technique allows identifying most nitrogen species in conventional diesel or liquefied coal samples, with no use of mass spectrometry.GC × GC-NCD was also applied to a wide range of diesel feedstocks obtained from distillation, cokefaction, FCC, ebullated bed hydroconversion units to correlate nitrogen species to the origin of the feedstocks or distillation end points, giving interesting indications on reaction mechanisms involved in the processes.     

加氢催化剂器外预硫化技术

简述了器外预硫化技术的优点,介绍了加氢催化剂器外预硫化技术的发展历程,并以浙江某化学公司采用的抚研院开发的FRIPP EPRES器外预硫化型催化剂一次开车成功的工业应用说明,器外预硫化技术可以消除开工过程中硫化剂对人体健康、安全的危害以及对环境的污染,减少装置污油排放,简化炼油装置的开工过程,大大降低开工成本。此项新技术具有良好的推广前景。     

Stability of bitumens produced by thermal processes

A study was made of the behaviour, when heated in the presence of air, of visbreaker bitumens obtained at different cracking severities. During thermal treatment, two separate groups of reactions were detected by DSC; this behaviour is not a characteristic of distillation bitumens, and therefore allows a distinction to be made between them and cracker bitumens. In visbreaker bitumens, oxidation is expedited by an amount which is dependent on the conditions of the production process: the temperature at which oxidation starts is correlated to the severity of the visbreaking process.     

Hydroprocessing of straight run diesel mixed with light cycle oil from fluid catalytic cracking,using sulfide NiMo catalyst on zeolite-containing supports

It is proposed that the sulfide NiMo system supported on alumina-SAPO-31 composite (NiMo/Al₂O₃-SAP catalyst) be used to obtain high-quality diesel fuel from a mixture of straight run diesel (SRGO) and light cycle oil (LCO) produced by fluid catalytic cracking (FCC). It is shown that the use of this catalyst ensures the synthesis of diesel fuel of higher quality upon hydroprocessing a feedstock with 30 wt % LCO, compared to the traditional sulfide NiMo/Al₂O₃ or CoMo/Al₂O₃ catalysts. It is found that the content of aliphatic hydrocarbons is raised in the products of hydrotreatment, compared to the initial feedstock. This confirms the ability of NiMo/Al₂O₃-SAP catalyst to facilitate the reaction of ring opening. Using the proposed catalyst should improve the quality of diesel fuels obtained via the hydroprocessing of LCO-containing feedstock.     

Prediction of sulphur content in the industrial hydrotreatment process

The artificial neural network models were developed to determine sulphur content in the hydrotreatment product. Two models for two different types of feed were developed: light gas oil and vacuum gas oil. The developed ANN models use 6 input variables that are continuously measured in the process and are in accordance with the engineering knowledge and thermodynamics of hydrotreatment processes. Given models show good predictability of sulphur content in the hydrotreatment product and are, therefore, used in practice for continuous monitoring and optimization. This kind of application can be easily developed in any other hydrotreatment process with the available adequate historical data.     

渣油加氢催化剂的研究和应用

渣油加氢处理技术是近年发展最快的技术领域。渣油加氢处理催化剂是此技术的关键。多种固定床渣油加氢处理催化剂在国外已进行了开发和工业应用。我国也开发了多种固定床渣油加氢处理催化剂，实践表明这种催化剂具有良好的活性和稳定性，产品质量良好，收率高，可为RFCC提供优质的原料。悬浮床渣油加氢处理催化剂也在开发之中，中试试验取得了良好的结果。     

高比例掺炼催化汽油预加氢单元的优化设计

以某厂60万t/a连续重整装置为例,从原料油优化处理、采用催化剂级配装填技术以及优化注冷氢位置等方面探讨了高比例掺炼FCC汽油石脑油加氢单元的工程设计。通过采取多种优化设计,使加氢精制油中杂质含量完全满足重整进料要求,解决了炼厂重整原料不足的问题,满足了企业汽柴油产品质量升级的需求。