GC-AED法研究催化裂化柴油中硫氮化合物

采用气相色谱-原子发射光谱（GC-AED）联用技术对FCC柴油中的含硫化合物、含氮化合物进行定性定量研究。结果表明：FCC柴油中硫化物的类型主要是噻吩类衍生物、苯并噻吩、苯并噻吩类衍生物、二苯并噻吩、二苯并噻吩类衍生物,其中苯并噻吩类衍生物、二苯并噻吩类衍生物的硫质量分数占总硫质量分数的93．6％以上。氮化物主要为碱性氮化物（Nb）和非碱性氮化物（Np）两大类型,其中碱性氮化物主要是苯胺及其衍生物,喹啉含量很低,约占总氮质量分数的0．1％,非碱性氮化物主要包括吲哚及其衍生物和咔唑及其衍生物,而咔唑类氮化物一般约占总氮质量分数的64％。不同来源的FCC柴油,其所含硫化物、氮化物的含量和分布不同。应根据其硫化物、氮化物的分布类型及规律,开发合适的柴油脱硫脱氮催化剂及相关工艺。     

Inhibition of nitrogen compounds on the hydrodesulfurization of substituted dibenzothiophenes in light cycle oil

The influence of nitrogen compounds on the hydrodesulfurization (HDS) activities of a series of substituted dibenzothiophenes in light cycle oil (LCO) was studied over a NiMo/Al₂O₃ commercial catalyst. Three types of light cycle oil with nitrogen compounds of different concentrations and chemical natures were used as feed—an original fluid catalytic cracking light cycle oil (LCO), LCO with most of its basic nitrogen removed, and an ultra-low nitrogen LCO. Experiments were conducted in a fixed-bed microreactor at a total pressure of 70 atm, temperatures between 330 and 400 °C, and liquid hourly space velocities (LHSV) in the range of 1.0 to 3.5 h⁻¹. The inhibition effects of nitrogen compounds on the HDS reactivity of the three sulfur groups—total sulfur, hard sulfur, easy sulfur—and 14 specific mono-, di- and tri-alkyl substituted dibenzothiophenes were investigated. The results showed that the HDS rate significantly increased using ultra-low nitrogen LCO. Pseudo first-order rate constants were estimated for the 14 mono-, di- and tri-alkyl substituted dibenzothiophenes. The HDS rates could be classified into three groups based on the position of the substituents. It was found that 4 and 6 substituted dibenzothiophenes had the lowest HDS rates. The HDS rate of the 14 substituted dibenzothiophenes were all increased when the ultra-low nitrogen feed was used. The improvement was greater for 4 and 6 substituted dibenzothiophenes than for those with one of the substituents at either the 4 or 6 positions. This finding indicates that the hydrogenation route is more strongly suppressed than hydrogenolysis route by nitrogen compounds since the hydrogenation route is believed to be the predominant reaction pathway for 4 and 6 alkyl-substituted dibenzothiophenes.     

High quality diesel by hydrotreating of atmospheric gas oil/light cycle oil blends

An improved process for high-quality diesel fuel production by hydrotreating atmospheric gas oil (SRGO) and light cycle oil (LCO) blends is presented in this paper. For this purpose, a set of blends of 5, 10 and 15% by volume of LCO with final boiling points of 300, 325 and 350 °C with a full range gas oil (FBP 350 °C) was hydrotreated in a pilot plant at 340-380 °C, 5.4 MPa, 2.5 h⁻¹ LHSV using a commercial Co-Mo catalyst. A relationship between the concentration of refractory sulfur compounds (those boiling above 316 °C) and aromatics content in the feedstock with the hydrotreating temperature required for meeting a 0.05% sulfur specification was found.The experimental data obtained during the desulfurization was quantitatively represented by a 1.50 to 1.56 order rate equation, with activation energies between 18.9 and 34.1 kcal/mol, depending on the feedstock.     

提高煤焦馏分油储存安定性的研究

为改善煤焦馏分油在贮存及运输过程中的安定性,以甲苯、四氢化萘、萘作为模拟基础油,以苯酚、氧芴、吲哚、喹啉、噻吩分别模拟含氧、含氮和含硫化合物,研究了单一和复合模拟化合物对基础油安定性的影响。结果表明：单一模拟化合物中吲哚对基础油的安定性影响最大,当两种或两种以上复合模拟化合物同时存在于基础油中时,由于相互作用,基础油的不稳定性加剧。在轻油、洗油和蒽油3种煤焦馏分油中,分别加入0．1％的稳定剂,常温储存40天后,其色度、胶质和沉渣等安定指标能够满足国标一级品柴油的规格要求。     

Solvent evaluation for desulfurization and denitrification of gas oil using performance and industrial usability indices

A new strategy for screening of solvents for sulfur, nitrogen, and aromatic compounds removal from gas oil is presented. This ranking is based on comparative assessment of solvents’ capacity, selectivity, performance, and newly defined industrial usability indices. Twenty eight solvents comprising of six most widely used industrially proven conventional solvents and 22 imidazolium‐based ionic liquids solvents were selected to illustrate the strategy. The solvents were ranked for removal of sulfur compounds namely benzothiophene, dibenzothiophene and their alkylated derivatives, and nitrogenous compounds namely quinoline, indole and carbazole from gas oil. Performance index (P_I) which combines the effect of both capacity and selectivity seems to be better index than individual capacity and selectivity indices to rank the solvents. Industrial usability index (S_IUI) of solvents which includes P_I and process complexity factor for solvent recovery section seems more practical and realistic criteria for solvent assessment. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2257–2267, 2015     

催化柴油中含氮化合物的研究

采用气相色谱-氮化学发光检测器联用技术建立了催化柴油中氮化物类型分布的分析方法,考察了色谱条件对各种氮化物分离的影响,对柴油中60多种氮化物进行了定性、归类。以N,N-二甲基苯胺、4-甲基喹啉、2,4-二甲基喹啉、吲哚、1-甲基吲哚、2,3-二甲基吲哚、2,3,3-三甲基吲哚作为标准样品,考察了各种含氮化合物在氮化学发光检测器上的响应,证实该方法具有很好的重复性和准确度,可用于不同来源和不同加工工艺的柴油馏分中各种氮化物类型及分布的研究。     

微波辐射脱除催化裂化柴油中碱性氮化物研究

在微波辐射的条件下,用乙酸-w(乙醇)=95%络合萃取催化裂化柴油中碱性氮化物,考察了剂油体积比、乙酸加入量、微波辐射功率、辐射时间、辐射压力等工艺条件对碱性氮化物脱除率和柴油回收率的影响。结果表明:在剂油体积比1.0、乙酸与95%乙醇体积比0.05、辐射压力0.5 MPa、恒压辐射时间10 min、微波功率375 W最佳反应条件下,碱性氮化物脱除率82.4%,柴油回收率90.1%,较无微波辐射的条件下,碱性氮化物脱除率显著提高。     

First principles study of heavy oil organonitrogen adsorption on NiMoS hydrotreating catalysts

The adsorption of quinoline, acridine, indole, and carbazole on the well-defined NiMoS hydrotreating catalyst edge surface has been studied by means of density-functional theory (DFT) using a periodic supercell model. Quinoline and acridine, the basic nitrogen-containing molecules present in heavy oils, are preferably adsorbed on the Ni-edge surface through the lone pair electrons of the nitrogen atom, which produces relatively high adsorption energies (−ΔE_a = 16–26 kcal mol⁻¹). Indole and carbazole, the non-basic nitrogen-containing molecules, primarily interact with the NiMoS catalyst edge surface through the π-electrons of the carbon atoms. While indole preferentially adsorbs on the NiMoS surface through the β-carbon of the pyrrolic ring (−ΔE_a = 19 kcal mol⁻¹), carbazole primarily interacts with the NiMoS surface through the phenyl rings (−ΔE_a = 13 kcal mol⁻¹). The relative adsorptivities and energetically preferred adsorption modes of the nitrogen-containing molecules in heavy oils can provide insights into experimental observations about hydrodenitrogenation (HDN) kinetics and reaction pathways.     

减二线脱蜡油糠醛精制加助剂脱氮中试研究

采用络合萃取法对某炼油厂的减二线脱蜡油进行脱氮精制处理小试和中试研究.主要介绍减二线脱蜡油的中试,用糠醛与金属盐的混合溶剂脱除脱蜡油中的碱性氮化物.结果表明,精制油的碱氮含量为2.31 μg·g-1,旋转氧弹时间236 min,黏度指数 119,脱氮率高达99%.减二线脱蜡油糠醛精制工艺中试的操作条件为:抽提塔顶温度1...     

Preparation of bio-fuels by catalytic cracking reaction of vegetable oil sludge

Biofuel production from vegetable oil is potentially a good alternative to conventional fossil derived fuels. Moreover, liquid biofuel offers many environmental benefits since it is free from nitrogen and sulfur compounds. Biofuel can be obtained from biomass (e.g. pyrolysis, gasification) and agricultural sources such as vegetable oil, vegetable oil sludge, rubber seed oil, and soybean oil. One of the most promising sources of biofuel is vegetable oil sludge. This waste is a major byproduct of vegetable oil factories. It consists of triglycerides (61%), free fatty acid (37%) and impurities (2%). The hydrocarbon chains of triglycerides and free fatty acid are mainly made up of C₁₆ (30%) and C₁₈ (36%) hydrocarbons. The others consist of C₁₂-C₁₇ hydrocarbon chains. Transesterification can help in converting vegetable oil sludge into biofuel. The disadvantage of this method is that a large amount of methanol is required. The alternative method for this conversion is catalytic cracking. The objective of this research is to evaluate and compare the pyrolysis process with cracking catalytic reaction of vegetable oil sludge by Micro-activity test MAT 5000 of Zeton-Canada.A ZSM-5/MCM-41 multiporous composite (MC-ZSM-5/MCM-41), was successfully synthesized using silica source extracted from rice husk. The material has the MCM-41 mesoporous structure, and its wall is constructed by ZSM-5 nanozeolite crystals. The porous system of the material includes pores of the following sizes: 5 Å (ZSM-5 zeolite), 40 Å (MCM-41 mesoporous material), and another porous system whose diameter is in the range of 100-500 Å (mesoporous system) formed by the burning of organic compounds that remain in the material during the calcination process. This pore system contributes to an increase in the catalytic performance of synthesized material.The results of vegetable oil sludge cracking reaction show that the product consists of fractions such as dry gas, liquefied petroleum gas (LPG), gasoline, light cycle oil (LCO), and (heavy cycle oil) HCO, which are similar to those of petroleum cracking process.MC-ZSM-5/MCM-41 catalyst is efficient in the catalytic cracking reaction of vegetable oil sludge as it has higher conversion and selectivity for LPG and gasoline products in comparison to the pyrolysis process. Product distribution (% of oil feed) of cracking reaction over MC-ZSM-5/MCM-41 is coke (3.4), total dry gas (7.0), LPG (31.1), gasoline (42.4), LCO (8.9), HCO (7.2); and that of pyrolysis are coke (19.0), total dry gas (9.3), LPG (16.9), gasoline (28.8), LCO (13.7), and HCO (12.3).These results have indicated a new way to use agricultural waste such as rice husk for the production of promising catalysts and the processing of vegetable oil sludge to obtain biofuel.     

大庆和涠洲混炼油糠醛精制研究

以大庆和涠洲混炼油(体积比为1∶1)减二线脱蜡油为原料,糠醛为溶剂,考察了剂油比、抽提温度对润滑油基础油糠醛精制效果的影响。实验表明,精制油的粘度指数随剂油比的增加和精制温度的上升而增大,精制油的收率随剂油比的增加和精制温度的上升而下降。当温度增大到一定程度时,精制油收率有变化,而粘度指数与折光率基本不变。     

直馏柴油络合萃取脱硫

分别采用络合剂FeCl3,AlCl3,TiCl4对产自盘锦慧丰的直馏柴油进行络合脱硫,结果表明:AlCl3的脱硫效果最好,络合剂用量为2 g时,脱硫率达到73.9%。通过实验得到在络合脱硫时,直馏柴油中的碱性氮含量减少,说明碱性氮消耗了络合剂,降低了络合剂的脱硫效果。本文采用自制脱氮剂LCH-28对盘锦慧丰直馏柴油进行脱氮,脱氮率达到90.0%。使用络合剂AlCl3对已脱氮的直馏柴油比未脱氮的直馏柴油脱硫率提高约5%~10%。为了取得更好的脱硫效果,采用络合剂AlCl3和三种萃取剂95%乙醇,甲醇,DMF进行复配。结果表明:以40 g柴油为基准,LCH-28的剂油比为1:200,AlCl3用量为2 g,95%乙醇用量为0.25 mL,在反应时间为20 min,反应温度为50℃的工艺条件下,对直馏柴油的脱硫率达到83.4%。     

液化油中含氮化合物的研究进展

综述了液化油的研究现状,石油、焦化行业中含氮化合物的分离方法和技术现状,阐述了液化油中含氮化合物的研究现状,介绍了油品中含氮化合物的分离效果和性质表征,最后对液化油中含氮化合物的研究前景进行了展望。     

络合法脱除桦甸页岩油柴油馏分中碱性氮的研究

采用酸碱洗涤-溶剂萃取的方法对兰州窑街的页岩油中的氮类化合物进行了提取。产物经GC—MS进行了测定,用色谱峰面积归一化法确定各碱性氮的相对含量。结果显示,含氮化合物共检出87个。其中碱性氮化合物共有64个,主要分为吡啶、喹啉、苯胺3类。非碱性含氮化合物23个,主要分为吡咯、吲哚、咔唑3类。根据碱性氮的组成性质,分别考察了剂油比、不同反应时间、反应温度对脱氮效果的影响。结果表明,当剂油比为3％、反应温度55℃、反应时间为10min,脱氮效果最好,页岩油中碱氮脱除率可达到82．1％。     

Hydrotreating of straight run gas oil–light cycle oil blends

A pilot plant study was conducted to evaluate the effect of up to 50 vol% light cycle oil (LCO) on product quality when it is used together with straight run gas oil (SRGO) as a hydrotreating feedstock. Experiments were carried out at reaction pressures of 54, 70 and 90 kg/cm²; reaction temperatures of 350, 360, 370 and 380°C, liquid hourly space velocity (LHSV) of 1.0, 1.5 and 2.0 h⁻¹, and constant hydrogen-to-oil ratio of 2000 ft³/bbl, over a commercial Co–Mo/γ-Al₂O₃ catalyst. The experimental results were used to determine apparent reaction orders and activation energies, which agree with those reported in the literature.     

Comparison of steam and nitrogen in the physical deacidification of soybean oil

Deacidification in physical refining is one of the most sensitive steps in refining edible vegetable oils because of its large impact on the quality of the oil. The removal of volatile compounds such as FFA is accomplished at elevated temperatures and a high vacuum with a stripping gas, usually steam. The aim of this work was to verify, at the laboratory level, the advantages of using an alternative stripping gas, nitrogen, instead of steam. An ideal vapor-liquid equilibrium model (IVLE) was used to compare the stripping capacities of steam and nitrogen and to analyze the effects of various operational parameters (temperature, pressure, amount of stripping gas) on the residual acidity of the oil. There was no clear evidence that nitrogen showed a higher capacity to strip FFA than steam. The IVLE model seemed suitable to describe FFA laboratory distillation by using steam or nitrogen, provided the final residual content of FFA was not too low.     

Sensitivity analysis of a light gas oil deep hydrodesulfurization process via catalytic distillation

In this work, a sensitivity analysis of a light gas oil deep hydrodesulfurization catalytic distillation column is presented. The aim is to evaluate the effects of various parameters and operating conditions on the organic sulfur compound elimination by using a realistic light gas oil fraction. The hydrocarbons are modeled using pseudocompounds, while the organic sulfur compounds are modeled using model compounds, i.e., dibenzothiophene (DBT) and 4,6-dimethyl dibenzothiophene (4,6-DMDBT). These are among the most refractive sulfur compounds present in the oil fractions. A sensitivity analysis is discussed for the reflux ratio, bottom flow rate, condenser temperature, hydrogen and gas oil feed stages, catalyst loading, the reactive, stripping, and rectifying stages, feed disturbances, and multiple feeds. The results give insight into the qualitative effect of some of the operating variables and disturbances on organic sulfur elimination. In addition, they show that special attention must be given to the bottom flow rate and LGO feed rate control.     

抚顺页岩油碱性氮化物的脱除

用LCH-28脱氮剂脱除抚顺页岩油中的碱性氮化物.LCH-28脱氮剂主要由Bronsted酸和Lewis酸(占脱氮剂总重量的0.1％～10％)组成.当剂油质量比为1∶10、反应时间为10 min、反应温度为80～90℃、保温沉降时间为180 min时,碱性氮化物的脱除率达到85.2％,相应的页岩油损失率为18.3％,探...     

Multi-objective optimization of fuel oil blending using the jumping gene adaptation of genetic algorithm

Production and marketing of heavy fuel oil (HFO) are an easy, effective and economical way to dispose off certain very heavy refinery streams such as short residue (SR, available from the bottom of vacuum distillation units) and clarified liquid oil (CLO, available from the bottom of the main fractionators of fluidized-bed catalytic crackers). Certain lighter streams such as heavy cycle oil (HCO), light cycle oil (LCO) and kerosene, are added to the heavy residual stock to improve its quality in terms of fluidity, combustibility, etc., to be marketed as fuel oil. The present study aims at optimization of the fuel oil blending process to maximize profit, minimize quality give-away, maximize production, minimize use of lighter products such as LCO and kerosene, and maximize the calorific value, etc. Several multi-objective optimization problems have been formulated comprising of two and three-objective functions and solved using the elitist non-dominated sorting genetic algorithm (NSGA-II). This evolutionary technique produces a set of non-dominating (equally good) Pareto optimal solutions from which the operator can choose the one that is most suitable (preferred point). Also, a fixed-length macro–macro mutation operator, inspired by jumping genes in natural genetics, has been used with NSGA-II to solve this problem. This modified algorithm leads to a significant reduction in the computational effort. Indeed, this adaptation can be of immense use in reducing the computational effort for other problems in chemical engineering.     

从洗油中分离喹啉的新方法

以洗油为原料,通过精馏-共沸精馏法,研究了喹啉的分离精制。首先精馏洗油,切取不同温度段的馏分,然后分别与共沸剂乙二醇进行共沸精馏试验;在共沸精馏中,通过改变馏分与共沸剂的质量比和回流比,考察了不同条件对喹啉纯度的影响。结果表明:①精馏洗油切取喹啉馏分的较佳条件为:回流比为10∶1,切取温度范围为220~230℃;②共沸精馏的较佳条件为:回流比为10∶1,喹啉馏分与共沸剂的质量比为1∶2.4,切取温度范围为188.4~188.8℃,喹啉的纯度可达98.5%。该方法具有操作简单、步骤少、纯度高、无污染的特点。