Thermodynamic analysis of the gasification product composition of vacuum residuum from the hydroconversion of heavy crude fractions oil

Heavy residual stock obtained by the vacuum distillation of the hydroconversion products (T = 425°C; P = 6 MPa; a nanoheterogeneous catalyst based on molybdenum sulfide) of heavy residual carbonic (high-sulfur) oil is a starting material for gasification. The equilibrium composition of gasification products (P = 0.1 MPa; α = 0.3; 20 wt % H₂O) over the temperature range of 519–1626 K was calculated using chemical thermodynamics methods. The yields of the main compounds of Mo, V, Ni, Ag, Au, As, Co, Ga, Fe, Al, Si, Ca, and Mg (mol/kg residue) and their amounts in gas and condensed phases were determined. The volumes and compositions of gaseous products were also determined as functions of temperature at different sulfur concentrations of 9.5 and 4.75 wt % in the starting vacuum residue.     

减压柴油管式炉裂解制烯烃

中国某些产地的原油具有低硫、高石蜡烃和低芳烃含量的特性。用这类原油炼制所得的减压柴油馏分具有同样特征,因而预测将有良好的裂解性能。为此进行了工艺研究。 在处理量约为2公斤/时,温度和压力分布可以模拟的裂解装置中,进行了中国减压柴油动力学研究和裂解产品分布规律试验。根据模试结果;综合中试和部分工业数据,提出了减压柴油裂解反应速度常数方程的有关参数值,以及原料特性和工艺参数对裂解产品收率关联图及数学关联式。 在处理量为100公斤/时的中试裂解装置中进行产品分布试验和工艺过程有关技术研究,着重考察了炉管对流段、辐射段的运转情况、高压急冷锅炉的操作特性。 研究结果表明,在760℃中等裂解深度时,汽油比为0.75—1,停留时间0.4—0.5秒,烃分压0.8公斤/厘米~2,主要产品收率为:乙烯22.5—23%,丙烯16—17.5%,丁二烯4.7—5.2%,重质燃料油10—12%。该油品与国外中东轻柴油裂解所得产物收率相仿,是工业管式炉的一种好原料。     

尾油循环的煤焦油加氢实验研究

利用小型固定床加氢实验装置,将煤焦油和其加氢后的尾油混合,在温度(360~420)℃、压力(13~15)MPa、氢油体积比(1 500~1 700)∶1和液体体积空速0.25 h-1条件下进行加氢处理,所得产品切割得到的汽油馏分、柴油馏分和尾油馏分,分别占产物质量的16.12%、78.83%和5.05%,且产品中硫、氮含量很低,汽油中硫含量16.7μg·g~(-1),氮含量36μg·g~(-1),柴油中硫含量102.6μg·g~(-1),氮含量97μg·g~(-1),可用作清洁燃料。结果表明,尾油循环在煤焦油加氢过程中对煤焦油具有稀释作用,不仅减轻了设备负荷,同时也可以提高汽油和柴油收率。因此,以煤焦油加氢尾油循环加氢是一种高效、绿色环保制备燃料油的方法。     

Gasification and co-gasification of biomass wastes: Effect of the biomass origin and the gasifier operating conditions

Air gasification of different biomass fuels, including forestry (pinus pinaster pruning) and agricultural (grapevine and olive tree pruning) wastes as well as industry wastes (sawdust and marc of grape), has been carried out in a circulating flow gasifier in order to evaluate the potential of using these types of biomass in the same equipment, thus providing higher operation flexibility and minimizing the effect of seasonal fuel supply variations. The potential of using biomass as an additional supporting fuel in coal fuelled power plants has also been evaluated through tests involving mixtures of biomass and coal–coke, the coke being a typical waste of oil companies. The effect of the main gasifier operating conditions, such as the relative biomass/air ratio and the reaction temperature, has been analysed to establish the conditions allowing higher gasification efficiency, carbon conversion and/or fuel constituents (CO, H₂ and CH₄) concentration and production. Results of the work encourage the combined use of the different biomass fuels without significant modifications in the installation, although agricultural wastes (grapevine and olive pruning) could to lead to more efficient gasification processes. These latter wastes appear as interesting fuels to generate a producer gas to be used in internal combustion engines or gas turbines (high gasification efficiency and gas yield), while sawdust could be a very adequate fuel to produce a H₂-rich gas (with interest for fuel cells) due to its highest reactivity. The influence of the reaction temperature on the gasification characteristics was not as significant as that of the biomass/air ratio, although the H₂ concentration increased with increasing temperature.     

连续式FCC柴油萃取-光催化氧化深度脱硫

尽快降低燃料油中的硫含量是整个炼油业都无法回避的重大问题，炼油工业发达的国家已提出生产超低硫清洁燃料 （硫含量低于10 μg•g^-1）的目标。本文通过连续式FCC柴油萃取-光催化深度脱硫工艺，对FCC柴油进行精制，精制油中硫含量采用硫氮荧光分析仪测定，硫含量为45 μg•g^-1。实验结果表明：萃取操作的适宜条件为常压，萃取温度40℃，剂油比1.5∶1;反应操作的适宜条件为反应温度40℃，反应时间1 h，氧化剂用量为4%。在以上操作条件下，精制油中的硫含量为达到欧Ⅳ标准，精制油总收率超过96%。     

Behaviour of heavy metals in the partial oxidation of heavy fuel oil

The behaviour of heavy metals in the partial oxidation of heavy fuel oils under a pressure of up to 100 bar (10 MPa) has been investigated. The tests were carried out in a 5 MW HP POX (High Pressure Partial Oxidation) test plant, that is operated by the IEC (Department of Energy Process Engineering and Chemical Engineering, TU Bergakademie Freiberg) in cooperation with Lurgi GmbH. In several test campaigns preheated oil with a viscosity of up to 300 cSt (= 300 mm²/s) at the burner inlet has been gasified. The heavy metals nickel Ni, iron Fe and vanadium V occur in heavy residual oils in considerable concentration and may seriously impact the gasification itself and the synthesis gas conditioning and usage. While iron is largely recovered in the gasification residue, the recovery rates of nickel and vanadium depend on the process conditions. Volatile nickel compounds were detected in the raw synthesis gas. It was found that an incomplete carbon conversion enables the capture of nickel Ni and vanadium V in the solid residue phase and can thus mitigate the problem of volatile metal compounds in the raw synthesis gas.     

Sulfur transfers from pyrolysis and gasification of direct liquefaction residue of Shenhua coal

The sulfur transformation during pyrolysis and gasification of Shenhua direct liquefaction residue was studied and the release of H₂S and COS during the process was examined. For comparison, the sulfur transfer of Shenhua coal during pyrolysis and that of pyrolyzed char during gasification were also studied. The residue was pyrolyzed at 10 °C /min to 950 °C. During pyrolysis about 33.6% of sulfur was removed from the residue, among which 32.1% was formed H₂S in gas and 1.5% was transferred into tar, 66.4% of the sulfur was remained in residue char. Compared with coal, the residue has generated more H₂S due to presence of Fe_1−xS which was enriched in residue during liquefaction process. There is a few COS produced at 400-500 °C during pyrolysis of coal, but it was not detected form pyrolysis of the residue. During CO₂ gasification, compared with pyrolysis and steam gasification, there are more COS and less H₂S formation, because CO could react with sulfide to form COS. During steam gasification only H₂S was produced and no COS detected, because H₂ has stronger reducibility to form H₂S than CO. After steam gasification no sulfur was detected in the gasification residue. The XRD patterns show after steam gasification, only Fe₃O₄ is remained in the gasification residue. This indicates that the catalyst added during the liquefaction of coal completely reacted with steam, resulting in the formation of H₂ and Fe₃O₄.     

基于赤铁矿载氧体的煤化学链燃烧试验

化学链燃烧是一种具有CO₂内分离特性的燃烧方式。以赤铁矿为载氧体,在1 kW_th级串行流化床上进行了煤化学链燃烧试验。讨论了燃料反应器温度对气体产物组分的影响;比较了各反应参数对煤气化效率、煤气化产物的转化效率及碳捕集效率的影响情况,分析了煤中硫的排放问题。试验结果表明：温度由900℃升高到985℃,燃料反应器中CO体积份额逐渐增加,CO₂体积份额逐渐减小,空气反应器中CO₂浓度呈线性下降。燃料反应器温度的升高促进煤气化效率及碳捕集效率大大提高。载氧体量和系统负荷是煤气化产物转化效率的主要影响因素,载氧体量的增加和负荷的增加分别会使煤气化产物转化效率提高和下降。燃料反应器中的硫主要以SO₂形式存在于燃料反应器,随温度的升高,SO₂浓度由515×10^-6逐渐增加到562×10^-6相似文献   

Ultradispersed particles in heavy oil: Part I, preparation and stabilization of iron oxide/hydroxide

In this study, ultradispersed colloidal particles of iron oxide/hydroxide were prepared in-situ in heavy oil matrices adopting (w/o) microemulsion approach for nanoparticle preparation detailed in our previous work [1-3]. The effect of composition of heavy oil on the stable concentration of colloidal particles, particle uptake, was investigated. The following trends in particle uptake were common between the (w/o) microemulsions and the heavy oil matrices. An optimum water content was found for which a maximum particle uptake was attained. Particle uptake increased as the content of vacuum residue, VR, and precursor salt concentration increased. Vacuum residue contributes high asphaltene content, which acts as a surface active agent. The iron oxide/hydroxide particles had been recently shown to effectively remove H₂S_(g) from oil phase [4]. H₂S_(g) is a hazardous by-product of heavy oil recovering and upgrading which should be removed as soon as it forms. Results pertaining to H₂S_(g) removal from heavy oil employing ultradispersed particles are communicated in Part II of this study.     

Oxidative desulfurization of simulated light fuel oil and untreated kerosene

An experimental investigation was conducted on the oxidative desulfurization of model sulfur compounds such as dibenzothiophene and benzothiophene in toluene as a simulated light fuel oil with a mixture of hydrogen peroxide as the oxidant and various acids as the catalyst. The influences of various parameters including reaction temperature (T), acid to sulfur molar ratio (Acid/S), oxidant to sulfur molar ratio (O/S), type of acid, and the presence of sodium tungstate and commercial activated carbon as a co-catalyst on the fractional conversion of the model sulfur compounds were investigated. The experimental data obtained were used to determine the reaction rate constant of the model sulfur compounds and the corresponding activation energy. Moreover, the adsorption of model sulfur compounds on the commercial activated carbons supplied by Jacobi Co. (Sweden, AquaSorb 101) was studied and the effects of different parameters such as temperature, and various chemical treatments on the adsorption of the sulfur compounds were investigated. Furthermore, the oxidative desulfurization of untreated kerosene with the total sulfur content of 1700 ppmw produced by an Iranian refining company (Isfahan refinery) was successfully investigated. These experiments were performed using formic acid as the catalyst and hydrogen peroxide as the oxidant at the mild operating conditions of T = 50 °C, O/S = 5, and the Acid/S = 10. It was realized that about 87% of the total sulfur content of untreated kerosene could be removed after 30 min oxidation followed by liquid–liquid extraction.     

长庆原油适宜加工方案分析

摘要：介绍了对长庆原油进行的综合评价。结果表明：长庆原油属于优质的轻质低硫含蜡原油,馏分分布状况好。在生产装置炼制时,常、减压负荷均衡,易于平衡操作。初馏点-180℃馏分可做大乙烯裂解原料,但更适合做重整原料;145-240℃喷汽燃料组分收率较高,铜片腐蚀、硫醇硫不合格,说明长庆原油喷汽燃料中活性硫化物较多,在精制时应注意;柴油馏分柴油指数高、十六烷值大,腐蚀、酸度均符合成品柴油的标准。减压蜡油酸值小、粘度指数高,是生产润滑油基础油的理想原料,同时其Cp高、残炭值低,重金属含量不高,也是理想的催化裂解原料;〉520℃的渣油沥青质含量较高,是生产沥青的理想原料,如果作为催化裂化原料,必须考虑调配比例,以防催化剂中毒。     

Gasification of heavy fuel oils: A thermochemical equilibrium approach

Combustion of heavy fuel oils is a major source of production of particulate emissions and ash, as well as considerable volumes of SO_x and NO_x. Gasification is a technologically advanced and environmentally friendly process of disposing heavy fuel oils by converting them into clean combustible gas products. Thermochemical equilibrium modeling is the basis of an original numerical method implemented in this study to predict the performance of a heavy fuel oil gasifier. The model combines both the chemical and thermodynamic equilibriums of the global gasification reaction in order to predict the final syngas species distribution. Having obtained the composition of the produced syngas, various characteristics of the gasification process can be determined; they include the H₂:CO ratio, process temperature, and heating value of the produced syngas, as well as the cold gas efficiency and carbon conversion efficiency of the process. The influence of the equivalence ratio, oxygen enrichment (the amount of oxygen available in the gasification agent), and pressure on the gasification characteristics is analyzed. The results of simulations are compared with reported experimental measurements through which the numerical model is validated. The detailed investigation performed in the course of this study reveals that the heavy oil gasification is a feasible process that can be utilized to generate a syngas for various industrial applications.     

Experimental and numerical simulation of lignite chemical looping gasification with phosphogypsum as oxygen carrier in a fluidized bed

Phosphogypsum (PG) is a solid waste produced in the wet process of producing phosphoric acid.Lignite is a kind of promising chemical raw material.However,the high sulfur of lignite limits the utilization of lig-nite as a resource.Based on fluidized bed experiments,the optimal reaction conditions for the production syngas by lignite chemical looping gasification (CLG) with PG as oxygen carrier were studied.The study found that the optimal reaction temperature should not exceed 1123 K;the mole ratio of water vapor to lignite should be about 0.2;the mole ratio of PG oxygen carrier to lignite should be about 0.6.Meanwhile,commercial software Comsol was used to establish a fuel reaction kinetics model.Through computational fluid dynamics (CFD) numerical simulation,the process of reaction in fluidized bed were well captured.The model was based on a two-fluid model and coupled mass transfer,heat transfer and chemical reac-tions.This study showed that the fluidized bed presents a flow structure in which gas and solid coexist.There was a high temperature zone in the middle and lower parts of the fluidized bed.It could be seen from the results of the flow field simulated that the fluidized bed was beneficial to the progress of the gasification reaction.     

调和制备船用燃料油的研究

由糠醛抽出油、乙烯焦油和减压渣油调和制备船用燃料油,考察了温度、调和比、表面活性剂对调和油黏度和闪点的影响。结果表明,当糠醛抽出油∶乙烯焦油∶渣油=1∶5∶1,2∶5∶1和3∶5∶1时,调和油的黏度和闪点达到120#船舶燃料油产品指标;当糠醛抽出油∶乙烯焦油∶渣油=2∶3∶1时,调和油达到180#船舶燃料油产品指标要求。研究还发现,调和油中添加一定量的非离子表面活性剂,能显著减低调和油的黏度,当表面活性剂添加量达到3‰时,黏度降到最低。     

Fuel properties of biodiesel produced from Camellia oleifera Abel oil through supercritical-methanol transesterification

The fuel properties of the biodiesel produced from Camellia oleifera Abel oil through supercritical-methanol transesterification with no catalyst was investigated in this study. An emulsion of raw C. oleifera Abel oil dispersed in methanol was prepared prior to being poured into a supercritical-methanol reaction system to undergo the transesterification reaction. The fuel properties of the resulting biodiesel were analyzed and compared with those of a commercial biodiesel and with ASTM No. 2D diesel fuel. The experimental results show oleic acid (C18:1) and palmitic acid (16:0) to be the two major components of the C. oleifera Abel oil biodiesel. It also contains significantly higher mono-unsaturated fatty acids and long carbon-chain fatty acids ranging from C20 to C22 than those found in the commercial biodiesel. However, relative to the commercial biodiesel, the C. oleifera Abel oil biodiesel has significantly fewer poly-unsaturated fatty acids with more than three double bonds, which implies that it also has a much higher degree of oxidative stability. In addition, the biodiesel produced from C. oleifera Abel oil was also found to have more favorable fuel properties than the commercial biodiesel produced from waste cooking oil, including a higher heat of combustion and flash point and lower levels of kinematic viscosity, water content, and carbon residue. Moreover, the former appears to have much lower peroxide and acid values, and thus a much higher degree of oxidative stability than the latter.     

Fuel Properties of Biodiesel/Ultra-Low Sulfur Diesel (ULSD) Blends

Biodiesel is an alternative fuel and fuel extender easily derived from vegetable oil or animal fat. In 2006, the US Environmental Protection Agency mandated that maximum sulfur content of diesel fuels be reduced to 15 ppm to protect catalysts employed in exhaust after-treatment devices. Processing to produce this ultra-low sulfur petrodiesel (ULSD) alters fuel lubricity, density, cold flow, viscosity, and other properties. Consequently, there is a need to develop a better understanding of the basic fuel properties of biodiesel/ULSD blends. This work evaluates the effects of biodiesel volumetric blend ratio (V _BD) on cloud point (CP), kinematic viscosity (ν), specific gravity (SG), and refractive index (RI) of blends with petrodiesel. Properties measured for various blends of methyl esters of soybean oil (SME) and used cooking oil (UCOME) in ULSD were compared with those for blends with low sulfur (≤500 ppm) petrodiesel fuel (LSD). With respect to increasing V _BD, CP and SG increased and RI decreased with each parameter demonstrating a linear correlation. In contrast, ν showed a curvilinear relationship with respect to increasing V _BD. Calibration curves were derived from regression analyses to determine V _BD in biodiesel/ULSD blends from measurements of each individual property. While the models had generally high coefficients of regression (R ² > 0.986), SG models were most accurate for predicting V _BD to within 1.3 vol%.     

High temperature air-blown gasification of Korean anthracite and plastic waste mixture

Korean anthracite is too high in ash contents and low in calorific value to be used as an industrial energy source, the demand for anthracite has rapidly decreased and its competitiveness weakened. To overcome the problem, a mixture of Korean anthracite and plastic wastes low in ash and high in calorific value was manufactured. A 1.0T/D fixed bed gasification process was developed to understand the gasification characteristics of the mixtures and secure operation technology using Korean and Chinese anthracite. For the Korean anthracite, the syngas composition and heating value are varied from 10 to 20% and from 300 to 800 kcal/Nm³ as a function of steam/air/fuel ratio. Therefore, it is concluded that Korean anthracite is hard to gasify because of low reactivity. For the Chinese anthracite low ash content and higher heating value than domestic anthracite, the syngas composition was maintained at about 20–40% and the calorific value was 800–1,300 kcal/Nm³. A reformer using high-temperature air/steam was installed just after the gasifier to combust and convert tar and soot into syngas. We confirmed that the amount of generated tar and soot showed a salient difference after running the reformer. In the future, gasification experiments of manufactured mixtures of anthracite and plastic waste using 1.0T/D fixed bed gasifier will be performed. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

10MWth高硫石油焦化学链气化制合成气耦合硫磺回收新系统模拟研究

基于化学链气化技术依靠气固反应定向调控气化产物中H₂S和SO₂摩尔比为2的优势，将化学链气化与Claus工艺中的催化转化单元相结合，提出了高硫石油焦化学链气化制合成气和回收硫磺的新系统。针对系统核心单元，即化学链气化过程，基于Aspen Plus，开展热输入10 MW_th的高硫石油焦化学链气化过程模拟，以赤铁矿石为载氧体，水蒸气为气化介质，重点考察了氧碳比、气化温度对化学链气化过程及硫转化过程的影响。结果发现，氧碳比的增大导致合成气产率显著降低，但系统从需要外部提供能量逐渐转变为对外部放热，在氧碳比0.8669～0.9535区间内，系统可以达到热量自平衡。同时，气化温度的提高对合成气产率是有利的，在975℃时达到2.15 m³/kg，主要是由于CO体积分数随气化温度增加而增加。氧碳比和气化温度的提高都会导致H₂S浓度的降低和SO₂浓度的提高。并且研究了当H₂S和SO₂摩尔比为2的最佳工况时，氧碳比和气化温度为反相关，其中氧碳比为0.8669，气化温度为900℃时，冷煤气效率为64.09%。     

Use of ultrasound in petroleum residue upgradation

Conventional processes for the upgradation of residual feedstocks, viz., thermal cracking and catalytic cracking are carried out in the temperature range of 400–520°C. Such high temperatures can in principle be substituted by acoustic cavitation. In the present work, two vacuum residues, namely, Arabian mix vacuum residue (AMVR) and Bombay high vacuum residue (BHVR) and one asphalt, viz., Haldia asphalt (HA) were subjected to acoustic cavitation for different reaction times from 15 min to 120 min at ambient temperature and pressure. An attempt has been made to seek a performance comparison of two devices of acoustic cavitation, namely, ultrasonic bath and ultrasonic horn with regard to their ability to upgrade the petroleum residues to lighter, more value‐added products mainly the hydrocarbons boiling in the range of gas oil fraction. Another attempt has been made to study the effect of ultrasound on the upgradation of the residue when it is emulsified in water with the help of different surfactants. For all the cases, a kinetic model has been developed based on the constituents of the residue so as to get an insight into the reaction mechanism. The study revealed that ultrasonic horn is more effective in bringing about the upgradation than ultrasonic bath and that the acoustic cavitation of the aqueous emulsified hydrocarbon mixture could reduce the asphaltenes content to a greater extent than the acoustic cavitation of non‐emulsified hydrocarbon mixture. The reduction in asphaltenes content of BHVR was found to be more followed by AMVR followed by HA. The variation in the rate constants was found to be feed specific and the rate constants for the conditions of maximum conversion of asphaltenes to gas oil for AMVR, BHVR and HA were found to be 0.29 × 10^?4 s^?1, 1.4 × 10^?4 s^?1 and 0.23 × 10^?4 s^?1, respectively.     

松木成型燃料水蒸气气化反应特性

采用自制蒸气气化炉试验系统,以废弃松木屑为原料制作成型颗粒燃料,采用高温水蒸气气化,考察不同气化温度及气料比（S/B）对生物质水蒸气气化反应的影响,利用XRD射线衍射和傅里叶红外图谱分别分析生物质反应残留物及气化焦油,反应残留物的比表面积及空隙特性由BET多点法和BJH法测得。结果表明,蒸汽流量和反应温度有利于促进蒸汽重整、碳还原、CO的变换反应,当S/B由0.5增加到1.5时,温度为900℃,H₂体积分数由52.32%增长到67.3%;随温度升高（750~950℃,S/B=1）,松木颗粒的失重率由82.91%升高到91.27%,其微孔结构充分发展,平均孔直径由20.96 nm降低到3.76 nm,焦油中脂肪烃含量增加,芳香烃因发生开环反应使其含量降低,有益于降低气化气中焦油含量。