RS-1000催化剂在生产欧Ⅴ柴油中的应用

采用超深度加氢脱硫催化剂RS-1000,分别以高硫直馏柴油和催化裂化柴油为原料,在中试装置上进行满足欧V排放要求的清洁柴油生产的试验,并考察RS-1000催化剂在工业装置上长期生产硫含量小于10μg/g清洁柴油的性能。结果表明,以直馏柴油或直馏柴油掺炼10%的催化裂化柴油为原料,在较高空速1.7～2.0h－1和常规反应温度、压力下,或以催化裂化柴油为原料,在较低空速1.00～1.25h－1和常规反应温度、压力下,采用RS-1000催化剂,均可生产出硫含量小于10μg/g的清洁柴油,且在运转过程中催化剂具有良好的选择性和稳定性。     

生产超低硫柴油的S-RASSG催化剂级配技术的工业应用

为满足炼油企业生产国Ⅳ及欧Ⅴ标准清洁柴油的需要,抚顺石油化工研究院(FRIPP)开发了适合不同原料、分别以W-Mo-Ni(Mo-Ni)及Mo-Co为活性金属的FHUDS系列催化剂,并根据加氢反应器内催化剂床层不同的工况条件和反应特点,结合不同类型催化剂的超深度脱硫反应机理,开发了催化剂级配的S-RASSG柴油超深度脱硫技术。工业应用结果表明:采用S-RASSG技术及配套的FHUDS-2/FHUDS-5催化剂体系,加工常压柴油掺兑质量分数为40%左右催化柴油及焦化汽柴油或减压柴油的高硫混合油,在反应器入口压力8.0 MPa,主催化剂体积空速1.85～2.25 h-1、平均反应温度350℃左右等条件下,可以长周期稳定生产硫质量分数小于50μg/g、满足国Ⅳ标准的低硫柴油;加工常压柴油掺兑质量分数为30%左右减压柴油及少量焦化柴油的混合油,在反应器入口压力8.0MPa,主催化剂体积空速1.85 h-1、平均反应温度350℃左右等条件下,可以稳定生产硫质量分数小于10μg/g、满足欧Ⅴ标准的超低硫柴油。S-RASSG催化剂级配技术为炼油企业生产满足国Ⅳ和欧Ⅴ标准的超低硫柴油提供了有力的技术支撑。     

Stabilization Studies of Middle Distillate Fuels: Structural Composition of Insoluble by FTIR Spectroscopy

Abstract

For reducing the supply-demand gap of diesel fuel, blending of cracked stocks is essential with straight run products. This enhances the instability problem. This problem can be reduced using various stabilization procedures. In the present paper blends of cracked stocks light cycle oil (LCO) with straight run gas oil (SRGO) were stabilized by methanol extraction and hydrostabilization techniques. The insoluble from these fuels as such and their blends were stabilized and characterized using FTIR spectroscopy.     

Stabilization Studies of Middle Distillate Fuels: Structural Composition of Insoluble by FTIR Spectroscopy

For reducing the supply-demand gap of diesel fuel, blending of cracked stocks is essential with straight run products. This enhances the instability problem. This problem can be reduced using various stabilization procedures. In the present paper blends of cracked stocks light cycle oil (LCO) with straight run gas oil (SRGO) were stabilized by methanol extraction and hydrostabilization techniques. The insoluble from these fuels as such and their blends were stabilized and characterized using FTIR spectroscopy.     

Desulfurization of Middle Distillates by Oxidation and Extraction Process

In this work, we studied the desulfurization of Straight Run Gas Oil (SRGO) and diesel by selective oxidation and extraction of sulfur-containing compounds. The oxidation was carried out with a mixture of hydrogen peroxide at 30 wt% and acetic acid as catalyst. The extraction of the corresponding sulfones was performed with polar solvents (e.g., acetonitrile, methanol, 2-ethoxyethanol, and γ-butyrolactone). The SRGO has a sulfur content of 13,985 ppmw while diesel has 390 ppmw, the results showed sulfur removal to levels as low as 92 ppmw for diesel. From a consideration of the above results, a preliminary estimation of investment for a desulfuration process for hydrotreated diesel was done.     

生产清洁汽柴油的加氢技术

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COMPARISON BETWEEN THE PERFORMANCE OF CONVENTIONAL AND HIGH-METAL Co-Mo AND Ni-Mo CATALYSTS IN DEEP DESULFURIZATION OF KUWAIT ATMOSPHERIC GAS OIL

Due to environmental constraints, sulfur content of diesel fuel has been restricted to very low levels (500 ppm maximum) in many countries. As a result, a greater emphasis has been placed in recent years on the development of catalysts and processes for deep desulfurization of diesel blending streams to produce low sulfur diesel fuel. In the present work we have compared the performance of a conventional Co-Mo catalyst with that of high metal loading Co-Mo and Ni-Mo catalysts in deep desulfurization of Kuwait atmospheric gas oil. The tests were carried out in a fixed bed reactor unit using 75 ml of catalyst under the conditions: P=32 bar; LHSV = 4h^-1; H₂/oil ratio = 100 ml/ml; temperature range = 330 - 390°C. HDS activity of the high molybdenum Co-Mo catalyst was superior to that of the conventional Co-Mo hydrotreating catalyst. High metal loading Co-Mo/Al₂O₃ catalyst also showed a substantially higher HDS activity than the Ni-Mo/Al₂O₃ catalyst containing a similar high metal loading. The unreacted sulfur compounds remaining in the product after high severity hydrotreating were identified as dibenzothiophenes with alkyl substituents next to the sulfur atom. The desulfiirization of such low reactive alkyl dibenzothiophenes was found to occur at a substantially lower temperature over the high metal loading Co-Mo catalyst compared with the conventional Co-Mo catalyst. The results have been explained on the basis of the stacking and dispersion of MoS₂ slabs as well as in terms of the nature of the sulfur vacancies in the MoS₂ layers in these catalyst systems.     

Effect of waste cooking-oil biodiesel on performance and exhaust emissions of a diesel engine

The ever increase in global energy demand, consumption of depletable fossil fuels, exhaust emissions and global warming, all these led to search about alternative fuels. Biodiesel was produced from waste cooking-oil by transesterification process. Blends of waste cooking-oil biodiesel and diesel oil were prepared in volume percentages of 10, 20 and 30% as B10, B20 and B30. Biodiesel blends have ASTM standards of physical and chemical characterization near to diesel fuel. Diesel engine performance and exhaust emissions were studied experimentally for burning waste cooking-oil blend with diesel fuel. This experimental was applied on a diesel engine at different engine loads from zero to full load. Thermal efficiencies for waste cooking-oil biodiesel blends were lower than diesel oil. Specific fuel consumptions of biodieselblends were higher than diesel fuel. Higher exhaust gas temperatures were recorded for biodiesel blends compared to diesel oil. CO₂ emissions for waste cooking-oil biodiesel blends were higher than diesel oil. CO, smoke opacity and HC emissions for biodiesel blends were lower than diesel fuel. NO_x emissions for biodiesel blends were higher than diesel fuel.     

COMPARISON BETWEEN THE PERFORMANCE OF CONVENTIONAL AND HIGH-METAL Co-Mo AND Ni-Mo CATALYSTS IN DEEP DESULFURIZATION OF KUWAIT ATMOSPHERIC GAS OIL

ABSTRACT

Due to environmental constraints, sulfur content of diesel fuel has been restricted to very low levels (500 ppm maximum) in many countries. As a result, a greater emphasis has been placed in recent years on the development of catalysts and processes for deep desulfurization of diesel blending streams to produce low sulfur diesel fuel. In the present work we have compared the performance of a conventional Co-Mo catalyst with that of high metal loading Co-Mo and Ni-Mo catalysts in deep desulfurization of Kuwait atmospheric gas oil. The tests were carried out in a fixed bed reactor unit using 75 ml of catalyst under the conditions: P=32 bar; LHSV = 4h^?1; H₂/oil ratio = 100 ml/ml; temperature range = 330 ? 390°C. HDS activity of the high molybdenum Co-Mo catalyst was superior to that of the conventional Co-Mo hydrotreating catalyst. High metal loading Co-Mo/Al₂O₃ catalyst also showed a substantially higher HDS activity than the Ni-Mo/Al₂O₃ catalyst containing a similar high metal loading. The unreacted sulfur compounds remaining in the product after high severity hydrotreating were identified as dibenzothiophenes with alkyl substituents next to the sulfur atom. The desulfiirization of such low reactive alkyl dibenzothiophenes was found to occur at a substantially lower temperature over the high metal loading Co-Mo catalyst compared with the conventional Co-Mo catalyst. The results have been explained on the basis of the stacking and dispersion of MoS₂ slabs as well as in terms of the nature of the sulfur vacancies in the MoS₂ layers in these catalyst systems.     

高稳定性超深度脱硫催化剂RS-3100在柴油加氢装置的工业应用

RS-3100催化剂是中国石化石油化工科学研究院开发的高稳定性超深度加氢脱硫催化剂,首次在中国石化九江分公司1.20 Mt/a柴油加氢装置进行了工业应用.该装置于2020年4月一次开车成功,加工焦化汽柴油、催化裂化柴油和直馏柴油的混合原料,产品柴油硫质量分数小于10μg/g,多环芳烃质量分数小于7％,达到了国Ⅵ车用柴油...     

复合催化氧化直馏柴油脱硫的研究

在高压反应釜中,采用均相催化氧化脱硫催化剂和纯Oz对直馏柴油进行催化氧化脱硫,可达到很好的脱硫效果,但此法得到的氧化柴油酸值较大,加入助剂可以抑制烃类化合物的氧化,降低了氧化柴油的酸值,提高了氧化油收率,且硫含量也可达到欧洲Ⅱ类柴油标准(总硫<300μg/g)。结果表明,复合催化氧化脱硫使柴油中硫的质量分数降到271μg/g,酸值下降89.2%,氧化油收率提高1.4%。     

Peroxide oxidative desulfurization of a mixture of nonhydrotreated vacuum gas oil and diesel fraction

Oxidative desulfurization of a model mixture on the basis of vacuum gas oil and diesel fuel by hydrogen peroxide in the presence of formic acid has been studied. A technology of a two-phase system with a phase-transfer catalyst has been employed for the desulfurization. The optimum reaction time is 6 h and the hydrogen peroxide: sulfur molar ratio is 4: 1. As a result of successive triple oxidative desulfurization, 90% of total sulfur is removed from the model mixture.     

汽柴油深度脱硫方法及发展现状

阐述了当前国内外对汽柴油中硫含量的要求以及汽柴油中的硫化物特点,结合这些特点对吸附脱硫、萃取脱硫、膜分离、生物技术脱硫、络合沉淀法和催化氧化法等几种深度脱硫方法进行了论述,并且提出了未来汽柴油深度脱硫技术的发展方向.     

低硫重质船用燃料油生产方案研究

对如何低成本生产低硫重质船用燃料油(硫质量分数不大于0.5％)进行了深入研究.研究结果表明:以固定床渣油加氢-催化裂化(催化)为代表的企业,通过调合加氢重油、脱硫脱固催化油浆和催化重柴油进行生产;以加工低硫原油为代表的企业,通过调合低硫减压渣油、加氢催化柴油和脱固催化油浆进行生产.生产过程中,需充分关注渣油加氢装置的脱...     

One-Step Oxidation–Desulfurization of FCC Gasoline Catalyzed by Tungstophosphoric Acid

Abstract

The sulfur compounds in fluid catalytic cracked (FCC) gasoline were removed with a one-step oxidation–extraction method. Tungstophosphoric acid (HPWA), tert-butyl hydroperoxide (TBHP), and ethanol were used as catalyst, oxidant, and solvent, respectively. TBHP has a higher desulfurization degree and oil yield than hydrogen peroxide, and HPWA exhibited higher desulfurization degree and oil yield than the other kinds of acids. The one-step process has a higher desulfurization degree than the two-step process. The optimal operating parameters were obtained as follows: the catalyst amount was 5 wt%, the mole ratio of oxygen in the oxidant to the sulfur in the gasoline (O/S) was 10, the reaction temperature was 60°C, and the reaction time was 2 hr. Under these conditions, the desulfurization degree and yield of oil were both in the range of 85–90%.     

Performance and emissions characteristics of C.I. engine fueled with palm oil/palm oil methyl ester blended with diesel fuel

The rapid increasing worldwide demand for energy, continuous increasing of fuel consumption and the progressive depletion of fossil fuels led to an intensive search for biodiesel as alternative fuel for diesel engine. Performance and emissions characteristics of C.I. engine fueled with palm oil/palm oil methyl ester blended with diesel fuel is investigated experimentally. Biodiesel was prepared from palm oil by transesterification process. Diesel, biodiesel and palm oil blends were prepared in volume percentages of 20 and 100% as B20, B100 and PO20. Physical and chemical properties of biodiesel blends were near to diesel fuel. The experimental study is conducted on a diesel engine at different engine loading from zero to full loads using palm oil and palm biodiesel and its blends with diesel fuel. Thermal efficiency of biodiesel and oil blends with diesel fuel was lower than diesel fuel. Specific fuel consumptions for biodiesel and oil blends were found to be higher than diesel oil. Unburned hydrocarbons and carbon monoxide emissions have been decreased for biodiesel blends but it increased for oil blends compared to diesel fuel. Nitrogen oxide emissions have slightly been increased for biodiesel and oil blends compared to diesel fuel. Blends of diesel – biodiesel up to 20% biodiesel percentage by volume are recommended because of the improvement in performance and emissions as compared to diesel fuel.     

双氧水／乙酸酐对焦化蜡油的氧化脱硫作用

采用氧化脱硫技术脱除焦化蜡油（CGO）中的含硫化合物,对氧化体系进行了筛选并对氧化及萃取工艺进行了优化。结果表明,以双氧水／乙酸酐为氧化剂体系时氧化脱硫效果最佳。氧化脱硫实验最佳工艺条件为：反应温度为65℃,反应时间为1h,n（H2O2）／n（s）为7,V（乙酸酐）／V（EGO）为0．3。革取实验最佳工艺条件为：以糠醛为萃取剂,油剂比[V（CGO）／V（糠醛）]为2,三级逆流萃取法。采用该工艺得到精制油收率为69．7％,硫质量分数由11．628×10^-3降至2．430×10^-3,脱硫率为79．1％。     

Kinetics of Oxidative Desulfurization of Sulfur Compounds in Diesel Fuel

Abstract

The oxidation of diesel fuel sample was carried out using tertiary butyl hydroperoxide oxidant in the presence of two commercially available Ni-Mo catalysts. The studies were carried out by changing reaction conditions such as treat ratios (oxidant/sulfur molar ratio), WHSV, temperature, etc., to achieve product diesel with sulfur content of <20 ppm. The results of the study on diesel were compared by carrying out similar experiments on model compound, namely, dibenzothiophene dissolved in sulfur-free liquid paraffin oil. GC-PFPD instrument was used to identify and group different sulfur compounds present in diesel and the kinetics of desulfurization was studied.     

Hydrofining and Catalytic Cracking of Coker Gas Oil

Abstract

The hydrofining of coker gas oil (CGO) was investigated on catalyst RN-2 in a micro hydrogenation apparatus. High reaction temperature favors the desulfurization and denitrogenation for the hydrofining of CGO, but it disfavors the yield of total liquids. Desulfurization degree, denitrogenation degree, and the total yield of liquid products increase with the enhancement of reaction pressure. As the hydrogen-to-oil ratio increases, the desulfurization degree increases, and the denitrogenation degree shows a maximum at a hydrogen-to-oil ratio of 800. Catalytic cracking of CGO, hydrofined CGO, and vacuum gas oil (VGO) on catalyst LMC-500 was investigated in a pilot-scale fluid catalytic cracking (FCC) unit. The catalytic cracking performance of hydrofined CGO is better than that of CGO.     

车用燃料油吸附法深度脱硫技术进展

综述了车用燃料油吸附法深度脱硫的技术及吸附机理,主要包括物理吸附脱硫、化学吸附脱硫、络合吸附脱硫和选择性吸附脱硫等。物理吸附是极性吸附,吸附剂对硫化物的选择性差,难以对燃料油进行深度脱硫;化学吸附能对燃料油进行深度脱硫,但吸附温度和吸附剂再生温度较高;络合吸附和选择性吸附脱硫技术操作条件温和、投资和操作费用低,能深度脱硫,可生产硫含量小于50μg/g的低硫车用燃料油,但目前吸附剂对含硫芳烃的选择性和容硫量还较低,不能满足工业应用的要求。