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Desulphurisation of petroleum sistillates using adsorption method

机译:吸附法对石油馏分进行脱硫

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摘要

Experiments were conducted to investigate the applicability of activated carbon in removing sulphur from petroleum distillate at different sulphur concentrations. The study was therefore divided into two: The first part was the desulphurisation of a diesel stream containing 5200 mg/kg sulphur. This was referred in this report as Case 1. On a typical refinery, this is the feed stream of the hydrotreater unit. The second part of the study was the desulphurisation of a diesel stream containing 120 mg/kg sulphur. This sulphur concentration referred to case 2, which resembles an exit stream of the hydrotreater unit on a typical refinery.udIn Case 1, the activated carbon managed to reduce the sulphur content from 5200 mg/kg to 3390 mg/kg. Only about 35% of the sulphur was removed. In Case 2 however, the diesel stream was desulphurised from 120 mg/kg to 22 mg/kg. About 82% of the sulphur was removed from the feed-stream depicting activated carbon’s desulphurisation capability when dealing with lower sulphur concentration petroleum distillate.udAdsorption isotherms and kinetics models were applied to the experiment data to understand the extent and rate of sulphur adsorption on the surface of the activated carbon. The applicability of both adsorption isotherm and kinetics models to the experiment data were evaluated by the correlation coefficient (R2) value with 5% statistical significance. The Langmuir isotherm model fitted well Case 1 experiment data. The obtained Langmuir isotherm constant (KL) was 1.19 X 10-4 g/mg. This KL value was lower compared to Case 2 value of 0.0123 g/mg. This indicated that each sulphur molecule on activated carbon adsorption surface had a better equal adsorption activation energy in Case 2 than in Case 1. In Case 2, the obtained Freundlich isotherm constants, KF and n were 5.22 and 1.04 respectively. The n value for Case 2 was higher than Case 1 n value (1.04 vs 0.55). This clearly indicated that the sulphur molecules adsorption intensity on the surface of the activated carbon was higher in Case 2 than in Case 1. The KF value for both cases indicated the activated carbon adsorptive capacity. Pseudo-first-order kinetic model fitted well case 2 experiment data. The kinetic rate constant obtained for Case 2 was 0.206 min-1, whilst the kinetic rate for Case 1 was 0.0423 min-1. This indicated a slower sorbate uptake rate in the higher sulphur concentrated diesel stream than the lower concentrated stream. It is well understood that no adsorption processes are exactly the same as many studies have indicated, however these comparisons of these Case’s isotherms and kinetics were highlighted to indicate the impact of higher sorbate concentration in the desulphurisation of petroleum distillate. For both case 1and 2, it was established that the adsorption of sulphur on activated carbon was particle diffusion in nature. The results of the study therefore indicated that application of adsorption desulphurisation method seem not capable to achieve ultra-low sulphur specification when treating diesel feed with high sulphur content. On the other hand, the results of the study also revealed that there is an opportunity for synergistically employing activated carbon adsorption in combination with hydrodesulphurisation to achieve low sulphur diesel specification.
机译:进行了实验以研究活性炭在不同硫浓度下从石油馏出物中去除硫的适用性。因此,研究分为两个部分:第一部分是对含5200 mg / kg硫的柴油流进行脱硫。在本报告中将此称为案例1。在典型的炼油厂中,这是加氢处理装置的进料流。研究的第二部分是对含120 mg / kg硫的柴油流进行脱硫。此硫浓度称为情况2,类似于典型精炼厂中加氢处理装置的出口流。在情况1中,活性炭设法将硫含量从5200 mg / kg降低至3390 mg / kg。仅除去了约35%的硫。然而,在情况2中,柴油流从120 mg / kg脱硫至22 mg / kg。从进料流中去除了约82%的硫,这说明了在处理低硫浓度的石油馏分时活性炭的脱硫能力。 ud吸附等温线和动力学模型应用于实验数据,以了解硫在吸附器上的吸附程度和速率。活性炭的表面。吸附等温线模型和动力学模型对实验数据的适用性均通过相关系数(R2)值(具有5%的统计显着性)进行评估。 Langmuir等温线模型很好地拟合了案例1的实验数据。得到的朗缪尔等温线常数(KL)为1.19×10-4g / mg。与病例2的0.0123g / mg相比,该KL值更低。这表明在情况2中,活性炭吸附表面上的每个硫分子具有比情况1中更好的均等吸附活化能。在情况2中,获得的Freundlich等温线常数KF和n分别为5.22和1.04。情况2的n值高于情况1的n值(1.04对0.55)。这清楚地表明,案例2中的硫分子在活性炭表面上的吸附强度高于案例1。两种情况的KF值均表明了活性炭的吸附能力。伪一阶动力学模型很好地拟合了案例2的实验数据。情况2的动力学速率常数为0.206 min-1,而情况1的动力学速率常数为0.0423 min-1。这表明在较高硫浓度的柴油流中,较低硫流中的吸附物吸收速率较慢。众所周知,没有许多研究表明吸附过程完全相同,但是这些Case等温线和动力学的比较结果突出了,表明了较高的山梨酸酯浓度对石油馏分的脱硫的影响。对于案例1和案例2,都可以确定硫在活性炭上的吸附本质上是颗粒扩散。因此,研究结果表明,吸附脱硫方法的应用似乎无法在处理高硫含量的柴油原料时实现超低硫规格。另一方面,研究结果还表明,有机会协同利用活性炭吸附和加氢脱硫来实现低硫柴油规格。

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    Nkosi Melusi;

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  • 年度 2015
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