Preparation, characterization and application of alumina nanoparticles with multiple active component for oxidation desulfurization Layth T. Abdulateef, Amer T. Nawaf, Qahtan A. Mahmood, Omar S. Dahham, N. Z. Noriman, and Z. Shayfull
Citation: AIP Conference Proceedings 2030, 020031 (2018); doi: 10.1063/1.5066672 View online: https://doi.org/10.1063/1.5066672 View Table of Contents: http://aip.scitation.org/toc/apc/2030/1 Published by the American Institute of Physics
Preparation, Characterization and Application of Alumina Nanoparticles with Multiple Active Component for Oxidation Desulfurization Layth T Abdulateef 1, Amer T Nawaf 2,a), Qahtan A Mahmood 3,b), Omar S Dahham4,c), N Z Noriman4,d), Z Shayfull5,6 1
Chemical Engineering, Middle Technical University, IRAQ Chemical Engineering, College of Petroleum & Minerals Engineering, Tikrit University, IRAQ 3 Chemical Engineering, College of Petroleum & Minerals Engineering, Tikrit University, IRAQ 4 Center of Excellence Geopolymer and Green Technology (CEGeoGTech), Faculty of Engineering Technology (FETech), Universiti Malaysia Perlis (UniMAP), Level 1 Block S2, UniCITI Alam Campus, Sungai Chucuh, Padang Besar, 02100, Perlis, Malaysia. 5 School of Manufacturing Engineering, Universiti Malaysia Perlis, Kampus Tetap Pauh Putra, 02600 Arau, Perlis, Malaysia. 6 Green Design and Manufacture Research Group, Centerof Excellence Geopolymer and Green Technology (CEGeoGTech), Universiti Malaysia Perlis, 01000 Kangar, Perlis, Malaysia 2
a)
Corresponding author:
[email protected] b)
[email protected] c)
[email protected] d)
[email protected]
Abstract. This study investigated the oxidation desulfurization; by new metal salts used in the preparation of Nano catalyst. Alumina nanoparticles were successfully treated by multiple active components of zinc oxide and magnesium oxide to improve its surface properties for oxidative desulfurization of feedstock (kerosene). The alumina Nanoparticles with 12.5%ZnO and 12.5%MgO metal oxides loading showed significant oxidation desulfurization efficiency. The alumina Nano particles with multiple oxides containing 25% optimum metals loading showed higher desulfurization efficiency. Characterization of the home-prepared Nano catalyst was made by precipitation on surface area of Nano alumina analyzer using N2 adsorption. The Nano catalyst properties (surface area =107.4292 m2 g-1, total pore volume = 0.633291 cm3g-1, Langmuir surface area= 154.6115 m²g-1) and surface chemistry of the as-synthesized alumina with zinc and magnesium oxides, oxidation sulfur content with higher removal desulfurization. Three principal operating parameters have been considered which are reaction temperature, reaction time, and weight of Nano catalyst. The experimental results showed that the chemical nature of multiple oxides showed higher conversion (84.6%) at 190 oC, 45 min and 1gm used in batch reactor.
INTRODUCTION Supported develop metal nanoparticles are commonly used as catalysts in several industrially petroleum processes, for oxidation process [1, 2]. Many factors effect on the active catalyst in the application process, such as shape of Nano-catalyst, pore volume and particle size, metal support-interactions, metal dispersion, rule out the catalytic performance of metal. Consequently, the control and the optimization of all these parameters represent a challenging issue for the large-scale production of active and selective catalysts. From another point of view, significant efforts have been devoted to the development of an industrial mechanism for the development of highly
Green Design and Manufacture: Advanced and Emerging Applications AIP Conf. Proc. 2030, 020031-1–020031-8; https://doi.org/10.1063/1.5066672 Published by AIP Publishing. 978-0-7354-1752-6/$30.00
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controllable, highly efficient nanoparticles [3, 4]. Alumina-nanoparticles support (all type-Al2O3) are expected to play an important role in a variety of relevant applications and hence, the field has generated important contributions regarding the synthesis and processing of such particles [5, 6]. Corundum is referring to alumina (Al2O3). Alumina has several phases such as Gamma, Delta, Theta, and Alpha. However, the alpha (γ) alumina phase is the most thermodynamically stable phase in the processing. In general, alumina has many interesting properties, advantage very good hardness, good stability, good insulation, and transparency [7]. Metal oxide Nano particles and Nano structured materials have attracted the scientists and researcher for controlled synthesis via new method. Purpose, special properties of metal oxide expect several potential application in electronics optoelectronics, catalyst and thin film coatings [8, 9]. The environmental regulations on the reduction of sulfur content in feedstock (fuels) have been ongoing for the last two decades. The world is determine sulfur content from United States Environmental Protection Agency (USEPA) [10] set optimum allowable sulfur content to 15 and 30 ppm for diesel (light and heavy) and gasoline production. This is accuracy because; combustion of the fuel, the sulfur compound forms SOx that causes both acid rain and catalyst poisoning [11]. The hydrodesulphurization (HDS) process is the major industrial method for removing sulfur compounds from fuels like sulfides, disulfides, thiols, and mercaptans, however, thiophene and its alkylated derivatives are so difficult to remove by HDS process [12]. Besides, hydrodesulphurization (HDS) is characterized by high cost of operation, because high temperature, high pressure and excessive consumption of hydrogen reduction in catalyst efficiency [13]. Oxidative desulfurization (ODS) process has been considered new method for deep desulfurization technology because it can be carried out under mild conditions (temperature and pressure) [14], such as relatively low temperature, approach constant pressure and cost of operation when it is compared with hydrodesulphurization (HDS) process [15]. In this work, the structure of zinc oxide (ZnO) and magnesium oxide (MgO) was loaded on the structure of Nano supported (γ -Al2O3), the calcination temperature at 600 oC metal salt was converted to metal oxide in this temperature. The structure of the prepared Nano catalyst was analyzed by a Bet Surface Area (BET). The catalyst prepared was tested on oxidation desulfurization for sulfur content in kerosene.
EXPERIMENTAL WORK Feedstock (kerosene), used in this work, is provided by the AL-Dura Refinery-Iraq with the following specifications: 47.6 API, 4.05 cSt at 40 oC viscosity, 28 smoke point, 2500 ppm total sulfur, 0.01 wt% ash content and (–9 oC) Max in winter pour point, which are tested in AL-Dura Refinery Company Laboratories. Oxygen in air gas is used as oxidant agent in ODS. The chemical materials used for the preparation of Nano catalyst with multiple active compound from zinc acetate (C4H8O4Zn.2H2O) proved from (Sinopharm Chemical Reagent ≥99.0%) and magnesium sulphate anhydrous (MgSO4) (Himedia), Nano alumina particles (γ - Al2 O3, purity 99% ) (Skyspring/USA) and deionized water from AL-Dura Refinery.
Preparation of (12.5%ZnO-12.5%MgO)/ γ- Al2O3 Nano Support Magnesium oxide and zinc oxide loaded on Nano alumina composite was prepared in thermal co-precipitation method. Nano alumina was dried in oven for 1 h at 250 oC; to remove moisture in the supported. Weighted 8 g of Nano alumina powder and dispersed in 50 ml deionized water. This solution consisting of γ- Al2O3 with deionized water was mixed by magnetic stirrer plate for 2 hr to give best dispersion. 2.7g of zinc acetate salt and 3 gm magnesium sulfate anhydrous salt were dispersed in 30 ml deionized water to obtain approximately 12.5 wt. % loading of ZnO and 12.5 wt.% loading of MgO. Then the total solution was added slowly with mixing for 1.30 hr. Moreover, the mixture was heated under various temperature to calcination metal salts to metal oxides. Calcination temperature occur at 600 oC for 2.5 hr after that its temperature drops gradually. The obtained catalyst was dried. In addition, the content metal oxide for zinc oxide and manganese oxide on the surface of Nano alumina particle both dried as well. The preparation step of Nano catalyst is show in the Figure 1.
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FIGURE 1. Preparation Step of Nano Catalyst
Experimental Procedure for Oxidation Desulfurization The fuel in present work is kerosene with total sulfur content of 2500 ppm. The ODS experiments were carried out in batch reactor are adding 100 ml from feedstock; air was bubbled at constant flow rate by using compressor with constant pressure 1 bar. Operation conditions for tested Nano catalyst prepared in ODS, temperature (130 oC, 160 oC and 190 oC), reaction time (25 min, 35 min and 45 min) and weight of Nano catalyst (0.5 gm, 0.75 and 1 gm) using in the process. X-Ray Diffraction instrument was use to calculate the concentration of sulfur in kerosene. Figure 2 shows the experimental procedure design using for oxidation process.
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Sulfur Removel
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Thermometer
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X-Ray Diffraction Instrument (Sample)
FIGURE 2. Process low diagram of batch reactor
RESULTS AND DISCUSSIONS Characterization of (12.5%ZnO-12.5%MgO)/ Nano-γ-Al2O3 The pore volume of Nano catalyst and surface area for the multiple active components on supported alumina were observed and determine by BET (ASTM 9277-2010). The surface areas and pore structures of the samples were determined from N2 adsorption in Petroleum Research and Development Center / Ministry of Oil. The BET equation was found surface area of Nano catalyst is (107.4292 m2 g-1), Langmuir Surface Area (154.6115 m² g-1), total pore volume (0.633291 cm3g-1) and pore size (235.7984 Å). The chemical properties of the Nano catalysts (12.5%ZnO12.5%MgO)/ Nano-γ-Al2O3 are very important factors that affect the catalytic activity. Figure 3 as show to convert metal salts to metal oxides. The increase in temperature above 500 oC causes the surface area to increase. On the other hand, calcination temperatures above 700 oC results in lowering the surface area of the Nano catalyst because a melting point of metal oxide may have occurred above 700 oC causing the block of pore and specific surface area of Nano catalyst. The airflow used in the calcination process helps to convert the metal salt to metal oxide in this process and obtained zinc oxide and magnesium oxide. The BET surface is shown in the Figure 4. The chemical adsorption isotherm for the catalyst preparation show in the Figure 5, information about the active surface of a material has been employed for many years as a standard analytical tool for the evaluation of catalysts. Temperatureprogrammed reaction techniques used N2 in this process to chemisorption isotherm analyses in many areas of industry and research [16]. The process found a homogeneous distribution of particle sizes of active component on the support Nano particles, which can be checked by moving to different parts of the sample. It is also important to remember that the sizes of the particles are calculated from projected volumes this assumption holds very well for most catalyst nanoparticles.
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FIGURE3: Convert metal salts to metal oxides
FIGURE 4. BET surface area
FIGURE 5. Adsorption/Desorption isotherm
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Oxidation Desulfurization on Nano Catalyst Prepared This work aimed to improve an oxidative desulphurization process (ODS) with high reaction rate of oxidation and high selectivity for sulfur content in kerosene. The process occurs in batch reactor is design to combine complementary technique: oxidation of total organic sulfur compounds. Tables 1, shows the experimental results for ODS. TABLE 1. Experimental Results Run 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
Amount of Nano catalyst (gm), In 100 ml, Kerosene 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
Reaction of temperature, (o C) 130 130 130 160 160 160 190 190 190 130 130 130 160 160 160 190 190 190 130 130 130 160 160 160 190 190 190
Reaction time, (min) 25 35 45 25 35 45 25 35 45 25 35 45 25 35 45 25 35 45 25 35 45 25 35 45 25 35 45
Concentration in Kerosene, (ppm) 1400 1360 1329 1254 1200 1185 1145 1122 1010 1258 1189 1179 1021 1000 967 923 860 800 789 760 751 745 739 730 580 417 385
The effect of oxygen on desulfurization process used as oxidant, sulfur compounds are oxidized, because O 2 can be dissolved in kerosene, oxygen inter to pore of Nano catalyst, adding one or two oxygen atoms to the sulfur without breaking any carbon sulfur bonds, yielding the sulfoxide or sulfones[17]. This process is shown in Figure 6. The effect of reaction temperature from (130 °C to 190 °C) on the desulfurization of kerosene is shown in Figure 7. The reaction rate increased obviously, when the temperature increased from [18], 130 °C to 190 °C, the desulfurization reached the maximum 0.44% and 84.6% values, at different operating conditions (0.5 gm, 25 min and 1 gm , 45 min) respectively. The Nano Catalyst weight is raising from 0.5 to 1 g and keeping the other reaction conditions as show in the Table 1 and Figure 7, drop amount of catalyst from 1gm to 0.5 gm obtained low desulfurization efficiency. Oxidation desulfurization is drops from 1400 ppm to 879 ppm at constant operating conditions (25 min and 130 min) [19], on the other hand, weight of catalyst rises from 0.5 gm to 1 gm, high amount of catalyst give high surface area of reaction and high contact area sulfur and oxygen can be internal in pore of Nano catalyst. Figure 7c, temperature reaction is 190 oC and change of time reaction from (25-45) min oxidation reaction efficiency is higher 84.6%, temperature cause low viscosity of kerosene and with increase solubility of oxygen in feedstock increase chemical reaction and increase conversion. The test of amount of Nano catalyst weight together with change of operating conditions test prove that resistance to air absorption through liquid film at air–liquid interface, resistance to mass transfer through liquid film at liquid–solid interface, and resistance to diffusion within catalyst particle, can be neglected.
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FIGURE 6. Oxidation Process
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ht of
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Temperature = 130 oC Temperature = 160 oC Temperature = 190 oC
FIGURE 7. Effect operating conditions on desulfurization reaction
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(c)
CONCLUSIONS The airflow was found to be effective in the oxidation of sulfur components in fuel (kerosene) at different temperature (130-190) oC. The oxidation desulfurization process was achieved after increasing the reaction temperature and dissolving O2 in pore of Nano catalyst, oxygen was utilized for oxidizing the sulfur components to the corresponding sulfones. Improving the oxidation desulfurization method was observed by using the air as an oxidizing agent with Nano catalyst without changing the shape of the fuel or cracking the fuel chain. This proves the feasibility of desulfurization with a simple, mild of operation conditions and environmentally benign method in industry in the future.
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