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Effects of potassium aluminum sulfate and Kal (SO4) 2 on total petroleum hydrocarbons of diesel oil

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https://www.eduzhai.net International Journal of M aterials and Chemistry 2012, 2(3): 101-104 DOI: 10.5923/j.ijmc.20120203.03 Effect of Potassium Aluminium Sulphate, Kal(SO4)2on the Total Petroleum Hydrocarbon of Diesel Oil Inimfon A. Udoetok*, Nyenime W. Akpanudo, Emaime J. Uwanta, Emmanuel E. Ubuo, Emmanuel J. Ukpong Chemistry Department, Akwa Ibom State University, IkotAkpaden, M kpatEnin Local Government Area, Akwa Ibom State, Nigeria Abstract Possible effects of the treat ment of d iesel oil with various concentrations of an inorganic salt, Potassium Aluminiu m Sulphate (KA l(SO4)2) were studied at room temperature, with a view to assessing alterations in the total petroleum hydrocarbon of diesel oil. Results obtained revealed that various concentrations of the inorganic s alt had different effects on the total petroleum hydrocarbon (TPH) of the s amples. The sample treated with 55g of the salt had the lowes t TPH concentration of 2255.75mg/l while the sample treated with 35g of the salt had the highest TPH concentration of 12505.10mg/l. Two samples had higher TPH concentration than the untreated sample wh ile five samp les had lower TPH concentrations. This may be ascribed to the fact that some concentrations of the salt were able to catalytically crack heavier hydrocarbon molecules in the diesel oil to fractions lower than C6 (wh ich may have been gases) thus leading to a decrease in the TPH concentration of those sample, while other concentrations of the salt were able to breakdown heavier hydrocarbon mo lecules to fractions with in the C6 to C40 range thus leading to an increase in the TPH concentrations of the samples. The treatment also led to decrease and increase in the density of the samples. Keywords Diesel Oil, Inorganic Salt, Aliphatic Hydrocarbon, TPH, Cracking, Potassium A lu min iu m Sulphate 1. Introduction Petroleu m, also known as the black gold isa comp lex mixtu re that contains thousands of different organic compounds in three major forms namely crude o il, natural gas and condensates. Crude oil, the liquid form of petro leum is also a co mplex mixture of hydrocarbons or substituted hydrocarbons varying widely in both physical and chemical properties[1],[2],[3]. It may be characterized in terms of the following fractions namely; saturates, aromatics, resins and asphaltenes as well as heavy metals such as nicke l, vanadium and cadmiu m[4],[5]. It has an average density of 850kg / m3. Saturates include straight or branched chain n-alkanes, and the cycloalkanes with one or more saturated rings, while aromat ics include co mpounds with one or more fused aromat ic rings, each of wh ich may have saturated side-chains(alkyl-substituents) attached to them. In contrast to the saturated and aromatic fractions, both resins and asphaltenes consist of non-hydrocarbon polar compounds with trace amounts of nitrogen, sulphur and/or oxygen (NSO) in addit ion to carbon and hydrogen and often forming complexes with heavy metals[6]. When crude oil is distilled, variety of products such as * Corresponding author: eeneemphorn@yahoo.com (Inimfon A. Udoetok) Published online at https://www.eduzhai.net Copyright © 2012 Scientific & Academic Publishing. All Rights Reserved gases, petrol, kerosene, diesel and lubricating oil etc. are obtained at various temperatures[7]. Diesel oil which is one of the distillates is a mixture of hydrocarbons with between 10 to 20 carbon ato ms per mo lecule and distills over a temperature of 250℃ to 400℃[8],[9],[10]. It is used as fuel for heavy duty engines and as raw materials for cracking to obtain motor gasoline. Potash alum (Potassium Alu min iu m Su lphate) is an inorganic salt with the mo lecular formu la KA l(SO4)2. Potassium A lu min iu m Su lphate forms a solid, wh ite powder at room temperature. It is a hygroscopic material which when exposed to air, hydrates (absorbs water). Depending on the amount of water mo lecules present, these hydrates are represented by the chemical fo rmulas KA l(SO4)2 • 12H2O or K2SO4.Al2(SO4)3 • 24H2O. The powder form, made up of crystals, has a melting point of 198.5°F (92.5℃) and can be readily d issolved in water. Additionally, this material has a property known as astringency which is an ab ility to constrict body tissues, and restrict the flow of b lood. There have been many industrial applications of Potassium Aluminiu m Su lphate. It is an impo rtant part of many products created by the pharmaceutical, cosmetic, and food industries because of its astringency property. It is also used in the manufacture of paper, dyes, glue, and exp losives. Additionally, it helps in the water purificat ion process, is used to speed up the hardening of concrete and plaster, and acts as a catalyst in various chemica l reactions[11],[12],[13]. Reference[14] reported that the treatment of diesel o il with 102 Inimfon A. Udoetok et al.: Effect of Potassium Aluminium Sulphate, Kal(SO4)2on the Total Petroleum Hydrocarbon of Diesel Oil various concentrations of Potash and Alum for a maximu m of two days could not make it physically similar to kerosene. He reported that treatment of the sample with 35g of the salts produced the best results. This paper therefore investigates the ability of Potassium Aluminiu m Su lphate, KAl(SO4)2 to alter the TPH of d iesel oil by breaking down high molecu lar weight hydrocarbon fractions to smaller ones. 2. Experimental 2.1. Sample Collection About 1000ml of Diesel oil was collected fro m Onne port located in Port Harcourt, Rivers state, Nigeriausing a 1000ml glass bottle, while the inorganic salt was obtained fro m a vendor in Uyo, Akwa Ibom State, Nigeria. On arrival at the laboratory, the diesel oil sample was stored in a refrigerator at 4℃ till co mmencement of analyses while the Potash alum was stored in a cabinet. 2.2. Sample Preparation Potash alum was activated at 80℃ in the oven for about 12 hours. Specified quantities (5g, 10g, 20g, 35g, 55g, 80g and 100g) were introduced into 50mls of the diesel oil in seven preweighed dry and clean 100ml bottles. The mixtures were allowed to react at roo mtemperature for seven days and their weights were taken every mo rning. 2.3. Oil Extracti on and Gas Chromatographic Anal yses 1g of each of the samples was weighed into well labelled clean and dry vialsand 10mls of pentane was added to them. The samples were stirred using a magnetic stirrer for about 5 minutes before they were allowed to concentrate to 1ml.The extracts were fractionated into aliphatic fractions by adsorption liquid chro matography using a column of alu mina and silica gel, while pentane was used as gradient solvent. The extracts were concentrated to 1ml and these were subjected to analyses. The TPH of the samples were determined using a Hewlett Packard 6890 gas chromatograph made by Agilent (USA) with the follo wing operational conditions; flow rate (H2 30ml/ min, air 300ml/ min and N2 30ml/ min), injection temperature (50 ℃ ), detector temperature(320 ℃ ). For signals, the GC was interfaced to a Hewlett Parker (hp) computer[15]. 2.4. Density The densities of the samples were measured by taking weights of 50mls of the samples and then the corresponding weights of equal volu me of water. The d ifferent densities were finally obtained using: Density = weight of samp le Weight of equal volume of water 3. Results and Discussions The density of the untreated sample and treated samples are shown in table 1. The result reveals that after treat ment of the samples with various mass of the inorganic salt, their densities were lower than that of the untreated sample, with the sample treated with 10g of the salt having the lo west density of 0.769g/cm3. Th is reduction in density of the treated samples may be due to the breaking down of high mo lecular weight hydrocarbon fractions with in and above the diesel range to smaller hydrocarbons which may have been partly gases. Reference[14] also reported a reduction in the density of diesel fro m 0.8615g/cm3 to 0.8494g/cm3 when treated with 10g of Potash alum. The results of the gas chromatographic analyses on the treated sample and untreated samples are presented in table 2. The results reveal that the different masses of the salts added to the same volu me of diesel oil produced varying effects on the hydrocarbon chain of the d iesel. The Total petro leum hydrocarbon of the untreated diesel was 7688.38mg/l (figure 1) whereas after treat ment with the inorganic salt, all the samples had different Total petroleum hydrocarbons with some being greater than the untreated sample while so me were less than. This shows evidence of alterat ion of TPH of the diesel oil. Table 1. Density of samples Sample Density(g/cm3) Diesel Diesel +5g Diesel +10g Diesel +20g Diesel +35g Diesel +55g Diesel +80g Diesel +100g 0.834 0.805 0.769 0.793 0.798 0.803 0.797 0.785 Figure 1. Chromatogram showing the TPH of diesel International Journal of M aterials and Chemistry 2012, 2(3): 101-104 103 Hydroc arbon fract ion C6 C7 C8 C9 C10 C11 C12 C14 C16 C18 C20 C24 C28 C32 C36 C40 Tot al Diesel 1711.61 7.18 50.66 25.09 130.44 248.84 690.71 612.24 666.94 1507.06 545.01 1258.04 229.80 4.74 7688.36 Table 2. Table showing effect of Potassium Aluminium Sulphate on TPH of diesel Diesel +5g 30.07 12.00 88.33 28.51 275.45 534.34 1640.54 1566.38 1516.72 525.35 554.28 668.96 49.14 3.88 6.53 7500.50 Amount (mg/l) Diesel +10g 11.05 9.65 97.41 60.02 320.37 628.75 457.13 195.27 1962.50 1341.54 962.29 1279.54 263.29 4.63 3.91 7597.36 Diesel +20g - 31.80 132.61 319.53 296.17 841.83 668.89 628.96 1246.98 473.08 1303.38 244.51 4.10 3.24 6195.10 Diesel +35g 21.66 15.85 221.45 97.22 420.04 791.91 2232.73 2378.06 2327.04 891.65 1186.71 1555.30 349.94 12.43 3.05 - 12505.04 Diesel +55g - 530.24 - 6.29 8.57 28.77 71.26 47.08 87.38 43.18 429.02 946.43 51.03 3.68 2.81 2255.75 Diesel +80g - 2816.27 14.40 37.16 23.82 143.86 218.78 96.23 352.17 313.62 376.81 994.28 324.12 175.12 77.64 5964.27 Diesel +100g - 3186.37 28.10 5.10 45.16 258.96 344.83 128.02 757.28 766.65 735.23 1698.65 145.51 2.30 4.39 8106.56 Figure 2. Chromatogram showing the TPH of sample treated with 55g of the salt Figure 3. Chromatogram showing the TPH of sample treated with 35g of the salt The samples treated with 5g, 10g, 20g, 35g, 55g, 80g and 2255.75mg/ l, 5964.27mg/l and 8106.56mg/l respectively 100g of the salt had the following TPH concentrations; (table 2) after treat ment with hydrocarbon fractions within 7500.50mg/ l, 7597.36mg/l, 6195.10mg/l, 12505.10mg/l, the C12 to C28 range having better concentrations. This 104 Inimfon A. Udoetok et al.: Effect of Potassium Aluminium Sulphate, Kal(SO4)2on the Total Petroleum Hydrocarbon of Diesel Oil shows that samples treated with 35g and 100g of the salt had higher TPH values than the untreated diesel sample wh ile samples treated with 5g, 10g, 20g, 55g and 80g of the salt had TPH values which were less than that of the untreated sample. This may be ascribed to the fact that 35g and 100g of the salt may have been able to breakdown the heavier fractions to fractions within the C6 to C40 range whereas 5g, 10g, 20g, 55g, and 80g may have broken down the heavier hydrocarbon fractions to fractions less than C6 which are gases and may have diffused, thus leading to reduced TPH concentrations for these samples. This is supported by the reduction in the concentration of the C6 fractions in all the samples and the absence of this fraction in some of the samples though it had the highest concentration in the untreated sample. The severity of this effect was experienced in the samples treated with 55g of the salt as it had the lowest TPH content. Generally, the observed train shows that in the samples treated with the salt, there were variations in the concentrations of the hydrocarbon fractions, some of them increasing and some of them decreasing. The samp le treated with 55g of the salt had the lowest TPH concentration (figure. 2) and the sample treated with 35g of the salt having the highest (figure.3). This point to the fact that there are additions to and reductions fro m the concentrations of these hydrocarbon fractions and this may have resulted fro m the cracking of some of the fractions by the salt, depending on theconcentration of the salt. 4. Conclusions The result of analyses on diesel oil samples treated with different concentrations of Potassium Alu min iu m Su lphate revealed that the treat ment had variable effects on the density of the samples and on their hydrocarbon chain. These effects included but not limited to the increment and reduction in the TPH concentrations of the samples. While the sample treated with 35g of the salt had the h ighest TPH value after treat ment, the sample treated with 55g of the salt had the lowest. On the whole, it may be concluded that this research has revealed that Potash alum (Potassium Alu min iu m Sulphate, KAl(SO4)2 has the ability of altering the TPH of diesel o il under suitable conditions by breaking down higher mo lecular weight hydrocarbon fractions with in and above the diesel range to smaller ones.Therefore, there is need for further research to be carried out so as to elucidate the conditions with wh ich diesel oil may be treated with Potassium A lu min iu m Su lphate to make it similar to kero s en e. ACKNOWLEDGEMENTS The authors are grateful to the manage ment of Technology Partners International Nigeria Limited Port Harcourt for facilitating this research. REFERENCES [1] Udoetok, I. A. Associated Petroleum Hydrocarbons and Heavy M etals of an Oil Spillage site in Niger-Delta, Nigeria. Global Journal of Pure and Applied sciences, 17, (3), pp 261-265. 2011. [2] Atlas, R. M., M icrobial degradation of petroleum hydrocarbons: An environmental perspective. M icrobiol. Rev. 45, 180 -209.1981. [3] Leahy, J. G., and Colwell, R. R. M icrobial degradation of petroleum in the environment. M icrobial Reviews, 53 (3): 305 – 315.1990. [4] "Petroleum". Concise O xford English Dictionary. [5] "Petroleum." en.wikipedia.org. 2011. http://en.wikipedia.org/ wiki/Petroleum [6] Udoetok, I. A. Composition and Distribution of Petroleum Hydrocarbons of Idu-Ekpeye Oil Spillage site in Niger-Delta, Nigeria. M .Sc. Thesis, University of Port Harcourt, Nigeria. 2005. [7] Ababio, O. Y. New School Certificate Chemistry. pp. 83, 84 and 113. Academy Press, Lagos, Nigeria. 1993. [8] Dyroff, G. V. M anual on significance of test for petroleum products, Chapter 5, 6th ed. Wiley and sons, New York, NY, USA.1993. [9] http://en.wikipedia.org/wiki/Diesel_fuel#Petroleum_diesel [10] Chris Collins “Implementing Phytoremediation of Petroleum Hydrocarbons, M ethods in Biotechnology 23:99-108. 2007. [11] http://science.jrank.org/pages/5422/Potassium-Aluminum-Su lfate.html#ixzz1ibE3EqlR. [12] Bottomley, L. and Bottomley, L.A. School of Chemistry &Bichemistry, Georgia Institute of Technology, Chemistry 1310: Laboratory M anual. Plymouth, MI: Hayden-M cNeil Publishing. 2010. [13] http://simple.wikipedia.org/wiki/Potassium_aluminium_sulf ate [14] Jimoh, A. The use of diesel oil treated with inorganic salt: an alternative to kerosene. AU J. T. 8 (1): 27 – 34. 2004. [15] Osuji, L. C., Udoetok, I. A. and Ogali, R. E. Attenuation of Petroleum Hydrocarbons by weathering: A case study. Chem. &Biodiv. 3: 422 – 433. 2006.

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