(Microsoft Word - \323\341\355\343 \343\315\343\31751- 59) Al-Khwarizmi Engineering Journal Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, Sptember, (2019) P.P. 51- 59 Study the Effect of Residence Time Parameters on Thermal Cracking Extract Phase Lubricating Oil Saleem Mohammed Obyed Department of Chemical Engineering/ College of Engineering / Al-Nahrain university Email: Saleem_mo71@yahoo.com (Received 12 February 2019; accepted 11 June 2019) https://doi.org/10.22153/kej.2019.06.008 Abstract This work studies with produce of light fuel fractions of gasoline, kerosene and gas oil from treatment of residual matter that will be obtained from the solvent extraction process as by product from refined lubricate to improve oil viscosity index in any petroleum refinery. The percentage of this byproduct is approximately 10% according to all feed (crude oil) in the petroleum refinery process. The objective of this research is to study the effect of the residence time parameter on the thermal cracking process of the byproduct feed at a constant temperature, (400 °C). The first step of this treatment is the thermal cracking of this byproduct material by a constructed batch reactor occupied with control device at a selective range of residence time (duration of the reaction) 30, 45, 60 and 75 minutes respectively at a constant temperature (400 °C). The conversion of this byproduct by thermal cracking process reaches 90% for all these residence times. The second step for this study is distillation this cracked extract liquid by atmospheric distillation device, for these various residence times according to the ASTM-D86 method, to obtain light fuel fractions of gasoline, kerosene and gas oil,in volume percentages 15, 75 and 0 for residence time 30, 5, 60 and 25, for residence time 45, 5, 10, 75, for residence time 60 and (10, 60 and 20) for residence time 75, which separates according to its boiling point. The major physical and chemical properties for feed (extract phase) and cracking extract liquid with its light fuel fractions were experimentally calculated and the results refer to acceptable properties compared with other standard property. Keywords: Cracking, extract phase, feed liquid, residence time. 1. Introduction Crude oil is a complex liquid mixture that consist mainly of carbon and hydrogen and small amount of sulfur, oxygen, nitrogen and metals [1]. A petroleum refinery consists of many units such as a chemical separation (catalytic and thermal process) and a physical separation processes that consists of many units, like crude distillation, solvent de asphalting, solvent extraction, solvent de-waxing, and blending. The solvent extraction process is used to treat luboil by solvent, like furfural, N-methyl pyrrolidone (NMP), which can dissolve the aromatic components in one phase (extract) and the rest of the oil in another phase (raffinate). The solvent is removed from both phases [1, 2]. The use of furfural for lubricating oil manufacture has been gaining in comparison with most other solvents. The yield of high viscosity index raffinate varies with the stock being treated [5]. When furfural (or other common solvent) is added to a heavy lubricating oil stock, two liquid phases (or layers) are produced; one (extract) which contains a relatively large amount of furfural with some asphaltic materials dissolved in it, and one (raffinate) which is lean in furfural but rich in high viscosity index oil [1]. The extracts have gravities in arrange of 4 to 13 API and slightly higher boiling ranges than the raffinates and they contain much more sulfur [6]. The extraction operation consists of a series of counter Saleem Mohammed Obyed Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, P.P. 51- 59 (2019) 52 current contacts between oil and solvent, vertical packed towers are wider than settling tanks [6]. The general purpose of the solvent process is to separate a general group of materials or hydrocarbons from the oil. For example; propane de asphalting removes dark colored resinous materials, liquid sulfur dioxide extracts unsaturated and aromatic hydrocarbons from kerosene, and furfural treating produces lubricating oil of high viscosity index [1]. Speight 2015 Make combination between the temperature and residence time to get various conversions, he noticed that there ia a very small residence time when temperature high, similar to high residence time when temperature is low. The cracking temperatures are between 350 °C to 500 °C, the aromatic ring is estimated stable. Bianco et al 1993 studied the conversion reaction for the thermal cracking of vacuum residue (VR) at reaction time reaches to 120 minutes at 410 °C to 470 °C, the results which were obtained from this work were used as reference data for the study of residue thermal cracking. Kondo et al 2000 studied the thermal cracking for VR by using batch reactor at 400 °C to 440 °C and atmospheric pressure; He noticed the conversion of vacuum residue increased when the temperature of the reaction increased. Parkash 2003 viewed that the thermal decomposing for high molecular weight feed depends on many variables such as, temperature cracking, type of feed stock, residence time, and pressure. The main objectives of the present work are to study the physical and chemical properties for the byproduct matter (extract phase), and to study the effect of several residence times (30, 45, 60, and 75) minutes on the thermal cracking of the extract phase by using a batch reactor, and to study the physical and chemical properties for the cracking extract phase liquid and its light fractions. 2. Experimental Work 2.1. Procedure of the Work The process of thermal cracking for the extract phase feed was carried out in the designed batch reactor unit which in figures 1 and 2 its volume is about 300 cubic ml. occupied with many auxiliary parts, like an electrical heater, thermocouple, timer, temperature controller, and a hood. 100 ml of the feed (extract phase) will be put in the reactor. The controlled temperature inside the reactor was constant at 400 °C according to another research (was the best to conversion) and various residence time (30, 45, 60, and 75) minutes which is the period for reaction. The distillation process of extract phase feed and cracked extract phase liquid were done in a distillation device which behaves as one tray and the distillation is done at atmospheric pressure. Distillation process on the byproduct mater (extract phase feed) and cracked extract phase liquid all these types of residences time will be done by the ASTM- D86 method. And finely, calculate the major properties of the extract phase feed and cracked extract phase liquid also light fuel cuts in order to compare it with commercial types and the possibilities of the use it in various usages. Fig. 1. Experimental batch reactor unit with distillation unit. [1- Reactor 2-Heater 3-Valve 4-Thermocouple 5- Timer 6- Temperature controller 7-Electrical source] Fig. 2. Flow diagram of experimental batch reactor unit with control system. Saleem Mohammed Obyed Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, P.P. 51- 59 (2019) 53 3. Results and Discussion 3.1. Atmospheric Distillation Method The analysis of the extract phase and different cracked extract phase liquids, for all these ranges of residences time results are shown in table 1. Table 1, Atmospheric distillation for extract phase feed and various cracked extract feed. Volum e % Extract phase feed °C The cracked extract liquid feed (°C ) Residence time 30 minute Residence time 45 minute Residence time 60 minute Residence time 75 minute 0 70 82 70 76 75 5 122 164 120 150 90 10 160 180 200 220 180 15 170 180 220 230 190 20 178 190 240 270 220 25 182 200 250 290 225 30 190 205 260 300 250 35 200 210 270 310 240 40 205 215 290 310 230 45 210 220 296 300 240 50 215 200 300 300 220 55 220 208 210 300 230 60 225 200 220 260 250 65 230 192 224 210 260 70 240 180 260 210 250 75 245 176 270 212 255 80 250 190 270 220 250 85 260 200 276 230 260 90 280 210 280 225 264 95 Tave. 217 195 260 251 233 Table 1 represents the atmospheric distillation results for the extract phase feed and cracked extract liquid in deferent residence time of cracking feed in reactor and can be noticed from the above results. the cracking occurs in all selected residence times and the conversion of the extract phase feed reaches above 90% in all selected residence times but the best one is 30 minutes due to their high amount of gasoline product and summarized time for cracking extract phase feed. 3.2 Physical and Chemical Properties for Extract Phase The physical and chemical properties of extract phase at 400 °C for different residence times (30, 45, 60, and 75) are shown in tables 2, 3, 4, and 5. The properties of the thermal cracking process for extract phase feed at 400 °C and residence time 30 minute are shown in table 2. Saleem Mohammed Obyed Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, P.P. 51- 59 (2019) 54 Table 2, Physical and chemical properties for extract phase feed and its fractions. Property Extract phase feed The cracking liquid product Gasoline product Kerosene product Gas oil product Specific gravity 0.965 0.826 0.79 0.83 0.86 API gravity 15.2 39.8 47.6 38.98 33 Mean average boiling point.° C 217 195 155 219 310 Density gm. / ��� 0.966 0.821 0.786 0.826 0.855 Molecular weight 142 204 130 171 247 Refractive index 1.547 1.504 1.479 1.503 1.528 K-factor 10.7 11.6 11.7 11.31 11.24 Viscosity (40 °C) C.st 125.1 3 4 2 5.8 Viscosity (100 °C) C.st 8 1.3 1.5 0.8 1.9 Aniline point °F 50 120 120 130 166 Pour point °C -9 -7 ----- ------ ----- Cloud point °C -12 -12 ----- ----- ----- Flash point °C 89 74 45 90 150 Fire point °C 93 79 50 94 155 Refractivity intercept 1.06 1.093 1.086 1.09 1.1 Hydrogen % 11.52 13.61 14.15 13.55 13.1 Sulfur % 1.28 1.26 0.28 0.54 0.44 Carbon % 87.20 85.87 85.57 85.9 86.46 C/H 7.58 6.3 6.05 6.34 6.6 Aromatic % 53 20.27 11.8 21.21 28.26 The extract phase feed is rich with undesirable components such as aromatics, oxygen, nitrogen, and sulfur, so the physical and chemical properties of extract phase feed such as API gravity or specific gravity, density, viscosity and others properties are considerably influenced by high boiling point temperature for constituents like these undesirable components that are concentrated in extract phase feed, so it is important to characterize the heaviest fractions of extract phase feed in order to determine their properties as shown in table 2, 3, 4, and 5. The extract phase feed has high molecular weight so it has a high ability to produce light fractions like, gasoline, kerosene and gas oil. The cracking liquid product with lower average boiling point gives more gasoline yield as at residence time 30 minutes and this is correct for others residence times 45, 60 and 75 minutes as shown in table 1 but in different volume percentages content of gasoline, kerosene and gas oil. On the other hand, the properties of the thermal cracking process for extract phase feed at 400 °C and residence time 45 minutes were shown in table 3. Table 3, Physical and chemical properties for extract phase feed and its fractions. Property Extract phase feed The cracking liquid product Gasoline product Kerosene product Gas oil product Specific gravity 0.965 0.81 0.77 0.82 0.85 API gravity 15.2 43.19 52.26 35.24 34.97 Mean average boiling point.° C 217 229 162 235 305 Density gm. / ��� 0.961 0.806 0.766 0.815 0.845 Molecular weight 142 181 140 175 245 Refractive index 1.547 1.500 1.493 1.515 1.498 K-factor 9.7 11.67 11.71 11.57 11.30 Viscosity (40 °C) C.st 125.1 3 7.5 5.8 5.8 Viscosity (100 °C) C.st 8 1.3 2.1 1.9 1.9 Aniline point °F 50 155 135 150 170 Pour point °C -9 -18 ----- ----- ----- Cloud point °C -12 -21 ----- ----- ----- Flash point °C 89 97 50 102 151 Fire point °C 93 100 54 106 155 Refractivity intercept 1.06 1.097 1.11 1.04 1.075 Hydrogen % 11.52 13.85 14.45 13.7 13.25 Sulfur % 1.45 1.42 0.15 0.54 0.757 Carbon % 87.03 85.73 85.4 85.76 86 C/H 7.58 6.19 5.91 6.26 6.49 Aromatic % 53 16.51 7.1 18.86 25.9 Saleem Mohammed Obyed Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, P.P. 51- 59 (2019) 55 Also the properties of the thermal cracking process for the extract phase feed at 400 °C and residence time 60 minutes were shown in table 4. Table 4, Physical and chemical properties for extract phase feed and its fractions. Property Extract phase feed The cracking liquid product Gasoline product Kerosene product Gas oil product Specific gravity 0.965 0.82 0.8 0.84 0.87 API gravity 15.2 35.84 41.37 32.95 27.14 Mean average boiling point.° C 217 251 170 240 315 Density gm. / ��� 0.961 0.814 0.796 0.835 0.864 Molecular weight 142 198 141 186 249 Refractive index 1.547 1.521 1.505 1.527 1.532 K-factor 9.7 11.69 11.339 11.334 11.447 Viscosity (40 °C) C.st 125.1 2 24 9 7.5 Viscosity (100 °C) C.st 8 0.6 3.6 2.35 2.1 Aniline point °F 50 160 140 158 165 Pour point °C -9 -15 ----- ----- ----- Cloud point °C -12 -18 ----- ----- ----- Flash point °C 89 113 56 105 158 Fire point °C 93 118 60 110 162 Refractivity intercept 1.06 1.114 1.107 1.1095 1.1 Hydrogen % 11.52 13.7 14 13.4 12.96 Sulfur % 2.15 2.13 0.32 0.84 0.86 Carbon % 86.32 85.76 85.68 85.76 86.18 C/H 7.58 6.26 6.12 6.4 6.65 Aromatic % 53 18.86 14.16 23.56 30.45 Also the properties of the thermal cracking process for extract phase feed at 400 °C and residence time 75 minutes were shown in table 5. Table 5, Physical and chemical properties for extract phase feed and its fractions. Property Extract phase feed The cracking liquid product Gasoline product Kerosene product Gas oil product Specific gravity 0.965 0.835 0.795 0.83 0.86 API gravity 15.2 34.36 47 38.98 33 Mean average boiling point.° C 217 233 165 225 295 Density gm. / ��� 0.961 0.830 0.79 0.827 0.855 Molecular weight 142 182 133 173 242 Refractive index 1.547 1.510 1.483 1.500 1.550 K-factor 9.7 11.35 11.367 11.36 11.449 Viscosity (40 °C) C.st 125.1 3.5 38 45 29 Viscosity (100 °C) C.st 8 2.7 4.5 1.9 4 Aniline point °F 50 152 130 140 100 Pour point °C -9 -21 ----- ----- ----- Cloud point °C -12 -24 ----- ----- ----- Flash point °C 89 116 52 95 145 Fire point °C 93 120 58 100 150 Refractivity intercept 1.06 1.095 1.088 1.0865 1.1225 Hydrogen % 11.52 13.47 14.07 13.55 13.1 Sulfur % 1.65 1.64 0.39 0.55 0.7 Carbon % 86.82 86.06 85.54 85.9 86.2 C/H 7.58 6.39 6.08 6.34 6.58 Aromatic % 53 22.77 13.06 21.21 28.23 Saleem Mohammed Obyed Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, P.P. 51- 59 (2019) 56 3.2 Effect of Temperature on Volume Extract Phase In order to study the effect of the temperature on the process with the accumulated volume percentage was studied with increasing of temperature of the process. Fig. 3. Atmospheric distillation for extract phase feed. Figure 3 shows the relationship between the T &V% distillation curve for the extract phase feed. By this distillation curve, can calculate the mean average boiling point for the extract phase feed its equal to 217° C and by this temperature with specific gravity can calculate the molecular weight by empirical equation and other properties which listed in tables 2, 3, 4 and 5. Distillation curve for extract phase feed and extract feed cracked in various residence times Figures 4, 5, 6 and 7 show the relationship between the temperature and volume percentages distillation curve for the extract phase feed and extract feed cracked in 30, 45, 60 and 75 minutes respectively. The average boiling point temperature for the extract phase feed cracked in (30, 45, 60 and 75) minutes are 195, 229, 251 and 233°C respectively as shown in figures 4, 5, 6 and 7. That means, when this temperature is low, this cracked feed contains high amount of light fractions (gasoline, kerosene and gas oil) than another residence time cracking. The percentage volume of light fractions in various residence times are; 15, 75 and 0 for residence time 30, 5, 60 and 25 for residence time 45, (5, 10, 75) for residence time 60, and (10, 60 and 20) for residence time 75 minutes which separates according to its boiling point as shown in table 1. Fig. 4. Atmospheric distillation for extract phase feed and extract feed cracked in 30 minutes. Saleem Mohammed Obyed Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, P.P. 51- 59 (2019) 57 Fig. 5. Atmospheric distillation for extract phase feed and extract feed cracked in 45 minutes. Fig. 6. Atmospheric distillation for extract phase feed and extract feed cracked in 60 minutes. Fig. 7. Atmospheric distillation for extract phase feed and extract feed cracked in 75 minutes. As shown in table 1, by various residence time 30, 45, 60, and 75 minutes, ability to convert extract feed phase to another light benefit fuel fractions in high conversion, which reaches more than 90% and in different amount of the light fraction products according to their boiling point (IBP, 180 °C) for the gasoline cut, (180, 250 °C) for the kerosene cut, and (250, °350 C) for the gas oil cut, but the more economic one is 30 minutes residence time due to their high amount of gasoline cut production (15, 75 and 0) and summarized of time cracking reaction. Saleem Mohammed Obyed Al-Khwarizmi Engineering Journal, Vol. 15, No. 3, P.P. 51- 59 (2019) 58 As shown in figure 3, by the distillation curve for the extract phase feed, the average boiling point can be calculated, and this property will used to calculate other properties for example molecular weight, and then to compare it with commercial product to find the benefit of this work. As shown from tables 2, 3, 4, and 5 the physical and chemical properties for fuel fractions (gasoline, kerosene, and gas oil) which are products from treatment extract feed phase, are acceptable for commercial uses due to their similar property with a commercial one. So it can be said, success will be occur when converting the byproduct matter (extract phase) to another light fuel fraction which can be used as gasoline for automobiles, also it can be used domestically for kerosene, diesel fuel, and for gas oil. 4. Conclusions -The ability of thermal cracking for heavy byproduct matter (extract phase) in different residence time and constant temperature 400 °C but the best one was 30 minutes for economic consideration. - Possibilities obtained light fuel fractions (gasoline, kerosene, and gas oil) from byproduct matter (extract phase) with acceptable properties according to standard properties. - Possibilities to use these light products for automobile for gasoline and domestic uses for kerosene and diesel fuel for gas oil. 5. References [1] Alkilani.A. Haitham M. S. Taher A. AL- Sahhaf "fundamental of petroleum refining", Elsevier B. V. (2010) [2] Pillion L. Z, interfacial properties of petroleum products, by Tayler & Francis Group, LLC, (2005). [3] Gary, J. H., and Handwerk, G. H. Petroleum Refining Technology and Economics. 4th ed. Marcel Dekker, New York. (2001). [4] Alan G. Lucas "Modern Petroleum Technology", Vol.2 Downstream New York (2001). [5] Bhaskara Rao B.K. "Modern Petroleum Refining Processes" 4th ed. Indian Institute of Technology. (2004) [6] Speight, J.G. "The Chemistry and Technology of Petroleum,",3rd ed. Marcel Dekker, New York (1999). [7] Levenspiel, O., "Chemical reaction engineering" John Wiley and Sons Inc.3ed (1999). [8] Speight, J.G. "Hand book of petroleum product analysis", USA. (2002) [9] Lappas, A. 2nd European summer school on renewable motor fuels Warsaw, Poland (2007). [10] Salvatore J. Rand Significance of tests for petroleum products, seventh edition, USA, (2003) [11] Surinder Parkash "Petroleum fuels manufacturing Hand Book" The MC Graw – Hill companies. (2016). )2019( 51- 59، صفحة 3، العدد15دجلة الخوارزمي الهندسية المجلم سليم محمد عبيد 59 صدراسة تاثير زمن المكوث على التكسير الحراري لمادة االكسترات المتخلفة من استخال التزييت زيوت سليم محمد عبيد الكيمياوبة/ كلية الهندسة/ جامعة النهرينقسم الهندسة Saleem_mo71@yahoo.com :البريد االلكتروني الخالصة من عملية ةهي مادة المستخلص الناتج ة( كازولين ،كيروسين ،كازاويل ) من معالجة مادة فائض ةيتعلق هذا البحث بامكانية انتاج مقاطع وقود خفيف (طور المستخلص) هي بحدود ةنسبة هذه الماده العرضي .النفط الخامة من عملية تكرير لزيادة معامل اللزوجة لزيوت التزيت الناتج االستخالص بالمذيب مذيب وغيرها ، زيت،ةمثل ( مواد عطري ةمن اللقيم (النفط الخام ) الداخل الى وحدات التكرير وتركيبها الكيمياوي يحتوي على العديد من المواد النافع %١٠ في مفاعل دفعي على التكسير ةالغرض من هذا البحث هو بيان تاثير زمن المكوث لهذه المادللزيوت. ةالكثير...) والتي هي سبب انخفاض معامل اللزوج ةهي دراسة اهم الخواص الفيزياوي ةالمرحلة االولى من هذه المعالج وزمن مكوث متعدد. °م ٤٠٠وعند درجة حرارة ثابته ةالعرضي ةالحراري لهذه الماد ) زمن ،(حرارة ةمساعد ةباجزاء سيطرلتكسير الحراري لها في مفاعل دفعي تم تصميمه لهذا الغرض ومجهز كذلك لهذه المادة ومن ثم اجراء ا ةوالكيمياوي ةحيث كان مقدار التحول لهذه الماده العرضي. °م ٤٠٠) دقيقه وعند درجة حراره ثابته ٧٥ ،٦٠ ،٤٥. ٣٠وكان زمن المكوث المختار (فترة التفاعل) ( .لجميع هذه االوقات %٩٠بواسطة التكسير الحراري يزيد على للسائل الناتج من عملية التكسير الحراري وكذلك اجراء عملية التقطير الجوي ةالهام ةوالكيمياوي ةكانت دراسة بعض الخواص الفيزياوي ةالثاني ةالمرحل وحساب كميات على اساس درجة الغليان لها ةكازاويل ) والمفصول ،كيروسين، ( كازولين وذلك للحصول على مقاطع وقود خفيفه ASTM-D86له تبعا مع ةوالكيمياوي ةوكانت النتائج تشير الى تقارب المواصفات الفيزياوي لهذه المقاطع. ةالهام ةوالكيمياوي ةوقياس بعض الخواص الفيزياوي هذه المقاطع الخفيفه .كوقود للسيارات للكازولين ولالستخدام المنزلي للكيروسين او كوقود ديزل للمركبات وبالتالي امكانية االستخدام وحسب المقطع ةتلك القياسي