Additives of Base and Acid to Oxidative Desulphurization Process of Al-Sumoud Refinery at NRC Baiji

1-Introduction

        As fossil fuel prices continue to rise, oil companies will for environmental protection, desulfurization plays a critical role in mitigating the impacts of toxic pollutants. To this end, several experiments have been conducted on single metal oxides and mixed metal oxides as sorbents [1]. Kerosene is a liquid hydrocarbon fuel with multiple uses, including powering jet and rocket engines, heating homes, heating water, and cooking. To protect human health and reduce environmental hazards, environmental regulations that limit sulfur content to very low levels have been introduced in many countries over the past few decades [2]. Additionally, sulfur should be removed from petroleum fractions, as it can poison catalysts, corrode surfaces, and cause air pollution [3]. Abraham Gesner discovered kerosene, a petroleum byproduct, in 1853. Gesner, a British

surgeon, developed a method for removing asphalt from inflammable liquids [4]. Mercaptans, sulfides, disulfides, and thiophenes are the most prevalent chemicals found in gasoline. The presence of these groups in petroleum

products is undesirable because of the pollution they cause. However, this can represent significant challenges for petrochemical operations in meeting environmental criteria. The desulfurization procedure determines how these sulfur compounds are removed [5]. Gesner devised a method to separate the inflammable liquid from asphalt. The term kerosene comes from the Greek word kerosene. Kerosene (also known as jet fuel) is a flammable hydrocarbon liquid that is commonly used to power jet engines in aircraft and some rocket engines. It is also widely used as a cooking and lighting fuel for fire toys [6]. Kerosene is a liquid hydrocarbon fuel that is commonly used to power jet aircraft engines (jet fuel) and some rocket engines [7]. It is also widely used in fire toys as a cooking and lighting fuel [8]. Recently, researchers have sought alternative approaches to improve product quality [9]. The process does not change the chemical structure of fuel oil components. To make the separation process efficient, the solvent must be carefully selected to meet several requirements. The solvent must have a boiling point different than that of the sulphur-containing compounds, and it must be inexpensive to ensure the economic feasibility of the process [10]. The Sulphur compounds must be highly soluble in the solvent [11]. The aim of this study was to improve the kerosene product at Al Sumoud Refinery of the North Refineries Company, Baiji, by reducing its sulphur content. Thus, increasing combustion efficiency and reducing CO2 emissions, as well as reducing acidic residues and calcification resulting from sulfur in kerosene fuel.

Materials and Methods

2.1 Kerosene sample preparation

The sample of kerosene was used in this research, collected from North Refineries Company (NRC) Baiji. Obtained from Al-Sumoud refinery Kerosene sample with density of 0.7845 @15.6 °C g/cm3, tank number 3107 FA [12].

2.2 Additive processes

Figure 1 depicts the sweetening process of kerosene with varying percentages of acid and base additives. The percentage addition method was used, as following steps. The raw material was stored in the feed tank, and the heat exchanger exchanged temperatures with the final product. P1 exchanged the raw material's temperature with hot oil to reach a temperature of 60-70 °C. P H2SO4 1 mixes the feed material with H2SO4 at a concentration of 98 %, with an addition of 1%. Decanter No [13]. 1 straddled the product. The feed material is mixed with H2SO4 at a concentration of 98 % by mixer No. 2, with a 0.8 % addition by P H2SO4 2. Decanter No. 2 straddled the product. The feed material is mixed with H2SO4 at a concentration of 98% by mixer No. 3 with a 0.7% addition by P H2SO4 3. To extract the gases, the product was straddled by a decanter (3a - 3b) with a vacuum pump. The feed material is mixed with NaOH at a concentration of 25 % by mixer No. 4, with a 0.8% addition by P NaOH 1. Decanter No. 4 straddled the product. The nutrient is mixed with water at a 0.4% addition ratio by mixer No. 5. A decanter straddled the finished product (5a – 5b). P4 pumped the finished product to the heat exchanger, which reduced the temperature before delivering it to the distribution stations

2.3 Analytical procedure

The specific gravity (Sp.gr) of the kerosene test was calculated according to the standard method (ASTM D 1298) [12]. The physical properties were carried out based on the international code and standard American Society for Testing and Materials (ASTM D-3080) [15]. At the laboratories and quality control department in NRC Baiji. The FTIR test has been conducted before and after the desulphurization process via extraction.

Figure 1:Desulphurization process of the Kerosene product unit

3. 3. Results and discussions

3.1 Physical properties of kerosene sample

Table 1 shows the physical properties of the kerosene sample produced from Al-Sumoud refinery at NRC Baiji, before the desulphurization process. This specification was done depending on the (ASTM D-978) [16].

3.2 FTIR spectrum

The FTIR spectra of the kerosene samples before and after the process are shown in Figure 2. The results indicate the presence of mercaptans, as evidenced by a prominent band at 3398.57 cm-1 due to desulphurization. A less intense medium band at 1376 cm-1 represents the S=O asymmetric vibration, which gives an indication of the sulphone’s chlorides, sulphonates, sulphones, or sulphoxides. A wideband at 3417 cm-1 shows the presence of the NH or OH, which may correspond to the bond associated with sulphonamides31. The FTIR spectra of the kerosene oil treated with HgCl2 (10 %) and Ca (OH)2 (5%) is indicated in Figure 2 before and after. The spectra show that bands in this range, indicating mercaptans S-H (at 2365 cm-1) and S=O (at 1376 cm-1), are weaker in intensity in (after) as compared to the spectra of the original sample. In the spectrum (before), the band at 2356 cm-1 is absent, indicating that substituted thiols have undergone desulfurization. The FTIR results also indicated that the functional groups of the NRC Baiji fuel samples were identical [17].

Figure 2: FTIR Spectrum of raw material kerosene and after desulphurization process

3.3 The oxidative desulphurization process 

The oxidative desulphurization processes were conducted using an acid-base additive to the kerosene sample in order to reduce the sulfur content [18]. The effects of factors such as temperature, sodium hydroxide concentration, Sulfuric acid concentration, and water content on sulfur content were studied.  

3.3.1 Effect of temperatures

The effect of temperature on sulfur removal is determined as shown in Figure 3. The sulfur content was reduced, as shown in Figure 2. 2.5 of H2SO4 at a concentration of 98 % (a fixed amount) was added with 0.8 of NaOH at a concentration of 25 % (a fixed amount) with 0.4 of water (a fixed amount) to varying temperatures. The sulfur content of kerosene decreased, as shown in Table 5. The results showed that at 50 °C, sulfur content was 1000 ppm; at 60 °C, 800 ppm; at 70 °C, 580 ppm; and at 80 °C, 700 ppm, due to temperature and concentration effects. The best temperature was 70 °C with a low sulfur content of 580 ppm [19]. The sulfur concentration decreased from 1000 to below 600 ppm as the temperature increased, reaching 800 ppm at 80 °C, indicating that 70 °C is the optimal temperature for the reaction.

Table 2: Percentage of H2SO4, NaOH, and H2O added to kerosene at different temperature Sulpur

Figure 3: Relation between H2SO4,with  NaOH, and H2O at different temperature

3.3.2 Effect of sulfuric acid additive with 99 % H2SO4

 The best temperature was 70 °C to the reduced percentage of sulfur content in kerosene as in Figure 4. The temperature was fixed at 70 °C with 0.8 of NaOH at a concentration of 25 % (a fixed amount), with 0.4 of water (a fixed amount),  with varying H2SO4 1.0, 1.5, 2.0, and 2.5 with 99 % concentration. The results showed a decrease in the sulfur content in kerosene according to the results shown in Table 3. These results showed sulfur content was 1200 ppm at 1.0 of H2SO4,  sulfur content was 900 ppm at 1.5 of H2SO4, sulfur content was 700 ppm at 2.0 of H2SO4, sulfur content was 580 ppm at 2.5 of H2SO4. The best removal process was 580 ppm of sulfur at 2.5 of H2SO4 at 70 °C [20].

Table 3: Percentage 99% of H2SO4, NaOH, and H2O added to kerosene at 70 °C

Sulpur

Table 4: Percantage 0.8 of NaOH,  H₂SO4, and H₂O added to kerosene at 70 °C

Figure 4: Relation between H2SO4, NaOH, and H2O at 70 °C 

3.3.3 Effect of sodium hydroxide additive with 0.8 NaOH

       The best temperature was 70 °C to the reduce percentage of sulfur content in kerosene as in Figuer 5. The temperature was fixed at 70 °C with 2.5 of H2SO4 at a concentration of 99 % (a fixed amount), with 0.4 of water (a fixed amount),  with varying NaOH 0.3, 0.5, 0.7, and 0.8 with concentration 25 %. The results showed a decrease in the sulfur content in kerosene according to the results shows in Table 4. These results showed that sulfur content was 880 ppm at 0.3 NaOH, 750 ppm at 0.5 NaOH, 620 ppm at 0.7 NaOH, and 580 ppm at 0.8 NaOH. The best removal process was 580 ppm of sulfur at 0.8 of NaOH at 70 °C [21].

Table 4: Percentage 0.8 of NaOH,  H2SO4, and  H2O added to kerosene at 70 °C  Sulpur

Table 5: Specifications of kerosene sample results before and after desulphurization processing

Figure 5: Relation between H2SO4, NaOH, and H2O at 70 °C 

4. 4. Conclusion

The desulphurization of kerosene was studied via base and acid by washing. It was found that the washing method is a more effective. The kerosene sample has sulfur content was decreased from 1200 to 750 at 70 °C. The results showed that there was no effect on the density of kerosene, as well as the effect of distillation specifications. This indicates the effectiveness of the desulphurization process without affecting the basic specifications. This contributes to producing high-quality kerosene fuel and ignites by releasing fewer amounts of CO2 gas and does not cause damage to equipment because it contains a low percentage of sulfur.

5. Acknowledgment

The authors would like to thank Hussain Talib Abood, General Director of Oil Products Distribution Company (OPDC). The authors would like to express their appreciation to Eng. Raad Ahmed Abdullah deputy head of Salahuldeen Branch (OPDC) for their support in this study. They wish to extend their particular gratitude to Alnoor University for its support and cooperation throughout this research.

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إضافات القواعد والأحماض إلى عملية نزع الكبريت بالأكسدة في مصفى الصمود في شركة مصافي الشمال – بيجي

1غزوان جسام محمد ¹،  محمود عبدالكريم عبدالقادر^1،2*، عمر عبد حبيب³

¹شركة توزيع المنتجات النفطية، فرع صلاح الدين تكريت وزارة النفط،  ² قسم هندسة النفط، كلية الهندسة، جامعة النور³ شركة مصافي الشمال وزارة النفط

الخلاصة

تعتمد إزالة مركبات الكبريت من الكيروسين عن طريق الاستخلاص على حقيقة أن مركبات الكبريت أكثر قابلية للذوبان من الهيدروكربونات في المذيبات المناسبة. وتُعد أكثر المزايا جاذبية لعملية نزع الكبريت بالاستخلاص هي إمكانية تطبيقها عند درجات حرارة وضغوط منخفضة. وقد استُخدمت في هذا البحث عينات من الكيروسين مأخوذة من شركة مصافي الشمال – بيجي (NRC)، مصفى الصمود. إن إنتاج وقود كيروسين عالي الجودة يؤدي إلى خفض محتواه من الكبريت، وبالتالي احتراقه مع أقل كمية ممكنة من ثاني أوكسيد الكربون (CO₂). ويُعد من أهم المخاطر التي تؤثر في خصائص احتراق الكيروسين وفي البيئة الملوِّثات الثانوية مثل الكبريت والشوائب الأخرى. إذ إن تلوث الوقود بالكبريت يُسبب رائحة نفاذة قد تؤدي إلى مشكلات عدة في حال عدم إزالته. في هذه الدراسة، أُضيفت مواد مضافة إلى الكيروسين بهدف تقليل نسبة محتوى الكبريت وتحسين خصائصه الوقودية. وقد أظهرت نتائج البحث أن أفضل درجة حرارة لعملية الإزالة باستخدام القاعدة والحامض كانت 70°م، حيث بلغ متوسط إزالة الكبريت من 1880 جزءاً بالمليون، في حين تراوح متوسط إزالة الكبريت في مصفى الصمود من 1600 إلى أقل من 600 جزء بالمليون، دون التأثير في المواصفات الأخرى، ولاسيما الكثافة النوعية التي تُعد الخاصية الرئيسة في اختبار الحاكم (Ruler Test).