Desulfurization Of Crude Oil Research Articles

Sustainable crude oil desulfurization: A multi-objective fuzzy optimization for pollution prevention

The ultrasonic-assisted oxidative desulfurization (UAOD) process is employed to mitigate the environmental impact of sulfur emissions. Previous studies have focused on evaluating the efficiency of crude oil UAOD. This research assesses the desulfurization efficiency encompassing irradiation time, ultrasonic power, and oxidant amount, as well as the corresponding operational expenses, to ascertain the optimal conditions. The research employed a multi-objective fuzzy optimization (MOFO) method to assess the operational expenses of crude oil UAOD. It established the upper and lower limits and subsequently optimized the operational costs and desulfurization efficiency while accounting for uncertainties. The fuzzy model optimized the level of satisfaction on a scale from 0 (unsatisfied) to 1 (satisfied) using the max-min aggregation. The degree of satisfaction slightly decreased to 55.49 %, achieved under optimal conditions of 739.70 W ultrasonic power, 6.70 min irradiation, and 8.47 mL oxidant. This configuration yielded a desulfurization efficiency (YA) of 63.24 % at 2.02 USD/L. Compared to existing literature, the desulfurization of crude oil was found to be less efficient and less expensive. The outcomes presented by MOFO showcase economic feasibility with reduced overall operating expenses and simplified process conditions and provide valuable insights for optimizing potential large-scale UAOD processes.

Extractive desulfurization of crude petroleum oil and liquid fuels using trihexyl tetradecyl phosphonium bis(2-ethylhexyl) phosphate ionic liquid

Abstract Increasing environmental concerns have led to the development of alternative methods for the desulfurization of petroleum crude oil and liquid fuels. Phosphonium-based ionic liquids (PILs) have recently demonstrated promising potential for effective extractive desulfurization (EDS). The present study focuses on the synthesis and application of trihexyl tetradecyl phosphonium bis(2-ethylhexyl) phosphate [THTDP][D2EHP] for EDS of synthetic model fuels and real crude oils. The molecular confirmation and thermal stability of [THTDP][D2EHP] were investigated using FTIR and TGA analyses. In addition, the conductivity, solubility, and viscosity of the synthesized ionic liquid (IL) were analyzed. The impact of reaction time, temperature, and sulfur compounds, such as thiophene, benzothiophene, and dibenzothiophene (DBT), on the desulfurization efficiency from synthetic fuels was also investigated. The results indicated up to 63 and 57 % sulfur removal from DBT-based model fuels and Iranian crude oil, respectively. The optimum extraction conditions were found as 1:1 IL/fuel mass ratio, 35 °C, and 30 min. The findings of this study provide valuable insights into the synthesis and utilization of PILs as promising solvents for extractive desulfurization of crude oil and liquid fuels.

Efficient desulfurization of light crude oil using MOF and its composite

High sulfur content in petroleum fuels is a critical concern due to its significant contribution to environmental pollution through the formation of sulfur oxides during combustion. These sulfur compound not only degrade the quality of the fuel and quantity of finished petrochemical products, but also adversely affect the environment and damage equipment, tanks and pipelines. To address these issues and meet the rising need for both cleaner fuels and high-valued petrochemical products, desulphurization has become a key focus in crude oil refining. In this study, a MOF composite, ZIF-8/Co with montmorillonite clay was fabricated and tested for the desulfurization of light crude oil (LCO). For the first time, this composite adsorbent was applied to real crude oil system, achieving an impressive sulfur removal efficiency of 58.9%. The use of a green synthesis method further emphasizes the sustainability and cost effectiveness of this approach, presenting a promising advancement in crude oil desulfurization technology.

Utilization of Dibenzothiophene and Desulfurization of Crude Oil by a New Klebsiella sp. Strain BDS24 and the Proposed Metabolic Pathway

Utilization of Dibenzothiophene and Desulfurization of Crude Oil by a New Klebsiella sp. Strain BDS24 and the Proposed Metabolic Pathway

Green Copper Carbonate Nanoparticles Produced by the Ureolytic Fungus Alternaria sp. Strain ccf7 and Their Antibacterial Activity

Background: Copper carbonate nanoparticles have several applications in the fields of pigments, insecticides, and fungicides. They are also used as catalysts in chemical processes and crude oil desulfurization. Fungi can biosynthesize metal nanoparticles due to their high tolerance, extracellular synthesis, simplicity of extraction, and large-scale exploitation. Objectives: This study aimed to investigate the potential of fungal isolates (which are resistant to copper chloride with urease activity) as biocatalysts for the synthesis of copper carbonate nanoparticles. This approach was considered due to the advantages of using fungal isolates in nanoparticle biosynthesis. Methods: In a PDA culture medium with 25 mM copper chloride, an enrichment culture was used to isolate copper-resistant fungal isolates. Fungal isolates’ urease enzyme was qualitatively assessed using 2% urea agar-based culture media. Studies on the synthesis of copper carbonate nanoparticles and the effect of different parameters on the synthesis of these nanoparticles were conducted using a mycelium-free supernatant strategy. Field emission scanning electron microscope (FESEM), dynamic light scattering (DLS), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform infrared spectroscopy (FTIR) studies were used to determine the properties of calcium carbonate nanoparticles. The selected fungal isolate was identified using macroscopic and microscopic characteristics, as well as molecular analysis using amplification of the ITS1-5.8S-ITS2 gene sequences. Results: Alternaria sp. strain ccf7 (GenBank accession number OP242500) was chosen as the superior strain for copper carbonate nanoparticle synthesis tests based on the pattern of resistance to copper chloride salt and the qualitative assessment of urease activity. Based on the findings of the electron microscope studies, spherical copper carbonate nanoparticles with an average size of 66.7 nm were synthesized after 24 hours of incubation at the optimal concentration of 45 mM copper chloride, temperature of 25°C, and shaker speed of 100 rpm. The distribution of the produced nanoparticles was appropriate, as indicated by a polydispersity index (PDI) of 0.25. The strongest inhibitory impact of these copper carbonate nanoparticles was against Pseudomonas aeruginosa, with an average inhibition of 31 mm at a concentration of 50 mg/L, according to the results of their antibacterial activities. Conclusions: For the first time, the synthesis and development of a green approach for the fabrication of copper carbonate nanoparticles using the genus Alternaria have been proposed in this study.

Aquathermolysis of Heavy Crude Oil: Comparison Study of the Performance of Ni(CH3COO)2 and Zn(CH3COO)2 Water-Soluble Catalysts

Aquathermolysis is one of the crucial processes being considered to successfully upgrade and irreversibly reduce the high viscosity of heavy crude oil during steam enhanced oil recovery technologies. The aquathermolysis of heavy oil can be promoted by transition metal-based catalysts. In this study, the catalytic performance of two water-soluble catalysts Ni(CH3COO)2 and Zn(CH3COO)2 on the aquathermolytic upgrading of heavy oil at 300 °C for 24 h was investigated in a high pressure–high temperature (HP-HT) batch reactor. The comparison study showed that nickel acetate is more effective than zinc acetate in terms of viscosity reduction at 20 °C (58% versus 48%). The viscosity alteration can be mainly explained by the changes in the group composition, where the content of resins and asphaltenes in the upgraded heavy crude oil sample in the presence of nickel catalyst was reduced by 44% and 13%, respectively. Moreover, the nickel acetate-assisted aquathermolysis of heavy oil contributed to the increase in the yield of gasoline and diesel oil fractions by 33% and 29%, respectively. The activity of the compared metal acetates in hydrogenation of the crude oil was judged by the results of the atomic H/C ratio. The atomic H/C ratio of crude oil upgraded in the presence of Ni(CH3COO)2 was significantly increased from 1.52 to 2.02. In addition, the catalyst contributed to the desulfurization of crude oil, reducing the content of sulfur in crude oil from 5.55 wt% to 4.51 wt% The destructive hydrogenation of resins and asphaltenes was supported by the results of gas chromatography-mass spectroscopy (GC-MS) and Fourier-transform infrared (FT-IR) spectroscopy analysis methods. The obtained experimental results showed that using water-soluble catalysts is effective in promoting the aquathermolytic reactions of heavy oil and has a great potential for industrial-scale applications.

Desulfurization of Crude Oil by Laboratory Developed Multipumping Flow Injection Analysis System with Optimization by Response Surface Methodology

Desulfurization of Crude Oil by Laboratory Developed Multipumping Flow Injection Analysis System with Optimization by Response Surface Methodology

Adsorptive Desulfurization of Crude Oil with Clinoptilolite Zeolite

Crude oil; is a fossil fuel containing carbon, hydrogen, sulfur and many other components and is one of the world's largest and most widely used energy sources. However, in order for crude oil to be used as an energy source, it must be refined. With the use of petroleum products obtained as a result of refining, very high amounts of SOx gas are released into the atmosphere. These gases seriously harm both the environment and human health. This study aimed to reduce the amount of sulfur in crude oil and reduce its possible damages by using clinoptilolite zeolite (CZ). For this purpose, first of all, CZ; was characterized by SEM and XRF. Then, 0.1 g, 0.5 g, 1 g, 2 g and 5 g of the characterized CZ were weighed and added to the 50 mL crude oil samples separately. The mixture was mixed with a magnetic stirrer at 400 rpm for 60 and 120 minutes at room temperature before going through with an adsorptive desulfurization step. Afterwards, it was separated from the adsorbent by centrifugation and the residual sulfur amount was determined by ASTM D 1552-03 method. As a result of this study, which was carried out in an experimental laboratory environment; it has been observed that the desulfurization efficiency varies between 0.75 and 5.76 % (w/v) with the use of CZ adsorbent. Moreover; it was determined that the highest sulfur removal was obtained by using 5 g CZ.

Real heavy crude oil desulfurization onto nanoporous activated carbon implementing batch adsorption process: equilibrium, kinetics, and thermodynamic studies

Real heavy crude oil desulfurization onto nanoporous activated carbon implementing batch adsorption process: equilibrium, kinetics, and thermodynamic studies

Non-thermal plasma assisted catalytic thiophene removal from fuel under different atmospheres

Hydrodesulfurization is one of the most critical processes in the petroleum industry to increase the quality and economic value of crude oil. However, this process consumes a great amount of expensive hydrogen to convert sulfur-species to H2S, which causes a series of critical environmental issues. Herein, we report a novel method of non-thermal plasma assisted catalytic desulfurization of crude oil, while commonly used hydrogen is replaced with low-priced methane. As one of the most common sulfur-containing species in petroleum, thiophene is selected as the model compound in this study. It is proved that non-thermal plasma could effectively convert thiophene with a conversion higher than 90%, while thiophene is mostly converted into the solid deposit. Also, the H2S emission is well-controlled over a carefully designed Sn–Ga/SBA-15 catalyst. In a 12 h long-term experiment, the reactor still exhibits excellent desulfurization performance and low H2S emission during the whole test. Several control experiments are performed under N2 or H2 for comparison. Among all these atmospheres, N2 shows the best performance in terms of thiophene conversion and H2S emission minimization. The effect of CH4 and H2 incorporation is also investigated. As the product with the highest proportion, the composition of solid deposit is carefully analyzed, and a novel method of O2-plasma oxidation is tested to in-situ remove solid deposit over catalyst surface and reactor. In general, this research explores an economical and environmental-friendly alternative for the desulfurization of crude oil.

Experimental study and evaluation of heavy crude oil desulfurization process using combination of Alkalines Solutions and Catalytic Oxidative

Research on the desulfurization of heavy crude oil will be carried out utilizing Alkalines, Oxidative desulfurization, and a combination of Alkalines and Oxidative desulfurization, among other approaches. In this study, the effects of alkaline solutions with different weights (10–30 gm), temperatures (30–60°C), contact times (30–60 min), and mixing speeds (300–500 rpm) were studied. It was revealed that the removal efficiency of the individual alkaline process was very low. A number of tests are carried out with the goal of offering a suitable technique for the removal of sulfur from heavy crude oil while taking a variety of procedures into consideration. According to the findings of the study, the combination of oxidative and alkaline desulfurization generates the best desulfurization effect, which is around 64.45 %. This is followed by oxidative desulfurization, which produces a 56.54 % desulfurization effect. A study found that alkalines removed the least amount of sulfur (39.52 %) when no oxidative desulfurization was used It is also being researched the influence of different H2O2 concentrations, treatment times, and temperatures on crude oil desulfurization when using a combination of alkaline and oxidative procedures. The results show that when the temperature and H2O2 volume ratio increase, the ultimate sulfur removal rate increases, but virtually maintains constant as treatment time increases. These significant findings will pave the way for widespread usage of combination aulkaline and oxidative desulfurization procedures.

Choline chloride-based deep eutectic solvents for ultrasonic-assisted oxidative desulfurization of actual heavy crude oil

Deep eutectic solvents (DESs) are acquiring increasing interest as ionic liquid analogues because of their wide application, low-cost characteristics and environmentally friendly. In this study, choline chloride-based (ChCl) as a type of DESs were synthesized using polyethylene glycol (PEG), and applied to reduce sulfur content of actual heavy crude oil with sulfur content 37900 ppm (3.79 wt%). The synthesized DESs were characterized using Fourier-transform infrared spectroscopy (FTIR), as well as viscosity and density measurements. The DESs were evaluated for extractive ultrasound-assisted oxidative desulfurization (EUAODS), with 30 wt% H2O2 as the oxidant and formic acid as the catalyst. This study looked at the effects of oxidative desulfurization (ODS) and single ODS under ultrasonic treatment. Different systems for DESs were tested to find the desulfurization selectivity of the better reaction system; and it was found that extractive desulfurization (EDS) removed 24.57% of the sulfur, followed by extractive and ultrasonic-assisted desulfurization (EUADS) at 26.78%, then ODS at 37.28%, with ultrasonic-assisted oxidative desulfurization (EUAODS) providing the best result of 62%. According to the comparison trials, combining DESs with ultrasonic treatment improved processing. This study contributes to the body of information on the use of ultrasonic treatment in heavy crude oil desulfurization.

Mechanistic Understanding of Gordonia sp. in Biodesulfurization of Organosulfur Compounds.

Although conventional oil refining process like hydrodesulfurization (HDS) is capable of removing sulfur compounds present in crude oil, it cannot desulfurize recalcitrant organosulfur compounds such as dibenzothiophenes (DBTs), benzothiophenes (BTs), etc. Biodesulfurization (BDS) is a process of selective removal of sulfur moieties from DBT or BT by desulfurizing microbes. Therefore, BDS can be used as a complementary and economically feasible technology to achieve deep desulfurization of crude oil without affecting the calorific value. In the recent past, members of biodesulfurizing actinomycete genus Gordonia, isolated from versatile environments like soil, activated sludge, human beings etc. have been greatly exploited in the field of petroleum refining technology. The bacterium Gordonia sp. is slightly acid-fast and has been used for unconventional but potential oil refining processes like BDS in petroleum refineries. Gordonia sp. is unique in a way, that it can desulfurize both aliphatic and aromatic organosulfurs without affecting the calorific value of hydrocarbon molecules. Till date, approximately six different species and nineteen strains of the genus Gordonia have been recognized for BDS activity. Various factors such as enzyme specificity, availability of essential cofactors, feedback inhibition, toxicity of organic pollutants and the oil-water separations limit the desulfurization rate of microbial biocatalyst and influence its commercial applications. The current review selectively highlights the role of this versatile genus in removing sulfur from fossil fuels, mechanisms and future prospects on sustainable environment friendly technologies for crude oil refining.

The Study of the Desulfurization of Crude Oil in the Qatar Reservoirs System

According to problems of environmental pollution problems due to burning fuels having high Sulfur as furnace oil and because of related limitations, Sulfur removal methods have been emphasized to heavy crude oil patches. If Sulfur removal is necessary to furnace oil, and parts of crude oil would be processed but it should be pointed that this process include of operational problems as furnace oil Sulfur removal because of asphaltic components and metal contaminations developed chemical methods to mercaptan may not be used to crude oil and heavy parts. Therefore, it is attempted to provide new method to remove Sulfur composition from crude oil. in this paper all related methods to remove Sulfur compositions have been evaluated and operational problems have been assessed. Then, the best possible method has been introduced and supplementary discussion and economic evaluation have been provided.

Molecularly imprinted poly(methyl methacrylate)-nickel sulfide hybrid membranes for adsorptive desulfurization of dibenzothiophene

The ultra-deep desulfurization of crude oil to produce cleaner transportation fuels is essential for environmental protection. In this study, we present the development of molecularly imprinted poly(methyl methacrylate) (MIP)-based affinity membranes for adsorptive desulfurization of fuels. Hydrothermally-prepared nickel sulfide (NiS) nanoparticles are integrated into DBTh-imprinted polymer (MIP) to prepare MIP-NiS hybrid membranes with enhanced desulfurization capability. The surface morphology of non-imprinted (NIP), MIP and MIP-NiS hybrid membranes is studied by atomic force microscopy, which reveals the microstructure of MIP and finely dispersed NiS nanoparticles in the MIP matrix. The adsorptive removal of DBTh from n-hexane solution is investigated. The results indicated the removal of DBTh down to 1 ppmw with MIP-NiS hybrid membrane that is an order of magnitude superior to conventional hydrodesulfurization techniques (i.e. ~10 ppmw). The post-polymerization DBTh-imprinting effects of MIP combined with NiS-DBTh affinity interactions in MIP-NiS hybrid membranes offer the effective (97%) recognition and removal of DBTh at 1 ppmw.

Synthesis of Co/MoS2 by Laser Pyrolysis and its Catalyst Activity

Molybdenum sulfides (MoS2)are efficient hydrodesulfurization (HDS) catalysts widely used in crude oil desulfurization. This paper described the synthesis of MoS2 and Co/MoS2nanomaterials by laser pyrolysis method. Here, we investigated two catalysts sample MoS2 and Co/MoS2, which were active for deep hydrodesulfurization reaction. Sulfide catalysts were characterized by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM), and tested in the dibenzothiophene (DBT) HDS reaction. It was found that pure MoS2 and Co/MoS2 nanomaterials was obtained with hollow spheres form. And Co/MoS2catalyst has much better initial activity compared to the reference commercial catalyst.

Enzymatic Desulfurization of Crude Oil and Its Fractions: A Mini Review on the Recent Progresses and Challenges

The worldwide increasing demand for environmentally-friendly transportation fuels and the strict regulations by the environmental protection agencies have put a great pressure on crude oil refining and upgrading industry. The main current technology for the desulfurization of crude oil and its fractions is hydrodesulfurization. However, this process is plagued with several drawbacks. The growing pressure on petroleum refining industries to reduce sulfur contents in fuels has made hydrodesulfurization process even more unappealing. Hence, more effective alternatives have been (and are still) sought by petroleum refining industries. Enzymatic desulfurization process has recently emerged as a promising alternative that has the potential to be cost-effective, efficient and environmental-friendly. In enzymatic desulfurization process, enzymes (whether intracellular or extracellular) attack organosulfur components in the crude oil or its fractions and remove sulfur through a series of enzymatic reactions. The process is an energy-saving process, devoid of emission of harmful gases into the atmosphere, and utilizes completely biodegradable catalysts. This article reviews the recent progress in desulfurization of crude oil and its fractions using extracellular and intracellular enzymes. Challenges encountered during enzymatic desulfurization are highlighted, and some potential solutions to tackle the challenges are proposed. Future outlooks into the development of more efficient enzymatic desulfurization processes have been pinpointed.

Interfacial self-assembly of nanostructured silver octahedra for surface-enhanced Raman spectroscopy

A novel robust and effective approach is suggested to form thin film substrates for surface-enhanced Raman spectroscopy (SERS) using interfacial self-assembly in demixing water/toluene Pickering emulsions collecting silver octahedral mesocages onto a finally flat interfacial region. The freely floating self-assembled silver films obtained after toluene evaporation can be transferred onto various substrates including those with an ordered superficial relief causing a further alignment of silver octahedra. A special porous aggregative structure of the octahedra mesocages provokes a great number of hot spots allowing a large amplification of Raman scattering signal of model dye analytes and molecular thiol products of crude oil desulfurization. The suggested method seems to be an easy scaling route for SERS active material production.

Decomposition of Oxidized Sulfur-Containing Components of Crude Oil and Petrochemicals Under Conditions of Nanoheterogeneous Catalysis

The catalytic decomposition of dibenzothiophene sulfone is studied in the presence of nanosized iron(III) oxide with an average particle diameter of 10–12 nm; it is synthesized by the thermolysis of iron(III) acetylacetonate in the medium of diphenyl ether. The optimum conditions of the process are ascertained by varying the temperature and time of the reaction and the concentration of the nanosized catalyst. It is shown that the oxidative desulfurization of crude oil and petrochemicals may occur with the oxidized sulfur-containing components being decomposed under mild conditions in the presence of nanosized iron(III) oxide at the second stage. In some cases, the degree of desulfurization is above 80%.

Improving the Catalytic Power of the DszD Enzyme for the Biodesulfurization of Crude Oil and Derivatives.

The enhancement of the catalytic power of enzymes is a subject of enormous interest both for science and for industry. The latter, in particular, due to the vast applications enzymes can have in industrial processes, for instance in the desulfurization of crude oil, which is mandatory by law in many developed countries and is currently performed using costly chemical processes. In this work we sought to enhance the turnover rate of DszD from Rhodococcus erythropolis, a NADH-FMN oxidoreductase responsible for supplying FMNH2 to DszA and DszC in the biodesulfurization process of crude oil, the 4S pathway. For this purpose, we replaced the wild type spectator residue of the rate limiting step of the reduction of FMN to FMNH2 , a process catalysed by DszD and known to play an important role in the reaction energy profile. As replacements, we used all the naturally occurring amino acids, one at a time, using computational methodologies, and repeated the above-mentioned reaction with each mutant. To calculate the different free energy profiles, one for each mutated model, we applied quantum mechanics/molecular mechanics (QM/MM) methods within an ONIOM scheme. The free energy barriers obtained varied between 15.1 and 29.9 kcal mol-1 . Multiple factors contributed to the different ΔG values. The most relevant were electrostatic interactions and the induction of a favourable alignment between substrate and cofactor. These results confirm the great potential that chirurgic mutations have for increasing the catalytic power of DszD in relation to the wild type (wt) enzyme.