Advanced development in upstream of petroleum industry using nanotechnology

Nowadays,energy supply is one of the most important issues due to limitation of oil,gas and coal sources.Because of rapid population,civilization and energy consumption growth,the improved technologies to make optimal use of the sources,solving related problems and finding new energy sources are important.More than 10 years ago,nanotechnology as one of the most important technologies has also been applied to progress in the oil and gas industry(upstream,midstream and downstream).The experience of these years has shown that application of nanotechnology in the oil industry improves the exploration of crude oil and natural gas(underground or deep water),drilling and bringing the crude oil or raw natural gas to the surface,as well as transportation,storage,processing and purifying methods.Nanoparticles with high specific surface area,pore volume and small size show unique physical and chemical properties,which could be applied in several applications.In this regard,many researchers have been focused on various nanoparticles for upstream industries and studied their potential in oil exploration,drilling,production and enhanced oil recovery(EOR).Also,in downstream and midstream which involve refining of crude oil,processing and purifying of raw natural gas,transportation and storage of crude or refined petroleum products,the nanomaterials have been used to improve the quality of oil and make it appropriate for the environment.Lowering sulfur gasoline,enhancing the octane number and coating the transportation system are among the goals that have been achieved successfully using nanotechnology.In this work,various types of nanoparticles such as metallic,metal oxide,hybrid nanoparticles,carbon nanomaterials,nano-composites and their applications in oil upstream industry are reviewed.Also,their usage in different types of oil upstream processes is discussed.

Burial and thermal maturity modeling of the Middle Cretaceous-Early Miocene petroleum system,Iranian sector of the Persian Gulf

The Cretaceous Kazhdumi and Gurpi forma- tions, Ahmadi Member of the Sarvak Formation, and Paleogene Pabdeh Formation are important source rock candidates of the Middle Cretaceous-Early Miocene pet- roleum system in the Persian Gulf. This study characterizes generation potential, type of organic matter, and thermal maturity of 262 cutting samples （marls and argillaceous limestones） from these rock units taken from 16 fields in the Iranian sector of the Persian Gulf. In addition, the burial and thermal histories of these source rocks were analyzed by one-dimensional basin modeling. Based on the total organic carbon and genetic potential values, fair hydro- carbon generation potential is suggested for the studied samples. Based on Tma~ and vitrinite reflectance values, the studied samples are thermally immature to mature for hydrocarbon generation. The generated models indicate that studied source rocks are immature in central wells. The Gurpi and Pabdeh formations are immature and the Ahmadi Member and Kazhdumi Formation are early mature in the western wells. The Pabdeh Formation is within the main oil window and other source rocks are at the late oil window in the eastern wells. The hydrocarbon expulsion from the source rocks began after deposition of related caprocks which ensures entrapment and preserva- tion of migrated hydrocarbon.

Synthesis of boron nitride nanorod and its performance as a metalfree catalyst for oxidative desulfurization of diesel fuel

In order to reduce the sulfur compounds in diesel fuel,boron nitride(BN)has been used as a novel metal-free catalyst in the present research.This nanocatalyst was synthesized via template-free approach followed by heating treatment at 900℃ in nitrogen atmosphere that the characteristics of the sample were identified by the X-ray diffraction,Fourier-transform infrared spectroscopy,Raman spectroscopy,field emission scanning electron microscopy,transmission electron microscopy,atomic force microscopy,and N2 adsorption-desorption isotherms.The results of structural and morphological analysis represented that BN has been successfully synthesized.The efficacy of the main operating parameters on the process was studied by using response surface methodology based on the Box-Behnken design method.The prepared catalyst showed high efficiency in oxidative desulfurization of diesel fuel with initial sulfur content of 8040 mg·kg^(-1)S.From statistical analysis,a significant quadratic model was obtained to predict the sulfur removal as a function of efficient parameters.The maximum efficiency of 72.4%was achieved under optimized conditions at oxidant/sulfur molar ratio of 10.2,temperature of 71℃,reaction time of 113 min,and catalyst dosage of 0.36 g.Also,the reusability of the BN was studied,and the result showed little reduction in activity of the catalyst after 10 times regeneration.Moreover,a plausible mechanism was proposed for oxidation of sulfur compounds on the surface of the catalyst.The present study shows that BN materials can be selected as promising metal-free catalysts for desulfurization process.

Effect of valence and spin state on ethane dehydrogenation in Fe-S-1 catalyst

Light alkanes non-oxidative dehydrogenation is an attractive non-oil route for olefins production.The alkane dehydrogenation reaction is limited by thermodynamic equilibrium,and the C-H bond cleavage is commonly considered as the rate-determined step.The valence state of metal sites in catalysts will influence the stabilization of the vital intermediate(i.e.,C_(x)H_(y)...M^(δ+)...H)during the C-H bond cleavage process,which in turn affects the catalytic reactivity.Herein,we explicitly investigated the effect of different valence states of framework-Fe in silicate-1 zeolite on ethane dehydrogenation reaction through the combination of experimental and theoretical study.Fe(Ⅱ)-S-1 and Fe(Ⅲ)-S-1 catalysts are successfully synthesized by ligand-assisted in situ crystallization method,In-situ C_(2)H_6-FTIR shows the higher coverage of hydrocarbon intermediates on Fe(Ⅱ)-S-1,Under the same evaluation co nditio n,Fe(Ⅱ)-S-1 exhibits a higher space time yield of ethylene.Density functional theory(DFT)results reveal that the more coordinate-unsaturated and electron-enriched Fe(Ⅱ)sites boost the first C-H bond activation by slight deformation and efficient electron donation with C_(2)H_(5)^(*)species.Remarkably,the second C-H bond cleavage on Fe(Ⅱ)-S-1 undergoes a spin-crossing process from quintet state to triplet state,which involves a two-electro n-two-orbital interaction,further promoting the formation of ethylene.Microkinetic analysis is consistent with the experimental and DFT results.This work could provide methodology for elucidating the effect of metal valence states on catalytic performance as well as offer guidance for designing more efficient Fe-zeolite catalysts.

Reservoir Quality Controlling Factor of the Asmari Reservoir in an Oil Field in Dezful Embayment, SW Iran

The Asmari Formation Oligo-Miocene in age is one of the most important reservoir rocks in SW Iran and Zagros basin and composed of carbonate rocks and locally sandstones and evaporates. In this research, reservoir quality controlling factors have been investigated in a well in one of the oil fields in Dezful Embayment, SW Iran. Based on this research, depositional environment, diagenesis and fracturing have been affected on reservoir quality. 3 distinct depositional settings can be recognized in the studied interval including tidal flat, lagoon, and shoal. Among these depositional setting, shoal environment with ooid grainstone microfacies along with interparticle porosity shows good reservoir characteristics. Diagenetic processes also play an important role on reservoir quality;dolomitization and dissolution have positive effects on porosity and enhances reservoir quality, while cementation, anhydritization and compaction have negative effect on it. Fracturing is another important factor affected on the carbonate reservoirs especially in the Asmari Formation.

Efficient desulfurization of gasoline fuel using ionic liquid extraction as a complementary process to adsorptive desulfurization

The extractive desulfurization of a model gaso- line containing several alkyl thiols and aromatic thiophenic compounds was investigated using two imidazolium-based ionic liquids （ILs）, 1-butyl-3-methylimidazolium tetrachloroaluminate, and 1-octyl-3-methylimidazolium te- trafluoroborate, as extractants. A fractional factorial design of experiments was employed to evaluate the effects and possible interactions of several process variables. Analysis of variance tests indicated that the number of extraction steps and the IL/gasoline volume ratio were of statistically highly significant, but none of the interactions were significant. The results showed that the desulfurization efficiency of the model gasoline by the ILs could reach 95.2 % under the optimal conditions. The optimized conditions were applied to study the extraction of thiophenic compounds in model gasoline and several real gasoline samples; the following order was observed in their separation： benzothio- phenc 〉 thiophcne 〉 3-methylthiophene 〉 2-methylthiophene, with 96.1% removal efficiency for benzothiophene. The IL extraction was successfully applied as a complementary process to the adsorptive desulfurization with acti- vated Raney nickel and acetonitrile solvent. The results indicated that the adsorptive process combined with IL extraction could provide high efficiency and selectivity, which can be regarded as a promising energy efficient desulfurization strategy for production of low-sulfur gasoline.

A comprehensive experimental evaluation of asphaltene dispersants for injection under reservoir conditions

As the efficiency of dispersants with different origins is questionable for each typical oil sample, the present study provides a reproducible and reliable method for screening asphaltene dispersants for a typical asphal- tenic crude oil. Four different asphaltene dispersants （polyisobutylene succinimide, polyisobutylene succinic ester, nonylphenol-formaldehyde resin modified by polyamines, and rapeseed oil amide） were prepared and their performance on two oils from an Iranian field under laboratory and reservoir conditions was studied. A thorough analysis including ash content and SARA tests was performed on the solid asphaltene particles to characterize the nature of deposits. Then a highly efficient carrier fluid, which is crucial when injecting dispersant into the wells, was selected from a variety of chemicals by comparing their solubility. In the next step, using an optical microscope, a viscometer, and a Turbiscan, the screening of dispersants under laboratory conditions was done on a mixture of dead oil and dispersant to evaluate the onset of asphaltene precipitation and its stability when titrating by a precipitant. Finally, two different mixtures of the efficient dispersants, live oil, and carrier fluid were used with the solid detection system （SDS） and the filtration method to examine their effects on the onset pressure of asphaltene precipitation and the asphaltene content of the crude oil under reservoir conditions. The results show that the combination of experimental methods used in this work could be consistently applied to screening asphaltene dispersants. Among the four different dispersants applied here, the dispersant based on nonylphenol-formaldehyde resin modified by polyamines showed the best performance on the available live oils. This chemical modified the onset pressure of asphaltene precipitation of light oil from 4300 psi to about 3600 psi and decreased the precipitated asphaltene of heavy oil by about 30 %.

Co-optimization of carbon dioxide storage and enhanced oil recovery in oil reservoirs using a multi-objective genetic algorithm(NSGA-Ⅱ)

Climate researchers have observed that the carbon dioxide （CO2） concentration in the atmosphere have been growing significantly over the past century. CO2 from energy represents about 75% of the greenhouse gas （GHG） emissions for Annex B （Developed） countries, and over 60% of global emissions. Because of impermeable cap rocks hydrocarbon reservoirs are able to sequester CO〉 In addition, due to high-demand for oil worldwide, injection of CO2 is a useful way to enhance oil production. Hence, applying an efficient method to co-optimize CO2 storage and oil production is vital. Lack of suitable optimization techniques in the past led most multi-objective optimization problems to be tackled in the same way as a single objective optimization issue. However, there are some basic differences between the multi and single objective optimization methods. In this study, by using a non- dominated sorting genetic algorithm （NSGA-II） for an oil reservoir, some appropriate scenarios are proposed based on simultaneous gas storage and enhanced oil recovery optimization. The advantages of this method allow us to amend production scenarios after implementing the optimization process, by regarding the variation of economic parameters such as oil price and CO2 tax. This leads to reduced risks and time duration of making new decisions based on upcoming situations.

Support effects on the chemical property and catalytic activity of Co-Mo HDS catalyst in sulfur recovery

Effects of carbon nanotubes （CNT） and alumina （γ-Al2O3） supports on the catalytic activities of hydrodesulfurization （HDS） process over Co- Mo catalyst have been studied. XRD results indicated that the main active phases in CNT and γ-Al2O3 supported Co-Mo catalysts are MoO2 and MOO3, respectively. The TPR results reveal that the reduction peak temperatures of the active species on CNT supported Co-Mo catalyst is lower than those on alumina supported Co-Mo catalyst, indicating that the CNT supports favor the reduction of active species. Catalytic evaluation results displayed that the sulfur content in the reaction products on the CNT supported Co-Mo catalyst is lower than that on the alumina supported Co-Mo catalyst if the HDS reaction was carried out at a temperature above 583 K.

Comparison of dry reforming of methane in low temperature hybrid plasma-catalytic corona with thermal catalytic reactor over Ni/γ-Al_2O_3

In the current study, the hybrid effect of a corona discharge and γ-alumina supported Ni catalysts in CO2 reforming of methane is investigated. The study includes both purely catalytic operation in the temperature range of 923-1023 K, and hybrid catalytic-plasma operation of DC corona discharge reactor at room temperature and ambient pressure. The effect of feed flow rate, discharge power and Ni/γ-Al2O3 catalysts are studied. When CH4/CO2 ratio in the feed is 1/2, the syngas of low Ha/CO ratio at about 0.56 is obtained, which is a potential feedstock for synthesis of liquid hydrocarbons. Although Ni catalyst is only active above 573 K, presence of Ni catalysts in the cold corona plasma reactor （T≤523 K） shows promising increase in the conversions of methane and carbon dioxide. When Ni catalysts are used in the plasma reaction, H2/CO ratios in the products are slightly modified, selectivity to CO increases whereas fewer by-products such as hydrocarbons and oxygenates are formed.

Experimental and kinetic study of n-heptane isomerization on nanoporous Pt-(Re,Sn)/HZSM5-HMS catalysts

Pt-（Sn,Re）/HZSM5-HMS catalysts were evaluated for n-heptane isomerization at 200–350 ℃.To characterize the catalyst,X-ray diffraction,X-ray fluorescene,Fourier transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,temperature-programmed reduction of H2,temperature-programmed desorption of NH3,infrared spectroscopy of adsorbed pyridine,H2 chemisorption,nitrogen adsorption-desorption,scanning electron microscopy and thermogravimetric analysis were performed.Kinetics of n-C7 isomerization were investigated under various hydrogen and n-C7 pressures,and the effects of reaction conditions on catalytic performance were studied.The results showed that bi-and trimetallic catalysts exhibit better performance than monometallic catalysts for this reaction.For example,a maximum i-C7 selectivity（ 〉74%） and multibranched isomer selectivity（40%） were observed for Pt-Sn/HZSM5-HMS at 200 ℃.

Methane hydrate stability in the presence of water-soluble hydroxyalkyl cellulose

The effect of low-dosage water-soluble hydroxyethyl cellulose （approximate MW～90,000 and 250,000） as a member of hydroxyalkyl cellulosic polymer group on methane hydrate stability was investigated by monitoring hydrate dissociation at pressures greater than atmospheric pressure in a closed vessel. In particular, the influence of molecular weight and mass concentration of hydroxyethyl cellulose （HEC） was studied with respect to hydrate formation and dissociation. Methane hydrate formation was performed at 2℃ and at a pressure greater than 100 bar. Afterwards, hydrate dissociation was initiated by step heating from -10℃ at a mild pressure of 13 bar to 3℃, 0℃ and 2℃. With respect to the results obtained for methane hydrate formation/dissociation and the amount of gas uptake, we concluded that HEC 90,000 at 5000 ppm is suitable for long-term gas storage and transportation under a mild pressure of 13 bar and at temperatures below the freezing point.

Production of single-walled carbon nanotubes from methane over Co-Mo/MgO nanocatalyst:A comparative study of fixed and fluidized bed reactors

In this study,the performances of fixed and fluidized bed reactors in the production of single-walled carbon nanotubes（SWNTs）have been investigated.In both reactors,single-walled carbon nanotubes were grown by catalytic chemical vapor decomposition（CCVD）of methane over Co-Mo/MgO nanocatalyst under two different operating conditions.The synthesized samples were characterized by TEM,TGA and Raman spectroscopy.It is found that the performance of a fluidized bed in the synthesis of carbon nanotubes is much better than that of a fixed bed.The quality of carbon nanotubes obtained from the fluidized bed was significantly higher than that from the fixed bed and the former one with the ID/IG ratio of 0.11 while the latter one with the ID/IG ratio of 0.71.Also,the yield of SWNTs in the fluidized bed was 92 wt%,while it was 78 wt%in the fixed bed.These advantages of fluidized bed reactors for the synthesis of carbon nanotubes can be attributed to more available space for the growth of carbon nanotubes and more uniform temperature and concentration profiles.

Effects of preparation and operation conditions on precipitated iron nickel catalysts for Fischer-Tropsch synthesis

Iron nickel oxide catalysts were prepared using co-precipitation procedure and studied for the conversion of synthesis gas to light olefins.In particular,the effects of a range of preparation variables such as Fe/Ni molar ratios of the precipitation solution,precipitate aging times,calcination conditions,different supports and loading of optimum support on the structure of catalysts and their catalytic performance for the tested reaction were investigated.It was found that the catalyst containing 40%Fe/60%Ni/40wt%Al 2O3 ,which was aged for 180 min and calcined at 600 ℃ for 6 h was the optimum modified catalyst.The catalytic performance of optimal catalyst has been studied in different operation conditions such as reaction temperatures,H2 /CO molar feed ratios and reaction total pressure.Characterization of both precursors and calcined catalysts was carried out by powder X-ray diffraction（XRD）,scanning electron microscopy（SEM）,Brunauer-Emmett-Teller（BET） surface area measurements,thermal analysis methods such as thermal gravimetric analysis（TGA） and differential scanning calorimetry（DSC）.

Ce-promoted Mn/Na_2 WO_4/SiO_2 catalyst for oxidative coupling of methane at atmospheric pressure

A series of Ce-promoted Mn-Na2WO4/SiO2 catalysts were prepared by incipient wetness impregnation method, and their catalytic performance for oxidative coupling of methane （OCM） was investigated at atmospheric pressure in a micro-quartz-tube reactor. The catalysts were characterized by X-ray diffraction （XRD）, temperature program reduction （TPR） and BET surface area. Ce promoter increased surface area and Na2WO4 species dispersion, which enriched the amount of the surface species. In addition, Ce promoter increased the Na/W species reduction, but the reduction peak shifted to higher temperature. Stability test of 5wt%Ce catalyst indicated suitable performance and stability. The selectivity and yield of C^2＋ hydrocarbons after 50 h operation reached 65.5% and 19.6%, respectively, at 840 ℃ over 5wt%Ce-2wt%Mn5wt%Na2WO4/SiO2 catalyst.

Effect of nano-particle size on product distribution and kinetic parameters of Fe/Cu/La catalyst in Fischer-Tropsch synthesis

Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-emulsion method.The concept of two superimposed AndersonSchulz-Flory （ASF） distributions has been applied for the representation of the effects of reaction conditions and nano-particles size on kinetics parameters and product distributions.These results reveal that by reducing the particle size of catalyst,the break in ASF distributions was decreased.Also useful different kinetics equations for synthesis of C3 to C9 and C10 to C22 were determined by using α1 and α2 chain growth probabilities.

Deactivation studies of bifunctional Fe-HZSM5 catalyst in Fischer-Tropsch process

A physical mixture of alkali-promoted iron catalyst with binder based on Fischer-Tropsch synthesis and an acidic co-catalyst （HZSM5） for syngas conversion to hydrocarbons was studied in a fixed bed micro reactor. Deactivation data were obtained during the synthesis over a 1400 h period. The deactivation studies on iron catalyst showed that this trend followed the phase transformation Fe2.2C （ ε′） → Fe5C2 （χ） → Fe3C （θ）, and the final predominant phase of the catalyst was Fe3C （θ）. Deactivation of zeolite component in bifunctional catalyst may be caused by coking over the zeolitic component, dealumination of zeolite crystals, and migration of alkali promoters from iron catalyst under synthesis conditions. The deactivation rate of iron catalyst was also obtained.

Partial oxidation of methane in Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.1)Ni_(0.1)O_(3-δ) ceramic membrane reactor

Ba0.5Sr0.5Co0.8Fe0.1Ni0.1O3δ（BSCFNiO） perovskite oxides were synthesized using a combined EDTA-citrate complexation method,and then pressed into disk and applied in a membrane reactor.The performance of the BSCFNiO membrane reactor was studied for partial oxidation of methane over Ni/α-Al 2 O 3 catalyst.The time dependence of oxygen permeation rate and catalytic performance of BSCFNiO membrane during the catalyst initiation stage were investigated at 850 C.In unsteady state,oxygen permeation rate,methane conversion and CO selectivity were closely related to the state of the catalyst.After 300 min from the initial time,the reaction condition reached to steady state and oxygen permeation rate were obtained about 11.7cm 3 cm 2 min 1.Also,the performance of membrane reactor was studied at the temperatures between 750 and 950 C.The results demonstrated good performance for the membrane reactor,as CH 4 conversion and CO selectivity permeation rate reached 98% and 97.5%,respectively,and oxygen permeation rate was about 14.5 cm 3 cm 2 min 1 which was 6.8 times higher than that of air-helium gradient.Characterization of membrane surface by SEM after reaction showed that the original grains disappeared on both surfaces exposed to the air and reaction side,but XRD profile of the polished surface membrane indicated that the membrane bulk preserved the perovskite structure.

Performance investigation of solar thermal collector with auxiliary heater for space heating

In this paper,the performance of a solar thermal system with a focus on space heating was investigated.A 70 m^(2) detached house was considered in the weather conditions of the city of Tehran,Iran.A thermosyphon solar water heater with a flat plate collector combined with an auxiliary electrical heater supplies the heating demand of the house.The proposed system was modeled and analyzed using TRNSYS software.In this regard,the TRNBuild module was employed for the building load calculation.The model has been simulated for one year of operation.The effects of the solar collector’s surface area and storage volume were assessed.The results show that for a solar collector with a 15 m^(2) surface area,the solar fraction is 0.29 in January,during which the solar radiation is the lowest.Using solar collectors of10 m^(2) and 5 m^(2) surface areas,the solar fraction falls to 0.23 and 0.14,respectively in January.Besides,two cases of 150 L and 300 L storage tanks are taken into account.Eventually,it is found that using a 15 m^(2) solar collector and a 150 L storage tank can appropriately provide the building’ s heating demand taking the thermal performance and economic aspects into consideration.

Improvement of the prediction performance of a soft sensor model based on support vector regression for production of ultra-low sulfur diesel

A novel data-driven, soft sensor based on support vector regression （SVR） integrated with a data compression technique was developed to predict the product quality for the hydrodesulfurization （HDS） process. A wide range of experimental data was taken from a HDS setup to train and test the SVR model. Hyper-parameter tuning is one of the main challenges to improve predictive accuracy of the SVR model. Therefore, a hybrid approach using a combination of genetic algorithm （GA） and sequential quadratic programming （SQP） methods （GA-SQP） was developed. Performance of different optimization algorithms including GA-SQP, GA, pattern search （PS）, and grid search （GS） indicated that the best average absolute relative error （AARE）, squared correlation coefficient （R2）, and computation time （CT） （AARE = 0.0745, R2 = 0.997 and CT = 56 s） was accomplished by the hybrid algorithm. Moreover, to reduce the CT and improve the accuracy of the SVR model, the vector quantization （VQ） technique was used. The results also showed that the VQ technique can decrease the training time and improve prediction performance of the SVR model. The proposed method can provide a robust, soft sensor in a wide range of sulfur contents with good accuracy.