Journal of Molec tguis 345 (2021) 17585 Contents available a ScienceDirect Journal of Molecular Liquids journal homepage: www.elsevier.com/locat imotliq Effect of metal oxide nanoparticles on wax formation, morphology, and | @) rheological behavior in crude oil: An experimental study ss. Sajjad Vakili*, Saber Mohammadi”, Arash Mirzaei Derazi‘, Fatemeh Mahmoudi Alemi”, Nasrollah Hayatizadeh*, Omid Ghanbarpour”, Fariborz Rashidi* ‘conical Engineering Departmen. Anish Univers of Tcl (AUT. Tera, SperatearEngineeing partner Research stat fPelearInaty (RIP Tete, fan “Natal rain Dilirg Compo (IDC) UBD MPD Oe ska an ARTICLE INFO ABSTRACT Received 15 May 2021 ‘eceped 11 Septembe 2021 ‘valle onlin 20 september 2021 In this work Fe,0, 290, and MgO nanoparticles were syathesized via a chemi precipitation method to investigate tei eects on wax formation, morphological characteris, and rheological behavior i a uel sample For this purpose, diferent scanning calorimetry, rss polarized microscopy and vis= omecry have been utilized 25 the main experimental techniques It was observed tht 290 and MgO ‘anopariles ae the most positive eect on the wax appearance temperature (WAT) of the erade oi by reducing she WAT from 25 to 192 and 17 "Cat 500 ppm respectively. However, Fe,0> nanoparticles Kent Aid not have an aceptaleecieney in postoneznent of WAT. Addition of the nanoparticles to the am de ol caused deformation of wax crystals to more spherical and regular structures Ia adtion. pres Mtl anaes ence ofthe synthesized nanoparticles prevented formation ofthe strong three-dimensional aie of wax Gitlin Structures at high temperatures. XRD analysis of the wax deposits extracted from the ere ol showed war that 0 chemical Bonding occured between the nanopaces and wax molecules. However spedor Morpelgy size dependent properties othe nanoparticles are esponible fr conrling the growth of wax ystl !uelei and reduction of the WAT. Fek-emisio seanning electron microscopy images ofthe Wax depos its showed a smooth ad laveted sac of the wax with some fine prices, which conim piel {interaction ofthe nanopaticies with wax. Findings of ths work reveal the potental of 230 and MgO anapatcles as efficent and owscost aves or production storage, and atspotatin ofthe wany crude ol 1 2021 Elsevier BV. All igs reserve, 1. Introduction (pumping) faces with serious problems. Also, with increasing the wax deposition the thickness of the wax layer inside the pipeline The oil industry has been recognized as one of the most impor- tant industries in the world economy [1]. Crude oi is a complex mixture of light and heavy hydrocarbons including paraffins, aro- matics, resins. and asphaltenes | 2) Paraffinis the lightest compo- nent of the crude oil which usually contains Cs to Cso hydrocarbons. Generally. paraffin fraction dissolves in crude oi at a balanced state at high temperature conditions (3) In a pipeline or storage tank, paraffin fraction of the crude oil ‘will deposit, crystalize, and form a three-dimensional network structure when the crude oil temperature is lowered below the temperature of wax crystal formation, whichis called wax appear- ‘ance temperature (WAT) [4 As this process continues the viscos- ity of the crude oil increases and the transportation of crude oil Ema addres: monarymadl sabia om (5. Me ups eavee)t0 1015) 2021217366 (0167-7522/0 2021 Eber BY All rights serve increases and may even block the oil transfer pipelines (5.5), Induced issues by wax deposition increase the cost- effectiveness of the process. Therefore, researchers have developed diferent solutions to mitigate these concerns. Generali, parafinic ‘wax can be removed by two general techniques: physical and chemical methods (6,7), Heat transfer technology (8), mechanical [8], magnetic, microbial technologies, etc. are the main physically-based methods for removing the wax deposits. These ‘methods are not suitable due to their cost and waste of time. In addition applying mechanical method is risky due to the tools stucking in the oll well, or pipeline, and also stopping/disrupting the oil production. Therefore «the application of the chemical- based methods are more advantageous and have received more operational attentions in the last decades. Generally, the chemical methods include two scenarios: sol- vents or inhibitors. Solvents are used after the formation of paraffinwax and they are utilized to remove the deposits in the pipeline. Given the significant amount of required solvent, this method is ‘often the most expensive available option, Therefore, due to the ‘good performance of solvents in removing the deposits, they are ‘only sed in certain circumstances. The solvent is ustally medium molecular weight organic hydrocarbons such as toluene and xylene ‘Over the last decade, experimental-heoretical research studies and application of the inhibitors have received lots of attentions. Inhibitors are usually polymeric compounds consisting of a hydro- ‘carbon and polar fraction, The hydrocarbon part, binds the inhibi- tor and paraffin, and the polar fraction affects the crystallization process by changing the crystal structure and morphology. Some ‘of these compounds reduce the tendency of the waky compounds to form three dimensional network by changing the surface prop- ‘erties and reducing the growth of crystals. Thus, i results in reduc tion of the fluid pour point and viscosity. As well, neutralizing the sravitational force holds the paraffin components through the attachment to the deposit and preventing them from clumping. ‘Asa result, the parafin is dispersed throughout the fluid and flows as suspended particles 10-14), From the operational and econom- ical point of view. the use of inhibitors is often the best way to pre- vvent the wax crystallization and growth. Due to the presence of Inhibitors on the surface of the paraffinic crystals or their entry inco the crystal wax structure, the rate of growth process or wax ‘deposition are reduced [15.16]. As a result, chemical control sce- hario is the most efficent approach to prevent the aggregation and growth of wax crystals inthe early stages. ‘With the development of nanotechnology, different nanostruc- tured materials have been used for vatious process in the petro- leum industry such as enhanced oil recovery (EOR) processes 17-19}, controlling or stabilizing asphaltene precipitation (20- 22), enhancement of drilling fluid additives 22.24], catalysts 25.25}, ete. Due to their unique characteristics like electrical, opti- ‘al, and, magnetic properties, nanoparticles are used in nano- Sensors to prevent uncertainties in determining the source of hydrocarbon accumulation in the basement [27.25]. In the field ‘of drilling various materials, which are mainly polymeric, are used as drilling fuid additives [29]. Additives are used to improve the properties and performance of the drilling fluids such as thermal stability, salty Fesistance, and the rheological properties. Several types of nanoparticles including silica dioxide (Si0,), zine oxide (2n0), and copper oxide (CuO) have also been used in this fel, Which has led to the improvement of drilling fluid properties [20-32], Other application of nanoparticles in the petroleum industry include their use in nano-catalysts for the recovery of unconventional sources [23]. For example, several types of nano- catalysts such as nano-sized transition metals and metal oxide nanoparticles, have been used in aquathermolysis process to improve the production of heavy and extra heavy oils (34-36 However the potential application of nanoparticles for controlling the formation of waxy crystals and treatment of related issues have been grossly missing in the available literature, The properties, morphology, and flow characteristics of the crude oil are treated by adding nanoparticles to pour point depressants (PFDs). Espe- cially in areas with wax deposition problems. it can provide a new way fo improve the theological properties of the crude oil and so reduce the amount of wax deposits. Nanoparticles have supetior properties such as high active surface avea, high ads tion ability high thermal and chemical stability, high heat transfer 127-39}, Polymerfinorganic nanocomposites consist of an inorganic nanoparticle and polymer network known as nano-hybrid PPDs. ‘The operating mechanism of these nano-hybrid PPDs involves the creation of a large number of nucleation centers for wax depo- sitions, which lead to the growth of a large number of small-sized Jornal Maer iui 34 (2021) 17566 wax crystals. These inhibitors are absorbed on the surface of the wax crystals and prevent their further growth |40|. Song et al investigated the effect of SiOz nanoparticles on wax crystallites and the theological behavior of the crude oil containing different amounts of asphaltene and resin. They found that this nano- hybrid PPD acts as a nucleation center, increasing the number of ‘wax crystals but reducing their size. Also, with increasing the amount of asphaltene and resin, the deposition temperature of the wax decreases. The researchers believe that PPD nano- hybrids prevent the accumulation of asphaltene and reduce the ‘number of wax crystals, which leads to a slight increase in wax particle size [21), Yang et al. synthesized a new modified PPD using polyoctadecyl acrylate and Sid, nanoparticles and investigated the effect of this nano-hybrid PPD using differential scanning calorime- try (DSC) on wax deposition temperature. Nano-hybrid molecules increase the solubility of wax crystal molecules and reduce the cloud point value. They also observed that this nano-hybrid PFD changes the morphology of the wax crystals from the plate shape tospherical state, The results oftheir studies showed that the opti= ‘mum concentration of this nano-hybrid is 100 ppm and the resis- tance of the gel at concentrations higher than this value has increased, They stated that the use of PPD nano-hybrids reduced the crushing point of the crude oil and significantly improved the ‘low properties (40 In this work the influence of different metallic-type nanoparti- cles, ZnO and MgO and Fe,0, nanoparticles, on wax crystallization and flow behavior of the crude oil is studied. The synthesized ‘nanoparticles are characterized by fleld-emission scanning elec- {on microscopy (FESEM) and Brunauer-Emmett-Teller (BET) tech- niques. The utilized nanoparticles are cost-effective and environmentally fiendly. The WAT, crystal structure/morphology, and rheological behaviors of the crude oil are investigated by DSC. high resolution cross-polarized microscope (CPM), and a rotational rheometer. Finally, the performance of the synthesized nanoparti- cles was compared with polyethylene vinyl acetate (EVA) as an efficient and the most widely used wax inhibitors in oil industry. ‘To the best of aur knowledge, this isthe first study in which the potential applications of metallic-type nanoparticles for control- ling the formation and growth of wax crystals in crude oil are com- prehensively investigated 2. Experimental section 2.1. Materials 2.1.1. Synthesis and characterization ofthe nanoparticles and EVA wor inhibitor Pure MgO: Zn0, and Fe,0) nanoparticles are synthesized by a simple chemical precipitation method. As the synthesis of the nanoparticles is not the main subject of the paper, it is referred to published reference for detailed procedure of the nanoparticles fabrications 22], FESEM analysis are used with FEI Nova NanoSEM-450 to examine the morphology and particle size of, the synthesized nanoparticles. The FESEM images of the synthe- sized nanoparticles ate shown in Fig. 1. The FESEM images show well fabrication of the nanoparticles by chemical precipitation ‘method. The textural properties ofthe nanoparticles are analyzed by nitrogen adsorption-desorption experiment at ~196 °C with porosimeter apparatus, ASAP-2010 Micromeritics, USA. Sutface areas are calculated by Brunaver-Emmett-Teller (BET) model ‘The pore size distribution of the nanopatticles are measured from. the adsorption isotherms by the Barrett, Joyner, and Halenda (BJH) algorithm, The textural and surface properties of nanoparticles by Nz adsorption experiments are summarized in Table 1. The zeta potential of the synthesized nanoparticles were measured at pHJornal Maer ius 245 (2021) 17566 @ o © “Texan uae properties of yntesed stopaties by BETA method BET specie sac ea Arg) —-20187 96303 a58zP “ray AP ma Doerage parle 6d Sas nas’ toa Molec weigh (ee saa : “Average pore ameter, dy (am) wes7 19148221059 Initial being point (°C), 10 velx dstiled 95-105 ASTNED 2892. tal poce volume af pores (emg) 1188 0.4103 04314 Final boing pint °C), 10 90 dled ->565.——_ASTMCD2692 ‘of 7 and temperature of 20 °C by Malvern Zetasizer (Malvern ax coment mas 2 Bras Instruments, UK). The obtained results of zeta potential are given in Table 1 Echylene-vinyl acetate (EVA) (20 we of vinyl acetate) with a melt flow index of 20 g/10 min were purchased from Hanwha Chemical (South Korea) and used without further purification (commercial name: EVAtI56). The average molecular weight of the EVA was measured using size exclusion chromatography (SEC) which is about 95190, 2.12. Crude oil sample characteristics and solution preparation ‘A waxy crude oll sample from a reservoir located in south west of ran was selected for this study. The properties and general char- acteristics of the crude oil sample are given in Table 2 tt should be mentioned that the production reports for the reservoir oil, in which the crude oil sample was provided, confirm severe wax deposition in surface faclities and transportation lines, Thus, the crude oil used in this work is a waxy crude oil sample with high potential of causing problems and issues induced by wax precipi- tation and deposition To prepare the erude oil solution, frst, the crude oil containing paraffin is filtered with a 0.5 ym cylindrical filter to remove any contaminants or sludge material. Then, the filtration operation is repeated by Whatman 8 m filter paper to prevent the presence of any harmful substances in the crude oil. In the next step-the MgO: Zn0, and Fe,03 nanoparticles are mixed separately with crude oil in different concentrations of 250, 500, and 1000 ppm. ‘The sample is stirred by a magnetic stirrer at 700 rpm for 2 b,and then further sonicated at 30 °C for 1 h to form a stable dis- persed solution. The stability of the synthesized nanoparticles over time has been examined by sedimentation method. This method isa reliable techniqhte which has been widely aed for evalttation ofthe stabil- ity of nanoparticles nanofiuids, aso known as the settling bed |22 In sedimentation cechnique, the fluid (i.e. treated crude oil with different dosages of the nanoparticles) was filtered through a (02 um Cellulose Nitrate filter to assess the possible sedimentation ‘of nanoparticles versus time, After each time step, the crude oil ‘containing the nanoparticles has been filtered and the amount of hhanoparticles sedimentation has been measured. For al time steps (upto 120 h), no sedimentation was happened, which exhibits the high stability ofthe synthesized nanoparticles in studied crude ol ln addition, visual examination of the bulk medium of crude oil ‘demonstrates no phase separation/sedimentation ofthe nanopart- cles in treated crude oil for al time steps 22. Investigation ofthe effect of nanoparticles on wax formation behavior in crude oil In this section, different techniques including DSC, CPM, and viscometry are utilized to evaluate the wax theological properties and crystal formation and growth in crude oil inthe absence and presence of the synthesized nanoparticles. After preforming these ‘experiments, wax deposits ae extracted to assess the mechanisms ‘of Wax-nanopatticles interaction. For this purpose, X-ray difrac- tion (XRD), FESEM, and energy dispersive X-ray analysis (EDXA ‘or EDAX) techniques are utilized. The procedures of each experi- ‘mental method is described in the following sections: 221. Differential scanning calorimetry (DSC) experiments ‘Thermal DSC analysis ts used to study the effect of Fe,0;, MgO, and Zn0 nanoparticles on wax crystal formation (i.e, wax appear~ ance temperature-WAT) in bulk medium of the crude oil samples. DSC analysts is performed on a Perkin Elmer 8000 differential scan~ ning calorimeter. Calibration of the device is done using indium standard, Each samples (between 10 and 20 mg) are fist heated 3¢ 90 °C for 120 min to remove the heat date ane then, it cools ‘down in the temperature range from 80 to ~10 °C at a rate of 5 °C jmin, 222. Cross-polarized microscopy (CPM) The Cross-polarized microscopy is utilized to detect the first ‘rystal formed and to obtain wax appearance temperature. In addi- tion, CPM enables to monitor the wax crystal growth and their structure and morphology. Therefore, in this work, (OLYMPUS X51) polarized microscope with a 5-pixel camera is used to eval- uate the WAT as well as to obtain the shape and size ofthe crystals. Samples ae frst heated to 90 °C for 60 min to remove thermal his- tory and are cooled to ~5 °Cat a rate 0.5 *C/min. Finally, the images of wax crystals structure are analyzed for mentioned studies, 2.2.3, Wax rheological behavior by viscometry technique In order to analyze the changes in theological behavior of crude oil sample with temperature, the Physica MCR301 viscome- ‘er is used, For this purpose, fits the samples are preheated for 1 h at 60 °C and 1000 rpm by stirrer to remove their thetmal history ‘and all the wax crystals formed are dissolved and finaly loaded fn the viscometer to statt the tests The viscosity of each sample is obtained at temperatures of 10, 15,20, and 30°C and at diferent shear stresses 0.01 0.10, and 1.00 Pa. 2.24, FESEM and EDAX analyses FESEM is used to study the structure and morphology of the ‘wax crystals and their interaction with nanoparticles. For this pur= Jornal Maer igus 34 (2021) 17566 pose, first, the waxes in the oil samples are extracted by BP 237 [ASTM and in the next step, the paraffinic waxes are dried in the ‘ven so that the structure of the material ts not damaged. The sam- ples are then placed in the apparatus to be analyzed by FESEM. An EDAX detector is used to better understand the presence of the nanoparticles in the paraffinic wax as well as their distribution and concentration, When FESEM is joined with an EDAX detector, X-rays can also be used asa specific signal to produce the chemical information. This imaging procedure is done by FE-SEM TESCAN MIRA-3 microscope, 225. XRD analysis ‘The X-ray diffraction (XRD) patterns of the wax deposits are obtained by a XRD Rigaku Ultima [V X-ray diffractometer with (Cu LFF radiation (.~ 154598 A) First, the waxes in the oil sample are extracted by BP 237 ASTM and after drying, they are placed in the device. The scattering patterns are recorded over the range of angles corresponding to 20 from 10° to 80°. 53, Results and discussion 3.4. Differential scanning calorimetry (DSC) analysis In this method, the sample material and the reference material ate placed separately in containers called sample pan and refer ence pan, which are equipped with thermocouples and electric heaters. The temperature of both samples should be the same. Due to the difference in heat capacity of the sample material and the reference material, the energy used to maintain their temper- atures willbe different and the difference in amount of energy will be plotted in terms of temperature. In this section, DSC is utilized to find WAT ofthe crude oil sample. Therefore, oil samples are sub- jected to the cooling process, During the cooling process, at near the temperature of formation of the first crystal, a noticeable enthalpy change is seen in the diagram, which indicates a change in the heat capacity of the sample. This means that the ol is on the verge of phase change from the liquid to solid state, For mate- tials such as oil, which also have an amorphous part, the phase change is observed only as a falure in the diagram. However, for ‘matettals with high crystallinity, there are areas in the form of peak or valley during the phase change process. WAT is defined as the temperature at which the frst crystal forms which is a key parameter for oil to continue to crystallize until the solid state. ‘Therefore, the frst temperature at which the graph deviates from the uniform trend is considered as WAT of the crude oil sample. [At temperatures below the WAT, oil sample releases heat easily ddue to the formation of wax crystals (i. solid phase), ‘Synthesized Fe:03, MgO, and ZnO nanoparticles have been added to the crude oil in three concentrations of 250, 500, and 41000 ppm. So, the untreated crude oil (free of nanoparticles) and the treated crude oil (crude oil + nanoparticles) were analyzed by DSC to explore the effect of synthesized nanoparticles on WAT value. The obtained results in Table 3 show that for Fe;0} nanopar= ticles at concentrations of 250, 500, and 1000 ppm WATS are 24, sul DSC for measurement of WAT ith ferent nanoparticles em Feared more Naor)DSC-Untretaed Crude Oi Fig. 2. DSC cooing curve of unrated crude al fee of nanoparticles. 245, and 24 °C respectively. Compared to the untreated crude ol, ‘which has a WAT of 25 °C (Fig. 2), FesOs nanoparticles have been able to lower the WAT by 1,05, and 1 °C at corresponding concen- ‘uations. Thus, Fe;O; nanoparticles does not have a sensible posi- ‘ive effect on’ WAT of the crude oil. The results in Table 3 and Fig. 3 show that Zn0 nanopatticles at concentrations of $00 and ‘1000 ppm with WAT of 17 °C and 18.1 °C have succeeded in redue- ing the wax formation temperature of crude oil by 8 and 6. °C, respectively. However, ZnO nanoparticles at concentration of 250 ppm did not significantly decrease the amount of WAT. ‘According to the obtained results, MgO nanoparticles have reduced Jornal Molec ius 2422021) 117566 the WAT by 49, 5.8, and 5 °C for the tested concentrations in com- parison to the untreated oil sample (Fig. 3¢ and Table 3). It can be concluded that the best performance of the nanoparticles in post- pponement of the WAT has been attained for Zn0 nanoparticles at dosages of 500 and 1000 ppm, Generally, the efficiency of nanopar- ticles for reduction ofthe WAT in studied crude oil sample by DSC technique are in decreasing order of; 20 (500 ppm) > Zn0 {(1000 ppm} > MgO (500 ppm) » ZnO (250 ppm. 1000 ppm). It should be noted that, iron oxide nanoparticles have not been used in subsequent experiments due to their poor performance in reduction of WAT. With respect fo the size of nanoparticles and ‘wax crystals, different mechanisms are responsible forthe changes of the WAT in presence of nanoparticles as follows: + I the size of the nanoparticles is larger than the created wax nuclei: the nanoparticles, due to their high specific surface and porosity, physically adsorb small nuclei of wax crystals. By adsorption ofthe paraffins onto the surface ofthe nanopar- ticles, nucleation process is inactivated and the growth of the ‘wax crystals is slowed down. In fact, the wax nuclei are trapped between the cavities and surface pores of the nanoparticles. Accordingly, the growth of the wax crystals is slowed down, I the size ofthe nanoparticles is smaller than the created wax nuclei: nanoparticles surround the crystal nucle! without absorbing them and prevent the aggregation ofthe surrounding Crystal nuclei, AS a result, the formation of larger wax nuclei and the crystalline growth process (Le. aggregation theory) are pro- Iubited fn tis situation, the nanoparticles act as a stabilizing or dispersion agent, which reduce the wax-particle clustering and 4 more homogeneous distribution are obtained. 7 wat ~ => WaT i. a i~ dos i | —— Aj 7 > WAT i = — a @ &) war Ol © Fi. 3. DSC cooing cures of ere ol wit diferent concentrations a 250 (purple 50 (gren) ané 1000 (lu) ppm nanoparticles: a) sO (b) 2n0. and (e) MgO (Fr Interpretation the elerences to rin thi igre legend, the reste tered athe web er tierce!+ Ifthe size ofthe nanoparticles and the paraffinic wax nuclei are neatly in same order: the nanoparticles act as nucleation cen- te, are actively involved in the evolution of the wax crystals, buat in smaller sizes at the same concentration of paraffins. Thus, they prevent the formation of larger crystals and inhibit the arowth of wax crystals process, which really represents the homogeneous growth theory. Microscopic observations can also help to better understand the above mentioned findings 42, Cros-polarized microscopy (CPM) analysis (CPM analysis is performed to confirm the results obtained from the DSC tests. ig. 4 represents the recorded observations by CPM ‘at WAT point for untreated crude oll (Fig. 4a) and treated crude oil with ZnO and MgO nanoparticles at optimum concentration ‘of $00 ppm (Fig. 4b, c). In Fig. 4 the first appeared wax crystals under the microscope have been marked with red circles. The WAT via CPM analysis are in well agreement with the obtained results by DSC. However, the WAT-results obtained from the DSC analysis are more reliable than the CPM technique due to the non-intervention of manpower (operator) during the tes. ‘After the appearance ofthe fist wax particles and by more tem perature redilction below the WAT, the aggregation of the wax ‘rystals as well asthe changes in thei structures and morphology ‘can be monitored and analyzed, In Fig. 5 the CPM images at tem- perature of 0° for untreated crude ol (Pig. 5a) and treated crude ‘ll with 210 and MgO nanoparticles at $00 ppm (Fig. Sb, c) are shown. The CMP images in Fig. 5 have been analyzed by Java- based Image} package (National Institutes of Health) The results Jornal Maer igus 34 (2021) 17566 of images analysis are shown in Table 4. In the absence of the nanoparticles (t,, crude oil free of nanoparticles), there are large ‘number ofthe disk-like stacked wax aggregates. Large surface area and dise-shape morphology enables formation ofthe strong lattice Structures, When the nanoparticles are added to the crude ol, the ‘wax crystals become spherical particles with ultrz-smaller size in ‘more compact structures; as well, the number of the small wax crystals has been significantly increased, whereas the size of the wax crystals significantly decreased in comparison to the crude oil free of nanoparticles. This phenomenon indicates that the nanoparticles associated with paraffinic waxes modify the struc- tute of the wax ctystals and prevent the formation of larger aggre- gates of wax ciystals. Reduction of the wax crystal sizes by ‘Banopattices can control the deposition and gelation behavior of the wax crystals in oil wells flow lines. Actually in the presence of the nanoparticles, the wax particles have been dispersed and stabilized in the bulk medium of the erude oll, which pastpones the wax gelation threshold. Wax gelation on pipeline walls causes severe flow restrictions leading to losses in crude oil flowability and production associated to the flow restarting countermeasures, ‘Thus, appropriate nanoparticles can be implemented in oil produc tion system as efficient wax dispersantjinhibitor for wax bandling strategies. 3.3, Viscometry analysis, Viscosity isan important feature in wax precipitation analysis, which plays an important role in lowabiliy of erude oi. In fis, the apparent viscosity of the untreated oil sample and the treated © Fig. rat sages of ede oat WAT: a) the absence apeparties Reg ces shaw the @ © appeared Wax pares under te microscope Fo ierprecation othe elerences oe nt gure lege the reader seer©, © Fig 5. ceNumages feud lat temperature af 0°: (a te absence of the nanparies (a peseae a 500 ppm Z80 sanepartles ad (ca presence of 500 ppm. ‘eal and este ere ol with 50 pp of 20 ad MO naneparies Anaises ‘ree permed on CPM tages by eg aude (500 pp 20 pp ‘Number of deecabie 2 6 oa oil containing 500 ppm of ZnO and MgO nanoparticles a different temperatures of 0 5, 10, 15, 20 and 30 °C respectively are shown, ‘The main purpose of the low shear rate study is to investiga crude oil behavior in neat static mode: while. the medium and high shear rates are used fo study the crude oll performance in ol rans- mission lines. Generally, increasing the temperature, in ut, reduces the viscosity of the crude oil, which determines the changes in the rheological properties of the crude i, When the temperature ofthe crude ol falls below the formation temperature ofthe first erystal wax (Le, WAT), the wax crystals begin to inter- fact with each other to form a three-dimensional network that eventually leads to the bonding of the lighter components of the crude oi, This phenomenon leads tool trapping and thts increases the viscosity ofthe crude oil while it reduces the ol flow assurance and pressure drop in the tube or flowlines, Crude oil at high tem perature conditions behaves as a Newtonian fluid which shows viscosity-temperature dependence. AS the temperature of tt crude oil falls below the WAT point, formation of the wax crystals abruptly increases the crude oil viscosity entering into the non- Newtonian fluid region. As well, presence of solid particles leads to a change of the flow behavior of crude oil from Newtonian to rhon-Newionian condition. ‘Therefore, it causes a noticeable increase in the crude oil viscosity and hence additional pressure ddrop which increases consumption of pumping and decreases pipelinejtubing performance because of possible plugging In general, as shown in Fig. 6, at all temperatures and at all shear rates, in contrast to the MgO nanoparticles, ZnO nanoparti- cles have a negative effect on the crude oil viscosity, The effects of temperature changes are not noticeable and the only sensible effect is observed at temperatures below 10 °C. Therefore, it can be concluded that the effect of temperature is more pronounced than the effect of nanoparticles addition at temperatures below the WAT. At temperatures above the WAT, the effecs of tempera- ture and adding nanoparticles to the ctude oil are in the same direction and reduce the viscosity. Regarding the shear rate changes, it can be said that at shear rates above 0.1 (1/3), the viscosity-shear rate diagram forall samples is almost a constant line. This can be interpreted in such a way that for shear rates higher than 0.1 (1/s) the addition of the nanoparticles at low dosages to the crude oil cannot significantly change the viscosity ‘While passing through the shear rate of 0.1 (1/s) to lower shear rates, the changes in viscosity are quite noticeable. For untreated crude oil and oil sample containing MgO nanoparticles, the viscos- ity increases significantly in shear rates lower than 0.1 (1/5),Jornal of Maer ius 24 2021) 17566, is a ic Sanna i i sear 5) o “+-Treated crue ol wth 20 500 ppm + TWeated rte with go at 500 pom i + aad ce to 50pm i i ‘Shear Rate (1/5), * © atta @ ot reted cre O with MEO a 300 pom Voc Pas) sear ate 8) © strated crude of wth 20 #500 porn con + Treated crude of with MeO 3t 50 ppm ss = | shear nate (5) 0 Yocosty (Pas) 28 Fi. 6 Apparent vscony af way el vers hearse a eifeent shear ate in absence and presence of he nsnoparicies t conceieton of SO ppm (a) 0°C, 18) 5°C {0 10 fa) 15°, fe) 20°. an) 30 Fi 7. XRD paces af wax deposits for unrest crude ol and teste cree oi ‘wh nanoparticles For low temperature conditions well below the WAT (Le., 0.5, and 10 °C), the wax crystals grow severely, and thus. the viscosity of the untreated crude oil dramatically decreases. However, in ‘mentioned temperatures range, MgO nanopatticles at 500 ppm ‘efficiently controls the rheological behavior of the crude oil and Viscosity of the crude oil significantly decreases in comparison to the untreated crude oil. Consequently, asa general result, on aver- age, the effect of nanoparticles on viscosity i less than the effect of temperature and shear rate. ‘Wax crystallization results in formation of three-dimensional network structure that trap the eil specimen in small packets in the structure which increases the crude oil viscosity, The crude oil will ose its flowability with enough wax crystals formation, ‘which causes. problematic oil exploitation and transportation, and severely increases the cost of operation. As the results of ‘wax caystal analysis showed (Table 4), in presence of the nanopar~ ticles the crystal nuclei increase which leads to form more Wax ‘aystal number but with smaller size. Consequently, the more‘wax crystal number more easily obstruct the flow to increase the viscosity at higher temperatures, but the smaller erystal size more probably to be destroyed at lower temperature conditions. Along ‘with the molecular diffusion mechanism, reduction of the crude cil viscosity by temperature ot addition of the chemicals can be ‘beneficial fr the increase of ffusion coefficient of wax molecules, ‘Uncier the condition that the temperature gradient and solubility, coefficient of wax molecules are analogous, the decrease of crude oil viscosity is favorable to the diffusion of wax molecules (43). It is highlighted chat the presence of the asphaltene particles strongly affects the wax formation and growth, and favors the decrease of ‘the wax appearance temperature |4). The metallic nanoparticles ‘ean act as asphaltene inhibitor ot dispersant in crude oil medium [22.44.45]. Thus, the effect of asphaltene component of the crude oil on wax formation should be considered for better investigation ‘of the role of the nanoparticles on wax theological behavior. Fig. EDAXimage with mapping af wax deposit: Jornal Molec ius 2422021) 17566 34, XRD analysis Fig. 7 shows the XRD patterns of wax deposits extracted from the untreated crude oil and treated crude oil with 70 and MgO nanoparticles. In the XRD patter, each peak represents a crystal plate. The angle of each peak indicates the distance between the plates and the intensity of each peak can be related to the type, ‘number, and arrangement of atoms in the same plane, As can be seen from the X-ray graph, the sharp diffraction peak at 20 of 21.4" represents a crystal plate (110) in wax deposit from the untreated crude oll (45), in which 20 and MgO nanoparticles ‘did not change the crystallin plate ofthe wax. Actually the same characteristic peak in wax extracted fom the untreated oil has been also observed for the wax deposits inthe presence of the both ZnO and MgO nanoparticles, but with higher intensities. Also, the wide peak appeared at angle of 41/08 has been repeated in wax retested ere (for rested creo with 790 t 500 ppm for tested ede al with MED 3 500 ppmsamples containing the nanoparticles; however, the peak intensi- ties for the wax deposits in treated crude oil with nanoparticles are higher than the case of crude oil free of nanoparticles, The ‘observed differences in intensities disclose the efficient interaction between the wax particles and dispersed nanoparticles in bulk medium of the cruce oil, The observed behaviors in XRD patterns ‘of different wax deposits reveal that no chemical bond has been ‘created between the nanoparticles and the wax to produce adfer- ‘ent pattern trend, In other words, the noticeable changes in difrac~ tion intensities atthe sharp peaks indicate the physical interaction ‘of the nanoparticles with active sites of the wax particles. Thete- fore, the rays scattered by the atoms of MgO and Zn0 nanoparticles and the wax deposits interact with each other and increase the peak intensity on the same plane. 25, EDAX analysis EDAX (mapping) analysis detects the chemical elements pre- sent in the wax deposit and also shows the distribution and disper- sion of the elements in the samples. Therefore, iis a good evidence to justify the efficient interaction(s) between the wax molecules and nanoparticles, as well a ta describe the effect of nanoparticles ‘on changes ofthe the wax formation temperature, Actually, EDAX- mapping analysis have been employed to better understand the dispersion of the nanoparticles in the wax and the possible wax molecules-nanoparticles interaction Fis, 8a shows the EDAX image ‘with mapping of wax deposits for untreated crude oil (without nanoparticles). As can be seen, as expected, the main constituents ‘of crude oll are C, N, 0, and S, which have been displayed in sepa- rate colors, Fig. 8b shows the EDAX image of the wax deposit for ‘rude oil sample in the presence of the ZnO nanoparticles at 500 ppm. Green dots indicate the presence of the 2n0 nanoparti- les inthe wax deposit. This means that in addition tothe chemical ‘elements (C,N, 0,8) there is also Zn element, which represents the presence of the 230 nanoparticles. Fg. 8 also shows the EDAX image of the wax deposit for oil sample conlaining 500 ppm of the MgO nanoparticles. The light blue color in this image repre- sents MgO nanoparticles. Therefore, according to the analysis, the presence of the MgO nanoparticles in the wax deposit is verified, Some irrelevant elements are related to manpowerloperator oF conditions while extracting the wax deposits from the crude oil sample. I¢ should be emphasized that the results of the FESEM and EDAX analyses well confirm the results obtained via XRD. 3.6. Performance of nanoparticles versus EVA inhibitor ‘One of the most common wax inhibitor used in the industry is polyethylene vinyl acetate, EVA. which is product of the copoly- merization of ethylene and vinyl acetate (VA) [47~49]. The mea- sured WATs by DSC in crude oll treated with diferent concentrations of EVA are given in Table S. The measured WAT of the crude oil in the presence of $0, 100, 150, 250, $00, 500, and 1000 ppm of EVA are 21.5, 2055, 208, 268, 28.1, and 29.7 °C esl af WAT by DSC or deen concent ‘one of EVA Jornal Maer igus 34 (2021) 17566 respectively. Obtained results reveal that the most efficent dosage of the EVA for postponement of wax formation point has been achieved at dosage of 100 ppm. However, at high concentrations ff 250, 500, and 1000 ppm, the opposite effect is observed and the threshold of wax formation temperature decreases, Compa ison of the results for EVA and nanoparticles (Tables 3 and shows that at corresponding concentrations of 250, 500, and 1000 ppm the candidate nanoparticles (230 and MgO) have better performance for reduction of the WAT. with the most efficent dosage at 500 ppm. As well, comparison of the WAT by DSC at opti- ‘mum concentration for EVA (100 ppm) and MgO/Zn0 nanoparti- cles (500 ppm) exhibits that the synthesized nanoparticles more eliciently dectease the wax formation temperature, However, EVA at low dosages acts better than the Fe,0, nanoparticles Improper performance of EVA at dosages higher than 100- 150 ppm can be attributed to the EVA-asphaltene interaction, As the concentration of the EVA increases in the bulk medium of oil phase, it can adsorb on asphaltene flocs and form asphaltene EVA composite particles. The composite particles can act as the aggregation nuclei for wax molecules to precipitate, grow in size, and form large dense wax clustersflocs. The obtained results are inline with reported studies in the literature (50-52), Combination of the EVA with appropriate nanostructured materials can improve the performance of EVA for enhancement of flow behavior and wax ‘rystallization process in oi! medium [33], 4. Conclusions This study was performed to evaluate the effect of synthesized rmetallic-type nanoparticles, Fe,0;, 250, and MgO, on wax forma- tion, morphology of the wax crystals, and the theological behavior ina waxy crude oll sample. The results of DSC analysis showed that ZnO and MgO nanoparticles have a significant effect on reducing the WAT of the crude oil. The performance of the nanoparticles for retarding the WAT point in studied crude oil via DSC and CPM techniques are in decreasing order of: Zn0 (500 pprn} > 250 (1000 ppm) > Mgo (500 ppm) > Zn0 (250 ppm, 1000 ppm). Thus, he most efficiency of the ZnO and MgO nanoparticles were attained at concentration of $00 ppm. However, FeO; nanoparti- les did not considerably affect the WAT of the crude oil sample. Due to the high specific surface area and porosity af the nanopar- ticles, nanoparticles larger than the size of the crystalline nuclei inactivate the wax nucleation process and prevent wax crystals growth, For nanoparticles smaller than the wax nuclei, nanoparti- les surround the wax nuclei and prevent the aggregation of the nearby crystal muclei. Accordingly, the formation of the larger wax nuclei and the crystalline growth process (ie. aggregation theory) are controlled. For the same size of the nanoparticles and the wax nuclei, nanoparticles act as nucleation centers and they are involved in the evolution ofthe wax crystals. Therefore, forma- tion of the large wax crystals and their growth are inhibited, which signify the theory of the homogeneous growth, The results ‘obtained from the polarized microscopy confirm the decrease in WAT of oil samples by ZnO and MgO nanoparticles according to the DSC analysis. Presence of the nanoparticles in crude oil eff- ciently alter the wax morphology from the stacked disk-lke aggre- ‘tes in untreated crude oil to the small and narrow spherical structures. At the same time, by Increasing the number ofthe crys- tal cores and reducing their size, strong three-dimensional net- works of wax crystals are not formed. The effect of nanoparticles fon the crude oil viscosity was not significantly obvious AC all tem- peratures and tested shear rates, Zn0 and MgO nanoparticles have negative and positive effects on ol viscosity, respectively. Overally, the effect of nanoparticles on viscosity is less prominent than the effet of temperature. Comparison ofthe efficiency ofthe selectednanoparticles (ZnO and MgO) with EVA, as the most widely used polymeric-hased wax inhibitor, exhibits that the synthesized nanoparticles acts better than the used EVA for delaying the wax formation temperature, Findings of this work express potential applications ofthe nanostructured materials to imprave oil flowa- bility due to their unique properties such as the large specific sur= face area, high adsorption affinity, and good dispersion ability. AS a final point in this work, the effect of nanoparticles on formation and growth of wax crystals were studied using different static ‘experiments. However, better evaluation of the performance of ‘the nanoparticles for controlling wax precipitation and related issues requires dynamic experiments, which are recommended for future works. Funding This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors. (CRediT authorship contribution statement Saljad Vakili: Conceptualization, Investigation, Writing -origi- nal draft. Saber Mohammadi: Supervision, Methodology, Data ‘cutation, Project administration, Arash Mirzael Derazi: Data cura- tion, Visualization, Writing - review & editing. Fatemeh Mah- ‘moudi Alemi: Visualization, Validation, Data curation, Formal analysis. Nastollab Hayatizadeh: Writing - review & editing. Omid ‘Ghanbarpour: Formal analysis, Software. Fariborz Rashid: Supes- vision, Writing - review & editing Declaration of Competing Interest ‘The authors declare that they have no known competing finan cial interests or personal relationships that could have appeared ‘to influence the work reported in this paper. Acknowledgement ‘The authors would lke to thank Petroleum Engineering Depart- ment of Research Institute of Petroleum Industry (RIP), Tehran, Iran, for providing some experimental assemblies for this research work References IL Sigh s.r W Noga. rdcin of he yan coe of he ‘heomecer} Hwa 26) (3958) 13769, [a] LN fedakimaw rested conan ofthe [B15 then 6 ye, Sjoblom, Rhealopea properties of mods and cde ei Sytem ven wx prepate under guescen spe Mowing rons | ‘Btopers Se Tete (2007) 1020-1008 [6] C Let Zhu F Yang OL tne F Wang. C. Sun B. Ya, Eee of Aphatene Foley oo is Fecpan ng Depestion Cai of Wan [6] AAiveina, DP Chakabat, A Pgs, MKS. Ststy, Wax fmatin in 171 Bang ¥ Zhuo.) sobiem € RC Pao, Plynesc wax nhs and pour bolt depcessais or waxy ude os ial ceview) Dspets Se Teal Pao) 23-225. [a] E Wang engin zhang Yanfea Ding. kin Zhang Mingsbu Yang, aaeng sian. shin dang, MtuYang A CuangWen Lu she 2. Lanteng Hua Sujang LL The eet of saneyore mateals an the peur point ind Steeonty pressing of waxy erate Chinese Se, 19) 2014) 14-17 Io1 TI tesbahan. A Dahachin. Ke Kate et of solvent on rhelorca Senator of ranan any ere oil tet Teco 92017) 933-88, Ino] A Mangal Mant, 8 Furst, ME NitalanEvsluaon ofthese Jornal Molec ius 2422021) 17566 In1] Me Gatcla © bel ne ore, L carbgnant. A Ubi, The eect of praine son cre oll woe cstlzaton Pet. Se. Teel. 1=2 (2001 189- BC Lemos V. Giles GR Goncalves. EVE. De Cast, M.Dearelina. LW Gxrmea, de. S], Greco, Synthens raresetity reahanehy and valuation of pew neneplymere hema aes based on tay EA iil Ars Mae MFO. Cae. J Sx Mons, VX tea Eee Rade Botan VS Rsk Sie on he 1] i Dang Ne Ae nove ene dl wa Ing] Ks-redrsen, Stover. 1 Revalagen Wan precpttion ers aorta feos Themodyaamic Modeling Energy and Fuels § (1991) 924-552 1W7] AU One Abbas Kalsar Mansbag, Siyamak Mota jgar A A 5 ‘Manama Sua. leza Kesha, mat ad panne chemical FOR Ioding wing Fe Geese saocongetes | Mel Lig, 336 2020 11380, {a} w. Zeygham R kharret MLK. Ghazanfari, Investigation of the applicability of ano sca pares a tikenng aaa fr poles sluions apple i [n9] TSkauge.. pile. A Skauge,Nane-site Patil for EOR. SPE Improved Gil Recovery Sympositim 2010 [35]3 Faker M. Adaya, M Er. Aga shan. The sfc of tnconvensana rere nane pore se on te "ality of sopalene daring eben sioxide ineton Carbon Management “eemnlotyConerence, 2018 fay Fide orn Debgan, A Rabi N. Hovis 8 [subs on cphalem precptation snd egregaten ble cove (ay Ma inal ia Dade, Bam aie Ts SO, sas mechanistic understanding, seeing mogeling. and optinzatin. J Mo He-23e (2017) 325-340 ‘nanoparticles for Inhibiting asphaltene precipitation. In ve ol at reservoit [23] Ziss Viyeas, Vasilis C. Kelessiis, Nano-based ériling fuds: a review, Eneris 10) (2017) 5, hips eben 10339o}entovtose0 aay KP Mowecher G. DeStetine. Mies,” Young, Applicaton of Aanatensogy teeing duis, SP nteratoral Ole Nanoteheony Conference snd Exon 2012, [as] Wri, ancos ZHU. Janson Ql Appliaion of nano-icel ctl in she ‘ies rection of Linge excaesey ol by aguatheroly, | Pe hem Teche 33 (2) (2007) 176-100 It Raps alan FMT le Nasal pcan nol and 127) Say ea. Theoret and experimental vestigation ofthe mation of ‘ulphae de rossning paramagneteRanopastles In poous meds} (28) Csaba Kotstnas, Ki You! Yoon, Hlajang Yu, Seung Yup Ayoe, Joseph Barth, Keith P. johnston, Sule crate-ceated ion onde superpiamagnetic ne thigh ay, tng Chet Re a8 (4) 2010) 1205- [29] Sat ian, Vlas state, Eaton of polvacryamielcay composite as 2 [reol. sc Eng 133 (2015) 612-021. . . [30] NehanSadeghaivae, Saba abbagh The eet ofthe NOsIplyacrylamide anocompaste os water-based driling Tl properties, Fewae Teche 272 (1) Mint sharma, R Zhang, MLE. Chenevert. Ji @. Guo J Fiehelim, A new famiiy baka wt an, §. Penman Rr R Nagarajan} Sangwa Ect of CxO ‘hesloy ot water-based dling fi Fee Se Eng 117 (2014) 18207 Ina] Os Marae Cacia, Aguathecmel of feat ot ee and Bpespecve on ctalyt development Fuel 157 (2015) 218-231, toa Rta Wa betes Ning i. Heat opti in Ps) W210 a1 has pinot apc aati vcenty Xeebio) Fel Chem. Teal. 2(2007) 170-160. Las Yang en, Yn ane ne! a Chan Wu The wget eduction Soo) 09) Teas ha}5 Voi, 5. Matured A Nese: Dea ta [37] Hua zhang, Alex nolo, Dash Wasan Enbance nl ecovery (FOR) using imbiten experiments a 5. rhiminlad Reparation and theslogealcharacerzaon af arpa binder renorceé wt pte ‘these naepatesCont fle Mater oto) seco Dia bess "waton “caer yntber and ctabie properes of metal opal nize. hap. uppers cempostan snes tae ees Tino ime is 2s i200o sist, {4a fe Yang ister Pens Norman, hanna ans Onan, Johan ‘Stn ipl seaoparies tate wa itn ergy Fae 28 {411 song Yn Feng §. hag. Wang. ct 9S, te (fara eseaasen. (4a £ Wiha € Hodges, D. Xu Xa Ding Again and sting in Saueous polyp anion abepattie pins) Nanopt Re La iiss (aa] Evang 2h U8 Yas F Wang J Che. Sun tvesigaton onthe tnechais af wa depention inten indced by spate abd wot Inhiw) e Se. Sop 208 02 10872 {44} st fabaagh HAL, Ue of kel aaoparies for promening Susthemeiya escton ding ele eam smuaton SFE} 25 OV 14 Shon Ra SH Mousv ZDesvand, permet invention of the sabotage of meal oer atopic: on sephaene Decpraton Calo Sut A Fyaeshen xg hep 31 2017 Se. 2 Jornal of Maer ius 34 2021) 17566, [a6] 2H, Rae. Go. zhang. Thermal properties of prain wax-based composes fenianing graphite Energy Soures Part A? (2011) 587-583. a7) Clan Zhang, W. UN Wy, Molecule ynamice malation ging the Inpeovement of EVA-ipe pour poi eepesant, Fel 8415) [2009) 2038= ow, Ia0] Fe Yang, ho Y20, Couancian UX Shi Guaneyw sun, Xiobin Ma. Peiormance improvement of theethyenesiny acete copter (A) nr pain depressant by sal drape of he poymetisnieeseianane {pwd} micorhere: sn experimental ody, Fel 2072017) 204221. [Mo] ALC Machado EF Loew, onrae, Py thyenecosi sete (OVA twat af «Brain sods of eves: powr pot and phase iho of ergunie felons, Peto SeEag 322-4) (2001) 159-16, "Yao, husrsan 1s Zhong Ma, Kaopng ang Tel Yang Guang Sn. Yantong Zhao, Bhycnesintasatecopye (A) and fei-abiaed ‘hale: sjoegstcaly improve the flow behavior de! was inte of vit seat cote Energy Fuels 328) 2018) 6374-6582, Ist) Beladar'T Masenoy, Rass © Naber, Manap Xe Zhantaoy, Rashid K Nadiow, Eliyene-aay acetate opoymectuce Zool compostins 3 out pia degeessata or Wanye nt | Cer Eg 2020 2020) 1-7. 152] K’wing @ Deng. The thermal nd mechan properties of plyetiylene- oonny acetate) random copaines (PHVA) ane fs covalently Cesshnked ‘tulopes{cPevA} Polymers (Base) 1 (6) 2018) 1055. Iss] ZsunC tng 2 Tu, Eect of moeiednanosic[BVh on flaw behave and tran eoaliation of mage ol with aiteren wax content). Depts. Se “eehnel 39(2018) 71-75