The interaction of waxes with pour point depressants

Paraffin wax deposition from crude oils at low temperature is one of the serious and long-standing problems in petroleum industry. Addition of pour point depressants (PPD) has been proved to be an efficient way to inhibit wax deposition. The influence of PPD on wax precipitation at low temperature was investigated. The amount and composition of wax precipitated from paraffin solutions with and without PPD at different temperatures were studied by high speed centrifuge and gas chromatography (GC), respectively. The interactions between waxes and PPD were investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The results showed that PPD do not completely prevent the wax from precipitating, but just shift the precipitation toward a lower temperature. This conclusion was identified from the analysis of the amount and composition of precipitated wax as well as the transition temperatures and energies of wax. It was shown that this effect is due to the structure of wax is partly transformed from orthorhombic into hexagonal form by PPD.     

Study on wax precipitation characteristics of wax deposit in pipes

Wax deposit properties are a significant concern in pipeline pigging during waxy crude oil transportation. In the present work, the impacts of flow conditions and oil properties on the wax precipitation characteristics of wax deposits are investigated. A flow loop apparatus was developed to conduct wax deposition experiments using four crude oils collected from different field pipes. The differential scanning calorimetry (DSC) technique was employed to observe the wax precipitation characteristics of crude oil and wax deposit. The results show that the wax content and the wax appearance temperature (WAT) of the deposits increase with shear stress and radial temperature gradient, and decrease with radial wax molecule concentration gradient near the pipe wall. The DSC tests on the wax deposits revealed that the deposit wax content is strongly correlated to the oil wax content. Furthermore, an empirical correlation was developed to predict the wax content and the WAT of the wax deposit. Verification of the empirical correlation using the different oils indicated that the average relative error of the wax content prediction and average absolute error of WAT prediction were 13.2% and 3.6°C, respectively.     

不同加热温度和降温速率对含蜡原油析蜡点的影响

利用差示扫描量热法(DSC)对原油的析蜡特性进行分析,并得到了析蜡过程的热谱图和dh/d T-T曲线。以大庆原油为研究对象,对dh/d T-T曲线进行分析,探讨了加热理温度、温降速率对析蜡点的影响。结果表明:加热温度高于溶蜡点温度时,析蜡点随温变化小;加热温度低于溶蜡点温度,析蜡点随温度的降低先增大后减小。温降速率越大,析蜡点越低。     

Improvement of oil flowability by assembly of comb‐type copolymers with paraffin and asphaltene

Comb‐type (maleic acid alkylamides‐co‐α‐octadecene) copolymers (MACs) assemble with long‐chain n‐paraffins and asphaltenes by the hydrophobic alkyl branches and polar groups, respectively, and improve flowability of crude oils upon cooling. Their effects on the crystallization of paraffins from model oils were studied by rheology, optical microscopy, differential scanning calorimetry, and X‐ray diffraction. Upon cooling, MACs change the size and shape of paraffin crystals and reduce the yield stresses of gels generated by precipitated solids. Deposition of wax was significantly suppressed by MAC as observed using a laboratory‐scale deposition apparatus. MACs are more effective than poly(ethylene‐butene) copolymers in improving the flowability of crude oils containing asphaltenes. The interactions between the carboxyl and amide groups of MAC with the polar aromatic asphaltenes appear to stabilize crudes through the steric effects of the long alkyl groups of MAC polymers, thereby reducing the strength of paraffin/asphaltene gels formed on cooling. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Optical fiber extrinsic refractometer to measure RI of samples in a high pressure and temperature systems: Application to wax and asphaltene precipitation measurements

An optical fiber extrinsic sensor for measurement of changes in the refractive index of liquids confined in chambers for high pressure and temperature experiments is described. One head sensor composed by two fibers is fixed in front of a high pressure and temperature cell filled with the sample. The operation principle is based in the reflectivity dependence in the refractive index of the glass–liquid interface. Excellent results and a sensitivity of 10⁻⁵ RI were obtained for pure liquids. The applicability of the sensor is demonstrated following the changes in the refractive index for pure liquids at different pressure and temperatures and by measuring the asphaltenes and wax precipitation in crude oils under pressure. The extrinsic probe designed for refractive index measurement proves to be a reliable tool for measuring heavy organics deposition in crude oils under high pressures and temperatures where the sample to be measured is not very accessible.     

Analysis of paraffin precipitation from petroleum mixtures by means of DSC: Iterative procedure considering solid-liquid equilibrium equations

Wax deposition is a well known flow assurance risk in crude oil production due to temperature decrease which depends mainly on the crude oil nature and the type and content of paraffin. The prevention of this problem requires a detailed characterization of the crude oil and the availability of reliable predictive models.The experimental determination and quantification of the precipitation process is quite complex and time consuming and simpler techniques are of interest to carry out such study. Among them, differential scanning calorimetry (DSC) technique is appropriate to develop routine essays and has been extensively applied to determine wax appearance temperature in crude oil and fractions because the simplicity and fast response of the technique.However, the determination of wax precipitation curve from a quantitative DSC interpretation is usually based on pure n-alkane properties and involves some difficulties. In this work, a new procedure has been developed including the effect of the fluid composition on the precipitation temperature and the melting heat. Solid-liquid equilibrium equations were introduced through a simplified thermodynamic model in the integration procedure resulting in an iterative method combining experimental and calculated values. The final method yields the wax appearance temperature (WAT), the full wax precipitation curve and the estimated wax composition.In order to validate the procedure, several crude oil fractions were used as standards due to the advantage of a narrow n-alkane distribution. Experimental characterization for the cloud point temperature, the n-alkane distribution (determined by gas chromatography with mass detector, GCMS) and DSC was carried out. The agreement between experimental results and those obtained from the DSC interpretation is a good check for the proposed procedure.     

A new method for the determination of wax precipitation from non-diluted crude oils by fractional precipitation

Wax precipitation is one of the most important flow assurance problems. Unfortunately, experimental data are very scarce to confirm existing models for prediction of such precipitation problem. This work reports a new experimental method. Multistage fractional wax precipitation was carried out by decreasing the temperature of crude oil. No solvent dilution was used, so the effect of solvent on temperature wax precipitation was avoided. The reproducibility of the method was tested with comparable results. The precipitation curve and the wax appearance temperature were obtained for two crude oils with different chemical nature using the reported method.     

A generalized model for predicting non-Newtonian viscosity of waxy crudes as a function of temperature and precipitated wax

Precipitated wax, shear and thermal history have pronounced effects on viscosity and rheological behavior of waxy crudes. On the basis of mechanism of waxy crude rheology, a shear-rate-dependent viscosity model has been developed by applying theory of suspension rheology. This model is characterized by its capability to predict viscosities of crude oils with various thermal and shear history and beneficiated with pour-point-depressants (PPD). Once viscosities at only two temperatures above the wax appearance temperature and apparent viscosities at one temperature in the non-Newtonian regime are known, viscosities or apparent viscosities at any temperatures above the gel point can be predicted by using the model together with the concentration of precipitated wax at that specified temperature. Verification by using 3458 viscosity data points ranging from 5 to 2900 mPa s from 33 virgin crudes and 14 PPD-beneficiated crudes with various thermal and shear history shows that the model predicts viscosities with an absolute average deviation of 7.43%. Furthermore parameters of rheological models such as the consistency coefficient K and the flow behavior index n of the power law model may be obtained by regressing predicted viscosity data and corresponding shear-rates.     

Investigation of glass transition temperatures of Turkish asphaltenes

Asphaltenes are a major concern in production operations, due to their role in conversion of vacuum residues by processes such as coking, catalytic cracking and hydroconversion. Six Turkish asphaltenes were characterized by elemental content, proton NMR, carbon NMR, GPC, DSC. Differential scanning calorimetry (DSC) provides parameters for comparing the glass transition temperatures, endothermic behavior of asphaltene and a hypothetical melting temperature of the asphaltenes which is within the range of the pyrolysis temperature of asphaltenes. The glass transition temperatures points (T_g) of asphaltenes were determined using DSC. Hypothetical melting point temperature (T_m) of the asphaltenes was also calculated. Among all the asphaltenes tested, Bati Raman showed much higher glass transition temperatures than the others.     

Evaluating the Oil‐Gelling Properties of Natural Waxes in Rice Bran Oil: Rheological,Thermal, and Microstructural Study

The main objective of this research was to enhance the understanding of the oil‐structuring properties of natural waxes. A number of natural food‐grade waxes were evaluated for their oil‐gelling properties using a combination of techniques, including rheology, differential scanning calorimetry, and polarized light microscopy. Based on the rheological measurements (oscillatory, flow, and thixotropic behavior), we found that rice bran wax, carnauba Brazilian wax and fruit wax showed weak gelling behavior in rice bran oil (prepared at concentrations as high as 5 % w/w), exhibiting relative low elastic moduli that displayed a high frequency dependency. On the contrary, carnauba wild wax, berry wax, candelilla wax, beeswax, and sunflower wax were efficient oleogelators forming strong gels at concentration of <2 % w/w. We attempt to explain these observed differences in gelling behavior by crystal morphology, network formation, and the final amount of crystalline phase.     

利用NIRS和RI技术测试石油流体析蜡温度新方法

析蜡温度是重要的石油流体性质参数,得到准确的析蜡温度是保证含蜡原油管道安全输送的前提。提出了近红外光谱温度扫描测试法和折射率测试法,改进了近红外光谱波长扫描测试法,并从可靠性、灵敏性和稳定性等方面与常用的偏光显微镜法和差示扫描量热法进行比较。结果表明,近红外光谱法和折射率法可以得到可靠的测试结果,并具有较高的灵敏性和稳定性;实验操作和数据分析方法简单,测试结果不易受到制样过程影响,尤其适合挥发性较强的油样。此外,近红外光谱法测试时油样处于运动状态,可有效减小过冷度的影响,但与实际管输条件仍存在一定差别。     

Thermorheological properties of asphalt binders

The rheological properties of different types of asphalt binders were studied and compared considering their constituents and physical characteristics. The saturate, aromatic, resin, and asphaltene (SARA) analysis and differential scanning calorimetry (DSC) have shown their individual constituents and two distinct glass transition temperatures, indicating the phase changes of the two main components of the asphalt binders, namely asphaltenes and maltenes. Rheological characterization was performed over a wide range of temperatures (−10°C-60°C) showing that these materials may exhibit viscoelastic solid to viscous liquid behaviour. Master curves of complex viscosity, storage modulus, and loss modulus were constructed by applying the time-temperature superposition principle, which was found applicable over the temperature range considered. Stress relaxation and steady-shear test were applied to the samples in order to determine their rheological behaviour in the nonlinear viscoelastic regime (viscosity and nonlinear relaxation modulus). The rheological results were modelled and revealed that the Kaye-Bernstein-Kearsley-Zappas (K-BKZ) constitutive equation is suitable in representing the rheological behaviour of asphalts. The SARA analysis and rheological measurements were found to be compatible.     

Synthesis of polymeric pour point depressants for Nada crude oil (Gujarat,India) and its impact on oil rheology

Five flow improvers have been synthesized to study rheological properties of Nada crude oil (Gujarat, India). Anhydride copolymers were prepared making use of the copolymerization of acrylates of different alkyls with maleic anhydride and the Poly (n-alkyl acrylates-co-N-hexadecylmaleimide) were prepared by the reaction of copolymer with hexadecylamine. The additives were purified and characterized by FTIR, GPC. The prepared polymeric additives shows dual function both as wax dispersants and flow improvers and all of them acts as good pour point depressants. Yield stress and the viscosity of the crude oil at different temperatures and concentrations of additives were evaluated by zero friction advanced rheometer AR-500 of TA instrument. Comparison of morphologies and structures of wax crystals or aggregates in waxy crude oils beneficiated with and without a PPD was also done by micro photographic studies which show the modification in wax crystal morphology due to additives.     

Characterization of air-blown asphalt/trans-polyoctenamer rubber blends

Air-blown asphalt (ABA) was modified by blending with trans-polyoctenamer rubber (TOR). The thermal properties examined by differential scanning calorimetry indicated that flexible aliphatic hydrocarbons in maltene phase or paraffin wax, preferentially dissolved into the TOR phase from the ABA phase. Rheological properties examined with a rheometer by frequency sweep and temperature sweep suggested that the polymer modified asphalt is a multiphase system composed of a phase formed by maltenes, a mesoscopic phase rich in asphaltenes, and a TOR phase swelled by dissolved maltenes. The elasticity, modulus, and the temperature susceptibility of ABA were improved by modification with TOR.     

Mixture temperature prediction of waxy oil–water two-phase system flowing near wax appearance temperature

Temperature sensitivity of waxy crude oils makes it difficult to study their flow behaviour in the presence of water especially near their wax appearance temperature(WAT). In this study a method was proposed and implemented to mitigate such difficulties which was applied in predicting mixture temperatures(Tm) of a typical Malaysian waxy crude oil and water flow in a horizontal pipe. To this end, two analytical models were derived firstly from calorimetry equation which based on developed two correlations for defining crude oil heat capacity actualized from the existed specific heat capacities of crude oils. The models were then applied for a set of experiments to reach the defined three predetermined Tm(26 °C, 28 °C and 30 °C). The comparison between the predicted mixture temperatures(Tm,1and Tm,2) from the two models and the experimental results displayed acceptable absolute average errors(0.80%, 0.62%, 0.53% for model 1; 0.74%, 0.54%, 0.52% for model 2). Moreover,the average errors for both models are in the range of standard error limits(±0.75%) according to ASTM E230.Conclusively, the proposed model showed the ease of obtaining mixture temperatures close to WAT as predetermined with accuracy of ± 0.5 °C approximately for over 84% of the examined cases. The method is seen as a practical reference point to further study the flow behaviour of waxy crudes in oil–water two-phase flow system near sensitive temperatures.     

Controlling the wax crystallization behaviors via the ratio of phenyl to aliphatic branches in block copolymer synthesized by RAFT copolymerization

The precipitation and deposition of waxes in high waxy crude oil often result in the low throughput and clogging of pipeline. Adding polymers is a practical approach to solve these problems. In this study, poly(styrene-co-docosyl maleate)s (PSDMs) were synthesized by reversible addition-fragmentation chain transfer polymerization. The chemical structure and molecular weight of copolymers were characterized using Fourier infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, and gel permeation chromatography. The ratio of phenyl to aliphatic branches varies from 10:8 to 25:8. The crystallization and morphology of waxes in model oil were investigated by x-ray diffraction, differential scanning calorimetry, and polarized light microscopy. The cold flow behaviors of crude oil were evaluated by rheological methods. With the increase of the ratio of phenyl to aliphatic branches, the crystallinity, viscosity, and yield stress of crude oil first increase and then decrease. In the presence of PSDM-2, the crystallinity and enthalpy of phase transition (ΔH) are reduced by 44.2% and 48.9%. Thus, the pour point, viscosity, and yield stress of crude oil are reduced by 6.0°C, 76.8% and 77.4%, respectively. Therefore, well-defined PSDMs are promising to be remarkable flow improvers for waxy crude oils.     

Effect of wax inhibitors on pour point and rheological properties of Iranian waxy crude oil

A variety of techniques have been employed in order to reduce problems caused by the crystallization of paraffin during the production and/or transportation of waxy crude oil. Flow improvers are used extensively to increase the mobility of crude oil. In this study, the influence of the ethylene-vinyl acetate copolymer (EVA), as flow improver, with different ranges of molecular weight on the viscosity and pour point of five Iranian waxy crude oils was evaluated. Five types of Iranian waxy crude oil were selected based on their similar wax (> 10%) but different asphaltene contents. Also, the effect of asphaltene content on the performance of this flow improver was studied. The rheological behavior of these crude oils, with middle range API gravity, in the absence/presence of flow improver was studied. The rheological data cover the temperature range of 5 to 40 °C. The results indicated that the performance of flow improver was dependent on the molecular weight and the asphaltene content. For crude oil with low asphaltene, higher molecular weight flow improvers are the best additive and lower molecular weight flow improvers showed good efficiency for crude oil with high asphaltene content. Addition of small quantities of asphaltene solvents such as xylene (1 wt.%), alone or in combination with flow improver, can improve viscosity of crude oil with high asphaltene content.     

Properties of Oleogels Formed With High‐Stearic Soybean Oils and Sunflower Wax

In an effort to develop alternatives for harmful trans fats produced by partial hydrogenation of vegetable oils, oleogels of high‐stearic soybean (A6 and MM106) oils were prepared with sunflower wax (SW) as the oleogelator. Oleogels of high‐stearic oils did not have greater firmness when compared to regular soybean oil (SBO) at room temperature. However, the firmness of high‐stearic oil oleogels at 4 °C sharply increased due to the high content of stearic acid. High‐stearic acid SBO had more polar compounds than the regular SBO. Polar compounds in oil inversely affected the firmness of oleogels. Differential scanning calorimetry showed that wax crystals facilitated nucleation of solid fats of high‐stearic oils during cooling. Polar compounds did not affect the melting and crystallization behavior of wax. Solid fat content (SFC) showed that polar compounds in oil and wax interfered with crystallization of solid fats. Linear viscoelastic properties of 7% SW oleogels of three oils reflected well the SFC values while they did not correlate well with the firmness of oleogels. Phase‐contrast microscopy showed that the wax crystal morphology was slightly influenced by solid fats in the high‐steric SBO, A6.     

Synthesis of comb‐type copolymers with various pendants and their effect on the complex rheological behaviors of waxy oils

To improve the flowability of waxy crude oil containing a high concentration of asphaltenes (AS), novel comb‐type copolymers of poly(maleic acid polyethylene glycol ester‐co‐α‐octadecene) (PMAC) and poly(maleic acid aniline amide‐co‐α‐octadecene) (AMAC) with various grafting ratios (R_g) of PEG/aniline to maleic anhydride are synthesized. Model oils containing wax mixtures and AS are prepared to explore the effect of asphaltene concentration and the copolymers on the yield stress. The influence of the copolymers on the wax appearance temperature (WAT) of Liaohe high waxy oil is examined by rheological and microscopic methods. Experimental flow curves of shear stress as a function of shear rate are fitted following the Casson model to interpret the rheological properties of gelled waxy crude oil in the presence of AMACs, PMACs, and MAC. Compared with MAC, PMACs, and AMACs are more efficient in reducing the yield stress of both model oil and crude oil, which indicates a better flowability. It is found that PMAC1.0 and AMAC1.0 with a medium R_g can balance the interaction of copolymers with waxes and AS and reduce the yield stress much more than others. Between them, AMAC1.0 that possesses aromatic pendants is better than PMAC1.0, which only has polar pendants. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41660.     

Heavy crude oil asphaltenes as a nanofiller for epoxy resin

Asphaltenes are harmful components of heavy crude oils and require rational utilization after oil refining or deasphalting. Asphaltenes are macromolecules containing various functional groups that self-assemble to nanoscale aggregates and can be used as nanofillers for polymers. In this research, mixtures of asphaltenes with the diglycidyl ether of bisphenol A were considered. The solubility of asphaltenes in this epoxy resin, the rheological properties of the mixtures, and the effect of asphaltenes on the curing with 4,4′-diaminodiphenyl sulfone were studied. In addition, the glass transition temperature, strength, and adhesion characteristics of the asphaltene-filled cured composites were evaluated. The dual role of asphaltenes in polymer modification was demonstrated: the asphaltenes simultaneously plasticize and reinforce the polymer matrix, and the transition from predominant plasticization to strengthening occurs with an asphaltene content at 20 wt%. The dual reinforcement/plasticization effect occurs because epoxy composites contain both nanosized and microsized particles of asphaltenes due to the partial dissolution of asphaltenes in the epoxy resin and the decrease in their solubility during high-temperature curing.