Catalytic Performance of Aquathermolysis and Viscosity Reduction of Heavy Oil over a WO_(3)/ZrO_(2) Solid Acid

Tungstated zirconia(WO_(3)/ZrO_(2))solid acid catalysts with different WO_(3) contents were prepared by a hydrothermal method and then used in the catalytic aquathermolysis of heavy oil from Xinjiang.The WO_(3)/ZrO_(2) solid acid catalyst was characterized by a range of characterization methods,including X-ray diffraction,NH3-temperature programmed desorption,and pyridine infrared spectroscopy.The WO_(3) content of the WO_(3)/ZrO_(2) catalysts had an important impact on the structure and property of the catalysts.When the WO_(3) mass fraction was 20%,it facilitated the formation of tetragonal zirconia,thereby enhancing the creation of robust acidic sites.Acidity is considered to have a strong impact on the catalytic performance of the aquathermolysis of heavy oil.When the catalyst containing 20%WO_(3) was used to catalyze the aquathermolysis of heavy oil under conditions of 14.5 MPa,340℃,and 24 h,the viscosity of heavy oil decreased from 47266 to 5398 mPa·s and the viscosity reduction rate reached 88.6%.The physicochemical properties of heavy oil before and after the aquathermolysis were analyzed using a saturates,aromatics,resins,and asphaltenes analysis,gas chromatography,elemental analysis,densimeter etc.After the aquathermolysis,the saturate and aromatic contents significantly increased from 43.3%to 48.35%and 19.47%to 21.88%,respectively,with large reductions in the content of resin and asphaltene from 28.22%to 25.06%and 5.36%to 2.03%,respectively.The sulfur and nitrogen contents,and the density of the oil were significantly decreased.These factors were likely the main reasons for promoting the viscosity reduction of heavy oil during the aquathermolysis over the WO_(3)/ZrO_(2) solid acid catalysts.

Molecular composition of naphthenic acids in a Chinese heavy crude oil and their impacts on oil viscosity

Most heavy crude oils underwent biodegradation and generated a significant amount of naphthenic acids. Naphthenic acids are polar compounds with the carboxylic group and are considered as a major factor affecting the oil viscosity. However, the relationship between the molecular composition of naphthenic acids and oil viscosity is not well understood. This study examined a “clean” heavy oil with low contents of heteroatoms but had a high content of naphthenic acids. Naphthenic acids were fractionated by distillation and caustic extraction. The molecular composition was characterized by high-resolution Orbitrap mass spectrometry. It was found that the 2- and 3-ring naphthenic monoacids with 15–35 carbon atoms are dominant components of the acid fractions;the caustic extraction is capable of isolating naphthenic acids with less than 35 carbons, which is equivalent to the upper limit of the distillable components, but not those in the residue fraction;the total acid number of the heavy distillates is higher than that of the residue fraction;the viscosity of the distillation fraction increases exponentially with an increased boiling point of the distillates. Blending experiments indicates that there is a strong correlation between the oil viscosity and acids content, although the acid content is only a few percent of the total oil.

Enhancing Heavy Crude Oil Flow in Pipelines through Heating-Induced Viscosity Reduction in the Petroleum Industry

The process of transporting crude oil across pipelines is one of the most critical aspects of the midstream petroleum industry.In the present experimental work,the effect of temperature,pressure drop,and pipe diameter on the flow rate of heavy crude oil have been assessed.Moreover,the total discharge and energy losses have been evaluated in order to demonstrate the improvements potentially achievable by using solar heating method replacing pipe,and adjusting the value of the initial pressure difference.Crude oil of API=20 has been used for the experiments,with the studied pipelines sections connecting the separator unit to the storage tank operating at a temperature of 25℃-100℃,pressure drop of 3,4,5,and 6 kg/cm^(2),and with pipe diameter of 4,6,and 8 in.The results show that on increasing the temperature and/or the pressure drop,the flow rate through the pipeline becomes higher,thus raising the total pumping energy(as the pipe diameter increase),while energy losses increase from the last separator to the storage tank in the field.A pipe diameter increase can also produce a growth of the total pumping energy(i.e.,energy losses increase).The results of the present analysis suggest that employing an optimal temperature(50℃)is needed to ensure good performance.

Study on the in situ desulfurization and viscosity reduction of heavy oil over MoO_(3)–ZrO_(2)/HZSM-5 catalyst

Heavy oil is characterized by high viscosity.High viscosity makes it challenging to recover and transport.HZSM-5,MoO_(3)/HZSM-5,ZrO_(2)/HZSM-5 and MoO_(3)–ZrO_(2)/HZSM-5 catalysts were developed to promote in situ desulfurization and viscosity reduction of heavy oil.The physical and chemical properties of catalysts were characterized by XPS,XRD,TEM,NH3-TPD,etc.The effects of temperature,catalyst type and addition amount on viscosity and composition of heavy oil were evaluated.The results showed that the presence of MoO_(3)–ZrO_(2)/HZSM-5 nanoparticles during aquathermolysis could improve the oil quality by reducing the heavy fractions.It reduced viscosity by 82.56%after the reaction at 280℃ and catalyst addition of 1 wt%.The contents of resins and asphaltic in the oil samples were 5.69%lower than that in the crude oil.Sulfur content decreased from 1.45%to 1.03%.The concentration of H2S produced by the reaction was 2225 ppm.The contents of sulfur-containing functional groups sulfoxide and sulfone sulfur in the oil samples decreased by 19.92%after the catalytic reaction.The content of stable thiophene sulfur increased by 5.71%.This study provided a basis for understanding the mechanism of heavy oil desulfurization and viscosity reduction.

Experimental investigation of the effects of various parameters on viscosity reduction of heavy crude by oil-water emulsion

The effects of water content, shear rate, temperature, and solid particle concentration on viscosity reduction （VR） caused by forming stable emulsions were investigated using Omani heavy crude oil. The viscosity of the crude oil was initially measured with respect to shear rates at different temperatures from 20 to 70℃. The crude oil exhibited a shear thinning behavior at all the temperatures. The strongest shear thinning was observed at 20℃. A non-ionic water soluble surfactant （Triton X-100） was used to form and stabilize crude oil emulsions. The emulsification process has significantly reduced the crude oil viscosity. The degree of VR was found to increase with an increase in water content and reach its maximum value at 50 % water content. The phase inversion from oil- oil emulsion occurred at 30 in-water emulsion to water-in- % water content. The results indicated that the VR was inversely proportional to temperature and concentration of silica nanoparticles. For water-in-oil emulsions, VR increased with shear rate and eventually reached a plateau at a shear rate of around 350 s^-1. This was attributed to the thinning behavior of the continuous phase. The VR of oil-in-water emulsions remained almost constant as the shear rate increased due to the Newtonian behavior of water, the continuous phase.

Rheological properties and viscosity reduction of South China Sea crude oil

The rheological properties of South China Sea （SCS） crude oil were studied. A group of synthetic long-chain polymers, including octadecyl acrylate-maleic anhydride bidodecyl amide copolymer （VR-D）, octadecyl acrylate-maleic anhydride bioctadecyl amide copolymer （VR-O） and octadecyl acrylate-maleic anhydride phenly amide copolymer （VR-A）, were employed to serve as viscosity reducers （VRs）. Their performance was evaluated by both experimental and computational methodologies. The results suggest that the SCS crude oil has low wax content yet high resin and asphaltene contents, which lead to high viscosity through formation of association structures. Additionally, the SCS crude oil appears to be a pseudoplastic fluid showing linear shear stress-shear rate dependence at low temperature. Interestingly, it gradually evolves into a Newtonian fluid with exponential relationship between shear stress and shear rate at higher temperature. Synthetic VRs demonstrate desirable and effective performance on improvement of the rheological properties of SCS crude oil. Upon the introduction of 1000ppm VR-O, which is synthesized by using octadecylamine in the aminolysis reaction, the viscosity of SCS crude oil is decreased by 44.2% at 15 ℃ and 40.2% at 40℃. The computational study suggests significant energy level increase and shear stress decrease for VR-containing crude oil systems.

Synthesis of Hierarchical Porous Fe_(2)O_(3)/Al_(2)O_(3) Materials and Study on Catalytic Viscosity Reduction of Heavy Oil

Fe_(2)O_(3) nanoparticles were first dispersed in a sol solution containing an aluminum component introduced by an initial doping method.Composite catalyst Hierarchical Porous Fe_(2)O_(3)/Al_(2)O_(3) materials(HPFA)were then synthesized through a sol-gel method via phase separation.The performance of HPFA was compared with that of Fe_(2)O_(3) nanoparticle catalysts.The structure of the composite catalyst was characterized by scanning electron microscopy,X-ray diffraction,N_(2) adsorption/desorption,and crush strength testing.The results showed that the Fe_(2)O_(3) nanoparticles could be loaded into the porous skeletons of Hierarchical Porous Al_(2)O_(3) materials(HPA)to achieve a uniform dispersion while avoiding agglomeration,which improved the mechanical strength of the porous materials significantly.The HPFA was then used as a catalyst in the hydrothermal viscosity reduction process of Tuha heavy oil,and the viscosity reduction was investigated.The viscosity reduction rate of HPFA was 81%,which was better than that of the Fe_(2)O_(3) nanoparticles(56%)and HPA(47%).

Synthesis and mechanism analysis of a new oil soluble viscosity reducer for flow improvement of Chenping heavy oil

Oil soluble viscosity reducers have gradually attracted the attention of petrochemical research due to their cleanliness and high efficiency.Considering the high viscosity and non-Newtonian fluid properties of Chenping heavy oil found in China,a series of new oil soluble viscosity reducers with different proportions and molecular weights were prepared by free radical polymerization using octadecyl acrylate,2-allylphenol and N-methylolacrylamide as monomers.The viscosity reducer was applied to different types of heavy oil and found that it exhibited a better effect on heavy oils with high asphaltene content.The test of rheological behavior of heavy oil with additive was performed at wide range of shear rate(3–90 s^(-1))and temperature range(30–100°C).The apparent viscosity reduction rate was up to 70.09%,which was better than the industrially relevant ethylene–vinyl acetate copolymer under the same test condition.In addition,the effect of viscosity reducers on the components of heavy oil and the energy change of the system simulated by molecular dynamics simultaneously was investigated.The consistency of the simulated and experimental results show that the effect of viscosity reduction closely related to the crystallization process of wax and the viscosity reducer can reconstruct the surface structure of asphaltene and diminish the connection of benzene ring.

Aquathermolysis of heavy crude oil with ferric oleate catalyst

Oil-soluble catalysts could be of special significance for reducing the viscosity of heavy crude oil, because of their good dispersion in crude oil and high catalytic efficiency toward aquathermolysis. Ferric oleate was synthesized and applied as catalyst in the aquathermolysis reaction of Shengli heavy oil. It was found that ferric oleate was more efficient for heavy oil cracking than Co and Ni oleates. Besides, it was superior to oleic acid and inorganic ferric nitrate and achieved the highest viscosity reduction rate of up to 86.1%. In addition, the changes in the components of Shengli heavy oil before and after aquathermolysis were investigated by elemental analysis, Fourier transform infrared spectrometry, and ^1H nuclear magnetic resonance spectroscopy. Results indicated that ferric oleate contributed to a significant increase in the content of light components and decrease in the content of resin, N and S. The as-prepared ferric oleate showed good activity for reducing the viscosity and improving the quality of the heavy crude oil, showing promising application potential in aquathermolysis of heavy crude oil.

Synthesis of silica/metatitanic acid nanocomposite and evaluation of its catalytic performance for aquathermolysis reaction of extra-heavy crude oil

A lipophilic silica/metatitantic acid（denoted as Si O2/H2 TiO 3） nanocomposite was synthesized by hydrothermal reaction with surface-modified Si O2 as the lipophilic carrier. As-synthesized Si O2/H2 TiO 3nanocomposite was used as a catalyst to promote the aquathermolysis reaction of extra-heavy crude oil thereby facilitating the recovering from the deep reservoirs at lowered temperature. The catalytic performance of the as-synthesized Si O2/H2 TiO 3catalyst for the aquathermolysis reaction of the heavy oil at a moderate temperature of 150 °C was evaluated in relation to the structural characterizations by TEM,FTIR,XRD and FESEM as well as the determination of the specific surface area by N2adsorption–desorption method. Findings indicate that as-synthesized Si O2/H2 TiO 3nanocomposite exhibits an average size of about 20 nm as well as good lipophilicity and dispersibility in various organic solvents; and it shows good catalytic performance for the aquathermolysis reaction of the extra-heavy oil extracted from Shengli Oilfield of China. Namely,the assynthesized Si O2/H2 TiO 3catalyst is capable of significantly reducing the viscosity of the tested heavy oil from58,000 c P to 16,000 c P（referring to a viscosity reduction rate of 72.41%） at a mass fraction of 0.5%,a reaction temperature of 150 °C and a reaction time of 36 h,showing potential application in downhole upgrading heavy crude oils.

Numerical Study on Viscosity Reduction in Mining Heavy Oil by Circulating Hot Water

Viscosity reduction is an important process in mining heavy oil.To predict the temperature variation and viscosity variation of heavy oil in flow direction,computational fluid dynamics(CFD) was adopted to simulate the process of heat transfer and flow in this paper.Moreover,an objective function,namely viscosity reduction efficiency,was established to analyze the effect of viscosity reduction.The results indicate that circulating hot water can reduce viscosity significantly,and that the effect of viscosity reduction depends on the inlet temperature and inlet volumetric flow rate of hot water.There is a maximum temperature of heavy oil in flow direction.With the inlet volumetric flow rate of 2.0m3/h and the inlet temperatures of 60,℃,70,℃ and 80,℃,viscosity reduction efficiencies are 94.6%,96.7% and 97.3%,respectively.With the inlet temperature of 70,℃ and the volumetric flow rates of 1.5m3 /h,2.0 m3/h and 2.5m3/h,viscosity reduction efficiencies are 94.4%,96.7% and 97.2%,respectively.

Aquathermolysis of conventional heavy oil with superheated steam

This paper presents a new aquathermolysis study of conventional heavy oil in superheated steam. A new high temperature autoclave was designed, where volume and pressure could be adjusted. Aquathermolysis was studied on two different conventional heavy oil samples under different reaction times and temperatures. Experimental results show that aquathermolysis does take place for conventional heavy oil. As reaction time increases, the oil viscosity reduces. However, the reaction will reach equilibrium after a certain period of time and won＇t be sensitive to any further reaction time any more. Analysis shows that, while resin and asphaltenes decrease, saturated hydrocarbons and the H/C ratio increase after reaction. The main mechanism of aquathermolysis includes hydrogenization, desulfuration reaction of resin and asphaltenes, etc.

Effects of Reservoir Minerals and Chemical Agents on Aquathermolysis of Heavy Oil during Steam Injection

In order to effectively reduce the viscosity of heavy oil during steam injection, a catalyst system, consisting of reservoir minerals, nickel sulfate, and formic acid, was used to exert catalytic effect on aquathermolysis of heavy crude oil extracted from the Liaohe oilfield. Experimental results indicated that all the reservoir minerals used in the experiment had catalytic effect on aquathermolysis and the oil viscosity reduction rate ranged from 24% to 36% after the aquathermolysis reaction. If nickel sulfate was used as the catalyst and added to the reaction system, the oil viscosity reduction rate could reach 50%. If formic acid was used as the hydrogen donor, the oil viscosity reduction rate could increase further, and could reach up to 71.8%. The aquathermolysis reaction of heavy oil under steam injection condition was affected by the reaction temperature, the reaction time, the dosage of minerals, the catalyst concentration, and the hydrogen donor. The experimental results showed that minerals, catalyst and hydrogen donor could work together to enhance aquathermolysis reaction of heavy oil in the presence of the high-temperature water vapor.

In situ preparation of well-dispersed CuO nanocatalysts in heavy oil for catalytic aquathermolysis

We developed an in situ synthesis strategy for preparing well-dispersed CuO nanoparticles as aquathermolysis catalyst for viscosity reduction in Shengli heavy oil(China). A Cu(OH)_2-contained microemulsion was employed as a carrier to disperse the precursor Cu(OH)_2 to the heavy oil phase. Under aquathermolysis condition(240 ℃, 2.5 MPa of N_2), the Cu(OH)_2 precursors would first be converted in situ to well-crystallized and size-homogeneous CuO nanoparticles naturally, catalyzed by which the viscosity of Shengli heavy oil could be reduced as much as 94.6%; simultaneously, 22.4% of asphaltenes were converted to light components. The agglomeration of the in situ prepared monoclinic CuO nanoparticles could be negligible throughout the catalytic reaction. Based on the characterization results of ~1 H NMR, elemental analysis and GC-MS of oil samples before and after catalytic aquathermolysis, the mechanism for viscosity reduction of heavy oil in the catalytic system was investigated.

Heating of heavy oil by circulating hot water in closed double casing in ultra-deep wells

In heavy oil production,the loss of energy to ambient surroundings decreases the temperature of the heavy oil flowing upwards in a vertical wellbore,which increases the oil viscosity and the oil may not flow normally in the wellbore.Therefore,it is necessary to lower the heavy oil viscosity by heating methods to allow it to be lifted easily.Heating of heavy oil in an oil well is achieved by circulating hot water in annuli in the well（tubing-casing annulus,casing-casing annulus）.In this paper,based on heat transfer principles and fluid flow theory,a model is developed for produced fluids and hot water flowing in a vertical wellbore.The temperature and pressure of produced fluids and hot water in the wellbore are calculated and the effect of hot water on heavy oil temperature is analyzed.Calculated results show that the hot water circulating in the annuli may effectively heat the heavy oil in the tubing,so as to significantly reduce both oil viscosity and resistance to oil flow.

Gathering and Transportation Technology of Heavy Oil in Liaohe Oilfield

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Experimental study of Iranian heavy crude oil viscosity reduction by diluting with heptane, methanol, toluene, gas condensate and naphtha

Due to the high viscosity of heavy crude oils,production from these reservoirs is a demanding task.To tackle this problem,reducing oil viscosity is a promising approach.There are various methods to reduce viscosity of heavy oil:heating,diluting,emulsification,and core annular flow.In this study,dilution approach was employed,using industrial solvents and gas condensate.The viscosity of two Iranian heavy crude oils was measured by mixing with solvents at different temperatures.Dilution of both oil samples with toluene and heptane,resulted in viscosity reduction.However,their effect became less significant at higher concentrations of diluent.Because of forming hydrogen bonds,adding methanol to heavy crude oil resulted in higher viscosity.By adding condensate,viscosity of each sample reduced.Gas condensate had a greater impact on heavier oil;however,at higher temperatures its effect was reduced.Diluting with naphtha decreased heavy oil viscosity in the same way as n-heptane and toluene.Besides experimental investigation,different viscosity models were evaluated for prediction of heavy oil/solvent viscosity.It was recognized that Lederer'model is the best one.

稠油化学复合冷采技术研究与应用

我国稠油储量可观,其中60%的是深层稠油,而主流的蒸汽吞吐等热采技术采收率不足20%;稠油资源开发潜力极大,积极探索新的开采方式以提高采收率是石油领域高质量发展的必然选择。本文着重阐述稠油化学复合冷采技术体系构建及其现场应用,为中深层稠油的新型绿色低成本接替技术发展提供有效方案。在分析稠油组分的基础上,细致剖析稠油结构致黏机理,包括化学降黏机理、降低启动压力梯度机理、提高驱油效果机理在内的提高采收率机理,以丰富理论认识。面向工程应用亟需,从水溶性降黏剂分子设计与合成、自组装调堵剂研发两方面出发,突破稠油绿色化学驱油体系。基于发展的稠油化学复合冷采技术,完成了3个稠油油田示范工程应用,在提高产油量、控制含水率方面取得了良好成效。进一步梳理了分子采油理论与技术、渗流理论与数值模拟技术等方面的后续发展要点,以为深层稠油的绿色高效开发接替技术研究、稠油化学复合冷采技术推广应用研究等提供启发和参考。

稠油乳化黏度测量曲线与乳液特性的关系

稠油化学驱过程中降黏剂浓度对稠油乳化影响明显,通过测量不同浓度降黏剂的稠油乳状液黏度-时间曲线,以黏度、降黏率为指标分析了黏度曲线与乳液特性的关系。结果表明,当降黏剂的浓度远大于临界乳化浓度时,形成稳定O/W乳状液,黏度低、降黏率大于95%。当降黏剂的浓度大于临界乳化浓度时,形成O/W乳状液,而后随着表面活性剂向油相的迁移,油滴聚并、分层。当降黏剂的浓度与临界乳化浓度相当时,乳状液油O/W转化为W/O,黏度大幅度提高。当降黏剂的浓度小于临界乳化浓度时,只能形成W/O乳状液。

表面活性剂对水驱普通稠油油藏的乳化驱油机理

为了研究乳化降黏驱油剂对不同渗透率的水驱普通稠油油藏的驱油效率和孔隙尺度增效机理,选取了烷基酚聚氧乙烯醚(J1)、α-烯基磺酸盐类表面活性剂(J2)、十二烷基羟磺基甜菜碱(J3)、J3与烷基酚聚氧乙烯醚羧酸盐复配表面活性剂(J4)作为驱油剂,开展了4种驱油剂一维驱油和微观驱油模拟实验,明确了乳化降黏驱油剂在孔隙尺度的致效机理。结果表明,降低界面张力对提高驱油效率的作用大于提高乳化降黏率。在油藏条件下,乳化降黏驱油剂需要依靠乳化降黏和降低界面张力的协同增效作用,才能大幅提高驱油效率。乳化降黏驱油剂的乳化能力越强、油水界面张力越低,驱油效率增幅越大。当化学剂乳化降黏率达到95%时,油水界面张力从10^(-1)mN/m每降低1个数量级,化学剂在高渗透和低渗透岩心中的驱油效率依次提高约10.0%和7.8%。乳化降黏驱油剂注入初期通过降低界面张力,使得高渗透岩心和低渗透岩心中的驱替压力分别为水驱注入压力的1/2和1/3,从而提高注入能力。注入后期大块的原油被乳化形成大量不同尺寸的油滴,增强原油流动性,提高驱油效率。乳化形成的界面相对稳定的稠油油滴,能暂堵岩石的喉道和大块稠油与岩石颗粒形成的通道。油滴的暂堵叠加效应,使高渗透和低渗透岩心的驱替压差分别为水驱压差的5.2倍和32.3倍,大幅提高了注入压力,从而扩大平面波及面积。降黏驱油剂驱油实现了提高驱油效率的同时扩大波及范围。研究结果为水驱稠油开发用驱油剂的研发提供参考,为大幅提高水驱普通稠油采收率奠定基础。