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.

Change of asphaltene and resin properties after catalytic aquathermolysis

Resin and asphaltene were separated from Liaohe heavy oil. Catalytic aquathermolysis of asphaltene and resin was investigated by using water soluble catalysts （NiSO4 and FeSO4） and oil soluble catalysts （nickel naphthenate and iron naphthenate）. Before and after aquathermolysis, the properties of the resin and asphaltene was compared by means of ultimate analysis, vapor pressure osmometer （VPO） average molecular weight, X-ray diffraction （XRD）,^13C and ^1H nuclear magnetic resonance （NMR）. The conversion sequence was as follows： No-catalyst〈NiSO4〈FeSO4〈nickel naphthenate〈iron naphthenate. In the presence of catalysts, the amount of H2 and CO increased significantly, while H2S in the gas product decreased. The molecular weight of asphaltene and resin increased after reaction without catalyst. But the catalysts restrained this trend. The H/C ratio of asphaltene and resin decreased after reaction. From the results of average structural parameters and molecular weight, it was found that asphaltene and resin were partly aggregated after aquathermolysis.

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.

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.

Catalytic aquathermolysis of Shengli heavy crude oil with an amphiphilic cobalt catalyst

An interfacially active cobalt complex,cobalt dodecylbenzenesulfonate,was synthesized.Elemental analysis,atomic absorption spectroscopy,Fourier transform infrared spectroscopy（FT-IR）,thermogravimetric analysis,and surface/interfacial tension determination were performed to investigate the properties of the catalyst.Results showed that the synthesized catalyst showed active interfacial behavior,decreasing the surface tension and interfacial tension between heavy oil and liquid phase to below 30 and 1.5 mN/m,respectively.The catalyst was not thermally degraded at a temperature of 400 ℃,indicating its high thermal stability.Catalytic performance of the catalyst was evaluated by carrying out aquathermolysis.The viscosity determination showed that the viscosity of the heavy oil decreased by 38%.The average molecular weight,group compositions,and average molecular structure of various samples were analyzed using elemental analysis,FT-IR,electrospray ionization Fourier transform ion cyclotron resonance（ESI FT-ICR MS）,and ～1H nuclear magnetic resonance.Results indicated that the catalyst could attack the sulfur- and O_2-type heteroatomic compounds in asphaltene and resin,especially the compounds with aromatic structure,leading to a decrease in the molecular weight and then the reduction in the viscosity of heavy oil.Therefore,the synthesized catalyst might find an application in catalytic aquathermolysis of heavy oil,especially for the high-aromaticity heavy oil with high oxygen content.

Stabilization of nickel nanoparticle suspensions with the aid of polymer and surfactant: static bottle tests and dynamic micromodel flow tests

Nickel nanoparticles can work as catalyst for the aquathermolysis reactions between water and heavy oil.A homogeneous and stable suspension is needed to carry the nickel nanoparticles into deeper reservoirs.This study conducts a detailed investigation on how to achieve stabilized nickel nanoparticle suspensions with the use of surfactant and polymer.To stabilize the nickel nanoparticle suspension,three surfactants including sodium dodecyl sulfate,cationic surfactant cetyltrimethylammonium bromide and polyoxyalkalene amine derivative(Hypermer) along with xanthan gum polymer were introduced into the nickel nanoparticle suspension.Static stability tests and zeta potential measurements were conducted to determine the polymer/surfactant recipes yielding the most stable nickel nanoparticle suspensions.Dynamic micromodel flow tests were also conducted on three suspensions to reveal how the nickel nanoparticles would travel and distribute in porous media.Test results showed that when the injection was initiated,most nickel nanoparticles were able to pass through the gaps between the sand grains and produced in the outlet of the micromodel;only a small number of the nickel nanoparticles were attached to the grain surface.A higher nickel concentration in the suspension may lead to agglomeration of nickel nanoparticles in porous media,while a lower concentration can mitigate this agglomeration.Moreover,clusters tended to form when the nickel nanoparticle suspension carried an electrical charge opposite to that of the porous media.Follow-up waterflood was initiated after the nanofluid injection.It was found that the waterflood could not flush away the nanoparticles that were remaining in the micromodel.