In situ catalytic conversion of biomass fast pyrolysis vapors on HZSM–5

In situ catalytic conversion of biomass fast pyrolysis vapors was carried out on HZSM-5 with varying Si/Al ratios(ranging from 20 to 300) at 450 °C. The effects of Si/Al ratios of HZSM-5 zeolites on the distribution of biomass fast pyrolysis products and carbon deposits on catalysts were investigated. It was quite remarkable that after in situ catalytic conversion the amount of light phenols and hydrocarbons increased significantly while that of heavy phenols decreased a lot. Besides, the yield of cyclopentenones with relatively low oxygen content generally increased. It also indicated that as the Si/Al ratios of HZSM-5 increased, the amount of hydrocarbons and light phenols was found to drop greatly. The amount of carbon deposits was found to be around 8.5% with the exception of HZSM-5 with the Si/Al ratio of 300,which is much lower. Moreover, the carbon deposits yield dropped gradually with increasing Si/Al ratios of HZSM-5.Calcination of spent catalysts at 600 °C helped to restore the catalytic activity to a large extent despite a relatively lower efficiency of deoxygenation. Results indicated that HZSM-5 with relatively high acidity displayed great catalytic performance.

In situ catalytic upgrading of heavy crude oil through low-temperature oxidation

The low-temperature catalytic oxidation of heavy crude oil（Xinjiang Oilfield,China） was studied using three types of catalysts including oil-soluble,watersoluble,and dispersed catalysts.According to primary screening,oil-soluble catalysts,copper naphthenate and manganese naphthenate,are more attractive,and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil.The heavy oil compositions and molecular structures were characterized by column chromatography,elemental analysis,and Fourier transform infrared spectrometry before and after reaction.An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity-temperature characteristics.Results show that the two oil-soluble catalysts can crack part of heavy components into light components,decrease the heteroatom content,and achieve the transition of reaction mode from oxygen addition to bond scission.The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil（oil viscosity and contents of heavy fractions）.It is found that the temperature,oil composition,and internal molecular structures are the main factors affecting its flow ability.Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.

Stabilizing the Extrinsic Porosity in Metal-Organic Cages-Based Supramolecular Framework by In Situ Catalytic Polymerization

Porous supramolecular frameworks based on metal-organic cages(MOCs)usually have poor structural stability after activation.This issue narrows the scope of their potential applications,particularly for the inclusion of guest molecules that demand high porosity.Herein,the authors have reported the stabilization of a mesoporous zirconium MOC-based supramolecular framework with an in situ catalytic polymerization strategy.Due to the passivation effect imparted by this strategy,the introduced polymer is primarily distributed on the surface of the crystals,which results in the hybrid material retaining its crystallinity and permanent porosity.A preliminary application of this type of stabilized mesoporous supramolecular framework shows that among MOC-based supramolecular frameworks,it has the highest high-pressure methane uptake.Such a facile strategy may provide a general way to stabilize fragile porous materials and facilitate exploration of their potential applications.

Effect of operating pressure on the performance of THAI-CAPRI in situ combustion and in situ catalytic process for simultaneous thermal and catalytic upgrading of heavy oils and bitumen

According to the analysis of the 2020 estimates of the International Energy Agency(2020),the world will require up to 770 billion barrels of oil from now to 2040.However,based on the British Petroleum(BP)statistical review of world energy 2020,the world-wide total reserve of the conventional light oil is only 520.2 billion barrels as at the end of 2019.That implies that the remaining 249.8 billion barrels of oil urgently needed to ensure a smooth transition to a decarbonised global energy and economic systems is provided must come from unconventional oils(i.e.heavy oils and bitumen)reserves.But heavy oils and bitumen are very difficult to produce and the current commercial production technologies have poor efficiency and release large quantities of greenhouse gases.Therefore,these resources should ideally be upgraded and produced using technologies that have greener credentials.This is where the energy-efficient,environmentally friendly,and self-sustaining THAI-CAPRI coupled in situ combustion and in situ catalytic upgrading process comes in.However,the novel THAI-CAPRI process is trialled only once at field and it has not gained wide recognition due to poor understanding of the optimal design parameters and procedures.Hence,this work reports the first ever results of investigations of the effect of operating pressure on the performance of the THAI-CAPRI process.Two experimental scale numerical models of the process based on Athabasca tar sand properties were run at pressures of 8000 kPa and 500 kPa respectively using CMG STARS.This study has shown that the higher the operating pressure,the larger the API gravity and the higher the cumulative volume of high-quality oil is produced(i.e.a 2300 cm3 of z24 oAPI oil produced at 8000 kPa versus the 2050 cm3 of z17.5 oAPI oil produced at 500 kPa).The study has further shown that despite presence of annular catalyst layer,the THAI-CAPRI process operates stably.However,it is found that a more stable and safer operation of the process can only be achieved at optimal pressure that should lie between 500 kPa and 8000 kPa,especially since at the lower pressure,should the process time be extended,it will not take long before oxygen breakthrough takes place.The simulations have shown in details that at higher pressures,the catalyst bed is easily and rapidly coked and thus the catalyst life will be very short especially during actual field reservoir operations.Since the oil drainage flux into the HP well at field-scale is different from that at laboratory-scale,and at field-scale,the combustion front does not propagate inside the HP well,it will be practically very challenging to regenerate or replace the coke-deactivated annular catalyst layer in actual reservoir operations.There-fore,it is concluded that during field operation designs,an optimum pressure must be selected such that a balance is obtained between the combustion front stability and the degree of catalytic upgrading,and between the catalyst life and its effectiveness.

In situ Fourier Transform Infrared Spectroscopy Diagnostic for Characterization and Performance Test of Catalysts

The present work establishes a systematic approach based on the application of in-situ Fourier transform infrared spectroscopy （FTIR） for the investigation of the crystal structure, thermal stability, redox behavior （temperature-programmed reduction/temperatureprogrammed re-oxidation） as well as the catalytic properties of Co3O4 thin films. The syntheses of Co3O4 were achieved by chemical vapor deposition in the temperature range of 400-500℃. The structure analysis of the as-prepared material revealed the presence of two prominent IR bands peaking at 544 cm-1 （υ1） and 650 cm-1 （υ2） respectively, which originate from the stretching vibrations of the Co-O bond, characteristic of the Co3O4 spinel. The lattice stability limit of Co3O4 was estimated to be above 650℃. The redox properties of the spinel structure were determined by integrating the area under the emission bands υ1 and υ2 as a function of the temperature. Moreover, Co3O4 has been successfully tested as a catalyst towards complete oxidation of dimethyl ether below 340 ℃. The exhaust gas analysis during the catalytic process by in situ absorption FTIR revealed that only CO2 and H2O were detected as the final products in the catalytic reaction. The redox behavior suggests that the oxidation of dimethyl ether over Co3O4 follows a Mars-van Krevelen type mechanism. The comprehensive application of in situ FTIR provides a novel diagnostic tool in characterization and performance test of catalysts.

Simulation of catalytic upgrading in CAPRI,an add-on process to novel in-situ combustion,THAI

Based on the analysis of recent projections by the International Energy Agency(IEA),to meet the growing and subsequently declining demands of oil from now to 2040,we need up to around 770 billion barrels of oil.Since the worldwide total proved reserves of easy-and-cheaper-to-produce conventional oils is roughly only 520.2 billion barrels,the remaining 249.8 billion barrels must be obtained from unconventional petroleum resources(i.e.heavy oils and bitumen).These resources are however very difficult and costly to upgrade and produce due to their inherently high asphaltene contents which are reflected in their very high viscosities and large densities.However,still they should prove attractive development prospects if,as much as practicably possible,their upgrading can be performed in conjunction with in situ or downhole catalytic upgrading processes.Such projects will contribute significantly towards smoother and greener transition to full decarbonisation.Advanced technologies,such as the toe-to-heel air injection coupled to its add-on in situ catalytic process(i.e.THAI-CAPRI processes),have the potential to develop these reserves,but require further developmental understanding to realise their full capability.In this work,a new detailed procedure for numerically simulating the THAI-CAPRI processes is presented.The numerical model is made-up of Athabasca-type bitumen and it has a horizontal producer(HP)well that is surrounded by an annular layer of alumina-supported cobalt-oxide-molybdenum-oxide(CoMo/γ-Al2O3)catalyst.The simulation is performed using the computer modelling group(CMG)reservoir simulator,STARS.This new work has shown that the choice of the frequency factor of the catalytic reactions allowed model validation based on the degree of catalytic upgrading in form of API gravity.Overall,the work herein identifies the important parameters,such as API gravity,peak temperature,oil production rate,cumulative oil production,produced oxygen concentration,temperature distribution profile,extent of coke deposition on the catalyst surface,etc.,governing the successful operation of the THAI-CAPRI processes.In particular,this study has shown that even in the vicinities of the mobile oil zone(MOZ)where the catalytic upgrading is expected to be taking place,the catalyst surfaces are covered with high concentration of coke.This finding is in parallel to the observations reported from experiment of CAPRI process alone.Therefore,it is concluded that when experimental studies of the THAI-CAPRI processes are to be conducted,a catalyst regeneration mechanism must be put in place in order to prolong the effectiveness and thus the life of the catalyst so that proper field operation design can be made.Additionally,the study has also shown that the temperature of the MOZ is less than 306°C and that implies that an external source of heating the annular catalyst layer must be provided in order to effect the catalytic upgrading in the THAI-CAPRI processes.Thus,a new study should look at the feasibility of targeted heating(in the case of microwave)or conductive or resistive heating(in the case of electrical heating)to raise the temperature of the annular catalyst layer to that required to achieve the catalytic upgrading.