Modeling of Crack Development Associated with Proppant Hydraulic Fracturing in a Clay-Carbonate Oil Deposit

Survey and novel research data are used in the present study to classify/identify the lithological type of Verey age reservoirs’rocks.It is shown how the use of X-ray tomography can clarify the degree of heterogeneity,porosity and permeability of these rocks.These data are then used to elaborate a model of hydraulic fracturing.The resulting software can take into account the properties of proppant and breakdown fluid,thermal reservoir conditions,oil properties,well design data and even the filtration and elastic-mechanical properties of the rocks.Calculations of hydraulic fracturing crack formation are carried out and the results are compared with the data on hydraulic fracturing crack at standard conditions.Significant differences in crack formation in standard and lithotype models are determined.It is shown that the average width of the crack development for the lithotype model is 2.3 times higher than that for the standard model.Moreover,the coverage of crack development in height for the lithotype model is almost 2 times less than that for the standard model.The estimated fracture half-length for the lithotype model is 13.3%less than that of for the standard model.A higher dimensionless fracture conductivity is also obtained for the lithotype model.It is concluded that the proposed approach can increase the reliability of hydraulic fracturing crack models.

Towards the insights into the deactivation behavior of acetylene hydrogenation catalyst

A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;finally, the deactivation behavior of the commercial catalyst for acetylene hydrogenation were studied. The influence of various possible deactivation factors on the catalytic performance was elucidated via detailed structural characterization, surface composition analysis, and activity evaluation.The results showed that green oil, carbon deposit and sintering of active metal were the main reasons for deactivation, among which green oil and carbon deposit led to rapid deactivation, while the activity could be recovered after regeneration by high-temperature calcination. The sintering of active metal components was attributed to the high-temperature regeneration in hydrothermal conditions, which was slow but irreversible and accounted for permanent deactivation. Thus, optimizing the regeneration is expected to extend the service life of the commercial catalyst.

Regulating metal-acid double site balance on mesoporous SiO_(2)-Al_(2)O_(3) composite oxide for supercritical n-decane cracking

The balance between metal and acid sites directly affects the preparation of high-performance cracking catalysts with high heat sink and low coking.Nevertheless,how to control acid-metal sites balance and its relationship with cracking performance are reported scarcely.In this work,a series of Pt/Al_(2)O_(3)-SiO_(2) dual sites catalysts with different metal to acid active sites ratio(C_(M)/C_(SA))were constructed by ethanolassisted impregnation method and the impact on n-decane cracking under supercritical conditions was systematically and deeply investigated.The results showed that the conversion and carbon deposition increased gradually with varied C_(M)/C_(SA)and reached the balance at C_(M)/C_(SA)of 0.13.The proper ratio C_(M)/C_(SA)(0.13)can balance the deep dehydrogenation coking over metal active sites and high heat sink of cracking over acid active sites,the chemical heat sink reaches amazing 1.75 MJ/kg and carbon deposition is only22.03 mg/cm^(2) at 750℃.Meanwhile,the few metal sites at low C_(M)/C_(SA)and the few strong acid sites at high C_(M)/C_(SA)are the main factors limiting the cracking activity.Low C_(M)/C_(SA)limit the activation of C-H bond and deep dehydrogenation of coking precursor,resulting in relative low cracking activity and carbon deposition,while high C_(M)/C_(SA)limit the activation of C-C bond and increase the deep dehydrogenation.In this contribution,design and construction of metal-acid dual sites can not only provide the technical solution for the preparation of high heat sink and low coking cracking catalyst,but also deepen the understanding of the cracking path of hydrocarbon fuel.

Pre-reduction of WO_(3)-Co_(3)O_(4)by H_(2)-C_(2)H_4 in a fluidized bed

In order to avoid the formation ofηphase(W_(6)Co_(6)C or W_(3)Co_(3)C)that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder,a technical route of prereduction of WO_(3)-Co_(3)O_(4)to WO_(2)-Co and then deep reduction carbonization to WC-Co powder has been proposed.This study mainly investigates the influence of gas partial pressure on the pre-reduction process of WO_(3)-Co_(3)O_(4)under a mixed atmosphere of H_(2)-C_(2)H_(4)-Ar at 600℃and establishes the kinetic equations of pre-reduction and carbon evolution.The results indicate that increasing the partial pressure of hydrogen is conducive to the rapid and complete conversion of WO_(3) to WO_(2).High carbon content can be generated by the deposition of C_(2)H_(4),and it hinders the diffusion of the reducing gas;WO_(3)still cannot be completely reduced to WO_(2)as the partial pressure of C_(2)H_(4) increases to 60%.For the carbon evolution of C_(2)H_(4),the carbon amount is positively related to the H_(2)partial pressure,but it shows the highest amount and evolution rate when the ethylene partial pressure is 20%.Based on the reduction rate curves of WO_(3) and carbon evolution rate curves of C_(2)H_(4),the rate equations of pre-reduction and carbon evolution of WO_(3)-Co_(3)O_(4)system at 600℃are established.The pre-reduction reaction belongs to the first-order reaction,and its equation is expressed as follows:r=-(dw_(WO_(3)))/dt=(9±0.15)×10^(-2)×P_(H_(2))^(0.44)P_(C_(2)H_(4))&(0.57)The carbon deposition rate equation of C_(2)H_(4) can be expressed as follows:r=-(dc_C)/dt=r_f-r_b≌7.35×10^(-2)×P_(C_(2)H_(4))^(0.31)

Distribution,Seismic Characteristics and Controlling Factors of Carbonate Platforms on the Northwestern Margin of the South China Sea

Newly-acquired seismic data reveal widespread carbonate deposits covering a large part of the northwestern South China Sea margin.Three carbonate platforms are identified to have developed on the topographic highs inherited from tectonic deformation and volcanic accretion.Across the carbonate platforms,the Miocene strata are characterized by high-amplitude seismic reflections and distinct platform architecture that overlaps older strata.The Guangle and Xisha carbonate platforms grew on faulted blocks due to South China Sea continental rifting,while the Zhongjian carbonate platform developed on a structural high induced by early Miocene volcanism.During the late Miocene,partial drowning resulted in the inhibition of platform growth,eventual platform drowning and termination of most carbonate deposition.The drowning of the Guangle and Zhongjian carbonate platforms is shown by the supply of siliciclastic sediments during the late Miocene and seems to be closely linked to late Neogene volcanic activity,whilst the drowning of the Xisha carbonate platform is primarily related to relative eustatic changes.Our results imply that tectonic activity,volcanism and eustasy are the dominant controls on the evolution of carbonate platforms on the northwestern margin of the South China Sea.

New Insights into the Depositional Environments of Ordovician Carbonate Formations in the Yubei Area of Tarim Basin Based on Standard Microfacies Types

Objective The Yubei area is located in the mid-east Maigaiti slope of southwestern Tarim Basin, China, with an exploration history of several years. Recent exploration has preliminarily indicated that the Ordovician carbonate formations in this area have some oil and gas potential. Carbonate microfacies provides material basis for reservoir development, seal formation and hydrocarbon generation. Therefore, this work utilized the standard microfacies （SMF） types to study the microfacies of the Ordovician formations in the Yubei area in order to provide theoretical basis for the next exploration.

The Sachakou Deposit in West Kunlun of Xinjiang: A Pb-Zn Polymetallic Deposit Associated with Magmatic Metasomatism of Carbonate Rock

Objective The Sachakou Pb-Zn polymetallic deposit is located in Hetian County, Xinjiang （geographical coordinates of E78° 57＇ 54.30＂-78°59＇ 53.63＂, N34° 39＇ 27.50＂-34° 40＇ 57.21＂）. It belongs to the West Kunlun orogenic belt on the northwest edge of the Qinghai-Tibet Plateau and is connected to the Sanjiang orogenic belt to the south （Spurlin et al., 2005）. In recent years, a series of Pb-Zn mineralized spots and deposits have been discovered in this area one after another, which is called the Huoshaoyun ore concentration area. Among them, the Sachakou Pb-Zn deposit has reserves up to140 Mt, which has reached a large scale. However, the study on the genesis of deposits in this area has only just begun. This work studied the genesis ofthis Pb-Zn deposit in order to provide new ideas for the genesis of regional deposits and regional prospecting.

REE geochemistry of auriferous quartz carbonate veins of Neoarchean Ajjanahalli gold deposit,Chitradurga schist belt,Dharwar Craton,India

REE composition of the carbonates of the auriferous quartz carbonate veins（QCVs） of the Neoarchean Ajjanahalli gold deposit.Chitradurga schist belt.Dharwar Craton,is characterized by U-shaped chondrite normalized REE patterns with both LREE and HREE enrichment and a distinct positive Eu anomaly.As positive Eu anomaly is associated with low oxygen fugacity,we propose that the auriferous fluids responsible for gold mineralization at Ajjanahalli could be from an oxygen depleted fluid.The observed positive Eu anomaly is interpreted to suggest the derivation of the auriferous fluids from a mantle reservoir.The location of Ajjanahalli gold deposit in a crustal scale shear zone is consistent with this interpretation.

Three dimensional microstructures of carbon deposition on Ni-YSZ anodes under polarization

In the present study,two Ni/YSZ anodes with different volume ratios of Ni and YSZ,30:70 and 45:55 vol%,are operated in dry methane under open circuit and polarized conditions.Three-dimensional(3D)Ni/YSZ microstructures after carbon deposition are reconstructed by the focused ion beam-scanning electron microscopy(FIB-SEM)with the help of machine learning segmentation.From the reconstructed mircostructures,volume fraction,connectivity,three phase boundary(TPB)density,and tortuosity are quantified.In addition,local carbon microstructures are quantitatively reconstructed,and the effect of polarization on carbon morphology is investigated.It is demonstrated that Ni surface in the vicinity of active TPB near the electrolyte is free from carbon formation,while remaining Ni surface at some distances from TPB exhibits severe carbon deposition.In average,total amount of carbon deposition is larger near the electrolyte.These observations imply complex interplay between the electrochemical steam generation and methane cracking on Ni surface which take place very locally near the active TPB.

Investigation of the transformation of organic matter of carbonate deposits of the Semiluksky-Mendymsky horizon under hydrothermal conditions

The paper presents the results of studies on the transformation of the organic matter of siliceous-clayey carbonate rocks of the Semiluksko-Mendymsky horizon of the Romashkino oil field in a hydrothermal fluid for an hour(with a water-to-rock ratio of 33)at 340℃and 380℃and pressu res of 17 and 20 MPa.As a result of hydrothermal treatment,at 340℃and 17 MPa,based on nitrogen porosimetry and electron microscopy data,transformations of rock-forming minerals in the rock are observed.They lead to an increase in the volume and average diameter of mesopores in it and the formation of micropores,as well,which improve its filtration properties.At the same time,the amount of kerogen in the composition of the organic matter decreases and the yield of the petroleum hydrocarbon extract increases,in which,according to the SARA analysis,the content of asphaltenes increases and the content of resins,aromatic and saturated hydrocarbons decreases.In the composition of aroatic hydrocarbons,the proportion of a lkyltri methyl benzenes and dibenzothiophenes increases,phenanthrene homologues appear,and in the composition of saturated hydrocarbons,the amount of iso-structure alkanes decreases relative to the content of linear alkanes.Raising the temperature and pressure of the hydrothermal fluid to 380℃and 20 MPa increases the degree of kerogen conversion from 12.4%to 23.6%.At the same time,changes occurring in the component composition of petroleum hydrocarbon extracts remains similar to the experiments carried out at 340℃and 17 MPa;the content of naphthalenes decreases,the content of dibenzothiophenes increases and C_(11)-C_(17),C_(19)-C_(22)alkyltrimethylbenzenes appear.According to IR spectroscopy,with increasing temperature and pressure of the hydrothermal fluid the intensity of the absorption bands of the aromatic ring,aliphatic fragments,and oxygen-containing groups increases in resins;the structural-group composition of asphaltenes changes little:aromaticity and the content of condensed structures slightly increase.The revealed distinctive features in the composition of organic matter after hydrothermal impact on siliceous-clayey carbonate rocks confirm the concept of staged destruction of kerogen,when large structural heteroatomic blocks(asphaltenes)are split off at the initial stages.Changes occurring in the composition of petroleum hydrocarbon extracts indicate their involvement in the process of hydrothermal transformation of organic matter of siliceous-clayey carmbonate rocks with the predominant reactions of dehydrogenation of naphthenic compounds and oxidative polycondensation of aromatic structures.The data of electron microscopy and nitrogen porosimetry of rocks after hydrothermal exposure at 380℃and 20 MPa indicate a deterioration in their reservoir properties.The most optimal thermobaric conditions of the hydrothermal fluid for the generation of petroleum hydrocarbons from kerogen of siliceous-clayey carbonate deposits of the Semiluksko-Mendymsky horizon of the Romashkino field,which improve their reservoir properties,are 340℃and 17 MPa;with implication of hard-to-recover heavy hydrocarbon resources and wellestablished catalytic methods of in-situ conversion.

Catalytic wet oxidation of aniline over Ru catalysts supported on a modified TiO_2

The catalytic wet air oxidation of aniline over Ru catalysts supported on modified Ti 2 （Ti 2, Ti0.9Ce0.1O2, Ti0.9Zr0.1O2） is investigated. A series of characterization techniques are conducted to determine the relationship between the physico-chemical properties and the catalytic performance. As a result of the good metal dispersion and large number of surface oxygen species, the Ru/Ti0.9 Zr0.1O2 catalyst presents the best catalytic activity among the tested samples. The effects of the operating conditions on the reaction are investigated and the optimal reaction conditions are determined. Based on the relationship between the by-products concentration and the reaction time, the reaction path for the catalytic oxidation of aniline is established. Carbonaceous deposits on the surface of the support are known to be the main reason for catalyst deactivation. The catalysts maintain a constant activity even after three consecutive cycles.

Promotion Effects of Ceria on Fischer-Tropsch Synthesis Performance of Co/Al_2O_3 Catalyst

The addition of small amounts of ceria to Co/Al2O3 catalysts increases the turnover rate of the catalyst and C5+ selectivity in the Fischer-Tropsch synthesis. In this work, the amounts of ceria, the calcination temperature, the temperature-programmed reduction (TPR), the temperature-programmed oxidation (TPO), and XRD are investigated. The results show that the addition of small amounts of ceria to Co/Al2O3 catalyst (Ce/Co≈1∶ 10 ～1∶ 7, atom) can increase the CO conversion and liquid yield, while the calcination temperature can control both the chain growth probability and CO conversion in a reverse trend. The TPR and TPO experiments show that small amounts of Ceria can improve the reducibility, but the amounts of carbon deposit increase, and two-type carbon deposition is found in the short-term reaction catalyst.

Ni/Al_2O_3 catalysts for CO methanation: Effect of Al_2O_3 supports calcined at different temperatures

The correlation between phase structures and surface acidity of Al2O3 supports calcined at different temperatures and the catalytic performance of Ni/Al2O3 catalysts in the production of synthetic natural gas(SNG) via CO methanation was systematically investigated. A series of 10 wt% NiO/Al2O3 catalysts were prepared by the conventional impregnation method, and the phase structures and surface acidity of Al2O3 supports were adjusted by calcining the commercial γ-Al2O3 at different temperatures(600–1200 C). CO methanation reaction was carried out in the temperature range of 300–600 C at different weight hourly space velocities(WHSV = 30000 and 120000 mL·g-1h-1) and pressures(0.1 and 3.0 MPa). It was found that high calcination temperature not only led to the growth in Ni particle size, but also weakened the interaction between Ni nanoparticles and Al2O3 supports due to the rapid decrease of the specific surface area and acidity of Al2O3 supports. Interestingly, Ni catalysts supported on Al2O3 calcined at 1200 C(Ni/Al2O3-1200) exhibited the best catalytic activity for CO methanation under different reaction conditions. Lifetime reaction tests also indicated that Ni/Al2O3-1200 was the most active and stable catalyst compared with the other three catalysts, whose supports were calcined at lower temperatures(600, 800 and 1000 C). These findings would therefore be helpful to develop Ni/Al2O3 methanation catalyst for SNG production.

Carbon dioxide reforming of methane over Ni/Mo/SBA-15-La_2O_3 catalyst:Its characterization and catalytic performance

The Ni/Mo/SBA-15 catalyst was modified by La2O3 in order to improve its thermal stability and carbon deposition resistance during the CO2 reforming of methane to syngas. The catalytic performance, thermal stability, structure, dispersion of nickel and carbon deposition of the modified and unmodified catalysts were comparatively investigated by many characterization techniques such as N2 adsorption, H2-TPR, CO2-TPD, XRD, FT-IR and SEM. It was found that the major role of La2O3 additive was to improve the pore structure and inhibit carbon deposition on the catalyst surface. The La2O3 modified Ni/Mo/SBA-15 catalyst possessed a mesoporous structure and high surface area. The high surface area of the La2O3 modified catalysts resulted in strong interaction between Ni and Mo-La, which improved the dispersion of Ni, and retarded the sintering of Ni during the CO2 reforming process. The reaction evaluation results also showed that the La2O3 modified Ni/Mo/SBA-15 catalysts exhibited high stability.

Synthesis of LiFePO_4 /C as cathode material by a novel optimized hydrothermal method

Olivine LiFePO 4 , as a cathode material for lithium ion batteries, was prepared by a novel optimized hydrothermal method; afterwards, the product mixed with glucose was two-step （350℃ and 700℃） calcinated under high-purity N 2 atmosphere to obtain the LiFePO 4 /C composite. The study on the hydrothermal preparation method, which focused on the influences of molar ratios, initial pH value, reaction temperature, and duration, was made to promote the resultant performances and to investigate the relations between the performances and the reaction conditions. The resultant samples were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and electrochemical tests, which include charge-discharge, electrochemical impedance spectroscopy, and cyclic voltammetry. The result shows that the optimal hydrothermal condition is to set the Li：Fe：P molar ratio at 3：1：1 and the reaction temperature at 180℃ for 5 h duration with an initial pH value of 7. The optimized sample, with an average particle size of 100 to 300 nm and a discharge capacity of 118.2 mAh·g-1 at 0.1C, exhibits a stable and narrow-gapped charge-discharge platform and small capacity losses after cycles.

Synthesis of Ni-CeO_2 catalyst for the partial oxidation of methane using RF thermal plasma

Ni‐CeO2 catalysts with a nickel content of 50 mol% were prepared using RF thermal plasma, and their catalytic activities for methane partial oxidation were characterized. For the synthesis of Ni‐CeO2 catalysts, a precursor containing Ni（～5‐μm diameter） and CeO2（～200‐nm diameter）powders were heated simultaneously using an RF plasma at a power level of ～52 kVA and a powder feeding rate of ～120 g/h. From the X‐ray diffraction data and transmission electron microscopy images, the precursor formed into high crystalline CeO2 supports with nanosized Ni particles（ 50‐nm diameter） on their surfaces. The catalytic performance was evaluated under atmospheric pressure at 500 °C and a CH4：O2 molar ratio of 2：1 with Ar diluent. Although the Ni content was high（～50 mol%）, the experimental results reveal a methane conversion rate of 70%, selectivities of CO and H2 greater than 90% and slight carbon coking during an on‐stream test at 550 °C for 24 h.However, at 750 °C, the on‐stream test revealed the formation of filament‐like carbons with an increased methane conversion rate over 90%.

Catalytic Partial Oxidation of Methane over Ni/CeO_2-ZrO_2-Al_2O_3

Nickel catalysts supported on CeO2-ZrO2-CeO2,ZrO2-Al2O3 and Al2O3 were prepared and characterized by means of X-ray diffraction（XRD）,BET areas,H2 temperature-programmed reduction（H2-TPR）,and X-ray photoelectron spectroscopy（XPS）.Through the test of catalytic partial oxidation of methane（CPOM）,Ni/CeO2-ZrO2-Al2O3 displayed the highest activity,which resulted from its largest BET area and best NiO dispersion.Furthermore,Ni/CeO2-ZrO2-Al2O3 maintained a long-time stability in CPOM,which was attributed to its best coking resistance among all the prepared catalysts.

Thermodynamic analysis of combined reforming process using Gibbs energy minimization method: In view of solid carbon formation

Thermodynamic analysis was applied to study combined partial oxidation and carbon dioxide reforming of methane in view of carbon formation. The equilibrium calculations employing the Gibbs energy minimization were performed upon wide ranges of pressure （1-25 atm）, temperature （600-1300 K）, carbon dioxide to methane ratio （0-2） and oxygen to methane ratio （0-1）. The thermodynamic results were compared with the results obtained over a Ru supported catalyst. The results revealed that by increasing the reaction pressure methane conversion decreased. Also it was found that the atmospheric pressure is the preferable pressure for both dry reforming and partial oxidation of methane and increasing the temperature caused increases in both activity of carbon and conversion of methane. The results clearly showed that the addition of O2 to the feed mixture could lead to a reduction of carbon deposition.

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.