Porosity model and pore evolution of transitional shales:an example from the Southern North China Basin

The evolution of shale reservoirs is mainly related to two functions:mechanical compaction controlled by ground stress and chemical compaction controlled by thermal effect.Thermal simulation experiments were conducted to simulate the chemical compaction of marine-continental transitional shale,and X-ray diffraction(XRD),CO2 adsorption,N2 adsorption and high-pressure mercury injection(MIP)were then used to characterize shale diagenesis and porosity.Moreover,simulations of mechanical compaction adhering to mathematical models were performed,and a shale compaction model was proposed considering clay content and kaolinite proportions.The advantage of this model is that the change in shale compressibility,which is caused by the transformation of clay minerals during thermal evolution,may be considered.The combination of the thermal simulation and compaction model may depict the interactions between chemical and mechanical compaction.Such interactions may then express the pore evolution of shale in actual conditions of formation.Accordingly,the obtained results demonstrated that shales having low kaolinite possess higher porosity at the same burial depth and clay mineral content,proving that other clay minerals such as illite-smectite mixed layers(I/S)and illite are conducive to the development of pores.Shales possessing a high clay mineral content have a higher porosity in shallow layers(<3500 m)and a lower porosity in deep layers(>3500 m).Both the amount and location of the increase in porosity differ at different geothermal gradients.High geothermal gradients favor the preservation of high porosity in shale at an appropriate Ro.The pore evolution of the marine-continental transitional shale is divided into five stages.Stage 2 possesses an Ro of 1.0%-1.6%and has high porosity along with a high specific surface area.Stage 3 has an Ro of 1.6%-2.0%and contains a higher porosity with a low specific surface area.Finally,Stage 4 has an Ro of 2.0%-2.9%with a low porosity and high specific surface area.

Application of Pore Evolution and Fracture Development Coupled Models in the Prediction of Reservoir "Sweet Spots" in Tight Sandstones

The Chang-63 reservoir in the Huaqing area has widely developed tight sandstone ＂thick sand layers, but not reservoirs characterized by rich in oil＂, and it is thus necessary to further study its oil and gas enrichment law. This study builds porosity and fracture development and evolution models in different deposition environments, through core observation, casting thin section, SEM, porosity and permeability analysis, burial history analysis, and ＂four-property-relationships＂ analysis.

Study on the relationship between hydrocarbon generation and pore evolution in continental shale from the Ordos Basin,China

The relationship between hydrocarbon generation and the evolution of shale pore structure and its heterogeneity of continental shale from the Ordos Basin,China was quantitatively studied based on thermal simulation experiment,mercury injection capillary pressure(MICP),gas adsorption,vitrinite reflectance(R_(o))analysis,and hydrocarbon generation test combined with Frenkel-Halsey-Hill(FHH)fractal model.The result shows that the pore volume(PV)and specific surface area(SSA)of pores with different pore sizes show a trend of decreasing first and then increasing as the maturity increases in general,R_(o)>1.59%is initially defined as a favorable stage for pore development in continental shale.Hydrocarbon generation has different effects on pore heterogeneity of different scales.For the N_(2)adsorption,the roughness of small pore surface(D_(1))decreases in the oil window;the complexity of large pore structure(D_(2))increases in the oil window but decreases in the gas window.For the MICP,the heterogeneity of small pore(D_(1))increases in the oil window and increases first and then decreases in the gas window;D_(2)remains basically constant during the whole stage and is close to 3,indicating that the heterogeneity of large pores is extremely strong and is not affected by hydrocarbon generation.

Types,Petrophysical Properties and Pore Evolution of Late Ediacaran Microbial Carbonates,Tarim Basin,NW China

The Upper Ediacaran microbial carbonates of the Tarim Basin are potential reservoir geobodies for future hydrocarbon exploration with rising interest in exploration for deeply-buried reserves.However,little knowledge has been acquired on the types of microbial carbonates that are present,the properties of the reservoir and the pore evolution,hampering predictions of high-quality reservoirs in these carbonates.Integrated with petrography and in-situ U-Pb dating geochronology analyses,this study aims to clarify the types of microbial carbonates present and to reconstruct the pore evolution processes of the potential reservoir rocks.The Upper Ediacaran microbial carbonates of the Tarim Basin can be divided into four types,based on their features in terms of different scales(macro-to micro-):microbial laminite,stromatolite,spongiomicrobialite and microbial-peloidal wackestone/mudstone.Petrophysical properties show that all these microbial carbonates have low porosity and very low permeability with poor connectivity.These carbonates were subject to long-term and complex diagenetic processes,mainly consisting of dissolution,compaction,pervasive dolomitization,cementation and fracturing.The most important reservoir spaces are contributed by vugs and dissolution-enlarged pores,which are likely to have been associated with the widespread uplift of the Aksu area in the terminal Ediacaran.In contrast,the cementation of the fine-to-medium crystalline dolomite greatly reduced the pre-existing pores.Pore types are closely related to different microbial fabrics,which played an important role in the pore evolution of the microbial carbonates.

Influencing mechanism of saline sediments on pore system formation and evolution in terrestrial shales

The majority of oil and gas resources in the world are related to saline sediments, which mainly occur in sedimentary strata in the form of cap rocks or salt-associated shales. A large number of shale oil resources have been discovered in the saline shale sediments of the Cenozoic terrestrial lake basin in China. The hydrocarbon generation ability and the reservoir capacity of shale control the oil and gas generation. The reservoir capacity is mainly characterized by pore type, structure and porosity. Most of China’s shale oil and gas resources belong to salt-bearing formations. The role of gypsum-salt rocks in the formation and evolution of organic matter (OM) in such formations has received extensive attention. However, systematic understanding is lacking. Research on the pore formation and evolution in shale under the action of gypsum-salt rock sediments is especially weak. Taking the shales in the third member of the Shahejie Formation (Es_(3)) of the Bohai Bay Basin as an example, the influence of halite on the formation and evolution process of pores was studied in this paper. The results show that halite and gypsum minerals were associated with OM, which made them more likely to develop OM pores. The samples with a high halite mineral content (HC) are more developed regarding the pore volume and specific surface area than those with a low HC. The formation of thick salt rocks is influenced by factors of deep thermal brine upwelling, sea erosion and arid environments. The frequent alternation between humid and arid environments led to the outbreak and death of organisms and the precipitation of gypsum-salt rock, which formed the simultaneous deposition of OM and halite minerals. Finally, we have established a model of shale pore evolution under the participation of the gypsum-salt rock, and halite minerals contribute to pore development in both Stage II and Stage IV. This study provides strong microscopic evidence for the pore system formation and evolution in salt-bearing reservoirs.

Conglomerate Reservoir Pore Evolution Characteristics and Favorable Area Prediction: A Case Study of the Lower Triassic Baikouquan Formation in the Northwest Margin of the Junggar Basin, China

This study examines the characteristics and pore evolution of the Baikouquan conglomerate reservoir in the Mahu sag of the Junggar Basin from original sedimentation and diagenesis.Analysis is based on core observation,thin section,X-ray diffraction,cathodoluminescence and image analysis,and combined with physical property and well log data.The results show that conglomerate reservoir in the Baikouquan Formation can be divided into three lithofacies types:TypeⅠis argillaceous filling conglomerate facies,in which cementation and dissolution are not developed,and the interstitial material is mainly argillaceous;TypeⅡis tuffaceous filling in fine conglomerate facies,in which volcanic rock debris,illite and dissolution are developed;TypeⅢis sandstone filling conglomerate facies,in which cementation and dissolution are developed.The reservoir undergoes complex diagenesis,and the diagenetic sequence is:compaction→early chlorite film→early calcite cementation→detritus,feldspar and tuffaceous dissolution→quartz secondary enlargement→late calcite cementation→oil invasion→forming illite.Quantitative study of pore evolution shows that dissolution and calcite cementation are relatively developed in lithofacies Type III,and that compaction has a great influence on lithofacies TypeⅠand II.According to comprehensive evaluation of lithofacies,diagenesis and pore structure characteristics,the reservoir space type is mainly the dissolution pore.It is mainly primarily mainly composed of lithofacies Type III,thickness of the gravel body is more than 25 m,porosity is generally more than 12%,which represents favorable conditions for the distribution of favorable reservoir.

Pore evolution in hydrocarbon-generation simulation of organic matter-rich muddy shale

For exploration and potential evaluation of deep shale reservoirs with high maturity,hydrocarbon generation and pore evolution of muddy shale in deep high evolution stage were investigated by the high-temperature high-pressure simulation experiment.Results indicated that under high pressure condition,nano-scale micropores in organic matter-rich muddy shale constantly increased as rise of temperature and pressure,leading to increase of shale porosity.However,in the high mature-overmature stage,shale porosity decreased with further increase of temperature and pressure.In contrast to micropores,micro-scale capillary pores and megapores in shale constantly decreased as rise of simulation temperature or pressure,indicating that deep-burial reservoirs was not favorable for free-gas storage;but significant increase of micropores and surface area during this stage could make up for a loss of adsorbed natural gas in shale due to decrease of adsorption capacity which was induced by increase of temperature and pressure,thus leading to high shale gas potential in deep layers.A large number of secondary micropores were developed in the simulated samples such as pyrite and dolomite,demonstrating that shale clasts and mineral matrix could also form abundant secondary micropores during the deep evolution stage;during the evolution process,shale as hydrocarbon source rock could generate a large amount of acidic fluid which was favorable for development of secondary porosity.

Pore Connectivity of Deep Lacustrine Shale and its Effect on Gas-bearing Characteristics in the Songliao Basin:Implications from Continental Scientific Drilling

The lacustrine shale of deep Shahezi Formation in the Songliao basin has great gas potential,but its pore evolution,heterogeneity,and connectivity characteristics remain unclear.In this work,total organic carbon analysis,rock pyrolysis,X-ray diffraction field emission scanning electron microscopy,the particle and crack analysis system software,low-temperature nitrogen adsorption experiment,fractal theory,high-pressure mercury injection experiment and nuclear magnetic resonance experiment were used to study the Shahezi shale from Well SK-2.The result indicated that the organic pores in Shahezi shale are not developed,and the intergranular and intragranular pores are mainly formed by illitedominated clay.As the burial depth increases,the pore size and slit-shaped pores formed by clay decrease,and dissolved pores in the feldspar and carbonate minerals and dissolved fractures in the quartz increase.The pore evolution is affected by clay,compaction,and high-temperature corrosion.Based on the pore structure characteristics reflected by the pore size distribution and pore structure parameters obtained by multiple experimental methods,the pore development and evolution are divided into three stages.During stageⅠandⅡ,the pore heterogeneity of the shale reservoirs increases with the depth,the physical properties and pore connectivity deteriorate,but the gas-bearing property is good.In stageⅢ,the pore heterogeneity is the highest,its gas generation and storage capacity are low,but the increase of micro-fractures makes pore connectivity and gas-bearing better.

Pore structure evolution of lacustrine organic-rich shale from the second member of the Kongdian formation in the Cangdong Sag,Bohai Bay Basin,China

Pyrolysis experiments were conducted on lacustrine organic-rich shale from Cangdong Sag in Bohai Bay Basin,China,to investigate the impact of hydrocarbon generation on shale pore structure evolution.Thermal evolution is found to control the transformation of organic matter,hydrocarbon products characteristics,and pore structure changes.Furthermore,pore volume and specific surface area increase with increasing maturity.In low-mature stage,the retained oil content begins to increase,pore volumes show slight changes,and primary pores are occluded by the generated crude oil of high molecular weight and density.In the oil-window stage,the retained oil content rapidly increases and reaches maximum,and pore volumes gradually increase with increasing thermal maturity.At high mature stage,the retained oil content begins to decrease,and the pore volume increases considerably owing to the expulsion of liquid hydrocarbon.In over mature stage,natural gas content significantly increases and kerogen transforms to asphalt.Numerous organic pores are formed and the pore size gradually increases,resulting from the connection of organic pores caused the increasing thermal stress.This study lays a foundation for understanding variation of hydrocarbon products during the thermal evolution of lacustrine shales and its relationship with the evolution of shale reservoirs.

Fatigue properties and damage constitutive model of salt rock based on CT scanning

To investigate the macroscopic fatigue properties and the mesoscopic pore evolution characteristics of salt rock under cyclic loading,fatigue tests under different upper-limit stresses were carried out on salt rock,and the mesoscopic pore structures of salt rock before and after fatigue tests and under different cycle numbers were measured using CT scanning instrument.Based on the test results,the effects of the cycle number and the upper-limit stress on the evolution of cracks,pore morphology,pore number,pore volume,pore size,plane porosity,and volume porosity of salt rock were analyzed.The failure path of salt rock specimens under cyclic loading was analyzed using the distribution law of plane porosity.The damage variable of salt rock under cyclic loading was defined on basis of the variation of volume porosity with cycle number.In order to describe the fatigue deformation behavior of salt rock under cyclic loading,the nonlinear Burgers damage constitutive model was further established.The results show that the model established can better reflect the whole development process of fatigue deformation of salt rock under cyclic loading.

Controlling Factors of Organic Nanopore Development: A Case Study on Marine Shale in the Middle and Upper Yangtze Region, South China

The Upper Ordovician Wufeng-Lower Silurian Longmaxi and the Lower Cambrian Qiongzhusi shales are the major targets for shale gas exploration and development in China.Although the two organic-rich shales share similar distribution ranges and thicknesses,they exhibit substantially different exploration and development results.This work analyzed the nanopore structures of the shale reservoirs in this region.Pore development of 51 shale samples collected from various formations and locations was compared using the petromineralogical,geochemical,structural geological and reservoir geological methods.The results indicate that the reservoir space in these shales is dominated by organic pores and the total pore volume of micropores,mesopores,macropores in different tectonic areas and formations show different trends with the increase of TOC.It is suggested that organic pores of shale can be well preserved in areas with simple structure and suitable preservation conditions,and the shale with smaller maximum ancient burial depth and later hydrocarbongeneration-end-time is also more conducive to pore preservation.Organic pore evolution models are established,and they are as follows:①Organic matter pore development stage,②Early stage of organic matter pore destruction,and③late stage of organic matter pore destruction.The areas conducive to pore development are favorable for shale gas development.Research results can effectively guide the optimization and evaluation of favorable areas of shale gas.

Experimental study on the activation of coal gasification fly ash from industrial CFB gasifiers

Coal gasification fly ash(CGFA)is an industrial solid waste from the coal circulating fluidized bed(CFB)gasification process,and it needs to be effectively disposed to achieve sustainable development of the environment.To realize the application of CGFA as a precursor of porous carbon materials,the physicochemical properties of three kinds of CGFA from industrial CFB gasifiers are analyzed.Then,the activation potential of CGFA is acquired via steam activation experiments in a tube furnace reactor.Finally,the fluidization activation technology of CGFA is practiced in a bench-scale CFB test rig,and its advantages are highlighted.The results show that CGFA is characterized by a high carbon content in the range of 54.06%–74.09%,an ultrafine particle size(d50:16.3–26.1 μm),and a relatively developed pore structure(specific surface area SSA:139.29–551.97 m^(2)·g^(-1)).The proportion of micropores in CGFA increases gradually with the coal rank.Steam activation experiments show that the pore development of CGFA mainly includes three stages:initial pore development,dynamic equilibrium between micropores and mesopores and pore collapse.The SSA of lignite fly ash(LFA),subbituminous fly ash(SBFA)and anthracite fly ash(AFA)is maximally increased by 105%,13%and 72%after steam activation;the order of the largest carbon reaction rate and decomposition ratio of steam among the three kinds of CGFA is SBFA>LFA>AFA.As the ratio of oxygen to carbon during the fluidization activation of LFA is from 0.09 to 0.19,the carbon conversion ratio increases from 14.4%to 26.8%and the cold gas efficiency increases from 6.8%to 10.2%.The SSA of LFA increases by up to 53.9%during the fluidization activation process,which is mainly due to the mesoporous development.Relative to steam activation in a tube furnace reactor,fluidization activation takes an extremely short time(seconds)to achieve the same activation effect.It is expected to further improve the activation effect of LFA by regulating the carbon conversion ratio range of 27%–35%to create pores in the initial development stage.

Organic matter occurrence and pore-forming mechanisms in lacustrine shales in China

The evolution of pore structure in shales is affected by both the thermal evolution of organic matter(OM)and by inorganic diagenesis,resulting in a wide variety of pore structures.This paper examines the OM distribution in lacustrine shales and its influence on pore structure,and describes the process of porosity development.The principal findings are:(i)Three distribution patterns of OM in lacustrine shales are distinguished;laminated continuous distribution,clumped distribution,and stellate scattered distribution.The differences in total organic carbon(TOC)content,free hydrocarbon content(S_(1)),and OM porosity among these distribution patterns are discussed.(ii)Porosity is negatively correlated with TOC and plagioclase content and positively correlated with quartz,dolomite,and clay mineral content.(iii)Pore evolution in lacustrine shales is characterized by a sequence of decreasing-increasing-decreasing porosity,followed by continuously increasing porosity until a relatively stable condition is reached.(iv)A new model for evaluating porosity in lacustrine shales is proposed.Using this model,the organic and inorganic porosity of shales in the Permian Lucaogou Formation are calculated to be 2.5%-5%and 1%-6.3%,respectively,which correlate closely with measured data.These findings may provide a scientific basis and technical support for the sweet spotting in lacustrine shales in China.

Classification and control factors of pore-throat systems in hybrid sedimentary rocks of Jimusar Sag, Junggar Basin, NW China

Aiming at the complicated problem of the genesis of high-quality hybrid sedimentary rocks,the pore-throat systems,controlling factors and fluid mobility of hybrid sedimentary rocks in the Permian Lucaogou Formation in Jimusar Sag were examined.The results show that the hybrid sedimentary rocks contain 5 types of pore-throat system,intergranular(Type A),mixed intergranular-dissolved-intercrystalline(Type B),dissolved(Type C),mixed dissolved-intercrystalline(Type D)and intercrystalline(Type E)ones.The pore-throat systems are controlled by 3 major factors,the component content and arrangement(CCA)of hybrid sedimentary rocks,sedimentary environment and diagenesis.CCA controls the matrix support mode of hybrid sedimentary rocks,and therefore controls the types and changes of pore-throat system.The sedimentary environment mainly controls the macroscopic distribution of pore-throat system,i.e.,hybrid sedimentary rocks deposited in the near source and high-energy environment are characterized by high content of coarse-grained component,granular/interbedded-support mode,and development of Type A and Type B pore-throat systems.Hybrid sedimentary rocks deposited in the medium-energy environment far from source are characterized by dolomitic/mud support mode and Type C and Type D pore-throat systems.Hybrid sedimentary rocks deposited in low-energy environment far from source have mainly Type E and Type D pore-throat systems.Diagenetic processes such as compaction and calcite cementation make the proportions of Type A and Type C pore-throat systems decrease further.In the hybrid sedimentary process of sandy-mud,pore-throat system types show a change of"A→B→C→D",in that of dolomite-sand,pore-throat system types show a change of"A→C→D→E"or"B→D→E",and in that of dolomite-mud,pore-throat system types show a change of"D→E",which are affected in details by the contents of coarse-grain component,feldspar and dolomite.The reservoir with Type A pore-throats has the best physical properties and fluid mobility,and the reservoirs with Type D and Type E pore-throats have the poorest.The movable fluid distribution is related to the matrix support mode,and the larger pores in hybrid sedimentary rocks of dolomite/mud support mode have no obvious advantage in fluid mobility.The findings of this study provide a geological basis for evaluating and building reasonable interpretation model of hybrid sedimentary rocks sweet spot.

Effects of cementation on physical properties of clastic rock-originated weathering crust reservoirs in the Kexia region,Junggar Basin,NW China

Cements are widely developed in clastic rock-originated weathering crust(CWC)reservoirs in the Kexia region along the northwestern margin of the Junggar Basin and significantly affect reservoir physical properties and oil and gas distribution in this area.Focusing on the CWC reservoirs at the top of both the Permian Jiamuhe Formation and the Triassic Karamay Formation,this study analyzed the types and characteristics of cements in the reservoirs and explored their effects on reservoir physical properties based on thin sections,SEM images,XRD results,and tests of physical properties.The main results are as follows.The cements in the CWC reservoirs in Kexia region mainly consist of carbonate minerals(41.5%),clay minerals(27.8%)and zeolite minerals(30%),as well as small amount of siliceous minerals.Among them,the carbonate minerals are dominated by siderite and calcite,the clay minerals mainly include kaolinite,interstratified illite/smectite(I/S)and chlorite,and the zeolite minerals primarily comprise heulandite and laumontite.These different types of multiphase cements are generally paragenetic or associated and affect reservoir physical properties to different degrees.Specifically,the carbonate and clay cements of the early diagenetic stage reduced the reservoirs’average porosity from 21%to 15%.The dissolution of some carbonate and zeolite cements in the early A substage of the middle diagenetic stage restored the average porosity to 18%,and the cementation in the late A substage decreased the average porosity to 13%again,of which about 4%was reduced by carbonate cements.The average porosity of the CWC reservoirs gradually decreased to the current value of approximately 10%in the B substage of the middle diagenetic stage.The impact of cementation on the CWC reservoirs can reach as far as 70 m below the unconformity.Moreover,the types and contents of cements vary with their depth below the unconformity surface,leading to the development of multiple zones with high cement content and the differentiated oil and gas distribution.

Diagenesis and Their Succession of Gas-bearing and Non-gas-bearing Reservoirs in the Sulige Gas Field of Ordos Basin,China

Comparisons have been made among lithology, diagenesis, and reservoir characteristics of gas-bearing and non-gas-bearing ones in the Sulige gas field of the Ordos Basin based on the laboratory analysis of thin sections, scanning electron microscope, and liquid inclusion of the reservoirs. The reservoirs of the Sulige gas field are now in the middle stage of diagenesis and have undergone compaction, cementation and dissolution. The secondary pore of the reservoir originated from the dissolution of the feldspar and tuff because of the organic acid action from the source rocks during the diagenetic middle stage. Gas-bearing reservoirs are common in soluble pore diagenetic facies of coarse detritus quartzose sandstone, whereas non-gas-bearing ones are common in tense compaction diagenetic facies of mud-bearing medium-fine detritus quartzose sandstone and residual intergranular pore diagenetic facies of mud-bearing medium-coarse detritus quartzose sandstone. The secondary pore is developed in gas-bearing reservoirs of the Sulige gas-field as the medium-coarse grain reservoirs formed in a powerful sedimentary environment and experienced strong dissolution. However, the sediments of fine grain size form the non-gas-bearing reservoirs because of less residual primary pore and secondary pore.

Mesoporous TiO2 microparticles formed by the oriented attachment of nanocrystals： A super-durable anode material for sodium-ion batteries

Spindle-shaped anatase TiO2 secondary particles were successfully fabricated via the oriented attachment of primary nanocrystals. By adjusting the concentration of tetrabutyl titanate, the size of the TiO2 nanocrystals and particles could be controlled, resulting in pore evolution. Pores for the random aggregation of secondary particles gradually transformed to nanopores originating from the oriented attachment of the primary nanocrystals, resulting in an excellent micro/nanostructure that increased the performance of a sodium-ion battery. The mesoporous TiO2 microparticle anode, with its unique combination of nanocrystals and uniform nanopores, displays super durability （95 mAh/g after 11,000 cycles at I C）, high initial efficiency （61.4%）, and excellent rate performance （265 and 77 mAh/g at 0.1 and 20 C, respectively）. In particular, at slow discharge （0.1 C） and fast charge （5, 50, and 100 C） rates, the anatase TiO2 shows remarkable initial charge capacities of 200, 119, and 56 mAh/g, corresponding to 172, 127, and 56 mAh/g, after 150 cycles, respectively, thus meeting the requirements for fast energy storage. This excellent performance can be attributed to the stability of the material and its high ionic conductivity, resulting from the stable architecture with a mesoporous microstructure and without the random aggregation of secondary particles. A fundamental understanding of the pore structure and controllable pore construction has been proven to be effective in increasing the rate capability and durability of nanostructured electrode materials.

Reaction kinetics and internal diffusion of Zhundong char gasification with CO_(2)

Mass transfer usually affects the rate of chemical reactions in coal.The effect of internal diffusion on char gasification with CO_(2) in the temperature range from 1123 K to 1273 K was investigated via thermo-gravimetric analysis and assessment of char morphology features.The results revealed that the effect of internal diffusion on the initial reaction rate was more significant with an increase of particle size,due to the concentration gradient of the gasification agent within the solid particles.In the early stage of gasification,the generation of new micropores and the opening of closed pores led to an increase in specific surface area.As the reaction proceeded,the openings were gradually expanded and the specific surface area continued to increase.However,with further reaction,disappearance of edge pores,melting and collapse of the pore structure led to a decrease in specific surface area.The intrinsic activation energy and reaction order based on the nth-order model were 157.67 kJ∙mol^(−1) and 0.36,respectively.Thus,temperature zones corresponding to chemical reaction and diffusion control were identified.Moreover,the calculated effectiveness factor provided a quantitative estimation of internal diffusion in the initial stage.