Modeling and analysis of air combustion and steam regeneration in methanol to olefins processes

Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However,the catalyst deactivation is an inevitable feature in MTO processes,and regeneration,therefore,is one of the key steps in industrial MTO processes.Traditionally the MTO catalyst is regenerated by removing the deposited coke via air combustion,which unavoidably transforms coke into carbon dioxide and reduces the carbon utilization efficiency.Recent study shows that the coke species over MTO catalyst can be regenerated via steam,which can promote the light olefins yield as the deactivated coke species can be essentially transferred to industrially useful synthesis gas,is a promising pathway for further MTO processes development.In this work,we modelled and analyzed these two MTO regeneration methods in terms of carbon utilization efficiency and technology economics.As shown,the steam regeneration could achieve a carbon utilization efficiency of 84.31%,compared to 74.74%for air combustion regeneration.The MTO processes using steam regeneration can essentially achieve the near-zero carbon emission.In addition,light olefins production of the MTO processes using steam regeneration is 12.81%higher than that using air combustion regeneration.In this regard,steam regeneration could be considered as a potential yet promising regeneration method for further MTO processes,showing not only great environmental benefits but also competitive economic performance.

Patterns of gas hydrate accumulation in mass transport deposits related to canyon activity: Example from Shenhu drilling area in the South China Sea

Since 2017, a plenty of gas hydrates have been drilled in a new area of Shenhu, and good heterogeneity has been found throughout the spatial distribution of the reservoir. After distinguishing different sedimentary sequence types and matching their formation with slope deposition settings, this study proposes three mass transport deposit(MTD) patterns related to canyon activity that occurred contemporaneously or epigenetically with it: well preserved MTDs, MTDs eroded by canyon migration, and MTDs dislocated by contemporaneous faults. Based on seismic reflection characteristics, this study proposed methods of quantitatively analyzing sedimentary factors,such as measuring the turbidities flow rate in the canyon, and results are interpreted with respect to canyon activity. Combining the above parameters and their relationship with gas hydrate accumulation, fine-grained seals overlapping coarse MTDs reservoirs are found to be indispensable to gas hydrate accumulation, as they prevent the release of free gas. Based on grain size data of hydrate samples from drilling wells, multi-layered gas hydrate reservoirs capped by fine-grained sediments and overlapping mud show favorable hydrate-bearing prospects. The release of gas hydrates, however, is mostly caused by the lack of mud sealing in relation to canyon activity, such as turbidities flow erosion and contemporaneous fault breaking. Canyon migration with respect to MTDs may be the actual cause of erosion of overlapping syn-sedimentary layers, and high bottom flows may contribute to an increase in the release of free gas. It is believed that contemporaneous faults caused by unstable canyon walls may break the muddy over layers and decrease the accumulation pressure of gas hydrate bearing.Thus, according to the sedimentary characteristics of MTDs and the hydrate accumulation process, three responding accumulation or releasing patterns are proposed, which respond to the different types of MTDs distinguished above: a well-preserved MTD accumulation pattern; a canyon migration eroded MTD release pattern; and a micro-contemporaneous fault dislocated MTD release pattern.

Mg/Ca,Ba/Ca,and S/Ca ratios as environmental and growth proxies for bivalve shells from the Haima cold seep,South China Sea

Bivalve shell fossils,cemented by authigenic carbonates,are widely spread in the Haima cold seep,Qiongdongnan Basin of the South China Sea(SCS).In this study,we examined an element profile of Gigantidas platifrons in the Haima cold seeps at a water depth of 1381 m.Based on the scanning electron microscope(SEM)analyses,the prismatic layer and nacreous layer were identified,which are characterized by prismatic structure and stratified structure,respectively.In addition,the profile can be subdivided into two parts:altered and unaltered zones.Laser inductively coupled plasma mass spectrometry(LA-ICP-MS)mapping shows that the element concentrations of the altered zones were influenced by the authigenic carbonate rocks,whereas the element concentrations of unaltered zones remain stable.In-situ X-ray diffraction(XRD)analyses show that the mineral constituent of the prismatic layer is mainly composed of aragonite.Along with the growth profile,Mg/Ca ratios of unaltered zones have minor variations,ranging 0.72-0.97 mmol/mol(mean=0.87 mmol/mol),with estimated temperatures of 3.8-4.1℃,indicating that the temperature of the surrounding seawater remains constant and agree with the measured data of 3.9℃which was conducted by a conductivity-temperature-depth system(CTD).The minor variations of Ba/Ca ratios(0.01-0.06 mmol/mol;mean=0.04 mmol/mol)indicate a relatively stabilized salinity of the surrounding seawater.S/Ca ratios show large variations of 0.04-4.15 mmol/mol(mean=1.37 mmol/mol).S/Ca ratios have regular variations which generally correspond to the variations of the Mg/Ca ratios,highlighting that the S/Ca ratios of bivalve shells show the potential to reflect the growth rate of the Gigantides.However,further studies should be carried out on the understanding of the links between the S/Ca ratios and seepage intensity of cold-seep fluids.

Sedimentary characteristics comparison and genesis analysis of the deepwater channel in the hydrate enrichment zones on the north slope of the South China Sea

Natural gas hydrate(NGH) is one of the important clean energy at present and even in the future. The study of its sedimentary environment and minerogenetic condition has long been a hot issue that has received much concern from geologists all over the world. China has successfully obtained the samples of NGH in Shenhu and Dongsha sea areas in 2007, 2013 and 2015, respectively. From this, the continental slope north of the South China Sea becomes an important test site for the study of NGH sedimentary genesis and minerogenetic condition. NGH has been found in Shenhu, Dongsha and Qiongdongnan areas within the continental slope north of South China Sea,at different depths of water, with different sedimentary characteristics, gas genesis, and minerogenetic conditions.Using a seismic sedimentology theory, combining seismic facies results of each facies, sedimentary facies and evolution of each area are documented in turn establishing a sedimentary model by considering palaeogeomorphology, sea level change and tectonic movement. The channel system and MTD(Mass Transport Deposition) system among these three areas were compared focusing on the developing position, appearance and controlling factors. Relative location among three areas is firstly defined that Dongsha area in a nearprovenance steep upper slope, Shenhu area in a normal gentle slope and Qiongdongnan area in an awayprovenance flat plain. Besides, their channel systems are classified into erosional, erosional-aggradational and aggradational channel, and MTD systems into headwall domain, translational domain and toe domain.

Sedimentary characteristics and genetic mechanism of the giant ancient pockmarks in the Qiongdongnan Basin,northern South China Sea

In the late Miocene,giant ancient pockmarks,which are fairly rare globally,developed in the Qiongdongnan Basin.In this paper,to determine the sedimentary characteristics and genetic mechanism of these giant ancient pockmarks in the Yinggehai Formation of the Qiongdongnan Basin,based on high-resolution 3D seismic data and multiattribute fusion technologies,we analyzed the planar distribution and seismic facies of the ancient pockmarks and compared the characteristics of the ancient pockmarks with those of channels,craters,and hydrate pits.Moreover,we also discussed the implications of the fluid escape system and paleo-bottom current activity in the ancient pockmark development area and analyzed the influence of the ancient pockmarks on the paleoclimate in this region.Finally,an evolutionary model was proposed for the giant ancient pockmarks.This model shows that the giant ancient pockmarks in the southern Qiongdongnan Basin were affected by both deep fluid escape and lateral transformation of paleobottom currents.In addition,the giant ancient pockmarks contributed to the atmospheric CO_(2)concentration in the late Miocene and played a great role in the contemporary evaluation of deepwater petroleum exploration.

Deposition processes of gas hydrate-bearing sediments in the inter-canyon area of Shenhu Area in the northern South China Sea

The Shenhu Submarine Canyon Group on the northern slope of the South China Sea consists of 17 slope-confined canyons,providing a good example for investigating their hosting sediments.Three drilling sites,including W07,W18,and W19,have proven the occurrence of gas hydrate reservoirs in the inter-canyon area between canyons C11 and C12.Whereas,variations of the geomorphology and seismic facies analyzed by high-resolution 3D seismic data indicate that the gas hydrate-bearing sediments may form in different sedimentary processes.In the upper segment,a set of small-scale channels with obvious topographic lows can be identified,revealing fine-grained turbidites supplied from the shelf region during a very short-term sea-level lowstand.In the middle part,gas hydrate units at Site W07 showing mounded or undulation external configuration are interpreted as sliding sedimentary features,and those features caused by gravity destabilization were the main formative mechanism of gas hydrate-bearing sediments that were sourced from the upper segments.In contrast,for the canyon transition zone of lower segments between C11-C12 inter-canyon and C12 intra-canyon areas,where W18 and W19 sites are located,the gas hydratebearing sediments are deposited in the channelized feature in the middle to lower segment and slide erosive surface.Gas hydrate-bearing sediments of the lower segment were migrated through channelized features interconnecting with the middle to lower slope by gravity-driven flows.The majority of deposits tended to be furtherly moved by lateral migration via erosive surface created by sediment failed to intra-canyon area.The conclusion of this study may help better understand the interaction between the formation mechanism of gas hydrate-bearing sediments and the geomorphologic effects of inter-canyon areas.

Geomorphological-geological-geophysical signatures of high-flux fluid flows in the eastern Pearl River Mouth Basin and effects on gas hydrate accumulation

Marine hydrate reservoirs can be divided into focused high-flux and distributed low-flux gas hydrate systems according to free gas migration control mechanisms. In focused high-flux hydrate reservoirs, fluids easily break through the pressure of overlying sediments and reach the shallows, creating a series of geomorphological-geological-geophysical anomalies at and near the seafloor. Based on detailed interpretation of pre-drilling data in the eastern Pearl River Mouth Basin(PRMB),many anomalies related to the high-flux fluid flow are found, including seafloor mounds with intrusive characteristics, bright spot reflections above the bottom-stimulating reflector(BSR), phase reversals in the superficial layer, and an efficient fluid migration and accumulation system composed of fractures and uplifts. The second hydrate drilling expedition was carried out in the eastern PRMB in 2013 to study these anomalies. The acquired data show that high-flux fluid flow occurred in these sites. Gas hydrate pingoes, bright spot reflection above the BSR, and an efficient fluid migration and accumulation system can be used as identification signatures for high-flux fluid migration. The modes of high flux fluid flow are different in deep and shallow sediments during upward migration of fluid. Gas dissolved within migrating water dominates deep fluid migration and upward migration of a separate gas phase dominates the shallow process. This difference in migration models leads to formation of upper and lower concentrated hydrate reservoirs in the drilling area. The discovery of signatures of high-flux fluid flow and their migration modes will help with site selection and reduce risk in gas hydrate drilling.

Submarine landslides, relationship with BSRs in the Dongsha area of South China Sea

Gas hydrate samples were first obtained in the Dongsha area,South China Sea(GMGS2)in 2013.High-resolution 3D seismic data in the area show various small 1andslide bodies developedas huge mass transport deposits.These bodies are divided into seven types on the basis of theirshapes,intermal structures and geneses(slide,collapse and deformation above BSRs,as well asthe slump wedge,lens,block and sheet below BSRs).Based on this classification,detailed studieswere conducted,including measurements of the slump body sizes and slope gradients of landslides,depiction of their three-dimensional characteristics,and research on the landslide distribution.Todetermine the genetic differences of these seven types,this study analyses the possibility of verticalflow-pattern-transformation and mechanisms of submarine landsltide formation.Results show that thedominant factor influencing the submarine landslides in the Dongsha area is the free gas emitted fromgas hydrate decomposition,with possible fransformation between flow patterns.Finally,there are twokinds of relationships between submarine landslides and BSRs since the free gas either influences thesubmarine landslide bodies below or above BSRs,resulting in two types of submarine landslide bodyassociations:Type A is characterized by submarine slide above BSRs and slump lens below BSRs,whereas Type B shows deformation above BSRs and slump blocks below BSRs.Type Ais favourablefor gas exploration because it indicates less decomposition and better sealing of gas hydrate layers.

Classification of mass-transport complexes and distribution of gashydrate-bearing sediments in the northeastern continental slope of the South China Sea

The drilling areas in Shenhu and Dongsha,South China Sea,studied from 2007 to 2015,reveal great heterogeneity in the spatial distribution of the gas hydrate reservoir.Various types of mass-transport complexes(MTCs)were developed in the study areas,which served as ideal reservoirs.To conduct exploration in these areas,it is necessary to study the different types of MTCs and the corresponding gashydrate accumulations.By integrating seismic reflection and log coring data,we classified three types of MTCs according to their stress distribution:the tension,extrusion,and shear types,and their corresponding gashydrate accumulation patterns.The results show that the accumulation of the gas-hydrate varies with the type of MTC and stress distribution depending on the MTC’s position(e.g.,in the headwall,translational,or toe areas).Owing to this variance of the MTC’s position,the corresponding kinemics situation in the MTCs also varies.Accordingly,we determined the corresponding location in which the gashydrate develops for various types of MTCs.Based on the bottom simulating reflectors(BSRs)and the hydrate core and image logging data,the gashydrate reservoir shows an obvious heterogeneity in various types of MTCs.The gashydrate in the tension-type MTCs are mostly borne in the toe and the headwall parts.In extrusion-type MTCs,the translational and toe parts constitute an ideal hydrate reservoir.In shear-type MTCs,the headwall and toe parts’coarse-grained sediments show an obviously hydrate response.After comparing the gashydrate saturation and MTCs morphology statics data,we were able to quantitatively prove that the main factors determining gashydrate accumulation in the different types of MTCs are the fault displacement,sedimentary rate,and flow erosion rate.