Mechanism and reservoir simulation study of the autothermic pyrolysis in-situ conversion process for oil shale recovery

The autothermic pyrolysis in-situ conversion process (ATS) consumes latent heat of residual organic matter after kerogen pyrolysis by oxidation reaction, and it has the advantages of low development cost and exploitation of deep oil shale resources. However, the heating mechanism and the characteristic of different reaction zones are still unclear. In this study, an ATS numerical simulation model was proposed for the development of oil shale, which considers the pyrolysis of kerogen, high-temperature oxidation, and low-temperature oxidation. Based on the above model, the mechanism of the ATS was analyzed and the effects of preheating temperature, O_(2) content, and injection rate on recovery factor and energy efficiency were studied. The results showed that the ATS in the formation can be divided into five characteristic zones by evolution of the oil and O_(2) distribution, and the solid organic matter, including residue zone, autothermic zone, pyrolysis zone, preheating zone, and original zone. Energy efficiency was much higher for the ATS than for the high-temperature nitrogen injection in-situ conversion process (HNICP). There is a threshold value of the preheating temperature, the oil content, and the injection rate during the ATS, which is 400 °C, 0.18, and 1100 m3/day, respectively, in this study.

Assessment of recoverable oil and gas resources by in-situ conversion of shale——Case study of extracting the Chang 7_(3) shale in the Ordos Basin

The purpose of this study is to investigate the entire evolution process of shales with various total organic contents(TOC)in order to build models for quantitative evaluation of oil and gas yields and establish methods for assessing recoverable oil and gas resources from in-situ conversion of organic matters in shale.Thermal simulation experiments under in-situ conversion conditions were conducted on Chang 7_(3) shales from the Ordos Basin in a semi-open system with large capacity.The results showed that TOC and R_(o) were the key factors affecting the in-situ transformation potential of shale.The remaining oil and gas yields increased linearly with TOC but inconsistently with R_(o).R_(o) ranged 0.75%—1.25%and 1.05%—2.3%,respectively,corresponding to the main oil generation stage and gas generation stage of shale in-situ transformation.Thus a model to evaluate the remaining oil/gas yield with TOC and R_(o) was obtained.The TOC of shale suitable for in-situ conversion should be greater than 6%,whereas its R_(o) should be less than 1.0%.Shales with 0.75%(R_(o))could obtain the best economic benefit.The results provided a theoretical basis and evaluation methodology for predicting the hydrocarbon resources from in-situ conversion of shale and for the identification of the optimum“sweet spots”.The assessment of the Chang 7_(3) shale in the Ordos Basin indicated that the recoverable oil and gas resources from in-situ conversion of organic matters in shale are substantial,with oil and gas resources reaching approximately 450×10^(8) t and 30×10^(12)m^(3),respectively,from an area of 4.27×10^(4) km^(2).

Connotation and strategic role of in-situ conversion processing of shale oil underground in the onshore China

In-situ conversion processing (ICP) of shale oil underground at the depth ranging from 300 m to 3 000 m is a physical and chemical process caused by using horizontal drilling and electric heating technology, which converts heavy oil, bitumen and various organic matter into light oil and gas in a large scale, which can be called"underground refinery". ICP has several advantages as in CO2capture, recoverable resource potential and the quality of hydrocarbon output. Based on the geothermal evolution mechanism of organic materials established by Tissot et al., this study reveals that in the nonmarine organic-rich shale sequence, the amount of liquid hydrocarbon maintaining in the shale is as high as 25%in the liquid hydrocarbon window stage (R o less than 1.0%), and the unconverted organic materials (low mature-immature organic materials) in the shale interval can reach 40%to 100%. The conditions of organic-rich shale suitable for underground in-situ conversion of shale oil should be satisfied in the following aspects, TOC higher than 6%, R o ranging between 0.5%and 1%, concentrated thickness of organic-rich shale greater than 15 meters, burial depth less than 3 000 m, covering area bigger than 50 km2, good sealing condition in both up-and down-contacting sequences and water content smaller than 5%, etc. The shale oil resource in China’s onshore region is huge. It is estimated with this paper that the technical recoverable resource reaches 70-90 billion tons of oil and 60-65 trillion cubic meters of gas. The ICP of shale oil underground is believed to be a fairway to find big oil in the source kitchen in the near future. And it is also believed to be a milestone to keep China long-term stability of oil and gas sufficient supply by putting ICP of shale oil underground into real practice in the future.

Environmental Protection Legislation on China's Energy Development and In-situ Conversion

China's poor energy development and in-situ conversion legislation, environment laws and energy laws lead to a severe environmental issue in energy source. This paper uses comparison and logical methods to discuss Chapter 4 of Energy Law (Draft for Soliciting Opinions). Energy development is taken as a separate chapter; in-situ energy conversion is added to energy processing and conversion, common features are summarized to form general provisions and other provisions. According to respective characteristics of system for total amount control of energy development, performance guarantee system, environmental trust fund system, energy retaining system and environmental lien system, incorporate them into energy development, in-situ energy conversion and energy processing and conversion, in the hope of solving China's shortage of supply for environmental protection laws on energy development and in-situ conversion, responding to times of environmental protection, and optimizing China's Energy Law.

Kinetic simulation of hydrocarbon generation and its application to in-situ conversion of shale oil

The kinetic parameters of hydrocarbon generation are determined through experimental simulation and mathematical calculation using four typical samples selected from the Cretaceous Nenjiang Formation in the northwest of Songliao Basin,Chang 7 Member of Triassic Yanchang Formation in the southwest of Ordos Basin,Paleogene in the southwest of Qaidam Basin,and Lucaogou Formation of Jimusar Sag in the east of Junggar Basin.The results show that activation energy of hydrocarbon generation of organic matter is closely related to maturity and mainly ranges between 197 kJ/mol and 227 kJ/mol.On this basis,the temperature required for organic matter in shale to convert into oil was calculated.The ideal heating temperature is between 270℃and 300℃,and the conversation rate can reach 90%after 50-300 days of heating at constant temperature.When the temperature rises at a constant rate,the temperature corresponding to the major hydrocarbon generation period ranges from 225 to 350℃at the temperature rise rate of 1-150℃/month.In order to obtain higher economic benefits,it is suggested to adopt higher temperature rise rate(60-150℃/month).The more reliable kinetic parameters obtained can provide a basis for designing more reasonable scheme of in-situ heating conversion.

Oxygen functionalization-assisted anionic exchange toward unique construction of flower-like transition metal chalcogenide embedded carbon fabric for ultra-long life flexible energy storage and conversion

The metal-organic framework(MOF)derived Ni–Co–C–N composite alloys(NiCCZ)were“embedded”inside the carbon cloth(CC)strands as opposed to the popular idea of growing them upward to realize ultrastable energy storage and conversion application.The NiCCZ was then oxygen functionalized,facilitating the next step of stoichiometric sulfur anion diffusion during hydrothermal sulfurization,generating a flower-like metal hydroxysulfide structure(NiCCZOS)with strong partial implantation inside CC.Thus obtained NiCCZOS shows an excellent capacity when tested as a supercapacitor electrode in a three-electrode configuration.Moreover,when paired with the biomass-derived nitrogen-rich activated carbon,the asymmetric supercapacitor device shows almost 100%capacity retention even after 45,000 charge–discharge cycles with remarkable energy density(59.4 Wh kg^(-1)/263.8μWh cm^(–2))owing to a uniquely designed cathode.Furthermore,the same electrode performed as an excellent bifunctional water-splitting electrocatalyst with an overpotential of 271 mV for oxygen evolution reaction(OER)and 168.4 mV for hydrogen evolution reaction(HER)at 10 mA cm−2 current density along with 30 h of unhinged chronopotentiometric stability performance for both HER and OER.Hence,a unique metal chalcogenide composite electrode/substrate configuration has been proposed as a highly stable electrode material for flexible energy storage and conversion applications.

Two-photon live imaging of direct glia-to-neuron conversion in the mouse cortex

Over the past decade,a growing number of studies have reported transcription factor-based in situ reprogramming that can directly conve rt endogenous glial cells into functional neurons as an alternative approach for n euro regeneration in the adult mammalian central ne rvous system.Howeve r,many questions remain regarding how a terminally differentiated glial cell can transform into a delicate neuron that forms part of the intricate brain circuitry.In addition,concerns have recently been raised around the absence of astrocyte-to-neuron conversion in astrocytic lineage-tra cing mice.In this study,we employed repetitive two-photon imaging to continuously capture the in situ astrocyte-to-neuron conversion process following ecto pic expression of the neural transcription factor NeuroD1 in both prolife rating reactive astrocytes and lineage-tra ced astrocytes in the mouse cortex.Time-lapse imaging over several wee ks revealed the ste p-by-step transition from a typical astrocyte with numero us short,tapered branches to a typical neuro n with a few long neurites and dynamic growth cones that actively explored the local environment.In addition,these lineage-converting cells were able to migrate ra dially or to ngentially to relocate to suitable positions.Furthermore,two-photon Ca2+imaging and patch-clamp recordings confirmed that the newly generated neuro ns exhibited synchronous calcium signals,repetitive action potentials,and spontaneous synaptic responses,suggesting that they had made functional synaptic connections within local neural circuits.In conclusion,we directly visualized the step-by-step lineage conversion process from astrocytes to functional neurons in vivo and unambiguously demonstrated that adult mammalian brains are highly plastic with respect to their potential for neuro regeneration and neural circuit reconstruction.

Dealuminated Hβ zeolite for selective conversion of fructose to furfural and formic acid

The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.

1.42-fold enhancement of formate selectivity by linker conversion on the Zn-based metal organic framework catalyst

Electro-reduction of carbon dioxide(ERCO_(2)) is considered an effective method to alleviate the greenhouse effect and produce value-added chemicals.Achieving the dominant selectivity of Zn-based catalysts for formate remains a challenge.In this article,the ZnIn-E_(12) catalyst is successfully prepared by solvent assisted ligand exchange(SALE) method to convert organic ligands,achieving a Faradaic efficiency of 72.28% for formate at-1.26 V vs.RHE(V_(RHE)),which is 1.42 times higher than the original catalyst.Evidence shows that the successful conversion of organic ligands can transform the catalyst from the original large size polyhedron to cross-linked network of particles with a diameter of about 30 nm.The increased specific surface area can expose more active sites and facilitate the electrocatalytic conversion of CO_(2) to formate.This work is expected to provide inspiration for the regulation of formate selectivity and catalyst size in Zn-based catalysts.

Intrinsic polarization conversion and avoided-mode crossing in X-cut lithium niobate microrings

Compared with well-developed free space polarization converters, polarization conversion between TE and TM modes in the waveguide is generally considered to be caused by shape birefringence, like curvature, morphology of waveguide cross section and scattering. Here, we study the polarization conversion mechanism in 1-THz-FSR X-cut lithium niobate microrings with multiple-resonance condition, that is the conversion can be implemented by birefringence of waveguides,which will also introduce an avoided-mode crossing. In the experiment, we find that this mode crossing results in severe suppression of one sideband in local nondegenerate four-wave mixing and disrupts the cascaded four-wave mixing on this side. Simultaneously, we propose one two-dimensional method to simulate the eigenmodes(TE and TM) in X-cut microrings, and the mode crossing point. This work will provide one approach to the design of polarization converters and simulation for monolithic photonics integrated circuits, and may be helpful to the studies of missed temporal dissipative soliton formation in X-cut lithium niobate rings.

Insight into structure evolution of carbon nitrides and its energy conversion as luminescence

A series of carbon nitride(CN)materials represented by graphitic carbon nitride(g-C3N4)have been widely used in bioimaging,biosensing,and other fields in recent years due to their nontoxicity,low cost,and high luminescent quantum efficiency.What is more attractive is that the luminescent properties such as wavelength and intensity can be regulated by controlling the structure at the molecular level.Hence,it is time to summarize the related research on CN structural evolution and make a prospect on future developments.In this review,we first summarize the research history and multiple structural evolution of CN.Then,the progress of improving the luminescence performance of CN through structural evolution was discussed.Significantly,the relationship between CN structure evolution and energy conversion in the forms of photoluminescence,chemiluminescence,and electrochemiluminescence was reviewed.Finally,key challenges and opportunities such as nanoscale dispersion strategy,luminous efficiency improving methods,standardization evaluation,and macroscopic preparation of CN are highlighted.

Reversible solid-liquid conversion enabled by self-capture effect for stable non-flow zinc-bromine batteries

Non-flow aqueous zinc-bromine batteries without auxiliary components(e.g.,pumps,pipes,storage tanks)and ion-selective membranes represent a cost-effective and promising technology for large-scale energy storage.Unfortunately,they generally suffer from serious diffusion and shuttle of polybromide(Br^(-),Br^(3-))due to the weak physical adsorption between soluble polybromide and host carbon materials,which results in low energy efficiency and poor cycling stability.Here,we develop a novel self-capture organic bromine material(1,10-bis[3-(trimethylammonio)propyl]-4,4'-bipyridinium bromine,NVBr4)to successfully realize reversible solid complexation of bromide components for stable non-flow zinc-bromine battery applications.The quaternary ammonium groups(NV^(4+)ions)can effectively capture the soluble polybromide species based on strong chemical interaction and realize reversible solid complexation confined within the porous electrodes,which transforms the conventional“liquid-liquid”conversion of soluble bromide components into“liquid-solid”model and effectively suppresses the shuttle effect.Thereby,the developed non-flow zinc-bromide battery provides an outstanding voltage platform at 1.7 V with a notable specific capacity of 325 mAh g^(-1)NVBr4(1 A g^(-1)),excellent rate capability(200 mAh g^(-1)NVBr4 at 20 A g^(-1)),outstanding energy density of 469.6 Wh kg^(-1)and super-stable cycle life(20,000 cycles with 100%Coulombic efficiency),which outperforms most of reported zinc-halogen batteries.Further mechanism analysis and DFT calculations demonstrate that the chemical interaction of quaternary ammonium groups and bromide species is the main reason for suppressing the shuttle effect.The developed strategy can be extended to other halogen batteries to obtain stable charge storage.

Novel high-voltage cathode for aqueous zinc ion batteries:Porous K_(0.5)VOPO_(4)·1.5H_(2)O with reversible solid-solution intercalation and conversion storage mechanism

Cathode materials that possess high output voltage,as well as those that can be mass-produced using facile techniques,are crucial for the advancement of aqueous zinc-ion battery(ZIBs)applications,Herein,we present for the first time a new porous K_(0.5)VOPO_(4)·1.5H_(2)O polyanionic cathode(P-KIVP)with high output voltage(above 1.2 V)that can be manufactured at room temperature using straightforward coprecipitation and etching techniques.The P-KVP cathode experiences anisotropic crystal plane expansion via a sequential solid-solution intercalation and phase co nversion pathway throughout the Zn^(2+)storage process,as confirmed by in-situ synchrotron X-ray diffraction and ex-situ X-ray photoelectron spectroscopy.Similar to other layered vanadium-based polyanionic materials,the P-KVP cathode experiences a progressive decline in voltage during the cycle,which is demonstrated to be caused by the irreversible conversion into amorphous VO_(x).By introducing a new electrolyte containing Zn(OTF)_(2) to a mixed triethyl phosphate and water solution,it is possible to impede this irreversible conversion and obtain a high output voltage and longer cycle life by forming a P-rich cathode electrolyte interface layer.As a proof-of-concept,the flexible fiber-shaped ZIBs based on modified electrolyte woven into a fabric watch band can power an electronic watch,highlighting the application potential of P-KVP cathode.

Options and survival benefits of conversion therapy for unresectable hepatocellular carcinoma

In the study by Wu et al,patients with unresectable hepatocellular carcinoma were subjected to transarterial chemoembolization(TACE)as a conversion therapy in order to render their tumors suitable for resection.A nomogram was devised and shown to be effective in predicting the survival of these patients.Generalization of the results,however,is questionable since the study subjects consisted of patients who had resection after TACE while excluding patients with the same disease but not suitable for TACE.Immunotherapy can be considered to be an option for conversion therapy.However,markers for determining responses to a conversion therapy and for guiding the decision between TACE and sequential immunotherapy have been lacking.The question of whether effective conversion therapy can truly enhance overall survival remains unanswered.

A review on electrocatalytic CO_(2) conversion via C-C and C-N coupling

Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.

Pathologically successful conversion hepatectomy for advanced giant hepatocellular carcinoma after multidisciplinary therapy:A case report and review of literature

BACKGROUND Hepatocellular carcinoma(HCC)is one of the leading causes of death due to its complexity,heterogeneity,rapid metastasis and easy recurrence after surgical resection.We demonstrated that combination therapy with transcatheter arterial chemoembolization(TACE),hepatic arterial infusion chemotherapy(HAIC),Epclusa,Lenvatinib and Sintilimab is useful for patients with advanced HCC.CASE SUMMARY A 69-year-old man who was infected with hepatitis C virus(HCV)30 years previously was admitted to the hospital with abdominal pain.Enhanced computed tomography(CT)revealed a low-density mass in the right lobe of the liver,with a volume of 12.9 cm×9.4 cm×15 cm,and the mass exhibited a“fast-in/fast-out”pattern,with extensive filling defect areas in the right branch of the portal vein and an alpha-fetoprotein level as high as 657 ng/mL.Therefore,he was judged to have advanced HCC.During treatment,the patient received three months of Epclusa,three TACE treatments,two HAIC treatments,three courses of sintilimab,and twenty-one months of lenvatinib.In the third month of treatment,the patient developed severe side effects and had to stop immunotherapy,and the Lenvatinib dose had to be halved.Postoperative pathological diagnosis indicated a complete response.The patient recovered well after the operation,and no tumor recurrence was found.CONCLUSION Multidisciplinary conversion therapy for advanced enormous HCC caused by HCV infection has a significant effect.Individualized drug adjustments should be made during any treatment according to the patient's tolerance to treatment.

Conversion therapy of a giant hepatocellular carcinoma with portal vein thrombus and inferior vena cava thrombus:A case report and review of literature

BACKGROUND The prognosis of hepatocellular carcinoma(HCC)combined with portal and hepatic vein cancerous thrombosis is poor,for unresectable patients the combination of targeted therapy and immune therapy was the first-line recommended treatment for advanced HCC,with a median survival time of only about 2.7-6 months.In this case report,we present the case of a patient with portal and hepatic vein cancerous thrombosis who achieved pathologic complete response after conversion therapy.CASE SUMMARY In our center,a patient with giant HCC combined with portal vein tumor thrombus and hepatic vein tumor thrombus was treated with transcatheter arterial chemoembolization(TACE),radiotherapy,targeted therapy and immunotherapy,and was continuously given icaritin soft capsules for oral regulation.After 7 months of conversion therapy,the patient's tumor shrank and the tumor thrombus subsided significantly.The pathology of surgical resection was in complete remission,and there was no progression in the postoperative follow-up for 7 months,which provided a basis for the future strategy of combined conversion therapy.CONCLUSION In this case,atezolizumab,bevacizumab,icaritin soft capsules combined with radiotherapy and TACE had a good effect.For patients with hepatocellular carcinoma combined with hepatic vein/inferior vena cava tumor thrombus,adopting a high-intensity,multimodal proactive strategy under the guidance of multidisciplinary team(MDT)is an important attempt to break through the current treatment dilemma.

Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass

Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.

Enabling heterogeneous catalysis to achieve carbon neutrality: Directional catalytic conversion of CO_(2) into carboxylic acids

The increase in anthropogenic carbon dioxide(CO_(2))emissions has exacerbated the deterioration of the global environment,which should be controlled to achieve carbon neutrality.Central to the core goal of achieving carbon neutrality is the utilization of CO_(2) under economic and sustainable conditions.Recently,the strong need for carbon neutrality has led to a proliferation of studies on the direct conversion of CO_(2) into carboxylic acids,which can effectively alleviate CO_(2) emissions and create high-value chemicals.The purpose of this review is to present the application prospects of carboxylic acids and the basic principles of CO_(2) conversion into carboxylic acids through photo-,electric-,and thermal catalysis.Special attention is focused on the regulation strategy of the activity of abundant catalysts at the molecular level,inspiring the preparation of high-performance catalysts.In addition,theoretical calculations,advanced technologies,and numerous typical examples are introduced to elaborate on the corresponding process and influencing factors of catalytic activity.Finally,challenges and prospects are provided for the future development of this field.It is hoped that this review will contribute to a deeper understanding of the conversion of CO_(2) into carboxylic acids and inspire more innovative breakthroughs.

The Conversion of Non-Dispersed Polymers into Low-Potassium Anti-Collapse Drilling Fluids

Different drillingfluid systems are designed according to mineral composition,lithology and wellbore stability of different strata.In the present study,the conversion of a non-dispersed polymer drillingfluid into a low potas-sium anti-collapsing drillingfluid is investigated.Since the two drillingfluids belong to completely different types,the key to this conversion is represented by new inhibitors,dispersants and water-loss agents by which a non-dispersed drillingfluid can be turned into a dispersed drillingfluid while ensuring wellbore stability and reason-able rheology(carrying sand—inhibiting cuttings dispersion).In particular,the(QYZ-1)inhibitors and(FSJSS-2)dispersants are used.The former can inhibit the hydration expansion capacity of clay,reduce the dynamic shear force and weaken the viscosity;the latter can improve the sealing effect and reduce thefiltrate loss.The results have shown that after adding a reasonable proportion of these substances(QYZ-1:FSJSS-2)to the non-dispersed polymer drillingfluid,while the apparent viscosity,plastic viscosity,structural viscosity andfluidity index under-went almost negligible changes,the dynamic plastic ratio increased,and thefiltration loss decreased significantly,thereby indicating good compatibility.According to the tests(conducted in the Leijia area),the density was 1.293 g/cm3,and after standing for 24 h,the SF(static settlement factor)was 0.51.Moreover,thefiltration loss was reduced to 4.0 mL,the rolling recovery rate reached 96.92%,with excellent plugging and anti-collapse performances.