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Co2C nanostructures play a vital role in selective production of value-added chemicals via syngas conversion. Recent advances in Co2C-based nanocatalysts for Fischer–Tropsch to olefin reactions are summarized in this feature article.

Alkaline-earth metal promoted CoMn catalysts with higher surface basicity benefit the carburization of CoMn oxides to form more Co2C nanoprisms for olefin formation, especially for long-chain olefins.

The RhK/Mo2C catalyst exhibited remarkable selectivity for higher alcohols synthesis from syngas under mild reaction conditions owing to the interface sites between Rh and Mo2C promoted by K, which greatly facilitated CO insertion.

Selective oxidation of methane to oxygenates using low-cost and environment-friendly molecular oxygen (O2) under mild reaction conditions is a promising strategy but still remains grand challenge. It is of great importance to accelerate the activation of O2 to generate highly active oxygen species, such as hydroxyl peroxide and hydroxyl species to improve catalytic performance for selective oxidation of methane. Selective oxidation of methane using O2 by coupling in-situ generation of hydrogen peroxide via tandem catalysis ensures the easy formation of active oxygen species for methane activation, leading to high oxygenates productivity under mild conditions. In this concept, we summarized the recent progresses for selective oxidation of methane to oxygenates using O2 based on tandem catalysis by coupling with in-situ generation of hydrogen peroxide. The remaining challenges and future perspectives for selective oxidation of methane to oxygenates via tandem catalysis were also proposed.

Na-promoted colloidal Ru NPs exhibit high efficiency for aqueous-phase FTS to produce oxygenates from syngas.

A multifunctional catalyst composed of CoMn and CuZnAlZr oxides can dramatically increase higher-alcohol selectivity. However, the role of Cu-based components and catalytic mechanism are still uncl...

Syngas conversion is a key platform for efficient utilization of various carbon-containing resources including coal, natural gas, biomass, organic wastes, and even CO2. One of the most classic routes for syngas conversion is Fischer-Tropsch synthesis (FTS), which is already available for commercial application. However, it still remains a grand challenge to tune the product distribution from paraffins to value-added chemicals such as olefins and higher alcohols. Breaking the selectivity limitation of the Anderson-Schulz-Flory (ASF) distribution has been one of the hottest topics in syngas chemistry.Metallic Co0 is a well-known active phase for Co-catalyzed FTS, and the products are dominated by paraffins with a small amount of chemicals (i.e., olefins or alcohols). Specifically, a cobalt carbide (Co2C) phase is typically viewed as an undesirable compound that could lead to deactivation with low activity and high methane selectivity. Although iron carbide (FexC) can produce olefins with selectivity up to ∼60%, the fraction of methane is still rather high, and the required high reaction temperature (300-350 °C) typically causes coke deposition and fast deactivation. Recently, we discovered that Co2C nanoprisms with preferentially exposed facets of (020) and (101) can effectively produce olefins from syngas conversion under mild reaction conditions with high selectivity. The methane fraction was limited within 5%, and the product distribution deviated greatly from ASF statistic law. The catalytic performances of Co2C nanoprisms are completely different from that reported for the traditional FT process, exhibiting promising potential industrial application.This Account summarizes our progress in the development of Co2C nanoprisms for Fischer-Tropsch synthesis to olefins (FTO) with remarkable efficiencies and stability. The underlying mechanism for the observed unique catalytic behaviors was extensively explored by combining DFT calculation, kinetic measurements, and various spectroscopic and microscopic investigation. We also emphasize the following issues: particle size effect of Co2C, the promotional effect of alkali and Mn promoters, and the role of metal-support interaction (SMI) in fabricating supported Co2C nanoprisms. Specially, we briefly review the synthetic methods for different Co2C nanostructures. In addition, Co2C can also be applied as a nondissociative adsorption center for higher alcohol synthesis (HAS) via syngas conversion. We also discuss the construction of a Co0/Co2C interfacial catalyst for HAS and demonstrate how to tune the reaction network and strengthen CO nondissociative adsorption ability for efficient production of higher alcohols. We believe that the advances in the development of Co2C nanocatalysts described here present a critic step to produce chemicals through the FTS process.

A green route for one−pot synthesis of acetals by tandem hydroformylation−acetalization of olefins using supported Rh−based catalysts was developed. Experimental results demonstrated that suitable Rh loading (1 wt%) with appropriate reaction temperature (120 °C) and reaction time (8 h) were favorable for the formation of acetals, and a high acetals selectivity of 94.6% was achieved. More importantly, the selectivity to valuable linear products was enhanced in this tandem catalysis. Based on the catalytic mechanism study, highly dispersed RhOx nanoparticles and abundant acid sites on the supports were responsible for the hydroformylation and acetalization, respectively. One-pot synthesis of acetals directly from olefins with high selectivity was achieved over heterogeneous bifunctional catalysts via tandem hydroformylation-acetalization.

Selectivity control of nitrobenzene hydrogenation remains a great challenge, and it is desirable to develop a green and highly efficient catalytic route toward value-added metastable intermediate products. Herein, we reported that isolated Ru single atoms coordinated with oxygen atoms in CeO2 (Ru-SAs/CeO2) can achieve chemoselective hydrogenation of nitrobenzene to azoxybenzene with a selectivity of 88.2% in a continuous flow reactor using H2 without using any bases or expensive organic reducing agents, while 82.7% aniline selectivity was obtained by Ru nanoparticles. We demonstrated that the unique coordinated structure between Ru single atoms and O atoms preferentially controls the reaction route toward the coupling of nitrosobenzene and phenylhydroxylamine intermediates to form azoxybenzene while greatly suppressing over-hydrogenation. The present work provides an efficient strategy to regulate the reaction pathway of nitrobenzene hydrogenation with a green and industry-friendly process by designing highly dispersed Ru single atoms.

A Ru single-atom (Ru SA) catalyst supported on activated carbon was adopted to synthesize 3-pentanone with 83.3% selectivity via heterogeneous ethylene hydroformylation, while 52.1% ethane selectivity was obtained for Ru nanoparticles (Ru NPs). The atomically dispersed Ru species with oxidation state (Ruδ+) and Ru-C4O coordination structure were identified as the active sites for efficient C–C coupling to generate 3-pentanone, while metallic Ru nanoparticles exhibited high activity for ethylene hydrogenation to ethane. Density functional theory (DFT) calculation revealed that the energy barrier of the direct coupling of C2H5CO* with C2H5* to form 3-pentanone on Ru SA was much lower than that on Ru NPs. As a result, the formation of 3-pentanone over Ru SA was more favourable than propanal, which was admittedly generated via coupling of C2H5CO* and H*. This strategy may provide a potential green route for the one-pot synthesis of 3-pentanone with high atomic economy.

Selective oxidation of methane to oxygenates with O

Microseismic data and production logs in our study area have confirmed asymmetric developments of the stimulation rock volume in shales with respect to the wellbore, while severe casing deformation problems have been reported frequently in this area. Here, we propose a systematic methodology to investigate the possibility of casing failure due to strong shear stresses induced by asymmetric stimulated zones. A mechanical earth modeling (MEM) is initially performed to determine the in situ stress field in the target layer before fracturing by incorporating the existing geological features, logging data, and rock anisotropy. Then, we provide a computationally cheap and efficient estimation for stimulated rock volume of each stage by considering the possible overlaps in adjacent stages based on the clustered microseismic clouds. Using this approach, a reservoir‐scale 3D coupled model tied to a more detailed near‐wellbore part incorporating the casing string and the cement sheath is established to simulate the development of stimulation zones, stress redistribution, and their impacts on casing deformation as each stage fracturing treatment chronologically goes on. Our numerical results indicate that continuous redistribution and re‐orientation of stress field near the borehole are tracked during pumping the treatment which reveals formation of some pockets of tensile stresses along and around the wellbore. Asymmetric stimulations are observed to generate strong shear stress on the suspended casing. These shear forces result in deflection and S‐shape deformations accompanied with cross‐sectional ovality. Some regions receive repeating treatments, which results in intensifying formation stress heterogeneity and worsen casing deformation severity. The calculation results are compared with measurement of multi‐finger imaging tool (MIT) to validate the accuracy. Our analysis has indicated that simply increasing the flexural strength by increasing thickness of casing cannot radically mitigate casing deformation problems. This paper presents a novel workflow for a coupled modeling of casing deformation during hydraulic fracturing operations, while current modeling efforts assume symmetric bi‐wing fracture geometries.

Cobalt carbide (Co2C) exhibits strong facet effect for Fischer-Tropsch to olefins (FTO) reaction. Herein, we report that the facet proportion of Co2C nanostructures can be tuned effectively by incorporating and altering the Mn content in the CoMn composite oxide as catalyst precursor. With the addition of Mn promoter, the Co2C nanoprisms with exposed (020) and (101) facets are generated under reaction conditions. In addition, the facet proportion of Co2C(020) facet can be effectively improved by enhancing the Mn/Co ratio. With the increase of facet proportion of Co2C(020)/Co2C(101) ratio, the as-obtained Co2C nanoprisms exhibit higher intrinsic activity and lower methane selectivity during the syngas conversion process. Kinetic experiments also demonstrate that the apparent activation energy (E-a) for CO conversion is significantly reduced as increasing the facet proportion of Co2C(020). This work provides a simple and feasible way to tune the exposed facet proportion for the rational design of Co2C nanocatalyst for FTO reaction.

Direct synthesis of aromatics from syngas was investigated by coupling Fischer–Tropsch to olefins (FTO) reaction and aromatization process. The CoMnAl composite oxides enabled the formation of olef...

Cobalt carbide (Co2C) nanoprisms derived from CoMn composite oxides exhibit promising catalytic performance for Fischer–Tropsch to olefins (FTO) synthesis via H2-lean syngas conversion, but with ne...

In order to prevent well leakage in high temperature and high pressure (HTHP) wells, pressure test is a very important leak prevention operation that causes artificial high-pressure environment in wellbore. However, failure of wellbore equipment due to harsh condition is a common problem that brings great economic losses. Ram blowout preventer (BOP) is an important component of wellbore integrity, which is subjected to heavy loads from the test gas and the push rod during the pressure test. Therefore, the serious stress concentration of ram BOP induced by heavy loads and complex geometry is a major reason of fracture. Hence, the focus is to find out the fracture mechanism of ram BOP with experimental method and finite elements (FE) model in this paper. A series of damage inspection and strength test of ram BOP is carried out to find out the fracture characteristics. Based on detection information, FE analysis is conducted to analysis stress distribution and fracture reason of ram BOP. The results show that the maximum stress exceeds the yield strength (705 MPa) of the material under the actual working condition. Serious stress concentration at the notch root of the ram BOP can be easily caused by test pressure (from test gas) and contact pressure (from push rod). Both experimental method and FE analysis show the characteristics of ductile fracture obviously. Stress concentration at notch root is very sensitive to the test pressure. The work presented in this paper can provide basis and reference for preventing failure of ram BOP and improve efficiency and production.

Selective synthesis of higher oxygenates (linear α-alcohols and α-aldehydes, C 2 + OH) from syngas is highly attractive but remains challenging owing to the low C 2 + OH selectivity and low catalytic stability. Herein we introduce a multifunctional catalyst composed of CoMn and CuZnAlZr oxides that dramatically increased the oxygenates selectivity to 58.1 wt %, where more than 92.0 wt % of the produced oxygenates are C 2 + OH. Notably, the total selectivity to value-added chemicals including oxygenates and olefins reached 80.6 wt % at CO conversion of 29.0 % with high stability. The appropriate component proximity can effectively suppress the formation of the undesired C1 products, and the selectively propulsion of reaction network by synergetic effect of different components contributes to the enhanced selectivity to higher oxygenates. This work provides an alternative strategy for the rational design of new catalysts for direct conversion of syngas into higher oxygenates with co-production of olefins.

Direct production of olefins via syngas conversion over a Co2C-based catalyst was investigated in a slurry bed reactor (SBR). It was found that the total selectivities to olefins and oxygenates reached 88.8C% at a CO conversion of 29.5% at 250 °C, 5 bar and H2/CO = 0.5. The hydrocarbon distribution greatly deviated from the classical Anderson–Schulz–Flory (ASF) distribution, with only 2.6C% methane selectivity was obtained. XRD and TEM characterization verified that the Co2C nanoprisms with special exposed facts of (101) and (020) constitutes the Fischer–Tropsch to olefins (FTO) active site. The catalytic activity increased gradually with rising the reaction temperature, while the product distribution almost kept unchanged under various reaction condition in SBR. Compared to the reaction in FBR, the Co2C-based catalyst exhibited relative better catalytic performance during FTO process in SBR. Specifically, a higher CO conversion, a lower methane selectivity and a higher total selectivities to olefins and oxygenates were achieved in SBR. In addition, the catalyst can be in situ reduced in slurry bed reactor at mild temperature (300 °C) and no obvious deactivation was found within nearly 100 h time-on-stream, which suggested a promising route for the direct production of olefins via syngas in industrial application.

Co2C-based catalysts with SiO2, γ-Al2O3, and carbon nanotubes (CNTs) as support materials were prepared and evaluated for the Fischer-Tropsch to olefin (FTO) reaction. The combination of catalytic performance and structure characterization indicates that the cobalt-support interaction has a great influence on the Co2C morphology and catalytic performance. The CNT support facilitates the formation of a CoMn composite oxide during calcination, and Co2C nanoprisms were observed in the spent catalysts, resulting in a product distribution that greatly deviates from the classical Anderson-Schulz-Flory (ASF) distribution, where only 2.4 C% methane was generated. The Co3O4 phase for SiO2- and γ-Al2O3-supported catalysts was observed in the calcined sample. After reduction, CoO, MnO, and low-valence CoMn composite oxide were generated in the γ-Al2O3-supported sample, and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst. However, only separated phases of CoO and MnO were found in the reduced sample supported by SiO2, and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms. The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C% and 12.0 C% of the γ-Al2O3- and SiO2-supported catalysts, respectively. These results suggest that a relatively weak cobalt-support interaction is necessary for the formation of the CoMn composite oxide during calcination, which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.

The size effect of the CoxMn1−xO precursor on the formation of Co2C nanoprisms and the structure–performance relationship for the Fischer–Tropsch to olefins (FTO) reaction was investigated. CoxMn1−xO precursors with different sizes from 6.5 nm to 16.7 nm were fabricated by calcination at different temperatures. The CoxMn1−xO with small size possessed high concentration of oxygen vacancies, which promoted the dissociation of CO to form active C* species, and more Co2C nanoprisms with small size could be generated. In addition, the catalytic performance also changed with the size of the precursor. The olefin formation rate significantly increased from 3.36 to 12.48 μmol gCoxMn1−xO−1 h−1 as the CoxMn1−xO size decreased from 16.7 to 6.5 nm. This work clearly elucidates the size effect of the CoxMn1−xO precursor on the structure–performance relationship and may provide a practical and simple strategy to fabricate highly efficient CoMn catalysts for the FTO reaction.

Cu single atoms embedded in the C3N4 (Cu-SAs/C3N4) matrix exhibited high activity with 95% oxygenate selectivity for the direct conversion of methane at ambient temperature. The presence of abundant anchoring sites in C3N4 led to highly dispersed Cu–N4 moieties, which were suggested to be the underlying active sites for methane conversion.

According to the tubing string failure statistics in the oilfield, fatigue crack of tubing joint thread in high temperature high pressure (HTHP) ultradeep gas wells remains a problem because it can cause tubing strength degradation, tubing fracture failure, well workover, and even well abandonment. In order to obtain a better understanding of tubing thread fatigue and quantify the fatigue life of tubing joint thread in HTHP ultradeep wells, experimental study, elastic–plastic mechanical simulation, and multi-axial fatigue calculation are carried out in this paper. Based on the similarity theory, the vibration mechanical testing device of the tubing string is designed, and the multi-axial load of the tubing joint thread in the actual working condition is obtained. Meanwhile, tubing joint BX1 thread model is established with ansys software, and the stress distribution of tubing joint thread is analyzed on the boundary condition acquired from experiments of vibration test of tubing string. Finally, according to the multi-axial fatigue theory, the fatigue life prediction value of the tubing thread made of Super 13Cr110 and Super 15Cr125 is compared and analyzed. The work presented in this paper can provide theoretical method and technological basis for the study on the frequent failure mechanism of tubing joint thread in HTHP ultradeep gas wells.

The fracture toughness (KIC) of high strength casing steel (1130 MPa) has been determined by a three-point-bend specimen. Three specimens with thicknesses of 5 mm, 8 mm and 10 mm, respectively have been used to observe the effect of thickness on the fracture toughness of steel. The analytical formula of the relationship between the fracture toughness and material thickness of high strength casing (1130 MPa) is proposed based on the energy theory and on linear elastic mechanics. The values of fracture toughness, K, measured by three thicknesses of parent metals are combined with the quantitative model of the relationship between fracture toughness and specimen thickness. The material constant (and κ) are calculated by using the least squares method. Furthermore, an analytic formula for the relationship between fracture toughness and specimen thickness is proposed which allows for the calculation of the KIC value. Plane-strain fracture toughness (KIC = 133.94 MPa × m1/2) is a fixed value only if the thickness of the specimen exceeds 43 mm. Fracture toughness values of different thicknesses of high strength casing are derived by fracture toughness tests of several thicknesses based on the model in question in order to save manpower and material resources. This method is also significant for measuring the fracture toughness of other OCTG, since their thicknesses do not meet the requirement of the standard test methods. For the present, it provides general methods and reference rules for obtaining the KIC of other metallic OCTG.