Zeolite Membrane-Based Low-Temperature Dehydrogenation of a Liquid Organic Hydrogen Carrier: A Key Step in the Development of a Hydrogen Economy.

Methylcyclohexane (MCH) dehydrogenation is an equilibrium-limited reaction that requires high temperatures (>300 °C) for complete conversion. However, high-temperature operation can degrade catalytic activity and produce unwanted side products. Thus, a hybrid zeolite membrane (Z) is prepared on the inner surface of a tubular support and used it as a wall in a membrane reactor (MR) configuration. Pt/C catalysts is packed diluted with quartz sand inside the Z-coated tube and applied the MR for MCH dehydrogenation at low temperatures (190-250 °C). Z showed a remarkable H2-permselectivity in the presence of both toluene and MCH, yielding separation factors over 350. The Z-based MR achieved higher MCH conversion (75.3% ± 0.8% at 220 °C) than the conventional packed-bed reactor (56.4% ± 0.3%) and the equilibrium state (53.2%), owing to the selective removal of H2 through Z. In summary, the hybrid zeolite MR enhances MCH dehydrogenation at low temperatures by overcoming thermodynamic limitations and improves the catalytic performance and product selectivity of the reaction.

Degradation potential and pathways of methylcyclohexane by bacteria derived from Antarctic surface water.

Cycloalkanes pose a tremendous environmental risk due to their high concentration in petroleum hydrocarbons and hazardous effects to organisms. Numerous studies have documented the biodegradation of acyclic alkanes and aromatic hydrocarbons. However, insufficient attention has been paid to studies on the microbial degradation of cycloalkanes, which might be closely linked to psychrophilic microbes derived from low-temperature habitats. Here we show that endemic methylcyclohexane (MCH, an abundant cycloalkane species in oil) consumers proliferated in seawater samples derived from the Antarctic surface water (AASW). The MCH-consuming bacterial communities derived from AASW exhibited a distinct species composition compared with their counterparts derived from other cold-water habitats. We also probed Colwellia and Roseovarius as the key active players in cycloalkane degradation by dilution-to-extinction-based incubation with MCH as sole source of carbon and energy. Furthermore, we propose two nearly complete MCH degradation pathways, lactone formation and aromatization, concurrently in the high-quality metagenome-assembled genomes of key MCH consumer Roseovarius. Overall, we revealed that these Antarctic microbes might have strong interactions that enhance the decomposition of more refractory hydrocarbons through complementary degradation pathways.

Occurrence and distribution of cyclic-alkane-consuming psychrophilic bacteria in the Yellow Sea and East China Sea.

Cyclic alkanes (c-alkanes) are toxic compounds that are abundant in subsurface oil reservoirs and spilled condensate; hence, their environmental risk is significant. Although numerous studies have focused on the decomposition of other compound classes, e.g., acyclic alkanes and aromatic hydrocarbons, very little is known about the biodegradation of c-alkanes in the marine environment. Here, we enriched methylcyclohexane (MCH)-degrading bacteria derived from the cold bottom water (10-20 °C) of China's marginal seas in summer and characterized the changes to the bacterial community using high-throughput amplicon sequencing. MCH-consuming bacteria failed to grow from the warmer surface water (25-29 °C) in the same geographic sites and seasons. Notably, MCH-consuming communities derived from the cold bottom water in the Yellow Sea exhibit distinct structures compared to the other treatments. Furthermore, almost all dominant species in this setting appear to be specifically adapted to deeper cold water as indicated by significantly negative correlations to temperature (P < 0.01). From these results, we proposed that the biodegradation of MCH is effectively limited to the colder waters (10-20 °C) of China's marginal seas, with uncultured psychrophiles acting as the key taxa for MCH decomposition. Overall, this study indicates key functions for uncultivated microbes in the marine environment.

Chemically synthesized hydrogen fuel from reaction of methylcyclohexane over nanoporous heterogeneous catalysts.

Nanoporous oxides have been prepared, as hosts for the encapsulation of metal nanoparticles, and tested for the catalytic decomposition of methylcyclohexane (MCH) to produce hydrogen gas as a potential fuel source. The aim of the work is to test a range of mixed metal nanoparticle catalysts in the MCH to hydrogen reaction. The work investigates the use of a range of inexpensive metals in conjunction with traditional precious metal e.g. Pt. The objectives of work are prepared nanoporous oxides, comprising MCM- and SBA-types using established methods. Encapsulated metal nanoparticles within the pores of nanoporous oxide. Catalysts have been characterized fully to confirm porosity, surface area, and nanoparticle dispersion. The activity of catalytic of the various nanoporous materials was determined in the MCH to hydrogen reaction, and kinetic models developed from the associated experimental findings.

Recent Advances in Catalysts and Membranes for MCH Dehydrogenation: A Mini Review.

Methylcyclohexane (MCH), one of the liquid organic hydrogen carriers (LOHCs), offers a convenient way to store, transport, and supply hydrogen. Some features of MCH such as its liquid state at ambient temperature and pressure, large hydrogen storage capacity, its well-known catalytic endothermic dehydrogenation reaction and ease at which its dehydrogenated counterpart (toluene) can be hydrogenated back to MCH and make it one of the serious contenders for the development of hydrogen storage and transportation system of the future. In addition to advances on catalysts for MCH dehydrogenation and inorganic membrane for selective and efficient separation of hydrogen, there are increasing research interests on catalytic membrane reactors (CMR) that combine a catalyst and hydrogen separation membrane together in a compact system for improved efficiency because of the shift of the equilibrium dehydrogenation reaction forwarded by the continuous removal of hydrogen from the reaction mixture. Development of efficient CMRs can serve as an important step toward commercially viable hydrogen production systems. The recently demonstrated commercial MCH-TOL based hydrogen storage plant, international transportation network and compact hydrogen producing plants by Chiyoda and some other companies serves as initial successful steps toward the development of full-fledged operation of manufacturing, transportation and storage of zero carbon emission hydrogen in the future. There have been initiatives by industries in the development of compact on-board dehydrogenation plants to fuel hydrogen-powered locomotives. This review mainly focuses on recent advances in different technical aspects of catalytic dehydrogenation of MCH and some significant achievements in the commercial development of MCH-TOL based hydrogen storage, transportation and supply systems, along with the challenges and future prospects.

Bench-Scale Membrane Reactor for Methylcyclohexane Dehydrogenation Using Silica Membrane Module.

Methylcyclohexane-toluene system is one of the most promising methods for hydrogen transport/storage. The methylcyclohexane dehydrogenation can be exceeded by the equilibrium conversion using membrane reactor. However, the modularization of the membrane reactor and manufacturing longer silica membranes than 100 mm are little developed. Herein, we have developed silica membrane with practical length by a counter-diffusion chemical vapor deposition method, and membrane reactor module bundled multiple silica membranes. The developed 500 mm-length silica membrane had high hydrogen permselective performance (H2 permeance > 1 × 10-6 mol m-2 s-1 Pa-1, H2/SF6 selectivity > 10,000). In addition, we successfully demonstrated effective methylcyclohexane dehydrogenation using a flange-type membrane reactor module, which was installed with 6 silica membranes. The results indicated that conversion of methylcyclohexane was around 85% at 573 K, whereas the equilibrium conversion was 42%.

Surface Protective and Catalytic Layer Consisting of RuO2 and Pt for Stable Production of Methylcyclohexane Using Solar Energy.

A particulate (ZnSe)0.85(CuIn0.7Ga0.3Se2)0.15 (ZnSe:CIGS)-based photocathode modified with RuO2 and Pt species exhibited improved photoelectrochemical activities and stability for hydrogen evolution as well as production of methylcyclohexane, the promising hydrogen carrier, from toluene using a highly alkaline aqueous solution as a hydrogen source under sunlight with almost 100% of faradaic efficiency. It was revealed that the co-loading of RuO2 with Pt changed the Pt oxidation state, partly explaining the improved activity and stability, associated with an anchoring effect of Pt. It was also determined that such highly alkaline conditions promote selective MCH production, possibly because of the improved performance of the anion exchange membrane. The present study involving the construction of a surface protective/catalytic layer suggests a novel approach to artificial photosynthesis for solar energy harvesting in the form of organic hydrides.

Structural and Conformational Aspects of Equatorial and Axial Trifluoromethyl, Difluoromethyl, and Monofluoromethyl Groups.

The X-ray crystal structures of cis- and trans-1-(indol-3-yl)-4-methyl cyclohexane and its congeners with stepwise fluorination of the methyl group are reported. The trans-configured compounds adopted diequatorial conformations, whereas the cis analogues adopted regular cyclohexane chair conformations with the methyl group preferentially assuming the axial position, even in the case of the CF3 group. Surprisingly, although the axial CF3 derivative displayed distinct valence deformations in the cyclohexane moiety, the observed structural changes were relatively modest. The cis derivatives with axial mono- and difluorinated methyl groups exhibited conformational disorder in the crystals with significant population levels for the staggered conformations that had one fluorine atom in the endo position; their respective trans counterparts adopted unique conformations, but again with one fluorine atom in the endo position. Theoretical calculations for a series of cis- and trans-1,4-dimethyl cyclohexane model compounds with stepwise fluorination of one equatorial or axial methyl group reproduced the experimentally observed structural response patterns very well, reproduced the experimentally determined nonlinear correlation of the axial-equatorial energy difference with the degree of methyl fluorination in a satisfactory manner, and provided further insights into important conformational aspects of partially fluorinated methyl groups.

Simultaneous determination of cyclohexane and methylcyclohexane in workplace air by solvent desorption-gas chromatography / 中国职业医学

OBJECTIVE: To explore an improved method for determination of cyclohexane and methylcyclohexane in workplace air by solvent desorption-gas chromatography. METHODS: Cyclohexane and methylcyclohexane in workplace air were collected by activated carbon tubes,desorbed with carbon disulfide,separated by DB-1 capillary chromatography column,detected by flame ionization detector and quantified using the standard calibration curves. RESULTS: The linear range of the concentration of cyclohexane and methylcyclohexane were 1. 0-1 402. 2 and 0. 8-1 999. 4 mg / L respectively.Both the correlation coefficients were 0. 999 9. Both the detection limits were 0. 3 mg / L. The limits of quantification were1. 0 and 0. 8 mg / L respectively. Both the minimum detectable concentrations were 0. 2 mg / m3. The minimum quantitative mass concentrations of cyclohexane and methylcyclohexane were 0. 7 and 0. 6 mg / m3respectively( sample volume was 1. 5L). The average desorption efficiencies were 98. 5%-99. 3% and 97. 6%-99. 0% respectively. The relative standard deviations( RSD) of within-run precision were 0. 36%-0. 59% and 0. 34%-0. 50% respectively. The RSD of between-run precision were 0. 89%-2. 04% and 0. 87%-2. 22% respectively. The samples could be stored for up to 7 days at room temperature. CONCLUSION: This method has features of simple operation,high sensitivity and good precision,which is suitable for simultaneous determination of cyclohexane and methylcyclohexane in workplace air.

Toxicity of Methylcyclohexane and Its Effect on the Reproductive System in SD Rats.

OBJECTIVES: There is limited data regarding the toxicity of methylcyclohexane, despite its wide use in rubber adhesives, paint diluents, and cleansing agents. This study aimed to verify the toxicity and influence on the reproductive system of methylcyclohexane after its repeated injection in Sprague Dawley (SD) rats. METHODS: Methylcyclohexane was injected subcutaneously into male and female SD rats once a day, five times a week, for 13 weeks at different doses (0, 10, 100, and 1,000 mg/kg/day) for each group. The toxicity of testing material was verified by observing the change in body and organ weight, hematological change, pathological findings, and effect on the reproductive system at each different concentration. RESULTS: In the 1,000 mg/kg/day group, there were cases of animal deaths. In animals that survived, hematological changes, including a decrease in the red blood cell count, were observed. A considerable weight gain or loss and pathological abnormalities in the liver, kidney, and other organs were found. However, the 10 and 100 mg/kg/day groups did not cause deaths or other specific abnormalities. In terms of reproductive toxicity, there were changes in hormone levels, including a significant decrease in hormones such as estradiol and progesterone (p < 0.001) in male animals. Menstrual cycle change for female animals did not show concentration dependency. CONCLUSION: When injected repeatedly for 13 weeks, methylcyclohexane proved to be toxic for the liver, heart, and kidney at a high dose. The absolute toxic dose was 1,000 mg/kg/day, while the no observed adverse effect level was less than 100 mg/kg/day. The substance exerted little influence on the reproductive system.

Toxicity of Methylcyclohexane and Its Effect on the Reproductive System in SD Rats

OBJECTIVES: There is limited data regarding the toxicity of methylcyclohexane, despite its wide use in rubber adhesives, paint diluents, and cleansing agents. This study aimed to verify the toxicity and influence on the reproductive system of methylcyclohexane after its repeated injection in Sprague Dawley (SD) rats. METHODS: Methylcyclohexane was injected subcutaneously into male and female SD rats once a day, five times a week, for 13 weeks at different doses (0, 10, 100, and 1,000 mg/kg/day) for each group. The toxicity of testing material was verified by observing the change in body and organ weight, hematological change, pathological findings, and effect on the reproductive system at each different concentration. RESULTS: In the 1,000 mg/kg/day group, there were cases of animal deaths. In animals that survived, hematological changes, including a decrease in the red blood cell count, were observed. A considerable weight gain or loss and pathological abnormalities in the liver, kidney, and other organs were found. However, the 10 and 100 mg/kg/day groups did not cause deaths or other specific abnormalities. In terms of reproductive toxicity, there were changes in hormone levels, including a significant decrease in hormones such as estradiol and progesterone (p < 0.001) in male animals. Menstrual cycle change for female animals did not show concentration dependency. CONCLUSION: When injected repeatedly for 13 weeks, methylcyclohexane proved to be toxic for the liver, heart, and kidney at a high dose. The absolute toxic dose was 1,000 mg/kg/day, while the no observed adverse effect level was less than 100 mg/kg/day. The substance exerted little influence on the reproductive system.