Clathrate Hydrate Capture of CO2 from Simulated Flue Gas with Cyclopentane/Water Emulsion

Capture of CO2 by hydrate is one of the attractive technologies for reducing greenhouse effect.The primary challenges are the large energy consumption,low hydrate formation rate and separation efficiency.This work presents a new method for capture of CO2 from simulated flue gasCO2(16.60%,by mole) /N2 binary mixture by formation of cyclopentane(CP) hydrates at initial temperature of 8.1°C with the feed pressures from 2.49 to 3.95 MPa.The effect of cyclopentane and cyclopentane/water emulsion on the hydrate formation rate and CO2 separation efficiency was studied in a 1000 ml stirred reactor.The results showed the hydrate formation rate could be increased remarkably with cyclopentane/water emulsion.CO2 could be enriched to 43.97%(by mole) and 35.29%(by mole) from simulated flue gas with cyclopentane and cyclopentane/water(O/W) emulsion,respectively,by one stage hydrate separation under low feed pressure.CO2 separation factor with cyclopentane was 6.18,higher than that with cyclopentane/water emulsion(4.01) ,in the range of the feed pressure.The results demonstrated that cyclopentane/water emulsion is a good additive for efficient hydrate capture of CO2.

MISCIBILITY BEHAVIOR AND PRESSURE DEPENDENCE OF THE SYSTEMS POLYSTYRENE/CYCLOPENTANE AND POLYSTYRENE/1-PHENYLDECANE ACCORDING TO A MODIFIED HOLE THEORY

The influence of pressure on miscibility behavior of the systems polystyrene/cyclopentan(?)and polystyrene/1-phenyldecane is studied with a modified hole theory.It is found that the pres-sure dependence of excess volume is responsible for the different kinds of behavior of these two sys-tems.Furthermore,the excess volume is decomposed into two separatc parts,one from the contri-bution of cell volume expansion and the other from the change of hole fraction,and their relation-ship with pressure dependence of the miscibility behavior is analysed.

Modification of POSS and their tribological properties and resistant to space atomic oxygen irradiation as lubricant additive of multialkylated cyclopentanes

Developing functional additive resistant to space atomic oxygen(AO)irradiation through simple molecular design and chemical synthesis to enhance the lubricating performance of multialkylated cyclopentanes(MACs)oil is a significant challenge.Herein,sulfur-containing polyhedral oligomere silsesquioxane(POSS)were synthesize via a click-chemistry reaction of octavinyl polyhedral oligomeric with alkyl sulfide.The reduce-friction(RF),anti-wear(AW)properties and anti-AO irradiation of POSS-S-R as MACs base oil additives in atmospheric and simulated space environments were systematically investigated for the first time.Results demonstrate that POSS-S-R not only possesses outstanding anti-AO irradiation capacity but also effectively improves the RF and AW of MACs in atmospheric or simulated space surroundings.This improvement is due to the excellent anti-AO irradiation properties of the POSS structure itself and the high load-carrying ability of silicon-containing and sulfur-containing compounds generated by tribo-chemical reactions,which effectively separates the direct contact of the friction interface.We believe that this synthesized POSS-S-R is a promising additive for space lubricants.

Highly enantio-stereoselective Ni-catalyzed reductive cyclization to cyclopentanes with chiral quaternary centres of trisubstituted allylic siloxanes

The construction of chiral quaternary carbon stereocenters is a significant challenge in asymmetric synthesis.Catalytic synthesis of these structures with trisubstituted allylic alcohols is highly important. However, most ofthe reported methodologies required noble transition-metals. Herein we reported the first highly asymmetricstereoselective synthesis of cyclopentanes bearing chiral quaternary carbon stereocenters of trisubstituted allylicsiloxanes by reductive cyclization of all carbon 1,6-alkynones with the non-noble nickel catalysis of Ni(cod)2 withP-chiral monophosphine ligand (S)-BIDIME. Various multi-substituted functionalized cyclopentanes were obtained in high yields (up to 96%), excellent enantioselectivities (up to >99% ee) and perfect stereoselectivities(>99:1 E/Z). Thirty-two examples were successfully established for this method. Clarified mechanism studieswere investigated first time by React-IR and DFT calculations to understand and explain the ligand-control ofexcellent enantio-stereoselectivity. Gram-scale reaction and control experiments were carried out. A new reactiondesign was proposed for further application of this type of catalysis.

Lithium-based ionic liquids as novel lubricant additives for multiply alkylated cyclopentanes(MACs)

Two lithium-based ionic liquids(ILs,L-C3N3,and L-P3N3)were synthesized and evaluated as novel lubricant additives for multiply alkylated cyclopentanes(MACs).They were found to be approximately 1.0%soluble in MACs at room temperature(RT),whereas traditional ILs,such as 1-ethyl-3-methylimidazolium tetrafluoroborate(L-B102),1-hexyl-3-methylimidazolium hexafluorophosphate(L-P106),and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide(L-F102),could not be dissolved in this base oil.Friction tests indicated that these ILs exhibit excellent friction-reducing and anti-wear properties both at RT and at 100°C.They can improve the tribological properties of MACs at RT to a greater extent than the commonly used lubricant zinc dialkyldithiophosphate(T204),even at a concentration of 0.1%.The load ramp test showed that MACs with L-C3N3 and L-P3N3 also exhibit high load-carrying capabilities.Scanning electron microscope(SEM)and X-ray photoelectron spectrometer(XPS)results indicated that physical adsorption and complex tribochemical reactions occurred between the ILs and metal surfaces during the sliding process,thereby forming a surface protective film that significantly contributed to the excellent tribological properties of the new ILs.

Adsorption, Diffusion and Thermal Desorption Features of Cyclopentane and Cyclohexane in Silicalite-1

Adsorption, diffusion and thermal desorption features of cyclopentane and cyclohexane in silicalite-1 have been investigated using the intelligent gravimetric technique. Both the saturation adsorption loadings and diffusion coefficient of cyclopentane were greater than those of cyclohexane. The diffusivity of cyclopentane was about one order of magnitude greater than that of cyclohexane at the same temperature and initial loading. For cyclopentane, there was only one kind of desorption process at adsorption loadings lower than 4 muc （molecule per unit cell）, but two desorption processes appeared at the adsorption loadings higher than 4 muc. While for cyclohexane, one desorption process was found in the whole range of loadings. Both thermal desorption peaks of cyclopentane and cyclohexane moved to higher temperature region with increasing loading.

Characterizing a lubricant additive for 1,3,4-tri-(2-octyldodecyl) cyclopentane: Computational study and experimental verification

In order to increase the life of spacecraft, it is important to improve the comprehensive lubrication performance. Multiple alkylated cyclopentane (MAC) lubricants are presently gaining wide acceptance for actual space applications; adding extreme pressure additive is a strategy to improve lubrication performance. In this study, taking 1,3,4-tri-(2-octyldodecyl) cyclopentane as base oil, tricresol phosphate (traditional additive) and tri-(2-octyldodecyl) phosphate (developmental additive) have been screened computationally for compatibility, shear film forming and energy dissipation. Theoretical results indicate that (a) tricresol phosphate additive is not suited for addition to 1,3,4-tri-(2-octyldodecyl) cyclopentane lubricant due to limited compatibility; (b) tri-(2-octyldodecyl) phosphate is an excellent lubricant additive due to its perfect compatibility, ease of forming a shear film on the surface of friction pairs, higher strength, and low energy dissipation; and (c) lubrication occurs through the solid-liquid composite lubrication mechanism. These theoretical results were confirmed experimentally.

Investigation on Gas Storage in Methane Hydrate

The effect of additives (anionic surfactant sodium dodecyl sulfate (SDS), nonionic surfactant alkyl polysaccharide glycoside (APG), and liquid hydrocarbon cyclopentane (CP)) on hydrate induction time and formation rate, and storage capacity was studied in this work. Micelle surfactant solutions were found to reduce hydrate induction time, increase methane hydrate formation rate and improve methane storage capacity in hydrates. In the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation were reduced. The critical micelle concentrations of SDS and APG water solutions were found to be 300×10-6 and 500×10-6 for methane hydrate formation system respectively. The effect of anionic surfactant (SDS) on methane storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduced hydrate induction time and improved hydrate formation rate, but could not improve methane storage in hydrates.

Experimental Study of Natural Gas Storage in Hydrates

Hydrate formation rate plays an important role in the making of hydrates for natural gas storage. The effect of sodium dodecyl sulfate (SDS), alkyl polysaccharide glycoside (APG) and cyclopentane (CP) on natural gas hydrate formation rate, induction time and storage capacity was studied. Micellar surfactant solutions were found to increase hydrate formation rate in a quiescent system and improve hydrate formation rate and natural gas storage capacity. The process of hydrate formation includes two stages with surfactant presence. Hydrate forms quickly in the first stage, and then the formation rate is slowed down. Surfactants (SDS or APG) reduce the induction time of hydrate formation. The effect of an anionic surfactant (SDS) on gas storage in hydrates is more pronounced compared to a nonionic surfactant (APG). CP also reduces the induction time of hydrate formation, but can not improve the natural gas storage capacity in hydrates.

Photocatalytic[3+2]Cycloaddition of Alkyl/aryl Iodides and Internal Alkynes by Merging Halogen and Hydrogen Atom Transfer

Comprehensive Summary A visible light photocatalytic[3+2]cycloaddition of alkynes with readily accessible organic iodides as the C3 synthon is developed herein.By merging halogen atom transfer(XAT)and hydrogen atom transfer(HAT),alkyl/aryl iodides serve as a formal diradical precursor and add across C-C triple bonds to deliver a number of functionalized cyclopentanes in moderate to high yields with exceptional regio-and diastereoselectivity.A reductive radical-polar crossover mechanism,involving the cascade XAT,radical addition,1,5-HAT,polar effect-promoted 5-endo annulation,single electron transfer(SET)reduction,and protonation,may account for this unprecedented dehalogenative[3+2]cycloaddition.This work not only expands the repertoire of the traditional RATC methodology,but also provides a robust platform for the expedient assembly of cyclopentanes,a valuable structural motif in the realms of medicinal chemistry and material sciences.

Asymmetric Hydrogenation of Tetrasubstituted α,β-Unsaturated Ketones:Access to Chiral 2-Substituted Cyclopentyl Aryl Ketones

Asymmetric hydrogenation of tetrasubstituted alkenes is an important but challenging research topic.Herein,we report an efficient iridium-catalyzed asymmetric hydrogenation of tetrasubstituted α,β-unsaturated ketones for the synthesis of chiral 2-substituted cyclopentyl aryl ketones,an important chiral structural motif for the preparation of chiral pharmaceuticals and bioactive molecules.The reaction proceeded very well with good functional group compatibility and delivered the hydrogenated products in high yields and stereoselectivities(up to 99% yield,>20:1 dr and 99%ee).In addition,the reaction could be carried out on a gram-scale,and all four stereoisomers of the hydrogenated products bearing two contiguous stereocenters were obtained.Furthermore,the hydrogenated product can be transformed into the ERβ agonist Erteberel,and the reaction pathway was also studied via deuterium-labelling experiments.

Bio-inspired Superhydrophobic Coating with Low Hydrate Adhesion for Hydrate Mitigation

In this paper,we fabricate a biomimetic superhydrophobic coating on an X90 pipeline steel substrate by electrodeposition of copper,hydrothermal treatment to form a copper oxide layer,and subsequent surface modification with Stearic Acid(SA).The coating exhibits static contact angles of water of 160°±-3.1°in the air and 170.7°±2.5°in cyclopentane,indicating the strongly water-repelling nature of the coating.The morphologies of the cyclopentane hydrate formed on steel substrates with and without the superhydrophobic coating are investigated.The results show that the hydrate particle on the coating exhibits spherical morphology and herein the interfacial contact area and adhesion force to the solid surface can be essentially reduced.The adhesion force reduction may be resulted by the decrease in the contact area between the hydrate and the solid surface.

Thermodynamic and Economic Studies of a Combined Cycle for Waste Heat Recovery of Marine Diesel Engine

In the present study,the thermodynamic and economic performance of a combined thermodynamic cycle formed by an ORC and a Kalina cycle,which can simultaneously recover waste heat of exhaust gas and cooling water of marine engine,has been analyzed.Two typical marine engines are selected to be the waste heat source.Six economic indicators are used to analyze the economic performance of this combined thermodynamic cycle system with different marine engine load and under practical comprehensive operating condition of marine engine.The results of the present study show that the combined thermodynamic cycle system with R123 as organic working fluid has the best performance.The system with cis-butene has the worst economic performance.Under practical comprehensive operating conditions of ships,R123 has the shortest Payback Periods,which are 8.51 years and 8.14 years for 8 S70 ME-C10.5 engine and 5G95 ME-C10.5 engine,respectively.Correspondingly,payback Periods of Cyclopentane are 11.95 years and 11.90 years.The above values are much shorter than 25 years which are the lifetime of a marine ship.Under practical comprehensive operating conditions of ships,the combined cycle system can provide output power which is at least equivalent to 25%of engine power.Considering that R123 will be phased out in near future,cyclopentane may be its good successor.Cyclopentane can be used safely by correct handling and installing according to manufacturer's instructions.