Merging polymers of intrinsic microporosity and porous carbon-based zinc oxide composites in novel mixed matrix membranes for efficient gas separation

Mixed matrix membranes(MMMs)have demonstrated significant promise in energy-intensive gas separations by amalgamating the unique properties of fillers with the facile processability of polymers.However,achieving a simultaneous enhancement of permeability and selectivity remains a formidable challenge,due to the difficulty of achieving an optimal match between polymers and fillers.In this study,we incorporate a porous carbon-based zinc oxide composite(C@ZnO)into high-permeability polymers of intrinsic microporosity(PIMs)to fabricate MMMs.The dipole–dipole interaction between C@ZnO and PIMs ensures their exceptional compatibility,mitigating the formation of non-selective voids in the resulting MMMs.Concurrently,C@ZnO with abundant interconnected pores can provide additional low-resistance pathways for gas transport in MMMs.As a result,the CO_(2) permeability of the optimized C@ZnO/PIM-1 MMMs is elevated to 13,215 barrer,while the CO_(2)/N_(2) and CO_(2)/CH_(4) selectivity reached 21.5 and 14.4,respectively,substantially surpassing the 2008 Robeson upper bound.Additionally,molecular simulation results further corroborate that the augmented membrane gas selectivity is attributed to the superior CO_(2) affinity of C@ZnO.In summary,we believe that this work not only expands the application of MMMs for gas separation but also heralds a paradigm shift in the application of porous carbon materials.

Rapid hydrate formation and efficient gas separation based on aqueous solid carrier

The long hydrate induction time and limited gas-liquid contact area leads to slow hydrate formation rate and low water-hydrate conversion rate.Porous media are often used to promote hydrate formation because of their large specific surface area.Consequently,we used 3A molecular sieve as a water-carrying solid in this work,and investigated the dynamic renewal of the gas-liquid interface and its effect on hydrate formation.The formation kinetics of ethane hydrate was first measured in an aqueous molecular sieve system.Then the separation of(H_(2)+CH_(4)+C_(2)H_(6)+C_(3)H_(8))gas mixture was conducted via hydrate formation.The results show that the formation rate and gas storage capacity of ethane hydrate can be greatly improved by using aqueous molecular sieve.Compared with a pure water system under the same temperature and pressure,aqueous molecular sieve has obvious advantages in separation effect and energy consumption for separating gas mixtures.

Dephosphorization of high-phosphorus iron ore by direct reduction of hydrogen-rich gases and melting separation

This study developed a direct reduction route to smelt refractory high-phosphorus iron ores by using hydrogen rich gas.The effects of temperature,gas composition,and gangue on the reduction behavior of iron ore pellets were investigated.Additionally,the migration behavior of phosphorus throughout the reduction-smelting process was examined.The apparent activation energy of the reduction process increased from 64.2 to 194.2 kJ/mol.Increasing the basicity from 0.5 to 0.9 increased the metallization rate from 85.9%to 89.2%.During the reduction process,phosphorus remained in the gangue phase.Carbon deposition and phosphorus removal behaviors of the pellets were investigated and correlated with the gas composition,temperature,pressure,metallization rate,and basicity.Increasing the FeO and CaO contents led to an increase in the liquidus temperature.A high metallization rate of the pellets reduced the phosphorus removal rate but increased the carbon content of the final iron product.Increasing basicity restricted the migration of phosphorus and improved the rate of phosphorus removal.The optimum dephosphorization parameters were separation temperature of 1823 K,basicity of 2.0,and metallization rate of 82.3%.This study presents a high-efficiency and low carbon method for smelting high-phosphorus iron ores.

Separation Properties of a New Polysiloxane-Anchored β-Cyclodextrin Derivative as Gas Chromatography Stationary Phase

A new capillary gas chromatography stationary phase, monokis (2,6 di O benzyl 3 O propyl (3’)) hexakis(2,6 di O benzyl 3 O methyl) β CD bonded polysiloxane, was synthesized. It exhibited separation abilities to disubstituted benzene isomers and some chiral solutes. It was also found that the polarity of CD derivatives can be lowered both by chemically bonding it to polysiloxane and by diluting it in polysiloxane. The separation abilities of the polysiloxane anchored CDs (SP CD) are higher than that of the unbonded CDs (S CD) and the diluted S CD at lower column temperature. Hydrosilylation reaction is one of the best methods to lower the operating temperature of CDs.

聚氨酯多孔材料制备及对油水分离研究

以热塑性聚氨酯塑料(TPU)颗粒为原料,采用热致相分离法制备了具有疏水亲油性的聚氨酯多孔材料。通过扫描电子显微镜(SEM)、静态接触角测试仪和氮气吸附-脱附测试仪等手段对制备的多孔材料进行表征,并对材料的吸油能力及循环利用性进行测试。结果表明:聚氨酯质量分数为4%时,在-20℃下相分离24 h,-50℃真空冷冻干燥48 h,所得的TPU-3-4多孔材料具有良好的疏水亲油性,该材料表面具有均匀的孔结构,比表面积为11 m^(2)/g,对水的接触角为123°;该材料对各种油/有机溶剂的饱和吸附量为13.4~16.1 g/g,具有较强的循环吸附能力,且在多次吸附-脱附后测得的植物油回收率仍保持在85%~90%。此外,该材料在不同温度和不同pH下,饱和吸附量波动较小,对环境具有较强的适应性。

Separation and Characterization of Nitrogen-Rich Components in Coker Gas Oils from Athabasca Bitumen

It is well known that gas oils from oilsands bitumen are difficult to hydrotreat. In order to develop the most appropriate flow sheet and operating conditions, a thorough knowledge of the molecular structure and behaviour of bitumen and its gas oil products is needed. In this work, the gas oil samples are fractionated in an attempt to isolate and identify the problematic molecular species for hydrotreating. It is found that the major nitrogen sources in coker gas oils are associated with relatively small pentane insoluble species and an even smaller, highly polar, hexane insoluble species. Structural information obtained for these fractions indicates that they are formed during the cracking of resin molecules. Nitrogen speciation shows that the pyrroles are the primary nitrogen type, with pyridines also being an important species. Both nitrogen species are undesirable in the hydrotreating process. Pyrroles in particular are subject to polymerisation, producing gums and sediments that foul filters and other equipment while pyridines can directly deactivate the hydrotreating catalyst.

基于臭氧化法的磷酸铁锂正极材料与集流体 高效分离技术研究

探讨了酸性溶液单独以及与臭氧协同作用对磷酸铁锂正极材料分离效果的影响。引入特定浓度的臭氧能有效诱发过氧化氢(H_(2)O_(2))的产生,赋予其极强的氧化能力,进而能够与聚偏氟乙烯(PVDF)结构中的氟基团发生键合反应,形成含氢氟酸(HF)的化合物,使PVDF失去原有的黏结性,更有利于活性材料的高效分离。与传统的回收手段相比,这种新型的臭氧化方法不仅操作简便、安全性高,还具有显著的环保优势和成本效益。

Progress in carbon dioxide separation and capture: A review

This article reviews the progress made in CO2 separation and capture research and engineering. Various technologies, such as absorption, adsorption, and membrane separation, are thoroughly discussed. New concepts such as chemical-looping combustion and hydrate-based separation are also introduced briefly. Future directions are suggested. Sequestration methods, such as forestation, ocean fertilization and mineral carbonation techniques are also covered. Underground injection and direct ocean dump are not covered.

Recent advances on mixed matrix membranes for CO_2 separation

Recent advances on mixed matrix membrane for CO2 separation are reviewed in this paper. To improve CO2 separation performance of polymer membranes, mixed matrix membranes (MMMs) are developed. The concept of MMM is illustrated distinctly. Suitable polymer and inorganic or organic fillers for MMMs are summarized. Possible interface morphologies between polymer and filler, and the effect of interface morphologies on gas transport properties of MMMs are summarized. The methods to improve compatibility between polymer and filler are introduced. There are eight methods including silane coupling, Grignard treatment, incorporation of additive, grafting, in situ polymerization, polydopamine coating, particle fusion approach and polymer functionalization. To achieve higher productivity for industrial application, mixed matrix composite membranes are developed. The recent development on hollow fiber and flat mixed matrix composite membrane is reviewed in detail. Last, the future trend of MMM is forecasted.

Studies on Oxygen Characteristics of YBa_2Cu_3O_(7-x) and Its Applications to Air Separation and Gas Purification

Oxygen diffusion and oxygen selective adsorption properties of rare earths material YBa_2Cu_3O_(7-x) (YBCO) were investigated by thermogravimetric, oxygen static adsorption and selectivity adsorption experiments. The results show that YBCO is a very good deoxidizing material. The oxygen desorption of YBCO begins remarkably at about 400 ℃, mass loss can arrive at 1.2% of its original quantity at 800 ℃. Oxygen can be completely absorbed back into the sample again when temperature descends to 400 ℃. The oxygen adsorption selectivity, reproducibility and oxygen adsorption under very low oxygen partial pressure make the material desirable for air separation and gas purification. High purity nitrogen gas was produced with the YBCO molecular sieves in the air separation and gas purification experiments. 0.017 m^3 of high purity nitrogen (>99.9999%) can be obtained with 1 kg YBCO molecular sieve in one cycle. As a deoxidant, an obvious advantage of YBCO is that no hydrogen is needed in its applications.

Performance of Inner-core Supersonic Gas Separation Device with Droplet Enlargement Method

To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a method of droplet enlargement was applied. A series of experiments were carried out in the improved separation device under various conditions, using air-ethanol vapor as the medium and micro water droplets as nucleation cen- ters. The effects of the inlet pressure, temperature and relative humidity, the swirling intensity, and mass flow rate of water on the separation performance were investigated. The separation was improved by increasing the inlet pressure and relative humidity. With the decrease of swirling intensity and mass flow rate of water, the separation efficiency increased first and then decreased. The inlet temperature had a slight effect on the separation. The results showed that the separation performance was effectively improved using the proposed structure and method, and the best separation in this study was obtained with the ethanol removal rate about 55% and dew point depression 27 K. The addition of water had little pollution to the air-ethanol vapor system since the water carry-over rate was within the range of -2 %-0 in most cases.

Applications of metal–organic frameworks for green energy and environment: New advances in adsorptive gas separation, storage and removal

The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.

Beyond graphene oxides: Emerging 2D molecular sieve membranes for efficient separation☆

Recent decades witnessed the significant progress made in the research field of 2D molecular sieve membranes.In comparison with their 3D counterparts, 2D molecular sieve membranes possessed several unique advantages like significantly reduced membrane thickness(one atom thick in theory) and diversified molecular sieving mechanisms(in-plane pores within nanosheets & interlayer galleries between nanosheets). M. Tsapatsis first carried out pioneering work on fabrication of lamellar ZSM-5 membrane. Since then, diverse 2D materials typically including graphene oxides(GOs) have been fabricated into membranes showing promising prospects in energy-efficient gas separation, pervaporation, desalination and nanofiltration. In addition to GOs, other emerging 2D materials, including 2D zeolites, 2D metal–organic frameworks(MOFs), 2 D covalent-organic frameworks(COFs), layered double hydroxides(LDHs), transition metal dichalcogenides(TMDCs), MXenes(typically Ti3C2TX), graphitic carbon nitrides(typically g-C3N4), hexagonal boron nitride(h-BN) and montmorillonites(MT) are showing intriguing performance in membrane-based separation process. This article summarized the most recent developments in the field of 2D molecular sieve membranes aside from GOs with particular emphasis on their structure–performance relationship and application prospects in industrial separation.

Recent advances on the membrane processes for CO_2 separation

Membrane separation technology has popularized rapidly and attracts much interest in gas industry as a promising sort of newly chemical separation unit operation. In this paper, recent advances on membrane processes for CO_2 separation are reviewed. The researches indicate that the optimization of operating process designs could improve the separation performance, reduce the energy consumption and decrease the cost of membrane separation systems. With the improvement of membrane materials recently,membrane processes are beginning to be competitive enough for CO_2 separation, especially for postcombustion CO_2 capture, biogas upgrading and natural gas carbon dioxide removal, compared with the traditional separation methods. We summarize the needs and most promising research directions for membrane processes for CO_2 separation in current and future membrane applications. As the time goes by, novel membrane materials developed according to the requirement proposed by process optimization with increased selectivity and/or permeance will accelerate the industrialization of membrane process in the near future. Based on the data collected in a pilot scale test, more effort could be made on the optimization of membrane separation processes. This work would open up a new horizon for CO_2 separation/Capture on Carbon Capture Utilization and Storage(CCUS).

Economic Comparison of Three Gas Separation Technologies for CO2 Capture from Power Plant Flue Gas

Three gas separation technologies,chemical absorption,membrane separation and pressure swing adsorption,are usually applied for CO2 capture from flue gas in coal-fired power plants.In this work,the costs of the three technologies are analyzed and compared.The cost for chemical absorption is mainly from $30 to $60 per ton(based on CO2 avoided),while the minimum value is $10 per ton(based on CO2 avoided).As for membrane separation and pressure swing adsorption,the costs are $50 to $78 and $40 to $63 per ton(based on CO2 avoided),respectively.Measures are proposed to reduce the cost of the three technologies.For CO2 capture and storage process,the CO2 recovery and purity should be greater than 90%.Based on the cost,recovery,and purity,it seems that chemical absorption is currently the most cost-effective technology for CO2 capture from flue gas from power plants.However,membrane gas separation is the most promising alternative approach in the future,provided that membrane performance is further improved.

Effect of montmorillonite on hydrate-based methane separation from mine gas

Three types of mine gas samples were used in the solutions of tetrahydrofuran(THF),sodium dodecyl sulfate(SDS)and THF-SDS with/without MMT respectively to investigate the effect of montmorillonite(MMT)on separation characteristics of methane recovered from mine gas based on hydrate method.The partition coefficient,separation factor and recovery rate were used to evaluate the effects of MMT,and the selection factor was primarily proposed to define the selectivity of mine gas hydrate in the relative target gases.The experimental results indicate that MMT could improve the following factors including hydration separation factor,the selection factor,the partition coefficient,and the recovery rate.Furthermore,the effect of SDS on the function of MMT is analyzed in the process of hydration separation.Finally,due to the results of the experiment,it is concluded that MMT hydration mechanism explores the effect of MMT enrichment methane from mine gas.

Separation of CO_2/CH_4 and CH_4/N_2 mixtures using MOF-5 and Cu_3(BTC)_2

In this paper we used MOF-5 and Cu3（BTC）2 to separate CO2/CH4 and CI-I4/N2 mixtures under dynamic conditions. Both materials were synthesized and pelletized, thus allowing for a meaningful characterization in view of process scale-up. The materials were characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. By performing breakthrough experiments, we found that Cu3（BTC）2 separated CO2/CH4 slightly better than MOF-5. Because the crystal structure of Cu3 （BTC）2 includes unsaturated accessible metal sites formed via dehydration, it predominantly interacted with CO2 molecules and more easily captured them. Conversely, MOF-5 with a suitable pore size separated CH4/N2 more efficiently in our breakthrough test.

Performance of Dual-throat Supersonic Separation Device with Porous Wall Structure

In this paper, a dual-throat supersonic separation device with porous wall has been proposed to solve the starting problem of supersonic separator, and the feasibility of the proposed device has been tested numerically and experimentally. Its flow characteristics have been investigated and the effect of some important parameters includ-ing nozzle pressure ratio(RNP), inlet temperature and swirl intensity were examined. In the device, the supersonic flow state and strong centrifugal acceleration of 240000g can be obtained, which are necessary for the condensation and separation of water vapor. The supersonic region in the device enlarged and the shock wave shifted downstream along with the increasing RNP. The separation performance was improved with the increasing RNP and the inlet temperature. The best separation performance in this study was obtained with ΔTd? 28 K.

Two-dimensional material separation membranes for renewable energy purification, storage, and conversion

The current energy crisis has prompted the development of new energy sources and energy storage/conversion devices. Membranes, as the key component, not only provide enormous separation potential for energy purification but also guarantee stable and high-efficiency operation for rechargeable batteries and fuel cells. Remarkably, two-dimensional(2D) material separation membranes have attracted intense attention on their excellent performance in energy field applications, owing to high mechanical/chemical stability, low mass transport resistance, strict sizeexclusion, and abundant modifiable functional groups. In this review, we concentrate on the recent progress of 2D membrane and introduce 2D membranes based on graphene oxide(GO), MXenes, 2D MOFs, 2D COFs, and 2D zeolite nanosheets, which are applied in membrane separation(H2 collection and biofuel purification) and battery separators(vanadium flow battery, Li–S battery, and fuel cell). The mass transport mechanism, selectivity mechanism, and modification methods of these 2D membranes are stated in brief, mainly focusing on interlayer dominant membranes(GO and MXenes) and pore dominant membranes(MOFs, COFs, and zeolite nanosheets). In conclusion, we highlight the challenges and outlooks of applying 2D membranes in energy fields.

The combination of 1-octyl-3-methylimidazolium tetrafluorborate with TBAB or THF on CO2 hydrate formation and CH4 separation from biogas

[C_8min] BF_4 was used in this work to combine with TBAB or THF for the investigation about thermodynamic and kinetic additives on CO_2 and CH_4/CO_2 hydrates. The results show that [C_8min] BF_4 has the inhibition effect on the equilibrium of hydrate formation. About the kinetic study, [C_8 min] BF_4 could improve the rate of CO_2 hydrate formation and increase the gas uptake in hydrate phase. At the same time, the combination of TBAB and [C8 min] BF_4 could increase the mole friction of CH_4 in residual gas comparing with the data in THF solution. CH_4 separation efficiency was strongly enhanced. Since that the size of CO_2 and CH_4 molecules are similar, CH_4 and CO_2 could form the similar hydrate, so the recovery of CH_4 from biogas decreases lightly. The CH_4 content in biogas can purified from 67 mol% to 77 mol% after one-stage hydrate formation. In addition, the combination of THF and[C_8 min] BF_4 do not have obvious promoting effect on CH_4 separation comparing with the gas separation results in pure THF solution.