Molecular Simulation on Competitive Adsorption Differences of Gas with Different Pore Sizes in Coal

Micropores are the primary sites for methane occurrence in coal. Studying the regularity of methane occurrence in micropores is significant for targeted displacement and other yield-increasing measures in the future. This study used simplified graphene sheets as pore walls to construct coal-structural models with pore sizes of 1 nm, 2 nm, and 4 nm. Based on the Grand Canonical Monte Carlo (GCMC) and molecular dynamics theory, we simulated the adsorption characteristics of methane in pores of different sizes. The results showed that the adsorption capacity was positively correlated with the pore size for pure gas adsorption. The adsorption capacity increased with pressure and pore size for competitive adsorption of binary mixtures in pores. As the average isosteric heat decreased, the interaction between the gas and the pore wall weakened, and the desorption amount of CH₄ decreased. In ultramicropores, the high concentration of CO₂ (50–70%) is more conducive to CH₄ desorption; however, when the CO₂ concentration is greater than 70%, the corresponding CH₄ adsorption amount is meager, and the selected adsorption coefficient S_CO2/CH4 is small. Therefore, to achieve effective desorption of methane in coal micropores, relatively low pressure (4–6 MPa) and a relatively low CO₂ concentration (50–70%) should be selected in the process of increasing methane production by CO₂ injection in later stages. These research results provide theoretical support for gas injection to promote CH₄ desorption in coal pores and to increase yield.     

Direction of temperature gradient for normal-phase temperature gradient interaction chromatography in polystyrene fractionation

Temperature gradient interaction chromatography (TGIC) is a powerful technique for molecular weight fractionation of polymers, in which the interaction strength is controlled by varying the column temperature. In the present paper, the effects of the sign of the temperature dependence of the retention and the direction of the temperature gradient (raising or lowering) on TGIC in the normal-phase mode were studied for the molecular weight fractionation of polystyrene samples in organic mobile phases. It was found that a positive temperature gradient was effective in the system consisting of amino-modified silica (NH(2)) column and the eluent mixture of tetrahydrofuran and n-hexane where retention decreased with increasing temperature. A negative temperature gradient was effective for the systems consisting of a bare-silica column//chloroform/n-hexane and NH(2)-column//chloroform/n-hexane, where retention increased with increasing temperature. Increasing retention with increasing temperature has been found, so far, only for a water-soluble polymer (PEO) in an aqueous mobile phase in RP-TGIC.     

球磨时间对浆态床CO甲烷化Ni-Al_2O_3催化剂性能的影响

结合行星式球磨机,采用低温固相法制备Ni-Al_2O_3催化剂,考察了球磨时间对Ni-Al_2O_3催化剂晶相结构(XRD)、还原特征(H2-TPR)、孔道结构(BET)、粒径分布(PSD)、表面形貌(SEM)和浆态床CO甲烷化性能的影响.结果表明,球磨时间为60 min,催化剂(CT-60)平均粒径最小,为141 nm;比表面积最大,为329 m2/g.随球磨时间延长,Ni-Al_2O_3催化剂的甲烷化性能(CO转化率、CH_4选择性和CH_4收率)均先增加后减少.其中,球磨时间为60 min制备的催化剂(CT-60)甲烷化性能最佳,其CO转化率、CH_4选择性和CH_4收率分别达87.9%、8 6.8%和74.3%.结合催化剂表征可知,CT-60优异的性能与其具有较小的颗粒尺寸(141 nm)和较大的比表面积(329 m2·g-1)有很大的关联.即,催化剂颗粒尺寸越小,比表面积越大,其性能越好.     

Molecular Simulation of the Adsorption Characteristics of Methane in Pores of Coal with Different Metamorphic Degrees

In order to study differences in the methane adsorption characteristics of coal pores of different metamorphic degrees, 4 nm pore structure models based on three typical coal structure models with different metamorphic degrees were constructed. Based on the molecular mechanics and dynamics theory, the adsorption characteristics of methane in different coal rank pores were simulated by the grand canonical Monte Carlo (GCMC) and molecular dynamics methods. The isothermal adsorption curve, Van der Waals energy, concentration distribution, and diffusion coefficient of methane under different conditions were analyzed and calculated. The results showed that at the same pore size, the adsorption capacity of CH₄ is positively correlated with pressure and metamorphic degree of coal, and the adsorption capacity of CH₄ in high metamorphic coal is more affected by temperature. The relative concentration of CH₄ in high-order coal pores is low, and the relative concentration at higher temperature and pressure conditions is high. The CH₄ diffusion coefficient in high-rank coal is low, corresponding to the strong Van der Waals interaction between CH₄ and coal. The research results are of great significance for further exploration of the interaction mechanism between CH₄ and coal with different metamorphic degrees and can provide theoretical support for the selection of gas extraction parameters.     

Characterization of Hydrophobic SiO2 Powders Prepared by Surface Modification on Wet Gel

Hydrophobic porous silica has been prepared by surface modification of TEOS (tetraethylorthosilicate) wet gel with 6 and 12 vol.% of TMCS (trimethylchlorosilane). We characterized the products by using FT-IR, TGA, DTA, N₂ adsorption/desorption, contact angle and SEM. Surface silanol groups of the gel were widely replaced by–Si(CH₃)₃ to result in a hydrophobic SiO₂ powder as confirmed by contact angle measurements with H₂O, 1-butanol and ethanol. The modified dried gels had a surface area of 950–1000 m²/g (average pore size 120 Å), compared to the non-modified surface which had a surface area of 690 m²/g (average pore size 36 Å). The adsorption/desorption isotherm curves indicated they had similar pore characteristics as aerogels prepared by the supercritical drying process.     

Towards the simultaneous detection of the low nmol/mol range of CO, CH4 and CO2 in nitrogen using GC-FID

The trace detection of carbon monoxide (CO), methane (CH₄) and carbon dioxide (CO₂) by gas chromatography with flame ionisation detection (GC-FID) can be enhanced by paying attention to several practical aspects of the measurement process. Choosing the appropriate column material, column conditioning, sample loop size, methaniser temperature, detector temperature, flow rate, back-pressure regulation and peak integration method can all affect the repeatability of peak areas of very small peaks. The relative effect of each of these variables is discussed in the context of achieving simultaneous detection of CO, CH₄ and CO₂ in nitrogen in the low nmol/mol range.     

High performance liquid chromatography characterization of macromolecules

A new method, temperature gradient interaction chromatography(TGIC) is employed for the characterization of macromolecules. Fine and reproducible control of interaction between polymer chains and the alkyl chain bonded silica packing material can be achieved by varying the temperature of the column. This method provides a far superior resolution to the conventional size exclusion chromatography. In addition, this method has a high sample loading capacity to be effective for preparative purpose. Furthermore, this method can be used to characterize binary polymer mixtures, where one component of a polymer mixture is separated by the size exclusion mechanism and the other is by the interaction mechanism simultaneously from single isocratic elution.     

Co3(HCOO)6 microporous metal-organic framework membrane for separation of CO2/CH4 mixtures

Continuous metal–organic framework‐type Co₃(HCOO)₆ intergrown films with a one‐dimensional zigzag channel system and pore aperture of 5.5 Å are prepared by secondary growth on preseeded macroporous glass‐frit disks and silicon wafers. The adsorption behavior of CO₂ or CH₄ single gases on the Co₃(HCOO)₆ membrane is investigated by in situ IR spectroscopy. It is shown that the isosteric heats of adsorption for CO₂ (17.7 kJ mol^?1) and CH₄ (14.4 kJ mol^?1) do not vary with increasing amount of adsorbed gases. The higher value of isosteric heat for CO₂ is an indication of the stronger interaction between the CO₂ and the Co₃(HCOO)₆ membrane. The Co₃(HCOO)₆ membrane is studied by binary gas permeation of CO₂ and CH₄ at different temperatures (0, 25, and 60 °C). The membrane has CO₂/CH₄ selectivity with a separation factor higher than 10, which is due to the unique structure and molecular sieving effect. Upon increasing the temperature from 0 to 60 °C, the preferred permeance of CO₂ over CH₄ is increased from 1.70×10^?6 to 2.09×10^?6 mol m^?2 s^?1 Pa^?1, while the separation factor for CO₂/CH₄ shows a corresponding decrease from 15.95 to 10.37. The effective pore size of the Co₃(HCOO)₆ material combined with the pore shape do not allow the two molecules to pass simultaneously, and once the CO₂ molecules are diffused in the micropores, the CH₄ is blocked. The supported Co₃(HCOO)₆ membrane retains high mechanical stability after a number of thermal cycles.     

Molecular orbital calculation of Mössbauer parameters for tin compounds in low temperature matrices

Mössbauer parameters of tin compounds, Sn(CH₃)_nCl_4–n (n=0, 1, 2, 3, 4), isolated in low temperature matrices are correlated with electronic properties at the tin nuclei obtained by molecular orbital calculations. The Mössbauer isomer shift and quadrupole splitting show good correlation with electron density and electric field gradient estimated by molecular orbital calculations, respectively. Structures of novel species (Sn(CH₃)₂CH₂ and [Sn(CH₃)₂CH₂]₂) produced via photodissociation of Sn(CH₃)₄ in low temperature matrices were estimated by means of molecular orbital calculations as compared with Mössbauer parameters.     

Adsorption separation performance of H2/CH4 on ETS-4 by concentration pulse chromatography

To exploit an effective adsorbent to separate hydrogen and methane, microporous titanium silicate molecular sieve NaETS-4 was synthesized and modified by strontium. The adsorption characteristics and diffusion behaviors of the prepared titanosilicate molecular sieve were studied by concentration pulse chromatography. And the effects of ion-exchange and dehydration temperature on adsorbent structure and gas diffusion were also discussed. The results showed that the thermal stability and Henry's Law constants were enhanced and micropore diffusivity decreased after exchanging Na⁺ with Sr²⁺. With the increase of dehydration temperature, Henry's Law constant and micropore diffusivity of CH₄ decreased in both NaETS-4 and SrETS-4. While for H₂ in SrETS-4, the increase of Henry's Law constant and the decrease of diffusion rate can be attributed to the shrinks of pore diameter resulting from the relocation of Sr²⁺. Correspondingly, the kinetic selectivity of H₂/CH₄ reached 8.91 indicating its potentiality in separating H₂ and CH₄.     

One-step synthesis of hydrothermally stable mesoporous aluminosilicates with strong acidity

Using tetraethylorthosilicate (TEOS), polymethylhydrosiloxane (PMHS) and aluminium isopropoxide (AIP) as the reactants, through a one-step nonsurfactant route based on PMHS-TEOS-AIP co-polycondensation, hydrothermally stable mesoporous aluminosilicates with different Si/Al molar ratios were successfully prepared. All samples exclusively showed narrow pore size distribution centered at 3.6 nm. To assess the hydrothermal stability, samples were subjected to 100 °C distilled water for 300 h. The boiled mesoporous aluminosilicates have nearly the same N₂ adsorption-desorption isotherms and the same pore size distributions as those newly synthesized ones, indicating excellent hydrothermal stability. The ²⁹Si MAS NMR spectra confirmed that PMHS and TEOS have jointly condensed and CH₃ groups have been introduced into the materials. The ²⁷Al MAS NMR spectra indicated that Al atoms have been incorporated in the mesopore frameworks. The NH₃ temperature-programmed desorption showed strong acidity. Due to the existence of large amount of CH₃ groups, the mesoporous aluminosilicates obtained good hydrophobicity. Owing to the relatively large pore and the strong acidity provided by the uniform four-coordinated Al atoms, the excellent catalytic performance for 1,3,5-triisopropylbenzene cracking was acquired easily. The materials may be a profitable complement for the synthesis of solid acid catalysts.     

Facile one‐pot synthesis of linear and radial block copolymers of styrene and isoprene through a novel coupling agent by living anionic polymerization

A new methodology is successfully used for the concurrent synthesis of three different copolymers; diblock, triblock, and three‐armed star‐block copolymers of styrene and isoprene via the living anionic polymerization with control over the molecular weight and weight fractions of each block. The room temperature polymerization process has resulted in the well defined linear and radial block copolymers, when the living di‐block of poly(styrene‐b‐isoprene) was coupled using cheap and readily available malonyl chloride as a novel coupling agent giving nearly 100% yield. The resulting block copolymers have narrow polydispersity index (PDI = 1.01–1.09) with a good agreement between the calculated and the observed molecular weights. The results are further supported by fractionation of the block copolymers by reversed‐phase temperature gradient interaction chromatography (RP‐TGIC) technique followed by size exclusion chromatography (SEC). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2636–2641, 2010     

Effect of pyrolysis temperature and operating temperature on the performance of nanoporous carbon membranes

Technology designed to capture and store carbon dioxide (CO₂) will play a significant role in the near-term reduction of CO₂ emissions and is considered necessary to slow global warming. Nanoporous carbon (NPC) membranes show promise as a new generation of gas separation membranes suitable for CO₂ capture.We have made supported NPC membranes from polyfurfuryl alcohol (PFA) at various pyrolysis temperatures. Positron annihilation lifetime spectrometry (PALS) and wide angle X-ray diffraction (WAXD) results indicate that the pore size decreases whilst the porosity increases with increasing pyrolysis temperature. The membrane performance results support these findings with a significant increase in permeance being seen with increasing pyrolysis temperature, which relates to the increase in porosity.Mixed gas performance measurements also show an increase in CH₄ permeance as the operating temperature is increased from 35 to 200 °C, which can be related to an increase in the rate of diffusion. However, the selectivity decreases with increasing operating temperature due to the smaller changes in the CO₂ permeance. These smaller changes in CO₂ permeance can be related to the stronger adsorption of this gas on the carbon surface at lower operating temperatures. Interestingly, regardless of the original pyrolysis temperature, the selectivity at higher operating temperatures is similar, whereas the permeance remains related to this pyrolysis temperature.     

Hydrogen purification using a SAPO-34 membrane

A SAPO-34 membrane separated CO₂/H₂ and H₂/CH₄ mixtures at feed pressures up to 1.7 MPa. Strong CO₂ adsorption inhibited H₂ adsorption and decreased H₂ permeances significantly, especially at low temperatures, so that CO₂ preferentially permeated and CO₂/H₂ selectivities were higher at low temperatures. At 253 K, CO₂/H₂ separation selectivities were greater than 100 with CO₂ permeances of 3 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹. The CO₂/H₂ separation exceeded the upper bounds (selectivity–permeability plot) for polymer membranes. The SAPO-34 membrane separated H₂ from CH₄ because CH₄ is close to the SAPO-34 pore size and has a lower diffusivity than H₂. The H₂/CH₄ separation selectivity had a small maximum with temperature, and decreased slightly with feed pressure and CH₄ feed concentration.     

Reduced sample recovery in liquid chromatography at critical adsorption point of high molar mass polystyrene

Low sample recovery may represent an important drawback in liquid chromatography at the critical adsorption point (LC-CAP) if the critical eluent is not carefully fitted to the system. So far, this problem was often overlooked and only few experimental examples can be found in literature. We showed that in the case of polystyrene (PS) in a tetrahydrofuran (THF)/n-hexane critical mixed eluent, PS with molar masses higher than 100 kg mol⁻¹ were not eluted from a tandem of two columns packed by bare silica gels with 30 nm and 100 nm pore size, respectively. The polymer trapped within the columns was well recovered after injection of a small volume of pure THF as demonstrated using 2D chromatography. We studied PS conformations by means of small angle neutron scattering and found that the THF/n-hexane critical eluent is in fact a theta solvent for PS. By replacing it by a CH₂Cl₂/n-hexane critical mixture, which is a good solvent for PS, the limits of reduced sample recovery was displaced towards far higher molar masses. Thus, thermodynamic quality of eluent - theta or good solvent - plays an important role on the phenomenon of sample recovery.     

Controlling Gas Selectivity in Molecular Porous Liquids by Tuning the Cage Window Size

Control of pore window size is the standard approach for tuning gas selectivity in porous solids. Here, we present the first example where this is translated into a molecular porous liquid formed from organic cage molecules. Reduction of the cage window size by chemical synthesis switches the selectivity from Xe‐selective to CH₄‐selective, which is understood using ¹²⁹Xe, ¹H, and pulsed‐field gradient NMR spectroscopy.     

The effects of silica gel (carrier) on the activity (hydrogen yield) of photocatalytic decomposition of water over [pol-Ti(OBu)4 + CH3OH]-complex

A significant effect of pore size has been found on the yield of photolysis of water to hydrogen, ozone (oxidising product) and methane (decomposing product of catalyst or solvent) using [pol-Ti(OBu)₄ + CH₃OH]-complex/SiO₂. The pore structure of silica gel has been found to provide good conditions for forming this type of catalyst.     

Temperature Gradient Interaction Chromatography: A Perspective

Chromatographia - The application of temperature gradient interaction chromatography (TGIC) as an advanced technique for the characterisation of polymers is discussed, in comparison to other liquid...     

The effect of F-doping and temperature on the structural and textural evolution of mesoporous TiO2 powders

Mesoporous F⁻-doped TiO₂ powders were prepared by hydrolysis of titanium tetraisopropoxide (TTIP) in a mixed NH₄F-H₂O solution. Effects of F⁻ ion content and calcination temperatures on the phase composition and porosity of mesoporous titania were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and BET surface areas. The results showed the BET surface area (S_BET) of the pure and doped powders dried at 100°C ranged from 260 to 310 m²/g as determined by nitrogen adsorption. With increasing calcination temperatures, the S_BET values of the calcined titania powders decreased due to the increase in crystalline size. The pore size distribution was bimodal with fine intra-particle pore and larger inter-particle pore as determined by nitrogen adsorption isotherms. The peak pore diameter of intra-particle pore increases with increasing F⁻ ion content. At 700°C, all the titania powders exhibit monomodal pore size distributions due to the complete collapse of the intra-particle pores. The crystallization of anatase was obviously enhanced due to F⁻-doping at 400°C and 500°C. Moreover, with increasing F⁻ ion concent, F⁻ ions not only suppressed the formation of brookite phase at low temperature, but also prevented phase transition of anatase to rutile at high temperature.     

Influence of coagulation temperature on pore size and properties of cellulose membranes prepared from NaOH–urea aqueous solution

The morphology and structure of the regenerated cellulose membranes prepared from its NaOH–urea aqueous solution by coagulating with 5 wt% H₂SO₄–10 wt% Na₂SO₄ aqueous solution with different temperatures and times were investigated. The pore size, water permeability and physical properties of the membranes were measured with scanning electron micrograph (SEM), wide X-ray diffraction (WXRD), Fourier transfer infrared spectroscopy (FTIR), flow rate method, and tensile testing. The SEM observation revealed that the structure and pore size of the membranes changed drastically as a function of the coagulation temperature. The membranes coagulated at lower temperatures tended to form the relatively small pore size than those at higher temperatures. On the contrary, the membranes coagulated at different times exhibited similar pore size. Interestingly, the mean pore size and water permeability of the membranes increased from 110 nm with standard deviation (SD) of 25 nm and 12 ml h⁻¹ m⁻² mmHg⁻¹ respectively to 1,230 nm with SD of 180 nm and 43 ml h⁻¹ m⁻² mmHg⁻¹ with an increase in coagulation temperature from 10 to 60°C. However, the membranes regenerated below 20°C exhibited the dense structure as well as good tensile strength and elongation at break. The result from FTIR and ultraviolet-visible (UV-vis) spectroscopy indicated that the relatively strong intermolecular hydrogen bonds exist in the cellulose membranes prepared at lower coagulation temperatures. This work provided a promising way to prepare cellulose materials with different pore sizes and physical properties by controlling the coagulation temperature.