Preparation and characterization of Ag~+ ion-exchanged zeolite-Matrimid~5218 mixed matrix membrane for CO_2/CH_4 separation

In this work, the zeolite-Y was ion-exchanged by introducing silver cations into the framework of microsized nano-porous sodium zeolite-Y using a liquid-phase ion exchanged method. The Ag+ion-exchanged zeolite, was then embedded into the Matrimid~5218 matrix to form novel mixed matrix membranes(MMMs). The particles and MMMs were characterized by ultraviolet-visible diffuse reflectance spectroscopy(UV–vis DRS), N_2 adsorption–desorption isotherm, X-ray diffraction(XRD), Fourier transform infrared(FTIR) and scanning electron microscopy(SEM). Furthermore, the effects of filler content(0–20wt%) on pure and mixed gas experiments, feed pressure(2–20 bar) and operating temperature(35–75 oC)on CO_2/CH_4 transport properties of Matrimid/Ag Y MMMs were considered. Characterization results confirmed an appropriate ion-exchange treatment of the zeolites. The SEM results confirmed the superior interfacial adhesion between polymer and zeolites, particularly in the case of Matrimid/Ag Y membranes.This is due to the proper silverous zeolite/Matrimid functional groups' interactions. The gas permeation results showed that the CO_2 permeability increased about 123%, from 8.34 Barrer for pure Matrimid to18.62 Barrer for Matrimid/Ag Y(15 wt%). The CO_2/CH_4 selectivity was improved about 66%, from 36.3 for Matrimid to 60.1 for Matrimid/Ag Y(15 wt%). The privileged gas separation performance of Matrimid/Ag Y(15 wt%) was the result of a combined effect of facilitated transport mechanism of Ag+ions as well as the intrinsic surface diffusion mechanism of Y-type zeolite. In order to survey the possibility of using the developed MMMs in industry, the CO_2-induced plasticization effect and mixed gas experiment were accomplished. It was deduced that the fabricated MMMs could maintain the superior performance in actual operating conditions.     

CO_2 residual concentration of potassium-promoted hydrotalcite for deep CO/CO_2 purification in H_2-rich gas

Elevated-temperature pressure swing adsorption is a promising technique for producing high purity hydrogen and controlling greenhouse gas emissions. Thermodynamic analysis indicated that the CO in H_2-rich gas could be controlled to trace levels of below 10 ppm by in situ reduction of the CO_2 concentration to less than 100 ppm via the aforementioned process. The CO_2 adsorption capacity of potassiumpromoted hydrotalcite at elevated temperatures under different adsorption(mole fraction, working pressure) and desorption(flow rate, desorption time, steam effects) conditions was systematically investigated using a fixed bed reactor. It was found that the CO_2 residual concentration before the breakthrough of CO_2 mainly depended on the total amount of purge gas and the CO_2 mole fraction in the inlet syngas.The residual CO_2 concentration and uptake achieved for the inlet gas comprising CO_2(9.7 mL/min) and He(277.6 mL/min) at a working pressure of 3 MPa after 1 h of Ar purging at 300 mL/min were 12.3 ppm and0.341 mmol/g, respectively. Steam purge could greatly improve the cyclic adsorption working capacity, but had no obvious benefit for the recovery of the residual CO_2 concentration compared to purging with an inert gas. The residual CO_2 concentration obtained with the adsorbent could be reduced to 3.2 ppm after 12 h of temperature swing at 450 °C. A new concept based on an adsorption/desorption process, comprising adsorption, steam rinse, depressurization, steam purge, pressurization, and high-temperature steam purge, was proposed for reducing the steam consumption during CO/CO_2 purification.     

Adsorption isotherms and kinetic characteristics of methane on block anthracite over a wide pressure range

It is important to quantitatively understand the methane adsorption and transport mechanism in coal for an evaluation of the reserves and for its production forecast. In this work, a block coal sample was chosen to perform the CH4 adsorption experiments using the gravimetric method at temperatures of 293.60 K, 311.26 K, 332.98 K and 352.55 K and pressures up to 19 MPa. The excess adsorption capacity of CH4 in dry block anthracite increased, followed by a sequence decrease with the increasing pressure. High temperature restrained the growth of the excess adsorption due to that the adsorption is an intrinsically physical and exothermic process. The excess adsorption peak decreased slowly with the increase of temperature and intersected at a pressure of more than 18 MPa; meanwhile, the pressure at the excess adsorption peak increased.The existing correlations were examined in terms of density rather than pressure. The DR+k correlation, with an average relative deviation of ±0.51%, fitted our data better than the others, with an average relative deviation of up to 2.29%. The transportation characteristics of CH4 adsorption was also investigated in this study, including the adsorption rate and diffusion in block coal. The kinetic data could be described by a modified unipore model. The adsorption rates were found to exhibit dependence on pressure and temperature at low pressures, while the calculated diffusivities exhibited little temperature dependence. In addition, the kinetic characteristics were compared between CH4 and CO2 adsorption on the block coal. The excess adsorption ratios of CO2 to CH4obtained from the DR+k model decreased with the increasing pressure.     

First assessment of Li_2O–Bi_2O_3 ceramic oxides for high temperature carbon dioxide capture

The capacity to capture CO_2 was determined in several stoichiometric compositions in the Li_2O–Bi_2O_3 system. The compounds(Li_7BiO_6, Li_5BiO_5, Li_3BiO_4 and LiBiO_2 phases) were synthesized via solid-state reaction and characterized by X-ray diffraction, scanning electron microscopy and N2 adsorption techniques.The samples were heat-treated at temperatures from 40 to 750 °C under the CO_2 atmosphere to evaluate the carbonate formation, which is indicative of the capacity of CO_2 capture. Moreover, Li_7BiO_6 shows an excellent CO_2 capture capacity of 7.1 mmol/g, which is considerably higher than those of other previously reported ceramics. Li_7BiO_6 is able to react with CO_2 from 240 °C to approximately 660 °C showing a high kinetic reaction even at CO_2 partial pressure values as low as 0.05.     

Preparation of CO_2 selective composite membranes using Pebax/CuBTC/PEG-ran-PPG ternary system

Three phase Pebax~? MH 1657/PEG-ran-PPG/CuBTC(polymer/liquid/solid) was successfully deposited as a selective layer on a porous Polysulfone(PSF) support. In fact, the beneficial properties of PEG(high selectivity) with those of PPG(high permeability, amorphous) have been combined with superior properties of mixed matrix membrane(MMMs). The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by CO_2 and CH_4adsorption test. Statistically based experimental design(central composite design, CCD) was applied to analyze and optimize the effect of PEG-ran-PPG(10–50 wt%) and CuBTC(0–20 wt%) mass contents on the CO_2 permeance and CO_2/CH_4 ideal selectivity. Based on the regression coefficients of the obtained models, the CO_2 permeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO_2/CH_4 ideal selectivity. Under the optimum conditions(PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%), nearly 620% increase in the CO_2 permeance and43% enhancement in the CO_2/CH_4 ideal selectivity was observed compared to the neat Pebax. The effect of pressure(3, 9 and 15 bar) on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of CO_2 in the membranes resulted in the enhancement of CO_2 permeability with increase in gas pressure.     

Synthesis of a PEBAX-1074/ZnO nanocomposite membrane with improved CO_2 separation performance

In this investigation, polymeric nanocomposite membranes(PNMs) were prepared via incorporating zinc oxide(ZnO) into poly(ether-block-amide)(PEBAX-1074) polymer matrix with different loadings. The neat membrane and nanocomposite membranes were prepared via solution casting and solution blending methods, respectively. The fabricated membranes were characterized by field emission scanning electron microscopy(FESEM) to survey cross-sectional morphologies and thermal gravimetric analysis(TGA)to study thermal stability. Fourier transform infrared(FT-IR) and X-ray diffraction(XRD) analyses were also employed to identify variations of the chemical bonds and crystal structure of the membranes, respectively. Permeation of pure gases, CO_2, CH_4 and N_2 through the prepared neat and nanocomposite membranes was studied at pressures of 3–18 bar and temperature of 25 °C. The obtained results showed that the fabricated nanocomposite membranes exhibit better separation performance compared to the neat PEBAX membrane in terms of both permeability and selectivity. As an example, at temperature of 25 °C and pressure of 3 bar, CO_2 permeability, ideal CO_2/CH_4 and CO_2/N_2 selectivity values for the neat PEBAX membrane are 110.67 Barrer, 11.09 and 50.08, respectively, while those values are 152.27 Barrer,13.52 and 62.15 for PEBAX/ZnO nanocomposite membrane containing 8 wt% ZnO.     

A flexible metal-organic framework with double interpenetration for highly selective CO2 capture at room temperature

A flexible metal-organic framework of 1a Cu(FMA)(4,4'-Bpe)0.5(FMA=fumarate; 4,4'-Bpe=trans-bis-(4-pyridyl)ethylene) that exhibits guest molecule-controlled gate-opening adsorption has been reported, in which the flexible pores can be enlarged by CO_2 molecules rather than CH_4 and N_2 under a certain gate-opening pressure. The CO_2 uptake can be sharply improved from 6.85cm~3 g~(–1) at 0.60 atm to 33.7 cm~3 g~(–1) at 1 atm due to the gate-opening effect, thus resulting in the notably enhanced adsorption selectivities for CO_2/CH_4(32:1, v/v) and CO_2/N_2(48:1, v/v) separations at room temperature.     

Synthesis of mechanically robust porous carbon monoliths for CO_2 adsorption and separation

Porous carbon materials with developed porosity,high surface area and good thermal-and chemicalresistance are advantageous for gas adsorption and separation.However,most carbon adsorbents are in powder form which exhibit high pressure drop when deployed in practical separation bed.While monolithic carbons have largely addressed the pulverization problem and preserved kinetics and usually suffer from abrasion during multiple adsorption-desorption cycles.Herein,we proposed the designed synthesis of mechanically robust carbon monoliths with hierarchical pores,solid nitrogen-containing framework.The synthesis started with the polymerization of resorcinol and formaldehyde under weakly acidic conditions generated from cyanuric acid,and then an appropriate amount of hexamethylenetetramine(HMTA)was added as a crosslinker to prompt the formation of three dimensional frameworks.After carbonization process,the as-obtained porous carbon monoliths have a high radial compressive strength of 886 N/cm as well as a BET specific surface area of up to 683 m~2/g.At approximately 1 bar,the CO_2 equilibrium capacities of the monoliths are in the range of 3.1–4.0 mmol/g at 273 K and of 2.3–3.0 mmol/g at 298 K,exhibiting high selectivity for the capture of CO_2 over N_2 from a stream which consists of 16.7%(v%)CO_2 in N_2.Meanwhile,they undergo a facile CO_2 release in an argon stream at 298 K,indicating a good regeneration capacity.After cycle testing,sieving and regeneration,the adsorbent has no mass loss,compared to that of its fresh counterpart.     

GAS SORPTION,DIFFUSION AND PERMEATION OF ORDERED POLYMERIC MEMBRANES

He, CO_2, O_2, N_2, CH_4, C_3H_8, and t-C_4H_(10) gas permeability coefficients and diffusion coefficients of poly(4-methylpentene-1) (PMP) with various degrees of crystallization were plotted against the degree of crystallization. The plotdemonstrated a linear relationship. The gas permeability coefficient and diffusion coefficient of pure amorphous and purecrystalline PMPs were evaluated by a linear extrapolation to zero and 100% crystallinity, respectively. The relationshipbetween the diffusion coefficient of crystalline parts of PMP and the kinetic diameter of penetrant gases was discussed.Syndiotactic polystyrene (SPS) could exist as δ form crystals complexed with organic solvents such as benzene, toluene,xylene, and ethylbenzene. The mesophase of SPS is prepared by annealing the δ form of crystalline complexes at a certaintemperature for 1 h. The desorption of solvent during annealing almost does not result in changes of both the conformation ofbackbone chains and the crystal lattice. We could prepare the mesophase containing molecular cavities with the size andshape of the organic solvent molecules. The mesophase could sorb the same solvent after the manner of Langmuir sorption atlow vapor pressure range while this would not be the case for solvents of different size and shape. This suggests a molecularrecognition of organic solvent, and mesophase SPS might be useful for separation membrane and adsorptive material.     

Catalytic performance of imidazole modified HZSM-5 for methanol to aromatics reaction

A facile approach was developed for the preparation of nano-sized HZSM-5 with a hierarchical mesoporous structure by adding imidazole into conventional zeolite synthesis precursor solution. The physicochemical properties of modified HZSM-5 were characterized by X-ray diffraction(XRD), N_2 adsorption–desorption isotherms, scanning electron microscopy(SEM), NH_3-temperature-programmed desorption(NH_3-TPD) and pyridine adsorption infrared spectroscopy(Py-IR). The coke in spent catalysts was characterized by thermogravimetry(TG). The results showed that hierarchical HZSM-5 zeolites with excellent textural properties, such as abundant porous structure, uniform particle size and suitable acidity, could be synthesized by the recipe of one-pot synthesis routes. Moreover, the obtained HZSM-5 exhibited higher selectivity of total aromatics as well as longer lifetime in the catalytic conversion of methanol to aromatics, comparing with conventional HZSM-5. It is expected that the synthesis approach demonstrated here will be applicable to other zeolites with particular textural properties and controllable particle sizes, facilitating the emergence of new-type porous materials and their related applications in catalysis and separation.     

CO_2在三聚氰胺酚醛纤维上的吸附分离

以三聚氰胺、间苯三酚和甲醛为原料,通过水热缩聚反应合成了三聚氰胺酚醛纤维(PMF),考察了温度对PMF合成的影响。以扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N_2吸脱附和傅里叶变换红外(FT-IR)光谱等表征了PMF的形貌和结构,并采用体积法测定不同温度下CO_2和N_2在PMF上的单组分吸附平衡等温线。结果表明,在393 K下合成的PMF具有较大的比表面积(64 m2/g)和较高的CO_2吸附量(1.83 mmol/g,298 K、118 k Pa)。穿透柱实验表明,在298 K、200-600 k Pa,CO_2-N_2混合气在PMF上均可实现有效分离。将PMF在873 K下,N_2、H2及水蒸气等多种气氛中进行后处理,其比表面积和微孔孔容均显著增加,其中,在15%H_2O气氛中处理后,样品CO_2吸附量提高至2.83 mmol/g(298 K、118 k Pa)。     

晶种法合成UZM-9分子筛及其CO2/CH4/N2吸附分离性能

以TEAOH和TMAOH为有机模板剂,酸处理的UZM-9分子筛为晶种,采用水热法在48 h内合成出分子筛UZM-9,并对其CO₂/CH₄/N₂的吸附分离性能进行了研究。采用XRD、ICP、TG、SEM与气体吸附等手段对晶种法合成的UZM-9分子筛结构、耐水稳定性与吸附性能进行了研究。结果表明,晶种法可以在2 d内合成出硅铝原子比在3以上、收率达到65%的UZM-9分子筛;所得分子筛的CO₂吸附容量可以达到5 mmol/g以上,吸附热为34 kJ/mol,CO₂/CH₄、CO₂/N₂与CH₄/N₂的平均分离因子分别为100、240与2.4,CO₂分离性能优良且具有一定耐水性能。     

二氧化碳/甲烷/氮气二元混合物在有序介孔碳材料CMK-3 中的吸附和分离

采用分子模拟与吸附理论研究了天然气成分在有序介孔碳材料CMK-3上的吸附和分离.巨正则系综蒙特卡罗(GCMC)模拟表明,CH4和CO2气体的较优存储条件分别为208 K、4 MPa和298 K、6 MPa,其最大超额吸附量分别为10.07和14.85 mmol· g-1.基于双位Langmuir-Freundlich (DSLF)模型,使用理想吸附溶液理论(IAST)预测了不同二元混合物在CMK-3中的分离行为,发现吸附选择性Sco2/CH4与ScH4/N2比较接近,在298 K和4 MPa下约等于3,而N2-CO2体系中的CO2吸附选择性较高,可达到7.5,说明CMK-3是一种适合吸附和分离天然气组分的碳材料.     

MgO/Al2O3吸附剂对CO2动态吸附性能的研究

以γ- Al₂O₃为载体,采用等体积浸渍法制取MgO/Al₂O₃吸附剂,利用BET、XRD等表征手段对吸附剂进行表征;并通过固定床测量穿透曲线的方法研究其对CO2动态吸附性能的影响,考察了MgO负载量、吸附温度、气体流量等因素对吸附剂吸附CO₂性能的影响,同时还通过多次吸脱附实验考察MgO/Al₂O₃吸附剂的稳定性和再生能力。结果表明,MgO负载量为10%的吸附剂,吸附温度在50℃左右,流量为45mL/min动态吸附量最大;经数次循环后材料的结构性质和吸附性能未见明显变化,可再生性能比较优异,是一种潜在的可工业化应用的CO₂吸附剂。     

新型类沸石金属-有机骨架材料用于天然气中CO2的分离

研究了在usf型类沸石金属-有机骨架材料(usf-ZMOF)中不同金属离子(Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Al³⁺)对天然气分离(以CO₂/CH₄, CO₂/H₂, CO₂/N₂为研究对象)的不同影响. 结果表明, 此类材料对于3种体系的分离选择性均高于现有材料. 其中性能最好的是Al-usf-ZMOF, 其对CO₂/CH₄, CO₂/N₂和CO₂/H₂的分离选择性分别为290, 1700和16800. 同时, 对于经不同的离子交换后的usf-ZMOF, 吸附选择性随着离子电荷值的增加而增大; 对于同一主族的离子, 选择性随着原子序数的增加而减小. 而上述现象的产生是由阳离子和CO₂间的强静电作用所致.     

WO3的引入对MnOx-Fe2O3催化剂上NH3-SCR反应中N2选择性的促进作用

采用溶胶-凝胶法制备了不同含量钨修饰的MnO_x-Fe₂O₃催化剂,重点考察WO₃的引入对NH₃-SCR反应中N₂选择性的影响,通过XRD、BET、XPS、H₂-TPR、Raman和In situ DRIFTS等手段对催化剂的物理化学性质进行表征。结果表明,钨的引入显著提高NH₃-SCR的N₂选择性,当WO₃质量分数为15%时,具有最佳的NH₃-SCR催化性能,且在50-250℃条件下N₂O浓度始终低于0.003%。这主要是由于适量WO₃的引入,导致催化剂物相由α-Fe₂O₃向γ-Fe₂O₃转变,并与锰相互作用形成新的无定型MnWO₄,获得较大的比表面积;使得Mn⁴⁺/（Mn³⁺+Mn⁴⁺）比例减少但Fe²⁺及表面化学吸附氧（O_α）含量增加,从而降低催化剂氧化性;增强催化剂表面的Lewis酸性位点的含量及强度,增强NH₃的吸附,促进了SCR反应,同时抑制了NO₂深度氧化形成硝酸盐物种,降低硝酸盐物种还原产生的副产物N₂O含量,从而显著提高WO₃-MnO_x-Fe₂O₃催化剂在NH₃-SCR中的N₂选择性。     

湿磨法制备纳米Li_4SiO_4材料用于高温捕集CO_2

采用不同硅源、锂源以湿磨法结合高温焙烧制备了纳米Li_4SiO_4材料,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)表征了合成材料的结构和表面形貌,利用热重分析仪(TG)研究了Li_4SiO_4材料高温下的CO_2吸收性能和循环使用稳定性。结果表明,湿磨法制备的Li_4SiO_4材料在550℃、2.5×104Pa下,10min可达吸收平衡,平衡吸收量为27.9%(质量分数),经五次吸收-解吸后仍保持初始吸收性能,显示了良好的循环稳定性。将25%CO_2-25%N2-50%He混合气通过Li_4SiO_4材料床层,发现在550℃下,CO_2能被高效捕集,在相对湿度为10%的水汽存在下,Li_4SiO_4捕集CO_2的性能没有明显下降。     

A型沸石/活性炭复合材料的制备及甲烷/氮气吸附分离性能

以沥青和煤矸石为原料,经炭化、活化后获得型体活性炭材料(AC),并在此基础上进行水热晶化,研究晶化时间对复合材料中4A沸石的形成、孔结构和甲烷、氮气吸附性能的影响。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、77 K下的氮气吸附-脱附以及273 K下的CO_2吸附等温线对样品进行表征,结果表明水热晶化后,复合材料中的硅铝形成立方结构的4A沸石,出现了0.45~0.6 nm的微孔,微孔孔容增加,并伴有少量的中孔和大孔。复合材料在298 K下的甲烷(CH_4)和氮气(N_2)吸附等温线的结果表明,晶化时间6 h的复合材料AC-2的甲烷吸附量被提高至10.8 m L/g,并保持较高的CH4/N2平衡分离比(3.7)。     

氨基修饰的金属有机框架Cu_3(BTC)_2的制备及其CO_2吸附性能研究

首先制备了嫁接氨基的均苯三甲酸,同时以其为原料通过溶剂热法合成了金属有机框架材料Cu_3(NH_2BTC)_2,利用XRD、N_2吸附-脱附、热重、红外、原位红外分析等表征手段对吸附剂进行了表征,并通过固定床测量穿透曲线的方法研究其CO_2吸附性能。结果表明,氨基被成功引入Cu_3(BTC)_2骨架中。氨基修饰的Cu_3(BTC)_2对CO_2有着较高的吸附容量,在10 kPa,50℃的条件下CO_2吸附量为1.41 mmol/g,这源于材料对于CO_2同时存在着物理吸附和化学吸附。     

High-throughput model-building and screening of zeolitic imidazolate frameworks for CO2 capture from flue gas

To find potential zeolitic imidazolate frameworks(ZIFs)for CO2 capture from flue gas,we built 169,898 ZIF models from 84,949 hypothetical zeolite networks.By calculating their lattice energies,accessible volumes to CO2,the isosteric adsorption heat(Qst)of H2 O,Henry’s constant ratio(SKH)of CO2/N2,percent regenerability(R%),CO2 working capacity(ΔNCO2),CO2/N2 adsorption selectivity(SCO2/N2))and adsorbent performance score(APS),we identi fied 49 hydrophobic ZIF structures that might outplay already-realised ZIFs built from the same imidazolate linkers for CO2 capture from flue gas.