Insights into carbon dioxide sequestration into coal seams through coupled gas flow-adsorption-deformation modelling

Injecting carbon dioxide(CO_(2))into coal seams may unlock substantial carbon sequestration potential.Since the coal acts like a carbon filter,it can preferentially absorb significant amounts of CO_(2).To explore this further,desorption of the adsorbed gas due to pressure drop is investigated in this paper,to achieve an improved understanding of the long-term fate of injected CO_(2) during post-injection period.This paper presents a dual porosity model coupling gas flow,adsorption and geomechanics for studying coupled processes and effectiveness of CO_(2) sequestration in coals.A new adsorption?desorption model derived based on thermodynamics is incorporated,particularly,the desorption hysteresis is considered.The reliability of the proposed adsorption-desorption isotherm is examined via validation tests.It is indicated that occurrence of desorption hysteresis is attributed to the adsorption-induced pore deformation.After injection ceases,the injected gas continues to propagate further from the injection well,while the pressure in the vicinity of the injection well experiences a significant drop.Although the adsorbed gas near the well also decreases,this decrease is less compared to that in pressure because of desorption hysteresis.The unceasing spread of CO_(2) and drops of pressure and adsorbed gas depend on the degree of desorption hysteresis and heterogeneity of coals,which should be considered when designing CO_(2) sequestration into coal seams.

Thermogravimetric Study on Oxygen Adsorption/Desorption Properties of Double Perovskite Structure Oxides REBaCo_2O_(5+δ)(RE= Pr,Gd,Y)

The oxygen adsorption/desorption properties of double perovskite structure oxides PrBaCo2O5＋δ,GdBaCo2O5＋δ,and YBaCo2O5＋δ were investigated by the thermogravimetry（TG）method in the temperature range of 400~900 ℃.The calculated oxygen adsorption/desorption surface reaction rate constants ka and kd of these double perovskite structure oxides were larger than the commonly used cubic perovskite oxides,such as Ba0.95Ca0.05Co0.8Fe0.2O3-δ and Ba0.5Sr0.5Co0.8Fe0.2O3-δ,whereas,the oxygen permeation flux was comparable to that of the latter,which was attributed to the smaller difference of oxygen vacancy in oxygen and nitrogen atmosphere（Δδ/Vmol）in these double perovskite structure oxides.The large oxygen adsorption/desorption rate constants of GdBaCo2O5＋δ and PrBaCo2O5＋δ made them nice catalyst coating materials,on other membrane surfaces,to improve the oxygen permeability.

Adsorption and Desorption Characteristics of Alkali Ions in Hydrated C_3S-nano SiO_2 Pastes

C3S pastes containing 0%,5%,10%,and 15%nano-SiO2 mixed with de-ionized water and alkali solutions were prepared.When C3S was completely hydrated,the pastes were ground into powders with a particle size less than 80μm.Adsorption and desorption characteristics of alkali ions adsorbed by C3S-nano SiO2 pastes mixed with de-ionized water immersed in alkali solutions and those in C3S-nano SiO2 pastes mixed with alkali solutions,were investigated.Meawhile,the adsorption mechanisms of alkali ions were discussed.Results showed that the contents of alkali ions adsorbed by C3S-nano SiO2 pastes mixed with de-ionized water increased with increasing substitution levels of nano-SiO2 and/or the initial alkali concentrations.In C3S-nano SiO2 pastes mixed with de-ionized water,each paste was characterized by having a fixed alkali-adsorption capacity that was essentially independent of alkali concentration.No obvious difference between the adsorption capacity of a given paste for K~＋and Na~＋was observed.Adsorption of alkali ions in the pastes is considered to be caused by surface force which is related to the BET specific surface area of the paste,and charge compensation of C-S-H gel,mainly by electrostatic interactions.In C3S-nano SiO2 pastes mixed with alkali solutions,alkali ions may enter the structure of C-S-H gel to replace a part of Ca^2＋in the interlayer.This assumption is supported by the structural characterization of C-S-H gel using ^（29）Si MAS NMR.

Systematic investigation of SO_(2) adsorption and desorption by porous powdered activated coke:Interaction between adsorption temperature and desorption energy consumption

Porous carbon materials have been widely used for the removal of SO_(2) from flue gas.The main objective of this work is to clarify the effects of adsorption temperature on SO_(2) adsorption and desorption energy consumption.Coal-based porous powdered activated coke(PPAC)prepared in the drop-tube reactor was used in this study.The N_(2) adsorption measurements and Fourier transform infrared spectrometer analysis show that PPAC exhibits a developed pore structure and rich functional groups.The experimental results show that with a decrease in adsorption temperature in the range of 50–150℃,the adsorption capacity of SO_(2) increases linearly;meanwhile,the adsorption capacity of H_(2)O increases,resulting in the increase in desorption energy consumption per unit mass of adsorbent.The processes of SO_(2) and H_(2)O desorption were determined by the temperature-programmed desorption test,and the desorption energies for each species were calculated.Considering the energy consumption per unit of desorption and the total amount of adsorbent,the optimal adsorption temperature yielding the minimum total energy consumption of regeneration is calculated.This study systematically demonstrates the effect of adsorption temperature on the adsorption–desorption process,providing a basis for energy saving and emission reduction in desulfurization system design.

Study of the Temperature-Programmed Desorption of Carbon Dioxide (CO2) on Zeolites X Modified with Bivalent Cations

Study of physisorbed and chemisorbed carbon dioxide (CO2) species was carried out on the NaX zeolite modified by cationic exchanges with bivalent cations (Ca2+ and Ba2+) by temperature-programmed desorption of CO2 (CO2-TPD). Others results were obtained by infrared to complete the study. The results of this research showed, in the physisorption region (213 - 473 K), that the cationic exchanges on NaX zeolite with bivalent cations increase slightly the interactions of CO2 molecule with adsorbents and/or cationic site. Indeed, the desorption energies of physisorbed CO2 obtained on the reference zeolite NaX (13.5 kJ·mol-1) are lower than that of exchanged zeolites E-CaX and E-BaX (15.77 and 15.17 kJ·mol-1 respectively). In the chemisorbed CO2 region (573 - 873 K), the desorption energies related to desorbed species (bidentate carbonates: CO32-) on the exchanged zeolites E-CaX and E-BaX are about 81 kJ·mol-1, higher than the desorbed species (bicarbonates: HCO32-) on the reference R-NaX (62 kJ·mol-1). In addition, the exchanged E-BaX zeolite develops the secondary adsorption sites corresponding to bicarbonates species with desorption energies of 35 kJ·mol-1 lower to desorption energies of bicarbonates noted on the reference zeolite NaX.

Adsorption and Desorption Behaviors of Bovine Serum Albumin on Gelatin/Chitosan Sponge

Gelatin (Gel) and chitosan (CTS) have several biomedical applications because of their biodegradability and biocompatibility. Crosslinking of Gel and Gel/CTS systems was evaluated using N-acetyl-D-glucosamine (GlcNAc) formed into sponges by lyophilization. The prepared sponges were used to study the adsorption and desorption of fluorescein isothiocyanate (FITC) labeled bovine serum albumin (BSA) as a model instead of a growth factor. The effect of FITC-BSA concentration and temperature on the adsorption behavior of Gel/CTS sponges was investigated. The Langmuir adsorption isotherm model was used on the basis of the assumption that monolayer adsorption occurs on the surface;the results fit with the experiment data. The adsorption constants were 5.77 and 9.68 mL/mg for Gel and Gel/CTS sponges, respectively. The adsorption thermodynamic constants were found;adsorption onto sponges was an exothermic reaction. In particular, Gibbs free energy (ΔG) exhibited negative values in the range of 283 - 343 K for both Gel and Gel/CTS sponges, demonstrating the spontaneous nature of adsorption reaction. In addition, desorption behavior was evaluated for different concentrations and pH values of the FITC-BSA solution. The high adsorbed amounts of FITC-BSA on sponge resulted in high desorbed amounts in sponge, up to 55% from 3.5 mg/mL adsorbed concentration (around 1.5 mg from 3 mg adsorb amount). Desorption decreased following the buffer solution pH decrease, from 7.4 to 4 and 2 in Gel and Gel/CTS sponges, respectively. Based on the results of this preliminary study, these composite sponges could have significant application in biomedical materials.

Preparation and Adsorption Property of Hydrophobic SiO_2 Aerogels Modif ied by Methyl Triethoxysilane

The hydrophobic SiO2 aerogels were prepared by in-situ polymerization sol-gel method and supercritical drying of ethanol method with tetraethylorthosilicate（TEOS） as silica source, methyl triethoxysilane （MTMS） as modifier, ethanol as solvent. Moreover, the structure and adsorption property of SiO2 aerogels were also studied. As results, the surface area of SiO2 aerogels was 863.59 m2/g, the pore volume was 3.57 cm3/g, and the contact angle was 150 °. Adsorption intensity of silica aerogels for organic liquid （alkanes, benzene compounds, and nitro-compounds） is bigger than that of activated carbon. The mass of the liquid absorbed increased linearly with the surface tension of the liquid. The lower surface tension and boiling point are, the shorter desorption time is. After regenerating 10 times, nitromethane regeneration rate remain the same, and almost more than 94%. So SiO2 aerogels have good absorption and regeneration property.

Synthesis of modified D401 chelating resin and its adsorption properties for Pb^(2+)

A novel chelating resin with sulfonic group was synthesized by chemical modification of D401 resin with sulphonation reaction and characterized by FT-IR spectrometry. The adsorption properties of the novel chelating resin for Pb2+ were studied by batch adsorption, and the adsorption process was analyzed from thermodynamics and kinetics aspects. The adsorption mechanism of Pb2+ on the modified D401 chelating resin was discussed by FT-IR spectrometry. Experimental results show that in the Pb2+ concentration range of 200-400 mg/L, the adsorption capacities of the modified D401 chelating resin for Pb2+ increase by 77%-129%, and Langmuir isothermal adsorption model is more suitable for the equilibrium adsorption data. Adsorption is an endothermic process that runs spontaneously. Kinetic analysis shows that the adsorption rate is mainly governed by liquid film diffusion. The best pH value under adsorption condition is 4-5. The saturated resin can be regenerated by 3 mol/L nitric acid, and the adsorption capacity remains stable after five consecutive adsorption-desorption cycles. The maximal static saturated adsorption capacity of the resin is 206 mg/g at 333 K in the Pb2+ concentration range of 200-400 mg/L. The modified D401 chelating resin is an efficient adsorbent for the removal of Pb2+ from its single-metal ion solution.

HREELS Studies on Adsorption and Decomposition of ^(15)NO on Mo(100)-c(2×2)N Surface

High resolution electron energy loss spectroscopy (HREELS) has been used to investigate the adsorPtion and decomposition of 15NO on the Mo(100)-c(2×2)14N surface. At 140K, the 15NO molecu1e could adsorb associatively on atop sites of the Mo and l4N atoms in the nitride layers. On the other hand, a small amount of dissociatCd 15NO also exists. The dissociation of surface nitric oxides species at elevated temperatures caused the oxidation of the surface Mo.

Adsorption Characteristics of 2,4-Dichlorophenoxybutric Acid Using Bamboo Activated Carbon in a Fixed Bed

Adsorption and desorption characteristics of 2,4-dichlorophenoxybutyric acid (2,4-DB) from aqueous solution on bamboo activated carbon (BAC) were studied in a fixed bed adsorber. The adsorption equilibrium capacity of 2,4-DB on BAC increased with decreasing initial pH of the solution and with a maximum adsorption capacity of 1.61 mol/kg. The adsorption rate of 2,4-DB on BAC could be best fitted by the pseudo first-order model. The adsorption model based on the linear driving force approximation (LDFA) was used for simulating the adsorption behavior of the 2,4-DB in a fixed bed. More than 95% desorption of 2,4-DB was obtained using distilled water.

Adsorption and Reaction of CO on Mo(100)-c(2×2)-N Surface Studied by HREELS

High resolution electron energy loss spectroscopy (HREELS) has been used to investigate the adsorption and reaction of CO on the Mo(100)-c(2×2)N surface. CO directly adsorbed on the N atoms from the c(2×2) layer to form isocyanate (NCO) surface species was found in addition to CO adsorbed on the molybdenum atoms at 120 K. indicating that both Mo and N atoms of the Mo(100)-c(2×2)-N surface are of high reactivities for CO adsorption.

二维C_(2)N材料在析氢反应中的理论设计

H的吸附自由能与析氢反应中的交换电流密度log(i 0)有强关联相互作用,因此密度泛函理论工作采信基于这样的关联相互作用,可以设计和寻找适合析氢反应的材料。密度泛函理论计算可以帮助我们进行快速筛选在电解水过程中的析氢反应表现优秀的催化材料。本文通过计算发现,过渡金属Cu、Ni、Pd锚定在单层C_(2) N上的催化材料,其氢吸附自由能变化ΔG H分别为0.95 eV、0.80 eV、0.71 eV,C_(2) N上负载Ni的材料接近C_(2) N上负载Pd的材料,这使得非贵金属Ni的单原子材料有可能成为取代贵金属的析氢材料。

TCN-TiO_(2)/Zn(CH_(3)COO)_(2)-ACF复合材料吸附耦合光催化降解烷烃类VOCs性能研究

采用Zn(CH_(3)COO)_(2)通过超声-真空浸渍法对活性炭纤维(ACF)进行改性,通过水热横向热剥离法制备了管状氮化碳(TCN),并将其与TiO_(2)复合并负载于改性ACF上制备成TCN-TiO_(2)/Zn(CH_(3)COO)_(2)-ACF复合材料。应用扫描电子显微镜、透射电子显微镜、X射线衍射、N_(2)吸附-脱附、X射线光电子能谱、傅里叶变换红外光谱、紫外-可见分光光谱、光致发光光谱、光电流响应曲线对复合材料进行表征,并对复合材料催化正己烷降解的机理与降解率进行了研究。结果表明:光照条件下,TCN质量分数为4%的复合材料对正己烷的降解效果最好,其最佳的制备条件为负载2次、450℃下煅烧。采用此条件所制复合光催化剂,在体积空速为1000 h-1的条件下,质量浓度为200 mg/m^(3)的正己烷气体降解率可达到87.9%。采用Zn(CH_(3)COO)_(2)对ACF进行改性,使ACF吸附能力得到增强;TCN与TiO_(2)复合形成异质结,降低了电子-空穴复合率,从而提高复合光催化剂的吸附耦合光催化效率。

辐射接枝制备聚甲基丙烯酸N,N-二甲氨基乙酯-TiO_(2)光催化剂及其对Cr(Ⅵ)的吸附还原性能

以二氧化钛(TiO_(2))为基材,甲基丙烯酸二甲氨基乙酯(DMAEMA)为单体,采用共辐射接枝法成功合成了聚甲基丙烯酸N,N-二甲氨基乙酯-TiO_(2)(TiO_(2)-g-PDMAEMA)吸附-光催化剂。同时探究了单体浓度和吸收剂量对重金属离子吸附作用的影响。利用扫描电镜、X射线衍射仪、傅里叶红外光谱分析仪、热重分析仪、X射线光电子能谱、接触角等表征手段,证实了电子束共辐射接枝法成功将DMAEMA单体接枝到TiO_(2)表面。在吸收剂量为60 kGy、单体浓度为20%时,TiO_(2)-g-PDMAEMA对10 mg/L Cr(Ⅵ)具有较佳的吸附能力,吸附容量可达10.75 mg/g。在可见光诱导下,吸收剂量为60 kGy、单体浓度为10%时,制备的TiO_(2)-g-PDMAEMA具有最佳的吸附-光催化还原能力,对10 mg/L Cr(Ⅵ)的去除率达85.56%。该新型光催化剂上的吸附-光催化协同效应可以满足去除水中Cr(Ⅵ)污染的要求。

颗粒状N-TiO_(2)的制备及其光催化活性

采用溶剂热法制备氮掺杂二氧化钛(N-TiO_(2))光催化剂,以亚甲基蓝(MB)为降解目标,探讨了不同的合成条件对产物的影响,以及催化剂质量、染料初始质量浓度和pH等因素对N-TiO_(2)催化性能的影响,初步研究了其催化和吸附的动力学过程。结果表明:在尿素与钛源质量比为1∶1,合成温度和时间为180℃和18 h条件下,合成的纳米N-TiO_(2)是由粒径为30~60 nm的纳米颗粒团聚形成的大颗粒,禁带宽度为3.1 eV;在可见光照射下,当N-TiO_(2)的质量为0.075 g,染料的初始质量浓度为25 mg/L,以及pH=5时,其催化效果良好;此外,其催化和吸附MB的过程分别符合一级动力学过程和准二级动力学模型。

Adsorption separation of carbon dioxide,methane,and nitrogen on Hβand Na-exchangedβ-zeolite

Adsorption isotherms of carbon dioxide （CO2）, methane （CH4）, and nitrogen （N2） on Hβand sodium exchanged β-zeolite （Naβ） were volumetrically measured at 273 and 303 K. The results show that all isotherms were of Brunauer type I and well correlated with Langmuir-Freundlich model. After sodium ions exchange, the adsorption amounts of three adsorbates increased, while the increase magnitude of CO2 adsorption capacity was much higher than that of CH4 and N2. The selectivities of CO2 over CH4 and CO2 over N2 enhanced after sodium exchange. Also, the initial heat of adsorption data implied a stronger interaction of CO2 molecules with Na＋ ions in Naβ . These results can be attributed to the larger electrostatic interaction of CO2 with extraframework cations in zeolites. However, Naβ showed a decrease in the selectivity of CH4 over N2, which can be ascribed to the moderate affinity of N2 with Naβ. The variation of isosteric heats of adsorption as a function of loading indicates that the adsorption of CO2 in Naβ presents an energetically heterogeneous profile. On the contrary, the adsorption of CH4 was found to be essentially homogeneous, which suggests the dispersion interaction between CH4 and lattice oxygen atoms, and such interaction does not depend on the exchangeable cations of zeolite.

Adsorption separation of carbon dioxide, methane and nitrogen on monoethanol amine modified β-zeolite

A new type of composite adsorbents was synthesized by incorporating monoethanol amine （MEA） into β-zeolite. The parent and MEA- functionalized β-zeolites were characterized by X-ray diffraction （XRD）, N2 adsorption, and thermogravimetric analysis （TGA）. The adsorption behavior of carbon dioxide （CO2）, methane （CH4）, and nitrogen （N2） on these adsorbents was investigated at 303 K. The results show that the structure of zeolite was well preserved after MEA modification. In comparison with CH4 and N2, CO2 was preferentially adsorbed on the adsorbents investigated. The introduction of MEA significantly improved the selectivity of both CO2/CH4 and CO2/N2, the optimal selectivity of CO2/CH4 can reach 7.70 on 40 wt% of MEA-functionalized β-zeolite （MEA（40）-β） at 1 atm. It is worth noticing that a very high selectivity of CO2/N2 of 25.67 was obtained on MEA（40）-β. Steric effect and chemical adsorbate-adsorbent interaction were responsible for such high adsorption selectivity of CO2. The present MEA-functionalized β-zeolite adsorbents may be a good candidate for applications in flue gas separation, as well as natural gas and landfill gas purifications.

不同类型生物炭对CO_(2)吸附性能及其机理

本研究以5种生物质为原料制备了生物炭,并对其进行理化表征,考察了生物炭对CO_(2)的吸附性能及机理。结果表明,椰壳(YK)、松木(SM)生物炭的比表面积是玉米芯(YM)、芦苇秆(LW)、椰衣(YY)生物炭的1.99~2.90倍。YK、SM对CO_(2)的吸附量(108.78~118.89 mg/g)高于YM、LW、YY(95.33~105.55 mg/g)。此外,YK中较高的S含量(2.17%)与碱度对CO_(2)吸附也起着促进作用。研究发现,生物炭的比表面积、孔径、碱度、官能团均是影响CO_(2)吸附的重要因素,当孔隙差异明显时,孔隙结构对CO_(2)吸附的影响会掩盖碱度带来的差异。Avrami模型和Langmuir模型可以较好地拟合生物炭对CO_(2)的吸附过程,表明CO_(2)在生物炭上的吸附以单层吸附为主。生物炭吸附CO_(2)是以物理吸附为主伴有化学吸附作用的过程,且受温度影响较大,当温度从0℃升高到65℃时,生物炭对CO_(2)的吸附量降低了73.42%~77.14%。经过5次CO_(2)吸脱附循环后,生物炭仍具有较高的可重复使用性(85.26%~98.41%),这表明生物炭具有良好的CO_(2)捕集潜力。

Theoretical study of small Mo clusters and molecular nitrogen adsorption on Mo clusters

This paper studies the small molybdenum clusters of Mon （n=2 8） and their adsorption of N2 molecule by using the density functional theory （DFT） with the generalized gradient approximation. The optimized structures of Mon clusters show the onset of a structural transition from a close-packed structure towards a body-centred cubic structure occurred at n = 7. An analysis of adsorption energies suggests that the Mo2 is of high inertness and Mo6 cluster is of high activity against the adsorption of N2. Calculated results indicate that the N2 molecule prefers end-on mode by forming a linear or quasi-linear structure Mo-N-N, and the adsorption of nitrogen on molybdenum clusters is molecular adsorption with slightly elongated N-N bond. The electron density of highest occupied molecular orbital and lowest unoccupied molecular orbital, and the partial density of states of representative cluster are also used to characterize the adsorption properties of N2 on the sized Mon clusters.

固化填埋污泥对Cu^(2+)、Zn^(2+)吸附特征的比较研究

比较研究了固化填埋污泥对Cu2+、Zn2+吸附特征差异.结果表明,固化填埋污泥对Cu2+、Zn2+的吸附量及吸附率均在pH 3时达最大值;当固化填埋污泥质量浓度为6.0g/L时,其对初始浓度为150mg/L的Cu2+、Zn2+吸附率均可达90%以上.固化填埋污泥对Cu2+、Zn2+的吸附等温式与Henry、Freundlich及Langmiur方程均具有较好的拟合性,且固化填埋污泥分别对Cu2+和Zn2+具有较高的吸附强度和吸附容量.解吸特性研究表明,盐酸仅在pH1时对固化填埋污泥中Cu2+、Zn2+的解吸率达90%以上;随EDTA浓度增加,其对固化填埋污泥中吸附态Cu2+的解吸率显著上升,0.5mmol/L EDTA即可解吸100%的吸附态Cu2+,但对固化填埋污泥中吸附态Zn2+的解吸率仅为10%左右.