Study on sulfur migration in activated carbon adsorption-desorption cycle: Effect of alkali/alkaline earth metals

Activated carbon(AC)has been widely used in the removal of SO_(2) from flue gas owing to its well-developed pore structure and abundant functional groups.Herein,the effect of alkali/alkaline earth metals on sulfur migration was investigated based on the dynamic adsorption and temperature programmed desorption experiment.The adsorption and desorption properties of six types of AC(three commercial and three laboratory-made)were carried out on a fixed-bed experimental device,and the physical and chemical properties of samples were determined by X-ray fluorescence,X-ray diffraction,scanning electron microscopy/energy dispersive X-ray,and X-ray photoelectron spectroscopy analysis.The experimental results showed that the adsorbed SO_(2) cannot be completely desorbed by increasing the regeneration temperature(350-850℃),while the SO_(2) fixed in the AC combines with the Ca-based minerals in the ash to form a stable sulfate.For different samples,higher ash content,higher CaO content in the ash and a more developed pore structure lead to a higher SO_(2) fixation rate.Moreover,the multiple adsorption-desorption cycles experiment showed that the effect of SO_(2) fixation is mainly reflected in the first cycle,after which the adsorption and desorption amount are approximately the same.This study elucidates the effect of alkali/alkaline earth metals on the adsorption-desorption cycle of AC,which provides a deeper understanding of sulfur migration in the AC flue gas desulfurization process.

Transformation of alkali and alkaline-earth metals during coal oxy-fuel combustion in the presence of SO_2 and H_2O

The occurrence modes of alkali and alkaline-earth metals（AAEMs） in coal relate to their release behavior and ash formation during combustion. To better understand the transformation of AAEMs,the release behavior of water-soluble,HCl-soluble,HCl-insoluble AAEMs during Shenmu coal（SM coal） oxy-fuel combustion in the presence of SO2 and H2O in a drop-tube reactor was investigated through serial dissolution using H2O and HCl solutions. The results show that the release rates of AAEMs increase with an increase in temperature under the three atmospheres studied. The high release rates of Mg and Ca from SM coal are dependent on the high content of soluble Mg and Ca in SM coal. SO2 inhibits the release rates of AAEMs,while H2O promotes them. The effects of SO2 and H2O on the Na and K species are more evident than those on Mg and Ca species. All three types of AAEMs in coal can volatilize in the gas phase during coal combustion. The W-type AAEMs release excessively,whereas the release rates of I-type AAEMs are relatively lower. Different types of AAEM may interconvert through different pathways under certain conditions. Both SO2 and H2O promote the transformation reactions. The effect of SO2 was related to sulfate formation and the promotion by H2O occurs because of a decrease in the melting point of the solid as well as the reaction of H2O.

Effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite

This work evaluated the effects of inherent alkali and alkaline earth metals on nitrogen transformation during steam gasification of Shengli lignite at the temperature of 873-1173 K in a fluidized-bed/fixed-bed quartz reactor. The results indicated that the alkali metal Na and alkaline earth metals Ca, Mg in coal have different effects on inherent nitrogen transformation to NH3, HCN and char-N during the lignite steam gasification. Specifically during the steam gasification of Shengli lignite, Na and Ca, Mg not only catalyze the inherent nitrogen conversions to NH3, but also promote the secondary reactions of the nascent char-N as well as the generation of NH3 from the generated HCN, meanwhile they also inhibited the inherent nitrogen conversion to HCN and char-N. The presence of Na, Ca and Mg hindered the formation of oxidized nitrogen (N-X) functional groups, but enhanced pyridinic nitrogen (N-6) and quaternary nitrogen's (N-Q) formation in char.

Additive effects of alkaline-earth metals and nickel on the performance of Co/γ-Al_2O_3 in methane catalytic partial oxidation

Nano-sized γ-alumina （γ-Al2O3） was first prepared by a precipitation method. Then, active component of cobalt and a series of alkaline- earth metal promoters or nickel （Ni） with different contents were loaded on the γ-Al2O3 support. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction （XRD） and thermogravimetry analysis （TGA）. The activity and selectivity of the catalysts in catalytic partial oxidation （CPO） of methane have been compared with Co/γ-Al2O3, and it is found that the catalytic activity, selectivity, and stability are enhanced by the addition of alkaline-earth metals and nickel. The optimal loadings of strontium （Sr） and Ni were 6 and 4 wt%, respectively. This finding will be helpful in designing the trimetallic Co-Ni-Sr/γ-Al2O3 catalysts with high performance in CPO of methane

Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids

Solvent extraction equiliria of four main alkaline earth metals (magnesium, calcium, strontium and barium) with di(2-ethylhexyl) phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acid mono-(2-ethylhexyl) ester, di(2,4,4-tri-methylpentyl) phosphinic acid and IR spectra of the extracts have been studied. The selectivity order is dependent of the e/r value and hydration energy of the metal ions. The minor shift of the P→O in IR absorption of the alkaline earth metal extracts indicates that the interaction between the metal ions and P→O is much weaker for alkaline earth metals than for transitional metals. The distribution of the four alkaline earth elements between aqueous solutions and solutions of DEHPA and neutral organophosphorus compunds, tri-n-butyl phosphate (TBP) or tri-octyl phosphine oxide (TOPO) in kerosene have been determined at varying ratio of TBP or TOPO to DEHPA and the positive synergism is observed. The synergic effects is explained by using IR spectra of the loaded organic phase.

Microcalorimetric study on host-guest complexation of naphtho-15-crown-5 with four ions of alkaline earth metal

Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.

Syntheses and Characterization of Two New Alkaline Earth Metal-organic Topological Frameworks with 3-Amino-1H-1,2,4-triazole-5-carboxylate

Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr（AmTAZAc）2（H2O）]}（1） and {[Ba（AmTAZAc）2（H2O）]}（2）（AmTAZAc = 3-amino-1H-1,2,4-triazole-5-carboxylate）,which have been synthesized by using the layering method and structurally characterized by elemental analysis,IR,and single-crystal X-ray diffraction.Complexes 1 and 2 are isostructural,and both crystallize in the orthorhombic system,space group Fdd2.X-ray structural analysis shows that 1 or 2 has an intriguing 3-D infinite network of（318.438.510） topology based on a 2-D sheet structure of（4,4） net.The result shows that noncovalent interactions play an important role in strengthening the whole structures of the compounds.

Photoabsorption cross sections of the alkaline-earth-metal elements under strong interaction conditions

The strong interatomic interaction effects on photoabsorption cross sections of a private atom have been interpreted by the contribution of both the real and imaginary parts of atomic polarizability in the present work. Some unresolved differences between the photoabsorption cross sections of isolated atoms and those of condensed atoms, especially near thresholds and resonances, probably could be interpreted by the competition between the imaginary and real parts of atomic frequency-dependent polarizabilities.

Blue-emissions Modulated by Packing Forces in Alkaline-earth Metal OrganicFrameworks Based on Thiophene-2,5-dicarboxylic: Structures and Theoretical Calculations

Solvothermal reactions of Ca(NO), Sr(NO)with thiophene-2,5-dicarboxylic in DMF afforded two new inorganic-organic hybrid frameworks, [M(TDC)(DMF)]n(M = Ca(1), Sr(2), TDC = thiophene-2,5-dicarboxylic, DMF = N,N?-dimethylformamide), which have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis and IR spectra. Both compounds feature three-dimensional(3D) frameworks based on the versatile coordinated modes(μ-η~2:η~2, μ-η~2:η~1, μ-η~2:η~1) of carboxylic groups in tdc ligands. C–H···S hydrogen bonds and C–H···π interactions contribute to the stabilization of the structures. They exhibit weaker packing force compared with their literature isomers. Consequently, blue and blue/green luminescence of two compounds has been observed. Their luminescence mechanism can be ascribed to ligand-to-metal charge transfer(LMCT) compared with the ligand-centered luminescence in their isomers. Electronic structural calculations illustrate that under the condition of weaker packing forces, larger gaps can be achieved, which facilitate the LMCT. This work suggests that the introduction of S-heteroatom can result in more electrons rich in the metal centers, thus giving rise to metal-involved luminescence.

Alkaline leaching of metal melting industry wastes and separation of zinc and lead in the leach solution

In this work, a thorough examinations on the extractability of zinc and lead present in the steelmaking dusts using alkaline leaching process and the effectiveness of the zinc and lead separation in the resultant leaching solutions using sulfide precipitation method were made. It was found that only about 53% of zinc and over 70% of the lead could be leached out of the dusts, while the other 47% of zinc and 30% of lead were left in the leaching residues. The zinc and lead in the resultant leaching solution can be effectively and selectively separated. When the weight ratio of sodium sulfide (M.W. = 222-240) to Pb was kept at 1.8, the lead in the solution could be precipitated out quantitatively while all the zinc was remained in the solution. The zinc left in the solution can be further recovered by the addition of extra sodium sulfide with a weight ratio of sodium sulfide to the zinc over 2.6. The resultant filtrate can be recycled to the leaching of dust in the next leaching process.

Syntheses of Alkaline Earth and Lanthanide Cryptates with Pyridine-Based Group

New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10（44）, 11, 18, 20, 22, 24（43）, 25, 31, 33, 35, 37（42）, 38-pentadecaene） were synthesized by [2 ＋ 3 ] template condensation of tris（2-aminoethyl） amine with 2, 6-diformylpyridine, and then by transmetallation reactions of the calcium cryptate [CaL] （NO3）2·2H2O with corresponding lanthanide ions; three lanthanide cryptates [ LnL] （NO）3·3H2O （Ln = Eu, Gd, Tb） were synthesized and characterized by physical methods. The crystal structure of the terbium cryptate [TbL] （NO）3·3H2O was studied by X-ray analysis. The central atom was coordinated by three pyridyl and six imino nitrogen atoms and exhibited a distorted tricapped trigonal prismatic coordination geometry.

Calculation of Interaction Parameters from Immiscible Phase Diagram of Alkali Metal or Alkali Earth Metal-Halide System by Means of Subregular Solution Model

In this paper, the interaction parameters in the subregular solution model, λ1 and λ2, are regarded as a linear function of temperature, T. Therefore, the molar excess Gibbs energy of A-B binary system may be reexpressed as follows:Gm^E=xAxB[(λ11+λ12T)+(λ21+λ22T)xB]The calculation of the model parameters, λ11, λ12, λ21and λ22, was carried out numerically from the phase diagrams for 11 alkali metal-alkali halide or alkali earth metal-halide systems. In addition, artificial neural network trained by known data has been used to predict the values of these model parameters. The predicted results are in good agreement with the .calculated ones. The applicability of the subregular solution model to the alkali metal-alkali halide or alkali earth metal-halide systems were tested by comparing the available experimental composition along the boundary of miscibility gap with the calculated ones which were obtained by using genetic algorithm. The good agreement between the calculated and experimental results across the entire liquidus is valid evidence in support of the model.

METALLIC PHASE AND INSULATING CHARACTER OF ALKALI-EARTH METAL DOPED C60①

The three dimensional EHMO crystal orbital calculations for crystalline Ba6 C60,Ca3 C60 and Ca5 C60 are reported.The ground state of partially doped Ca3 C60 is found to be insulating with an indrect energy gap of 0.5eV.In contrast,the Ca5 C60 forms a metallic conducting phase with a set of three half-filled bands crossing the Fermi level which is Found to locate close to a peak of the density of state. The character of crystal orbitals near the Fermilevel for both Ca3 C60 and Ca5 C60 is completely carbon-like.In both cases the Ca3 atoms are almost fully ionized and C60 molecules form a stable negative charge state with six to ten additional electrons.The conductivity of Ba6 C60 is resuted from the incomplete charge tranfer.The valance charge of every Ba ion is about 0.33.The total charge tranfer of six Ba atoms is almost the same as that of five Ca atoms.

东昆仑大格勒地区稀有和稀土矿化碱性杂岩体的发现及意义

稀有、稀土元素由于其特殊的属性对国民经济、国家安全和科技发展具有重要的战略意义。与碱性岩类相关的稀有、稀土矿产资源储量十分丰富,近年来对其勘探和开发越来越受到重视。青海省地质调查院在东昆仑中段大格勒地区首次发现了稀有和稀土矿化碱性杂岩体,岩石类型主要为含尖晶石磷灰石蛇纹石化橄榄岩、含磷灰石金云母霞石单斜辉石岩、橄榄辉长岩、含磷灰石金云母角闪石岩、磁铁矿化含橄榄石磷灰石碳酸岩等,其中含矿岩石为碳酸岩、橄榄岩、辉石岩等。矿石矿物主要为烧绿石、铌钽铁矿、磷灰石、独居石、钛铁矿。现初步圈定Nb、P矿体一条,矿体厚3.8~56.56 m,Nb_(2)O_(5)品位最高6.9%,平均0.71%;P_(2)O_(5)品位最高14.5%,平均品位5.6%,Ta和REE也伴有矿化,显示了很好的含矿性。这一发现大大拓展了青藏高原稀有、稀土矿的找矿空间,为发现新的、优质的稀有稀土矿产提供重要启示,具有重要的找矿和战略意义。

我国高碱煤燃烧特性研究和工程应用进展

我国具有丰富的高碱煤资源。从基础研究、关键技术和工程实践等方面对高碱煤燃烧技术的研究和工程应用进展做一个较为全面的综述和总结,特别介绍了液态排渣锅炉全烧新疆高碱煤的机理研究和实践最新状况,以期为后续开发更为经济、可长期安全大比例掺烧甚至纯烧新疆高碱煤的燃烧技术提供参考。

准东煤半焦赤铁矿载氧体化学链燃烧及碱(土)金属迁移特性

准东煤在常规燃烧利用过程中出现严重的积灰结渣和CO_(2)排放等问题,极大地限制了其低碳清洁高效利用。采用中低温热解低阶煤生产半焦、焦油和热解气是煤炭分质分级利用的龙头技术,准东高碱煤热解半焦气化活性高,采用化学链燃烧方式有利于实现其低碳清洁高效转化。以CO_(2)为气化介质,赤铁矿石为载氧体,在固定床上开展准东煤半焦原位气化化学链燃烧特性研究,并探究了准东煤半焦中碱(土)金属(AAEMs)的迁移转化规律。研究表明,赤铁矿载氧体能够显著提高固定床反应器出口烟气中CO_(2)体积分数,然而随着载氧体与半焦质量比(mOC/mC)不断增加,CO_(2)体积分数先急剧增加而后趋于不变,最佳的mOC/mC为50:1,而700℃热解制取的准东煤半焦经酸洗脱灰处理后固定床反应器出口相应烟气中CO_(2)的选择性降低了8.95%,这表明准东煤半焦中具有催化活性的AAEMs显著影响其化学链燃烧性能。赤铁矿载氧体对准东煤半焦表面AAEMs的分布也有显著影响,与未加入时相比,Na、K元素在半焦表面呈现较为明显的团簇富集,Ca、Mg元素在空间分布上呈更为明显的依赖关系。采用原位气化化学链燃烧方式后准东煤半焦中的AAEMs向赤铁矿载氧体中发生迁移与转化,并生成霞石(NaAlSiO_(4))、钾长石(KAlSi_(3)O_(8))、钙铝黄长石(Ca_(2)Al_(2)SiO_(7))、镁橄榄石(Mg_(2)SiO_(4))等高熔点矿物质,有效抑制了准东煤半焦中AAEMs向气相的挥发。

Carbon dioxide adsorption behaviors of aluminum-pillared montmorillonite-supported alkaline earth metals

The Al-pillared montmorillonite-supported alkaline earth metal 5M/Al-PILC(PILC = pillared clay, M = Mg, Ca, Sr, and Ba) and x Mg/Al-PILC( x = 1, 3, 5, and 7 wt.%) samples were prepared using an impregnation method. Physical properties of the materials were determined by means of X-ray diffraction(XRD) and N2 adsorption-desorption, and their CO2 adsorption behaviors were investigated using the thermogravimetric analyzer(TG), CO2 temperatureprogrammed desorption(CO2-TPD), and in situ diffuse reflectance infrared transform spectroscopy(in situ-DRIFTS) techniques. It is shown that 5 Mg/Al-PILC possessed the highest CO2 adsorption capacity(2.559 mmol/g). The characterization results indicate that Alpillaring increased the specific surface area of montmorillonite, which was beneficial for the adsorption of CO2. The CO2 adsorption process on the sample was mainly chemical adsorption, and alkalinity was the main factor influencing its adsorption capacity. The alkalinity of the sample was enhanced by loading an appropriate amount of alkaline earth metal, and the adsorbed CO2 was present in the form of bicarbonate and carbonate. In addition, the 5Mg/Al-PILC sample exhibited an excellent regeneration efficiency. We believe that the outcome of this research would provide a good option for developing highly effective CO2 adsorption materials.

MB_8^(2-) (M=Be,Mg,Ca,Sr,and Ba):Planar octacoordinate alkaline earth metal atoms enclosed by boron rings

Complexes involving planar octacoordinate alkaline earth metal atoms in the centers of eight-membered boron rings have been investigated by two density functional theory (DFT) methods.BeB82-with D8h symmetry is predicted to be stable,both geometrically and electronically,since a good match is achieved between the size of the central beryllium atom and the eight-membered boron ring.By contrast,the other alkaline earth metal atoms cannot be stabilized in the center of a planar eight-membered boron ring because of their large radii.By following the out-of-plane imaginary vibrational frequency,pyramidal C8v MgB82-,CaB82-,SrB82-,and BaB82-structures are obtained.The presence of delocalized π and σ valence molecular orbitals in D8h BeB82-gives rise to aromaticity,which is reflected by the value of the nucleus-independent chemical shift.The D8h BeB82-structure is confirmed to be the global minimum on the potential energy surface.

Three alkaline earth metal-organic frameworks based on fluorene-containing carboxylates:syntheses,structures and properties

Three metal-organic frameworks,{[Mg_2(MFDA)_2(DMF)_3]·0.5H_2O}_n(1),{[Ca(MFDA)(DMF)(H_2O)]·0.5DMF}_n(2)and[Ca(MFDA)(DMF)_2]_n(3)(DMF=N,N-dimethylformamide)have been synthesized by the solvothermal reactions between the ligand 9,9-dimethylfluorene-2,7-dicarboxylic acid(H_2MFDA)and the corresponding metal salts,respectively.The single crystal X-ray structural analyses reveal that compounds 1-3 display three-dimensional structures based on the M(Ⅱ)-O-C chains.It is interesting that the MFDA ligands in 1-3 have different dihedral angles between the two carboxylate groups ranging from 9.9(1)°to 41.8(2)°.All of compounds exhibit strong ligand-centered blue emissions under UV lights.Their thermal properties have also been studied.