NH_3-CO_2-H_2O三元体系相图查图方法的改进及其在氮肥生产中的应用

首先对以氨碳比和水碳比表示溶液组成的NH_3-CO_2-H_2O三元体系,在查阅其直角等腰三角形相图时不是采用传统的查图方法,而是借鉴了直角坐标的查图方法,使查图过程变得简单、准确和直观。然后,简单地探讨了新的查图方法在尿素生产中的应用。

NH_3-CO_2-H_2O三元体系相图查图方法的改进

对以氨碳比和水碳比表示溶液组成的NH3-CO2-H2O三元体系,在查阅其直角等腰三角形相图时不采用传统的查图方法,而采用直角坐标的查图方法,使查图过程变得简单、准确和直观。

煤气化装置中NH_3-CO_2-H_2O体系相平衡研究

煤气化过程中产生的NH3和CO2,在煤气洗涤、灰水处理、变换和热回收工段与水形成NH3-CO2-H2O三元体系,通过三元体系相平衡的热力学模型,能够预测NH3在系统中的分布,解决煤气化装置普遍存在的铵盐结晶、废水氨氮超标等问题。提出了NH3和CO2在水中的解离反应和酸碱反应,是造成Aspen中NH3-CO2-H2O三元体系电解质NRTL模型与实验数据产生偏差的原因。利用系统压力0—1.2 MPa条件下NH3-CO2-H2O三元体系的气液平衡实验数据,回归了NH3-CO2-H2O三元体系电解质NRTL模型的二元交互作用参数和亨利系数,得到修正的NH3-CO2-H2O三元体系电解质NRTL模型。模型计算结果与实验数据间的平均相对误差小于2.9%,能够准确地预测煤气化装置中低压含NH3系统的气液相平衡,对工程设计和装置运行具有一定指导意义。

Co[(C_2H_5O)_2PS_2]_2·2Py的合成及其晶体结构

用光谱法研究了Co[(C_2H_5O)_2PS_2]_3与吡啶的取代还原反应,测定了反应的平衡常数K=0.66±0.05(mol·dm^(-3))^(-3)。用X射线单晶衍射方法测定了Co[(C_2H_5O)_2PS_2]_2·2Py的晶体结构。晶体空间群为P2_(1/c),晶胞参数a=8.117(7),b=17.813(4),c=9.901(3)A;β=104.19(5)°; Z=2;晶体密度计算值D_o=1.406g·cm^(-3)。差热分析印证了标题化合物含二分子吡啶。提出了可能的取代还原反应的机理。

Thermodynamic assessment of Co-Cr-W ternary system

The Co-Cr-W ternary system was critically assessed using the CALPHAD technique.The solution phases including the liquid,γ-Co,ε-Co and α-Cr were described by a substitutional solution model.The σ,μ and R phases were described by three-sublattice models of（Co,W）8（Cr,W）4（Co,Cr,W）18,（Co,Cr,W）7W2（Co,Cr,W）4 and（Co,W）27（Cr,W）14（Co,Cr,W）12,respectively,in order to reproduce their homogeneity ranges.A self-consistent set of thermodynamic parameters for each phase was derived.The calculated isothermal sections at 1 000,1 200 and 1 350 ℃ are in good agreement with the experimental data.A eutectoid reaction of R μ＋γ-Co＋σ in this ternary system was predicted to occur at 1 022 ℃.

Phase equilibria of Co-Mo-Zn ternary system

To experimentally determine the isothermal sections of Co-Mo-Zn ternary system at 600 and 450℃,the equilibrated alloy and diffusion couple methods were adopted by using scanning electron microscopy coupled with energy-dispersive spectrometry,X-ray diffractometry and electron probe microanalysis.Experimental results show that there are six three-phase regions on the Co-Mo-Zn isothermal section at 600℃and nine three-phase regions on the Co-Mo-Zn isothermal section at 450℃.No ternary compound is found in these two isothermal sections.Both the maximum solubilities of Mo in the Co-Zn compounds(γ-Co5 Zn21,γ1-Co Zn7,γ2-Co Zn13 andβ1-Co Zn)and that of Zn inε-Co3 Mo are no more than 1.5 at.%.The maximum solubilities of Zn inμ-Co7 Mo6 are determined to be 2.1 at.%and 2.7 at.%at 600 and 450℃,respectively.In addition,the maximum solubilities of Co in MoZn7 and MoZn22 are 0.5 at.%and 4.7 at.%at 450℃,respectively.

Employing magnesium−lead melt for synergetic and selective extraction of copper from copper−cobalt alloy

This research aims to extract Cu from Cu-Co alloy with high efficiency and selectivity by employing binary Mg-Pb melt. The optimal conditions for the extraction of Cu were determined. The results showed under optimal conditions, 96.5% of Cu in the Cu-Co alloy could be selectively extracted after treatment at 800 ℃ for 1 h, with the extraction rates of only 0.2% Fe, 0.6% Co, and 1.4% Si. The dissolution mechanism involved the counter diffusion of Mg/Pb and Cu across the diffusion zone of the Cu-Co alloy, and Mg in the binary Mg-Pb melt played a major role in the selective dissolution of Cu, especially at the dissolution forefront. The rate-controlling step of the extraction was dominated by the interfacial reaction.

Facile synthesis of porous Pd nanoflowers with excellent catalytic activity towards CO oxidation

Microorganism-mediated, hexadecyltrimethylammonium chloride （CTAC）-directed （MCD） method was employed in this work to synthesize Pd nanoflowers （PdNFs）. Proper Pichia postoris cells （PPCs） dosage, ascorbic acid （AA）, Pd（N03）2 and CrAC concentrations were essential for the growth of the PdNFs. The size of the as- synthesized PdNFs could be tuned by adjusting the amount of Pal（N03）2 solution and dosage of PPCs used. Characterization techniques such as X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy were used to verify the nature of the PdNFs. Finally the PdNF/PPC nanocomposites were immobilized onto TiO2 supports to obtain bio-PdNF/Ti02 catalysts which showed excellent catalytic activity for CO oxidation, obtaining 100%; conversion at 100 ℃ and remaining stable over a period of 52 h of reaction time. @ 2015 The Chemical Industry and Engineering Sodety of China, and Chemical Industry Press. All rights reserved.

Transfer and Reaction Performances of Selective Catalytic Reduction of NzO with CO over Monolith Catalysts

This work tries to identify the relationship between geometric configuration of monolith catalysts, and transfer and reaction performances for selective catalytic reduction of N2O with CO. Monolith catalysts with five different channel shapes (circle, regular triangle, rectangle, square and hexagon), was investigated to make a comprehensive comparison of their pressure drop, heat transfer Nu number, mass transfer Sh number and N2O conversion. It was found that monolith catalysts have a much lower pressure drop than that of traditional packed bed, and for monolith catalysts with different channel shapes, pressure drop decreases in the order of regular triangle > rectangle > square > hexagon > circle. The order of Nu is in regular triangle > rectangle ≈ square > hexagon > circle, similar to that of Sh. N2O conversion follows the order of regular triangle > rectangular ≈ square ≈ circle > hexagon. The results indicate that chemical reaction including internal diffusion is the controlling step in the selective catalytic reduction of N2O removal with CO. In addition, channel size and gas velocity also have influence on N2O conversion and pressure drop.

Triazine COF-supported single-atom catalyst (Pd/trzn-COF) for CO oxidation

Single-atom catalysts(SACs) with well-defined and specific single-atom dispersion on supports offer great potential for achieving both high catalytic activity and selectivity. Covalent organic frameworks(COFs) with tailormade crystalline structures and designable atomic composition is a class of promising supports for SACs. Herein, we have studied the binding sites and stability of Pd single atoms(SAs)dispersed on triazine COF(Pd1/trzn-COF) and the reaction mechanism of CO oxidation using the density functional theory(DFT). By evaluating different adsorption sites, including the nucleophilic sp2C atoms, heteroatoms and the conjugated π-electrons of aromatic ring and triazine, it is found that Pd SAs can stably combine with trzn-COF with a binding energy around-5.0 eV, and there are two co-existing dynamic Pd1/trzn-COFs due to the adjacent binding sites on trzn-COF. The reaction activities of CO oxidation on Pd1/trzn-COF can be regulated by the anion–π interaction between a +δ phenyl center and the related-δ moieties as well as the electron-withdrawing feature of imine in the specific complexes. The Pd1/trzn-COF catalyst is found to have a high catalytic activity for CO oxidation via a plausible tri-molecular Eley-Rideal(TER) reaction mechanism. This work provides insights into the d–π interaction between Pd SAs and trznCOF, and helps to better understand and design new SACs supported on COF nanomaterials.

Mapping three-dimensional co-seismic surface deformations associated with the 2015 MW7.2 Murghab earthquake based on InSAR and characteristics of crustal strain

Three-dimensional(3 D) co-seismic surface deformations are of great importance to interpret the characteristics of coseismic deformations and to understand the geometries and dynamics of seismogenic faults. In this paper, we propose a method for mapping 3 D co-seismic deformations based on InSAR observations and crustal strain characteristics. In addition, the search strategy of correlation points is optimized by adaptive correlation distance, which greatly improves the applicability of the proposed method in restoring deformations in decorrelation areas. Results of the simulation experiment reveal that the proposed method is superior to conventional methods in both the accuracy and completeness. The proposed method is then applied to map the 3 D co-seismic surface deformations associated with the 2015 MW7.2 Murghab earthquake using ascending and descending ALOS-2 PALSAR-2 images. The results show that the seismogenic fault is the Sarez-Karakul fault(SKF), which is dominated by NE-SW strike slips with an almost vertical dip angle. The north section and the south segment near the epicentre have obvious subsidence along with a southwestward motion in the northwest wall, and the southeast wall has northeast movement and surface uplift trend along the fault zone. The strain field of the earthquake is also obtained by the proposed method. It is found that the crustal block of the seismic area is obviously affected by dilatation and shear forces, which is in good agreement with the movement character of the sinistral slip.

Mass production of Co3O4@CeO2 core@shell nanowires for catalytic CO oxidation

In this study, Co3O4@CeO2 core@shell nanowires were successfully prepared via thermal decomposition of Co（CO3）0.5（OH）.0.11H2O@CeO2 core@shell nanowire precursors. As a CO oxidation catalyst, Co3O4@CeO2 shows remarkably enhanced catalytic performance compared to Co3O4 nanowires and CeO2 nanoparticles （NPs）, indicating obvious synergistic effects between the two components. It also suggests that the CeO2 shell coating can effectively prevent Co3O4 nanowires from agglomerating, hence effecting a substantial improvement in the structural stability of the Co3O4 catalyst. Furthermore, the fabrication of the welbdisperse4 core@shell structure results in a maximized interface area between Co3O4 and CeO2, as well as a reduced Co3O4 size, which may be responsible for the enhanced catalytic activity of Co3O4@CeO2. Further examination revealed that CO oxidation may occur at the interface of Co3O4 and CeO2. The influence of calcination temperatures and the component ratio between Co3O4 and CeO2 were then investigated in detail to determine the catalytic performance of Co3O4@CeO2 core@shell nanowires, the best of which was obtained by calcination at 250 ℃ for 3 h with a Ce molar concentration of about 38.5%. This sample achieved 100% CO conversion at a reduced temperature of 160 ℃. More importantly, more than 2.5 g of the Co3O4@CeO2 core@shell nanowires were produced in one pot by this simple process, which may be beneficial for practical applications as automobile-exhaust gas-treatment catalysts.

Co_3O_4 nanosheets:synthesis and catalytic application for CO oxidation at room temperature

Hexagonal β-Co(OH)2 nanosheets with edge length of 50 nm and thickness of 10 nm were hydrothermally synthesized with the aid of triethylamine.Upon calcination at 350°C in air,the β-Co(OH)2 nanosheets was converted into Co3O4 nanosheets with a similar dimension.Structural analyses during the calcination process identified that the β-Co(OH)2 precursor was initially dehydrated to HCoO2 and subsequently transferred into Co3O4.When being applied to catalyze CO oxidation at room temperature,the Co3O4 nanosheets exhibited a higher activity than the conventional spherical nanoparticles.This was perhaps related to the partial exposure of the{112}planes over the Co3O4 nanosheets.The porous structure generated during the calcination process also provided significant amounts of surface defects,which might contribute to the enhanced catalytic activity as well.

3D Co(II, III) mixed-valence metal-organic framework affording field-induced slow magnetic relaxation

A 3D mixed-valence Co（Ⅲ）-Co（Ⅱ） compound [Co9（bta）10（Hbta）2（H2O）10]n·[22（H2O）]n （1） （H2bta=N,N-bis（1H-tetrazole-5- yl）-amine） was hydrothermally synthesized by reaction of Co（NO3）2·6H2O with H2bta·H2O. Compound 1 consists of three kinds of distorted-octahedral [CoⅡ（N4O2）] paramagnetic nodes which are separated by [CoⅢ（bta）2（Hbta）]2-/[CoⅢ（bta）3]3- dia- magnetic linkers to generate a 3D porous metal-organic framework （MOF） with alternative …Co（Ⅲ）…Co（II）… array and channels incorporating water molecules. Under an applied magnetic field of 4000 Oe, compound 1 exhibits slow relaxation of magnetization at low temperatures, giving AE/kB=30.O0 K and ι0=2.0×10^-8 s.