退役NCM333正极材料热化学还原转化过程研究

锂离子电池日前的爆发式增长使之将在未来的3~5年内面临大量的“退役”问题。退役锂离子电池尤其是退役正极材料的高效、可持续的回收利用,是实现新能源产业碳达峰和碳中和目标的关键。主要研究了玉米秸秆对退役正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)(NCM333)中有价金属的热化学还原过程,通过调控转化高价金属,选择性回收金属盐及单质,避免传统回收过程中化学试剂的添加,同时利用退役正极材料中的过渡金属特性,对玉米秸秆进行催化重整产气。使用X射线衍射仪、X射线光电子能谱等仪器分析热解后的正极材料和玉米秸秆,结果表明,玉米秸秆热解、气化产生的还原性气体和生物碳破坏了正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)中的高价金属—氧键,降低Ni,Co和Mn的金属价态,同时将Li转化为Li_(2)CO_(3)。不同的热解温度得到了不同的热解产物,较高的温度更易得到Ni-Co合金及MnO。热解还原过程中正极材料中的过渡金属对玉米秸秆热解来说是良好的催化剂,可以降低热解反应的所需温度,提升碳热反应的可能性,从而实现“废物+废物=资源”的目的。该工艺可以在不外加还原剂的情况下高效、高选择性和无污染地梯度回收有价金属,不仅提供了一条绿色可持续发展的退役锂离子电池回收路径,也为生物质的催化重整提供了一种成本低廉的催化剂的选择。

部分脱灰及碱金属对煤直接液化渣热化学过程的影响

以煤直接液化渣为原料,利用热重分析仪,考察了部分脱灰和碱金属对其在水蒸气气氛下热化学过程的影响,并计算了气化阶段的表观活化能。结果表明:部分脱灰提高了煤直接液化渣在热解和气化阶段的转化率,降低了半焦的表观活化能,对热化学过程产生积极的影响;NaCl在热解和气化过程中均未表现出明显的催化作用;KCl在热解过程中同样没有表现出明显的催化作用,在气化阶段,则提高了半焦在低温下的气化转化率,表现出了催化作用,并使半焦的气化反应进入到了内扩散过渡区。

相对论重离子反应的热化过程

本文从相对论ＢＵＵ理论出发研究了１ＧｅＶ／ｎ能区重离子反应全局（ｇｌｏｂａｌ）和局域（ｌｏｃａｌ）平衡性质，计算表明在该能区平均场对反应动力学过程仍有相当的作用；对有限核系统的反应动力学过程的时间演化的研究表明，有限核系统无论全局的还是局域的平衡均未能达到完全平衡，因而对有限核系统重离子反应基于完全热平衡概念的适用性值得怀疑．

热化学过程中生物电能的产生(英文)

目前,生物能被视为在未来有潜力提供大部分可再生能源的储备,它可以以气体、液体或固体燃料形式提供生物燃料或者用于发电和供热。有三种主要的提供生物能的途径,即热转换、生物转换和物理转换,这些方法都需要配置和设计各种各样的化学反应器。文章重点研究能高效、低成本、高度通用地提供大量能量、燃料和化学产品的热化学转换过程。特别研究和讨论了所谓的先进的气化和快速热解技术,其主要产品可以是气体、液体或固体燃料,而其副产品则是电能和/或热能、液体燃料及大量的化学品。文章还对阻碍不同技术的市场配置的主要技术性和非技术性壁垒进行了概述。

正电子寿命-动量关联技术

评述了国际正电子领域的新探测技术———寿命 动量关联技术.介绍了该技术的发展过程,讨论了该技术的分析方法,详细阐述了该技术在Ps形成和热化过程中的应用,并讨论了该技术在Ps化学上的应用.

生物质热裂解生产生物燃料的研究进展

生物质能源是一种绿色的可以替代化石能源的一种可再生的能源。尽管高温分解生物质处于发展阶段,但在目前水平,高温裂解因其可以在氧存在下热分解将生物材料直接转化为固态,液态和气态能源产品而受到广泛关注。本文介绍了生物质的热裂解,包括慢速热裂解、快速热裂解、闪解、催化热裂解等过程,重点讨论了在各种生物质材料的热裂解过程中各种操作参数如温度和生物粒子大小等对生物燃料收率的影响。

Self-heating tendency evaluation of sulfide ores based on nonlinear multi-parameters fusion

In order to reveal the nonlinear dynamics characteristics of unsteady self-heating process of sulfide ores, nine different kinds of sulfide ore samples from a pyrite mine in China were taken as experimental materials and their self-heating characteristics were measured in laboratory. Furthermore, the measured temperature was studied by integrating wavelet transform, nonlinear characteristic parameters extraction and fuzzy comprehensive evaluation. The results indicate that only the ore samples 1, 2, 6 and 9 have obvious self-heating phenomenon, and their self-heating initiative temperatures are 220 ℃, 239 ℃, 220 ℃ and 220 ℃, respectively, which means that they are difficult to produce self-heating under normal mining conditions. The correlation dimension of self-heating process is fraction and the maximum Lyapunov exponent is positive, which means that it is feasible to study the self-heating process based on chaotic dynamics theory. The nonlinearities of self-heating process of these four samples （ore samples 1, 2, 6 and 9） are 0.8227, 0.7521, 0.9401 and 0.8827 respectively and the order of the samples according to these results is： sample 6, sample 9, sample 1, sample 2, which is consistent with the measured results of self-heating characteristics. Therefore, the nonlinearity method can be used to evaluate the self-heating tendency of sulfide ores, and it is an effective verification of the reliability of measured results.

Analysis and modeling of alumina dissolution based on heat and mass transfer

A comprehensive heat and mass transfer model of dissolution process of non-agglomerated and agglomerated alumina particles was established in an aluminum reduction cell. An appropriate finite difference method was used to calculate the size dissolution rate, dissolution time and mass of alumina dissolved employing commercial software and custom algorithm based on the shrinking sphere assumption. The effects of some convection and thermal condition parameters on the dissolution process were studied. The calculated results show that the decrease of alumina content or the increase of alumina diffusion coefficient is beneficial for the increase of size dissolution rate and the decrease of dissolution time of non-agglomerated particles. The increase of bath superheat or alumina preheating temperature results in the increase of size dissolution rate and the decrease of dissolution time of agglomerated particles. The calculated dissolution curve of alumina（mass fraction of alumina dissolved） for a 300 k A aluminum reduction cell is in well accordance with the experimental results. The analysis shows that the dissolution process of alumina can be divided into two distinct stages： the fast dissolution stage of non-agglomerated particles and the slow dissolution stage of agglomerated particles, with the dissolution time in the order of 10 and 100 s, respectively. The agglomerated particles were identified to be the most important factor limiting the dissolution process.

Morphology and Growth Process of Bat-like ZnO Crystals by Thermal Evaporation

A novel bat-like ZnO nanostructure was synthesized on the silicon substrate by simple ther- mal evaporation of zinc powders without any catalyst. Each bat-like nanorod （＂nanobat＂） is composed of a hexagonal head, a continuous neck and a thin handle. High-resolution transmission electron microscopy and selected area electron diffraction results reveal the single-crystalline feature and the growing direction along [0001] of the nanobat. The vapor- solid mechanism was found suitable to explain the growth process of the nanobat and a schematic model was proposed in detail based on the experimental results.

Feasibility of Intermediate Fluid Vaporizer with Spiral Wound Tubes

A novel intermediate fluid vaporization (IFV) technology for LNG re-gasification process with spiral-wound heat exchanging tubes is proposed. The new IFV project combines the advantage of running the shell and tube heat exchangers at high pressure with the advantage of compact space of heat exchangers. Thermal analysis on the two processes of forced convection and vaporization type heat transfer in the spiral wound tubes and vapor condensation /re-boiling type of heat transfer via intermediate fluid in shell side shows the feasibility of this promising technology.

Structures and magnetic properties of nanocomposite CoFe_2O_4-BaTiO_3 fibers by organic gel-thermal decomposition process

The nanocomposite xCoFe2O4-(1-x)BaTiO3(x=0.2,0.3,0.4,0.5,molar fraction) fibers with fine diameters and high aspect ratios(length to diameter ratios) were prepared by the organic gel-thermal decomposition process from citric acid and metal salts.The structures and morphologies of gel precursors and fibers derived from thermal decomposition of the gel precursors were characterized by Fourier transform infrared spectroscopy,X-ray diffractometry and scanning electron microscopy.The magnetic properties of the nanocomposite fibers were measured by vibrating sample magnetometer.The nanocomposite fibers consisting of ferrite(CoFe2O4) and perovskite(BaTiO3) are formed at the calcination temperature of 900 ℃ for 2 h.The average grain sizes of CoFe2O4 and BaTiO3 in the nanocomposite fibers increase from 25 to 65 nm with the calcination temperature from 900 to 1 180 ℃.The single fiber constructed from these nanograins of CoFe2O4 and BaTiO3 has a necklace-like morphology.The saturation magnetization of the nanocomposite 0.4CoFe2O4-0.6BaTiO3 fibers increases with the increase of CoFe2O4 grain size,while the coercivity reaches a maximum value when the average grain size of CoFe2O4 is around the critical single-domain size of 45 nm obtained at 1 000 ℃.The saturation magnetization and remanence of the nanocomposite xCoFe2O4-(1-x)BaTiO3(x=0.2,0.3,0.4,0.5) fibers almost exhibit a linear relationship with the molar fraction of CoFe2O4 in the nanocomposites.

Effects of H_3PO_4 and Ca(H_2PO_4)_2 on mechanical properties and water resistance of thermally decomposed magnesium oxychloride cement

The effects of H3PO4 and Ca（H2PO4）2 on compressive strength, water resistance, hydration process of thermally decomposed magnesium oxychloride cement （TDMOC） pastes were studied. The mineral composition, hydration products and hydration heat release were analyzed by XRD, FT-IR, SEM and TAM air isothermal calorimeter, etc. After being modified by H3PO4 and Ca（HzPO4）2, the properties of the TDMOC are improved obviously. The compressive strength increases from 14.8 MPa to 48.1 MPa and 37.1 MPa, respectively. The strength retention coefficient （Kn） increases from 0.38 to 0.99 and 0.94, respectively. The 24 h hydration heat release decreases by 10% and 4% and the time of hydration peak appearing is delayed from 1 h to about 10 h. The XRD, FT-IR and SEM results show that the main composition is 5Mg（OH）z＇MgCIz＇8H20 in the modified TDMOC pastes. The possible mechanism for the strength enhancement was discussed. The purposes are to extend the potential applications of the salt lake magnesium resources and to improve the mechanical properties of TDMOC.

Sulfur speciation transformation during bioleaching of pyrite-containing sphalerite concentrate by thermophile Sulfolobus metallicus at 65 °C

Sulfur speciation transformation during bioleaching of pyrite-containing sphalerite concentrate by thermophile Sulfolobus metallicus （S. metallicus） at 65 ℃ was investigated by X-ray diffraction （XRD）, diffuse reflectance Fourier transform infrared spectroscopy （FT-IR） and sulfur K-edge X-ray absorption near edge structure spectroscopy （XANES）. The results show that the presence of S. metallicus effectively enhances the dissolution of the mineral. The yield of zinc increases from 0.5 g/L in sterile control to 2.7 g/L in bioleaching. The pyrite in the concentrate facilitates zinc dissolution in the early stage, but has hindrance role in the late stage for the formation of jarosite. Sulfur speciation analyses show that jarosite and elemental sulfur are main products in bioleaching process, and the accumulation ofjarosite is mainly responsible for the decline of leaching efficiency.

Influence of heating rate on reactivity and surface chemistry of chars derived from pyrolysis of two Chinese low rank coals

A series of char samples were derived from pyrolysis of two typical low-rank coals in China （Shengli lig- nite and Shenmu bituminous coal） at low, medium and fast heating rates, respectively, to the same pyrol- ysis temperature 750℃. Then these chars were characterized by means of thermogravimetric analysis and Fourier transform infrared spectrometer with the aim to investigate the influence of heating rate in pyrolysis process on gasification reactivity and surface chemistry of them. Besides, a homogeneous model was used to quantitatively analyze the activation energy of gasification reaction. The results reveal that Shengli lignite and its derived chars behave higher gasification reactivity and have less content of oxygen functional groups than Shenmu coal and chars. Meanwhile, chars derived from Shengli lignite at 50℃/min and Shenmu coal at 200℃/min have the greatest gasification reactivity, respectively. The oxygen functional groups in Shengli lignite are easily thermo-decomposed, and they are less affected by the heating rate, while that in Shenmu coal have a significant change with the variation of heating rate. In addition, there is no good correlation between the change of oxygen functional groups and that of the gasification reactivity of the derived chars from pyrolysis at different heating rates.

Heat Transfer Enhancement by Fluidized Solid Particles in Gas Carrying Evaporation

Heat transfer characteristics are studied for gas carrying evaporation with fluidized solid particles in a vertical rectangular conduit. Experimental results show that heat transfer of gas carrying evaporation is enhanced and the superheat of liquid in contact with heating surface lowers remarkably by introducing solid particles. Nucleate boiling on the heating surface is suppressed to a considerable degree. The mechanism of heat transfer enhancement by fluidized solid particles is analyzed with the consideration of collisions of solid particles with the boiling vapor bubbles.

A Novel Strategy for Simulating the Main Fractionator of Delayed Cokers by Separating the De-superheating Process

Delayed coking is an important process in refinery to convert heavy residue oils from crude distillation units （CDUs） and fluid catalytic cracking units （FCCUs） into dry gas, liquefied petroleum gas （LPG）, gasoline, die- sel, gas oils and cokes. The main fractionator, separating superheating reaction vapors from the coke drums into lighter oil products, involves a de-superheating section and a rectifying section, and couldn＇t be simulated as a whole column directly because of non-eouilibrium in the de-suoerheatine section. It is verv imoortant to correctlv simulate the main fractionator for operational parameter and energy-use optimization of delayed cokers. This paper discusses the principle of de-superheating processes, and then proposes a new simulation strategy. Some key issues such as composition prediction of the reaction vapors, selection of thermodynamic methods, estimation of tray efficiency, etc. are discussed. The proposed simulation approach is applied to two industrial delayed cokers with typical technological processes in a Chinese refinery by using PRO/II. The simulation results obtained are well consistent with the actual operation data, which indicates that the presented approach is suitable to simulate the main fraction- ators of delayed cokers or other distillation columns consisting of de-superheating sections and rectifying sections.

An Experimental Study on Thermal Characteristics of Laurie Acid as a Latent Heat Storage Material during Melting Process

The objective of this study was to establish the thermal characteristics of the lauric acid (95% purity) as a latent heat storage material filled in the annulus of vertical concentric double pipe during its melting process,The temperature data were used to determine the thermal characteristics,including the temporal temperature variations and the effects of the mass flow rate and the inlet temperature of the heat transfer fluid on the heat transfer coefficient and the heat charging fraction during the melting process,The results indicated that the time to reach to heat charging fraction of 1.0 could be altered by changing the mass flow rate and the inlet temperature of the heat transfer fluid.

Study on heat transfer for falling liquid film flow with consideration of interfacial evaporation

The interfacial evaporative heat transfer was included in the semi-empirical study of the heat transfer for the falling liquid film flow. The investigations showed that, the inclusion of the interfacial eveiporative heat transfer in the turbulent model would lower the predicted convective heat transfer coefficient. Predictions of the new model resulted in a prominent deviation from that predictions of the normal model in the case of large mass flow rate and low wall heat flux. This deviation will be decreased with increasing wall heat flux, such that it will be asymptotic zero at very high wall heat flux. Predictions of the new model agreed well with the current experimental measurements. This study has verified that the Reynolds number is not the sole crucial parameter for heat transfer of falling liquid film flow, and wall heat flux will be another important independent parameter. This result is consistent with our previous studies.

Thermodynamics of chromite ore oxidative roasting process

To explicate the thermodynamics of the chromite ore lime-free roasting process, the thermodynamics of reactions involved in this process was calculated and the phrases of sinter with different roasting times were studied. The thermodynamics calculation shows that all the standard Gibbs free energy changes of the reactions to form Na2CrO4, Na2O-Fe2O3, Na2O·Al2O3 and Na2O3 SiO2 via chromite ore and Na2CO3 are negative, and the standard Gibbs free energy changes of the reactions between MgO, Fe2O3 and SiO2 released from chromite spinel to form MgO-Fe2O3 and MgO·SiO2 are also negative at the oxidative roasting temperatures （1 173 1 473 K）. The phrase analysis of the sinter in lime-free roasting process shows that Na2O·Fe2O3, Na2O·Al2O3 and Na2O·SiO2 can be formed in the first 20 min, but they decrease in contents and finally disappear with the increase of roasting time. The final phase compositions of the sinter are Na2CrO4, MgO·Fe2O3, MgO·SiO2 and MgO. The results indicate that Na2CrO4 can be formed easily via the reaction ofNa2CO3 with chromite ore. Na2O·Fe2O3, Na2O-Al2O3 and Na2O·SiO2 can be formed as intermediate compounds in the roasting process and they can further react with chromite ore to form Na2CrO4. MgO released from chromite ore may react with iron oxides and silicon oxide to form stable compounds of MgO·Fe2O3 and MgO·SiO2, respectively.

Investigation into the surface active groups of coal

The oxidation heat of coal is the direct reason leading to coal spontaneous combustion. When coal is exposed in oxygen atmosphere, the physical adsorption and chemisorption happened, and then which resulting chemical reaction followed heat between coal and oxygen. Owing to the complexity and uncertain of molecular structure of coal,it was only reduced that bridge bonds, side chains and O 2 containing functional groups in coal may be prone to oxidation in last year, but not to deeply investigate into the structures and the type of the active radicals. In this paper, according to the last achievements in coal structure research, the hypomethylether bond, hypoalkyl bond of α carbon atom with hydroxyl and α carbon atom with hypomethy side chain and hypomethyl bonds linking up two aromatic hydrocarbon in bridge bonds, and methoxy,aldehyde and alkyls of α carbon atom with hydroxy in side bonds are inferred to be free radical easily to lead to oxidize coal under the ambient temperature and pressure. The order from strong to weak of oxide activation of the seven surface active groups is aldehyde side chains, hypomethylether bonds, hypoalkyl bonds of α carbon atom with hydroxyl, hypoalkyl bonds of α carbon atom with hypomethyl, hypomethyl bonds linking up two aromatic hydrocarbon,methoxy, alkyls side chains of α carbon atom with hydroxyl. Because of the two unsaturated molecular tracks of O 2, unpaired electron clouds of the part of surface active groups of coal enter molecular tracks of O 2 to lead to chemisorb on the conjugate effect and induced effect of surface active groups, and then chemical reaction followed heat happens in them. On the basis of change of bond energy, weighted average method is adopted to count the reaction heat value of each mol CO,CO 2 and H 2O. The property of coal spontaneous combustion is different for the different number and oxidability of the active structure in the coal resulting in the different oxidation heat.