A cascade of in situ conversion of bicarbonate to CO_(2) and CO_(2) electroreduction in a flow cell with a Ni-N-S catalyst

Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.

Engineering asymmetric electronic structure of cobalt coordination on CoN_(3)S active sites for high performance oxygen reduction reaction

The efficacy of the oxygen reduction reaction(ORR) in fuel cells can be significantly enhanced by optimizing cobalt-based catalysts,which provide a more stable alternative to iron-based catalysts.However,their performance is often impeded by weak adsorption of oxygen species,leading to a 2e^(-)pathway that negatively affects fuel cell discharge efficiency.Here,we engineered a high-density cobalt active center catalyst,coordinated with nitrogen and sulfur atoms on a porous carbon substrate.Both experimental and theoretical analyses highlighted the role of sulfur atoms as electron donors,disrupting the charge symmetry of the original Co active center and promoting enhanced interaction with Co 3d orbitals.This modification improves the adsorption of oxygen and reaction intermediates during ORR,significantly reducing the production of hydrogen peroxide(H_(2)O_(2)).Remarkably,the optimized catalyst demonstrated superior fuel cell performance,with peak power densities of 1.32 W cm^(-2) in oxygen and 0.61 W cm^(-2) in air environments,respectively.A significant decrease in H_(2)O_(2) by-product accumulation was observed during the reaction process,reducing catalyst and membrane damage and consequently improving fuel cell durability.This study emphasizes the critical role of coordination symmetry in Co/N/C catalysts and proposes an effective strategy to enhance fuel cell performance.

Clean production of Fe-based amorphous soft magnetic alloys via smelting reduction of high-phosphorus iron ore and apatite

Separated preparation of prealloys and amorphous alloys results in severe solidification-remelting and beneficial element removal-readdition contradictions,which markedly increase energy consumption and emissions.This study offered a novel strategy for the direct production of FePC amorphous soft magnetic alloys via smelting reduction of high-phosphorus iron ore(HPIO)and apatite.First,the thermodynamic conditions and equilibrium states of the carbothermal reduction reactions in HPIO were calculated,and the element content in reduced alloys was theoretically determined.The phase and structural evolutions,as well as element migration and enrichment behaviors during the smelting reduction of HPIO and Ca_(3)(PO_(4))_(2),were then experimentally verified.The addition of Ca_(3)(PO_(4))_(2)in HPIO contributes to the enrichment of the P element in reduced alloys and the subsequent development of Fe_(3)P and Fe_(2)P phases.The content of P and C elements in the range of 1.52 wt% -14.63 wt% and 0.62 wt% -2.47 wt%,respectively,can be well tailored by adding 0-50 g Ca_(3)(PO_(4))_(2)and controlling the C/O mole ratio of 0.8-1.1,which is highly consistent with the calculated results.These FePC alloys were then successfully formed into amorphous ribbons and rods.The energy consumption of the proposed strategy was estimated to be 2.00×10^(8) kJ/t,which is reduced by 30% when compared with the conventional production process.These results are critical for the comprehensive utilization of mineral resources and pave the way for the clean production of Fe-based amorphous soft magnetic alloys.

Recovery of valuable metals from spent lithium ion batteries by smelting reduction process based on FeO-SiO_2-Al_2O_3 slag system

NA novel smelting reduction process based on FeO-SiO2-Al2O3 slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and the mechanism of copper loss in slag were investigated. 98.83% Co, 98.39% Ni and 93.57% Cu were recovered under the optimum conditions of slag former/battery mass ratio of 4.0：1, smelting temperature of 1723 K, and smelting mass ratio of time of 30 min. The FeO-SiO2-Al2O3 slag system for the smelting process is appropriate under the conditions of m（FeO）：m（SiO2）=0.58：1？1.03：1, and 17.19%？21.52% Al2O3 content. The obtained alloy was mainly composed of Fe-Co-Cu-Ni solid solution including small amounts of matte. The obtained slag mainly consisted of fayalite and hercynite. Meanwhile, the mechanism of copper loss is the mechanical entrainment from strip-like fayalite particles in the main form of copper sulfide and metallic copper.

Recovery of cobalt from converter slag of Chambishi Copper Smelter using reduction smelting process

The reduction smelting process for cobalt recovery from converter slag of the Chambishi Copper Smelter in Zambia was studied. The effects of reducing agent dosage, smelting temperature and time and the addition of slag modifiers （CaO and TiO2） were investigated. In addition, the depleted slag and cobalt-bearing alloy were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Under the determined conditions, 94.02% Co, 95.76% Cu and less than 18% Fe in the converter slag were recovered. It was found that the main phases of depleted slag were fayalite and hercynite; and the cobalt-bearing alloy mainly contained metallic copper, Fe-Co-Cu alloys and a small amount of sulfide.

S型异质结光催化剂ZnFe_(2)O_(4)/WO_(3)的构筑及光催化还原CO_(2)性能

通过在WO_(3)纳米片表面负载ZnFe_(2)O_(4)纳米颗粒,构建了一系列S型异质结光催化剂ZnFe_(2)O_(4)/WO_(3),并研究了其光催化CO_(2)还原性能。在没有助催化剂和牺牲剂的条件下,所制备的ZnFe_(2)O_(4)/WO_(3)复合材料可对CO_(2)与水蒸汽进行光催化反应。优化后的材料光照5 h后CO_(2)还原产物CO和CH_(4)的产量分别为7.87和4.88μmol·g^(-1)。相对于单相组分,CO和CH_(4)的产量明显提高。光催化活性的提高,归因于ZnFe_(2)O_(4)和WO_(3)异质结的形成以及光生载流子的S型电荷传输模式。

S型异质结光催化剂的研究进展

光催化技术具有合成过程简便、反应条件易控制、充分利用太阳能且无二次污染等突出优势,在处理环境污染问题和缓解全球能源短缺等方面具有广阔的应用前景。然而,由于光生载流子低的转移和分离效率,实际的光化学转换效率提升受到了限制。新兴的S型异质结光催化剂由于其在空间上实现了光生载流子的有效转移分离并展现出强的氧化还原能力,在太阳燃料制备和环境治理领域受到了广泛关注和研究。综述了异质结光催化剂的发展历程和S型异质结的基本原理及在各领域中的应用。最后,总结了S型异质结光催化剂的突出优势,并提出S型异质结光催化剂的发展前景和面临的挑战,为开发具备高效光催化活性的新型异质结光催化剂提供思路和参考。

Study on Foaming Behaviour of Molten Slag during Smelting Reduction with Iron Bath

The molten slag in smelting reduction with iron bath has peculiar behaviour for its high FeO concentration. Slag foaming is effected by the concentration and reduction rate of FeO, basicity of slag and temperature. Addition of granulated coke can greatly decrease slag foaming extent in the process of smelting reduction with iron bath. The anti-foaming capacity of granulated coke is the best when the ratio of coke used for coke layer to total coke used in smelting reduction is controlled at about 20%.

Preparing high-purity iron by direct reduction?smelting separation of ultra-high-grade iron concentrate

A new process for preparing high-purity iron(HPI)was proposed,and it was investigated by laboratory experiments and pilot tests.The results show that under conditions of a reduced temperature of 1075°C,reduced time of 5 h,and CaO content of 2.5wt%,a DRI with a metallization rate of 96.5%was obtained through coal-based direct reduction of ultra-high-grade iron concentrate.Then,an HPI with a Fe purity of 99.95%and C,Si,Mn,and P contents as low as 0.0008wt%,0.0006wt%,0.0014wt%,and 0.0015wt%,respectively,was prepared by smelting separation of the DRI using a smelting temperature of 1625°C,smelting time of 45 min,and CaO content of 9.3wt%.The product of the pilot test with a scale of 0.01 Mt/a had a lower impurity content than the Chinese industry standard.An HPI with a Fe purity of 99.98wt%can be produced through the direct reduction?smelting separation of ultra-high-grade iron concentrate at relatively low cost.The proposed process shows a promising prospect for application in the future.

Recovery of iron and calcium aluminate slag from high-ferrous bauxite by high-temperature reduction and smelting process

A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w（CaO）/w（SiO_2） ratio, anthracite ratio, and reduction temperature and time on the recovery and size of iron nuggets and on the Al_2O_3 grade of the calcium aluminate slag were investigated through thermodynamic calculations and experiments. The optimized process conditions were the bauxite/anthracite/slaked lime weight ratio of 100：16.17：59.37, reduction temperature of 1450°C and reduction time of 20 min. Under these conditions, high-quality iron nuggets and calcium aluminate slag were obtained. The largest size and the highest recovery rate of iron nuggets were 11.42 mm and 92.79wt%, respectively. The calcium aluminate slag mainly comprised Ca_2 SiO_4 and Ca_（12）Al_（14）O_（33）, with small amounts of Fe Al_2O_4, CaAl_2O_4, and Ca_2Al_2SiO_7.

Mixture of ilmenite and high phosphorus iron ore smelted by oxygen-enriched top-blown smelting reduction

In order to reasonably utilize the abundant resources of high-phosphorus iron ore and ilmenite in China, the technology of top-blown smelting reduction with oxygen enrichment was used to smelt the mixed ore of high-phosphorus iron and ilmenite. The effect, which is related to basicity, reduction temperature, carbon-oxygen ratio and time of ventilated oxygen to iron recovery, dephosphorization rate, content of iron, phosphorus, sulfur and titanium in pig iron, was investigated in the experiment. The results show that an ideal outcome can be gained in condition of 6：4 ration on Mengqiao concentrate and Huimin iron ore, temperature of 1 500℃, basicity of 1.3, 1.0 on molar ration of carbon to oxygen, time of 10 min on blowing-oxygen. The outcome is that there is no foamy slag in generation, a good separation of slag and iron, iron recovery with 91.41%, content of phosphorus with 0.27% and tilanium content less than 0.001%, The atmosphere of strong oxidizing in the upper of reduction container and high potential of oxygen in the composition of slag in this technique bring phosphorus, titanium and silicon into slag, which ensures less content of impurity in pig iron.

Reduction Rate of Ferrous Oxide in Smelting Reduction

Reduction rate of ferrous oxide in smelting reduction with iron bath has been studied. The main affecting factors on reduction rate, such as composition of the melt, temperature of molten bath, basicity of slag and the way of supplying carbonaceous materials have also been investigated.

赣北彭山还原性S型花岗岩成因及其对Sn富集的启示:来自锆石微量元素的证据

彭山锡多金属矿集区成矿区划位于长江中下游成矿带与江南钨多金属成矿带的过渡部位。以前研究认为与锡大规模成矿有关的花岗岩通常为高分异的过铝质岩浆,但是关于Sn在还原性岩浆中与矿物相的分配和迁移的氧逸度阈值犹未可知,锡与钨在赣北地区成矿的分带分区(解耦)究竟是受岩浆源区特征的控制还是为氧逸度所制约,目前尚不清楚。本文对区内花岗岩岩石成因、锡的来源、岩浆演化早期的氧化还原条件,及其对锡在岩浆中的分配、萃取和迁移的控制过程开展了研究,即对彭山岩体进行了精细的锆石原位微区分析测试。结果显示,锆石P含量普遍较高,结合P(∑REE+Y)拟合的3条趋势线的斜率分别为0.91、0.85和0.81,与S型花岗岩(∑REE+Y)<1.15×P演变规律相符。在Eu/Eu^(*)Yb N/Gd N关系图解中未显示出与Ti分离曲线的同步协变关系,相反,各组岩石均显示为负相关关系,说明3组锆石Eu/Eu^(*)的比值受榍石与斜长石的共结晶的影响较为有限。依据Hf Ce^(4+)/Ce^(3+)zircon和Ti Ce^(4+)/Ce^(3+)zircon关系图,白云母花岗岩数据区域均位于趋势线末端,与黑云母二长花岗岩和花岗斑岩相比,显示出更低的氧逸度特点。Eu/Eu^(*)与Ce^(4+)/Ce^(3+)zircon比值在各岩石单元中所表现出的还原程度是相耦合的,即组成彭山岩体的3个岩石单元——成矿后花岗斑岩岩脉、黑云母二长花岗岩岩基和白云母花岗岩成矿岩株,其锆石Eu异常(Eu/Eu^(*))和Ce^(4+)与Ce^(3+)比值(Ce^(4+)/Ce^(3+)zircon)呈逐渐递减趋势。双桥山群中1.5~1.3 Ga砂泥质沉积岩与细碧角斑岩系组成的海相古火山喷发沉积建造,可能提供了本区Sn的初始来源。白云母花岗岩成矿岩株的氧逸度显著低于大湖塘石门寺矿床的花岗岩,锆石微量元素揭示了富锡岩浆演化比富钨岩浆具有更低的氧逸度。

S-Fe/C的制备及其对孔雀石绿和三氯乙烯的移除性能

为了提高纳米零价铁对污染物的吸附和还原性能,采用气溶胶辅助制得碳载纳米零价铁(Fe/C),并通过对Fe/C硫化改性制备得到改性材料(S-Fe/C),采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射分析(XRD)、X射线光电子能谱(XPS)等多种方法对材料进行表征,考察了S-Fe/C的材料特征。探究了该材料对孔雀石绿(MG)的吸附性能以及对三氯乙烯(TCE)的还原性能。结果表明,S-Fe/C对MG的吸附量达到1663 mg/g,对TCE 10 h去除率为85.57%,表明S-Fe/C具有良好的吸附性能和还原性能。

ZIF-8有机框架衍生的D-ZnO@Fe_(x)O_(y)S型异质结用于光辅助铀还原

光催化辅助铀提取作为一种新型的铀提取技术,有望克服传统工艺中多种金属离子与U(Ⅵ)的竞争配位以及富集容量有限的难题。在这项研究中,以ZIF-8为前驱体,通过浸渍和高温热解制备了S型ZIF-8衍生氧化锌@铁氧化物(D-ZnO@Fe_(x)O_(y))异质结,用于光辅助还原铀矿废水中的U(Ⅵ)。相比于铁氧化物(Fe_(x)O_(y))和ZIF-8衍生ZnO(D-ZnO),S型异质结D-ZnO@Fe_(x)O_(y)在竞争离子存在下,表现出优异的光辅助铀还原能力(>95%)。通过能带计算证实了在异质结界面形成内置电场,能够有效增强电子定向迁移,并为促进铀的光辅助还原提供了强大的驱动力。机理研究表明,羟基自由基和超氧自由基是参与光催化还原U(Ⅵ)的主要物质。本研究为探索具有高效光电子分离功能的光催化剂还原U(Ⅵ)提供了一条有价值的途径。

S Zorb装置产品汽油降烯烃的技术探索

根据国ⅥB汽油标准和洛阳石化公司汽油调和组分情况,要求S Zorb产品汽油烯烃含量按≤18%(体积分数)控制。通过分析S Zorb装置原料性质和操作条件对产品汽油中烯烃含量的影响,得出:一是可通过优化上游装置操作条件,降低原料汽油烯烃含量来降低产品汽油的烯烃含量;二是可通过适当降低反应温度,提高反应压力及氢油比,提高吸附剂活性及反应器吸附剂的藏量来降低产品汽油烯烃含量。通过调整,虽汽油降烯烃取得了一定的效果,但仅通过依靠两套催化装置和S Zorb装置进行汽油降烯烃操作调整,不论从装置能耗及成本,还是装置安全运行方面来说,既不经济,同时也存在很大的安全风险。因此,若想大幅降低出厂汽油的烯烃含量,还需从全厂考虑,多维度寻找突破口,一方面可以通过对2号催化装置进行汽油降烯烃技术改造,另一方面增加各种调和组分的生产能力及储存能力,以最经济的方式满足新标汽油的要求,为企业创造更大的经济效益。

Breaking the Fe_(3)O_(4)-wrapped copper microstructure to enhance copper-slag separation

The precipitation of Fe_(3)O_(4)particles and the accompanied formation of Fe_(3)O_(4)-wrapped copper structure are the main obstacles to copper recovery from the molten slag during the pyrometallurgical smelting of copper concentrates.Herein,the commercial powdery pyrite or anthracite is replaced with pyrite-anthracite pellets as the reductants to remove a large amount of Fe_(3)O_(4)particles in the molten slag,resulting in a deep fracture in the Fe_(3)O_(4)-wrapped copper microstructure and the full exposure of the copper matte cores.When 1wt%composite pellet is used as the reductant,the copper matte droplets are enlarged greatly from 25μm to a size observable by the naked eye,with the copper content being enriched remarkably from 1.2wt%to 4.5wt%.Density functional theory calculation results imply that the formation of the Fe_(3)O_(4)-wrapped copper structure is due to the preferential adhesion of Cu_(2)S on the Fe_(3)O_(4)particles.X-ray photoelectron spectroscopy,Fourier transform infrared spectrometer(FTIR),and Raman spectroscopy results all reveal that the high-efficiency conver-sion of Fe_(3)O_(4)to FeO can decrease the volume fraction of the solid phase and promote the depolymerization of silicate network structure.As a consequence,the settling of copper matte droplets is enhanced due to the lowered slag viscosity,contributing to the high efficiency of copper-slag separation for copper recovery.The results provide new insights into the enhanced in-situ enrichment of copper from mol-ten slag.

THERMODYNAMICS OF V REDUCTION IN SMELTING REDUCTION SLAG FOR V-Ti-CONTAINING MAGNETITE

For slag system of CaO-SiO_2-Al_2O_3-MgO-V_2O_5,the time of V reduction to appro ch the dynamical equilibrium is about 6 h,the equilibrium time is not evidently influenced by the ratio CaO/SiO_2 and shortens with the increase of temperature.It the ratio of the weight of slag to that of iron bath is 1/2,CaO/SiO_2 0.8 and tomperature 1773 K.the maxium distribution coefficeent of V reduction is 32.4 and maxium recovery of V is 96.1%.

STUDY OF SMELTING REDUCTION RATE FOR VANADIUM TITANIUM MAGNETITE

A comparative study was made of the reduction kinetics for high temperature smelting of vadium-titanium-containing magnetite,together with Hainan iron ore,using iron bath method.Three peaks were revealed on the reduction rate curves for the magnetite,while one peak only for Hainan ore.Under the same conditions,the smelting reduction rate of the magnetite was found to be lower than that of Hainan ore.The rate increases evidently with the increase of the bath volume.The expressions of smelting reduction rate were suggested for the reduction with and without iron bath respectively.

Laboratory Investigation of Zinc Recovery fromEAF Dust by Bath Smelting Reduction

Bath smelting reduction for recovering zinc from EAF (Electric Arc Furnace) dust has been investigated in the laboratory. A degree of zinc volatilization of more than 99% was obtained from the process. Temperature has a clear influence on the reduction rate of ZnO in slag. The reduction rate of (ZnO) by [C] is the first order with respect to the content of ZnO in the slag. The apparent activation energy of the (ZnO) reduction reaction is 312 kJ/mol at 1300-1500℃.