Selective reduction of carbon dioxide into amorphous carbon over activated natural magnetite

Natural magnetite formed by the isomorphism substitutions of transition metals, including Fe, Ti, Co, etc., was activated by mechanical grinding followed by H_2 reduction. The temperature-programmed reduction of hydrogen(H_2-TPR) and temperature-programmed surface reaction of carbon dioxide(CO_2-TPSR) were carried out to investigate the processes of oxygen loss and CO_2 reduction. The samples were characterized by X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), and energy-dispersive X-ray spectroscopy(EDS). The results showed that the stability of spinel phases and oxygen-deficient degree significantly increased after natural magnetite was mechanically milled and reduced in H_2 atmosphere. Meanwhile, the activity and selectivity of CO_2 reduction into carbon were enhanced. The deposited carbon on the activated natural magnetite was confirmed as amorphous. The amount of carbon after CO_2 reduction at 300°C for 90 min over the activated natural magnetite was 2.87 wt% higher than that over the natural magnetite.     

Investigation of the deterioration of passive films in H<Subscript>2</Subscript>S-containing solutions

The effect of H₂S on the corrosion behavior of 316L stainless steel was investigated using electrochemical methods by changing the gas condition from CO₂ to H₂S and then back to CO₂. The presence of H₂S showed an acceleration effect on the corrosion of 316L stainless steel in comparison with CO₂. The acceleration effect remained even after the complete removal of H₂S by CO₂, indicating that the passive film was irreversibly damaged. X-ray photoelectron spectroscopy (XPS) analysis indicated that the passive film was composed of Cr₂O₃, Fe₂O₃, and FeS₂ after being immersed in H₂S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott-Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

Growth behavior of the magnetite phase in the reduction of hematite via a fluidized bed

To understand the formation and growth mechanism of the magnetite phase during the fluidized reduction of hematite, a high-purity hematite ore was isothermally reduced using a 20vol% CO-80vol% CO₂ gas mixture in a micro-fluidized bed to examine the process of the selective conversion of hematite to magnetite. The micro-structural characteristics of the magnetite phase were investigated using scanning electron microscopy (SEM) and the Brunauer, Emmett, and Teller (BET) method, and the thickness of the magnetite layer was measured and evaluated using statistical analysis. The experimental results showed that the fresh magnetite nuclei were dense needles of different lengths, and the original hematite grains became porous after complete reduction to the magnetite phase. The thickness of the magnetite layer increased with an increase in reduction temperature and reduction time. The growth kinetics of the magnetite layer was investigated, and the value of the activation energy E was estimated to be 28.33 kJ/mol.     

Preparation of activated ceria and its desulfurization performance

Activated ceria (CeO₂/γ-Al₂O₃) prepared by impregnation was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and hydrogen temperature-programmed reduction (TPR). The desulfurization of the activated ceria was investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TG). The results showed that ceria could be highly dispersed or crystallized on the surface of γ-alumina. The reduction temperatures of 0.1CeO₂/γ-Al₂O₃, 0.45CeO₂/γ-Al₂O₃, and CeO₂ ranged from 250℃ to 470℃, 330℃ to 550℃, and 350℃ to 550℃, respectively. The reduction peak temperature of 0.45CeO₂/γ-Al₂O₃ was higher than that of 0.1CeO₂/γ-Al₂O₃, which was consistent with the reduction temperature of CeO₂. O₂ participated in the reaction between ceria and sulfur dioxide. The desulfurization product was cerium(Ⅲ) sulfate. The intensity of the hydroxyl band decreased with the formation of sulfate species.     

Mineralogy and carbothermal reduction behaviour of vanadium-bearing titaniferous magnetite ore in Eastern India

Vanadium-bearing titaniferous magnetite bands hosted by Precambrian gabbro-norite-anorthositic rocks or their metamorphic equivalents were discovered in some parts of Eastern Indian Shield, containing 48%–49% Fe (total), 10%–25% TiO₂, and 0.3%–2.20% V₂O₅ by mass. Mineralogical and petrological study, composition, and characterization of the vanadium-bearing titaniferous magnetite ore were carried out by scanning electron microscopy-energy dispersive X-ray (SEM-EDX), wave length X-ray florescence (WDXRF), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), etc. Chemical beneficiation for valuable metals, such as Fe, Ti, and V, was performed by reduction roasting. The direct and indirect reduction were investigated by mixing the lump ore with solid activated charcoal in a closed reactor and purging the reducing gas mixture in standard reducibility index apparatus at different temperatures and time intervals. The reduction roasting parameters were optimized. Finally, the reduced samples were crushed and upgraded by magnetic separation. The results show that, the maximum mass fractions of magnetic and nonmagnetic parts achieved are 69.36% and 30.64%, respectively, which contain 10.6% TiO₂ and 0.84% V₂O₅ in the magnetic part and 36.5% TiO₂ and 0.22% V₂O₅ in the nonmagnetic part.     

烧结铁矿中FeO含量对其在富氢高炉中还原行为的影响

Japan started the national project “COURSE 50” for CO₂ reduction in the 2000s. This project aimed to establish novel technologies to reduce CO₂ emissions with partially utilization of hydrogen in blast furnace-based ironmaking by 30% by around 2030 and use it for practical applications by 2050. The idea is that instead of coke, hydrogen is used as the reducing agent, leading to lower fossil fuel consumption in the process. It has been reported that the reduction behavior of hematite, magnetite, calcium ferrite, and slag in the sinter is different, and it is also considerably influenced by the sinter morphology. This study aimed to investigate the reduction behavior of sinters in hydrogen enriched blast furnace with different mineral morphologies in CO–CO₂–H₂ mixed gas. As an experimental sample, two sinter samples with significantly different hematite and magnetite ratios were prepared to compare their reduction behaviors. The reduction of wustite to iron was carried out at 1000, 900, and 800°C in a CO–CO₂–H₂ atmosphere for the mineral morphology-controlled sinter, and the following findings were obtained. The reduction rate of smaller amount of FeO led to faster increase of the reduction rate curve at the initial stage of reduction. Macro-observations of reduced samples showed that the reaction proceeded from the outer periphery of the sample toward the inside, and a reaction interface was observed where reduced iron and wustite coexisted. Micro-observations revealed three layers, namely, wustite single phase in the center zone of the sample, iron single phase in the outer periphery zone of the sample, and iron oxide-derived wustite FeO and iron, or calcium ferrite-derived wustite 'FeO' and iron in the reaction interface zone. A two-interface unreacted core model was successfully applied for the kinetic analysis of the reduction reaction, and obtained temperature dependent expressions of the chemical reaction coefficients from each mineral phases.     

钙化合物对钒钛磁铁矿精矿碳热还原的影响

Effects of calcium compounds on the carbothermic reduction of vanadium titanomagnetite concentrate (VTC) were investigated. It was found that calcium compounds had great effects on the metallization rate of the reduction product, the order of the metallization rate of reduction product being CaCO₃ > no additive > CaSO₄ > CaCl₂, which indicated that the addition of CaCO₃ was more conducive to promoting the reduction of iron than other calcium compounds. Gas analysis showed that there were mainly two processes in the carbothermic reduction of VTC, a solid–solid and a solid–gas reaction. The concentrations of CO and CO₂ were highest when CaCO₃ was added, while that in a roasting system decreased the most when CaCl₂ was added. X-ray diffraction (XRD) analysis showed that calcium compounds could change the reduction process of ilmenite in VTC. The phase compositions of the reduction products were changed from metallic iron (Fe) and anosovite (FeTi₂O₅) to metallic iron (Fe) and perovekite (CaTiO₃) when calcium compounds were added. Additionally, CaSO₄ and CaCl₂ could significantly promote the growth of metallic iron particles, though the existence of Fe-bearing Mg₂TiO₄ in reduction products was not conducive to the reduction of iron. The formation of FeS would further hinder the reduction of iron after adding CaSO₄.     

Study on reduction of MoS<Subscript>2</Subscript> powders with activated carbon to produce Mo<Subscript>2</Subscript>C under vacuum conditions

A method of preparing Mo₂C via vacuum carbothermic reduction of MoS₂ in the temperature range of 1350-1550℃ was proposed. The effects of MoS₂-to-C molar ratio (α, α=1:1, 1:1.5, and 1:2.5) and reaction temperature (1350 to 1550℃) on the reaction were studied in detail. The phase transition, morphological evolution, and residual sulfur content of the products were analyzed by X-ray diffraction, field-emission scanning electron microscopy, and carbon-sulfur analysis, respectively. The results showed that the complete decomposition of MoS₂ under vacuum is difficult, whereas activated carbon can react with MoS₂ under vacuum to generate Mo₂C. Meanwhile, higher temperatures and the addition of more carbon accelerated the rate of carbothermic reduction reaction and further decreased the residual sulfur content. From the experimental results, the optimum molar ratio α was concluded to be 1:1.5.     

Reduction mechanisms of pyrite cinder-carbon composite pellets

The non-isothermal reduction mechanisms of pyrite cinder-carbon composite pellets were studied at laboratory scale under argon (Ar) atmosphere. The composite pellets as well as the specimens of separate layers containing pyrite cinder and coal were tested. The degree of reduction was measured by mass loss. The microstructures of the reduced composite pellets were characterized by scanning electron microscopy (SEM). It is found that the reduction processes of the composite pellets may be divided into four stages:reduction via CO and H₂ from volatiles in coal at 673-973 K, reduction via H₂ and C produced by cracking of hydrocarbon at 973-1123 K, direct reduction by carbon via gaseous intermediates at 1123-1323 K, and direct reduction by carbon at above 1323 K. Corresponding to the four stages, the apparent activation energies (E) for the reduction of the composite pellets are 86.26, 78.54, 72.01, and 203.65 kJ·mol-1, respectively.     

Thermodynamic studies on gas-based reduction of vanadium titano-magnetite pellets

Numerous studies have focused on the reduction thermodynamics of ordinary iron ore; by contrast, the literature contains few thermodynamic studies on the gas-based reduction of vanadium titano-magnetite (VTM) in mixed atmospheres of H₂, CO, H₂O, CO₂, and N₂. In this paper, thermodynamic studies on the reduction of oxidized VTM pellets were systematically conducted in an atmosphere of a C-H-O system as a reducing agent. The results indicate that VTM of an equivalent valence state is more difficult to reduce than ordinary iron ore. A reduction equilibrium diagram using the C-H-O system as a reducing agent was obtained; it clearly describes the reduction process. Experiments were performed to investigate the effects of the reduction temperature, the gas composition, and two types of iron ores on the reduction of oxidized VTM pellets. The results show that the final reduction degree increases with increasing reduction temperature, increasing molar ratio of H₂/(H₂ + CO), and decreasing H₂O, CO₂, and N₂ contents. In addition, the reduction processes under various conditions are discussed. All of the results of the reduction experiments are consistent with those of theoretical thermodynamic analysis. This study is expected to provide valuable thermodynamic theory on the industrial applications of VTM.     

活性炭孔结构的混合碱改性

具有较大比表面积的且以微孔孔隙居多的活性炭对气体小分子具有较好的吸附性能,以椰壳活性炭为原料、KOH/NaOH为活化扩孔剂,考察了温度、时间以及KOH与NaOH的质量比对活性炭孔隙结构的影响,使用N2在77 K下对产品活性炭进行表征测试。表征结果表明,当m(KHO)∶m(NaOH)为4∶1、溶液浓度为50%时,活性炭在600℃下活化4 h所得的活性炭产品平均孔径最大。对比HK模型和DFT模型对微孔活性炭孔径分布的分析结果,表明DFT模型更符合实际情况。经过孔结构改性的活性炭对CH4与CO2吸附能力均有提高。     

富氢气体直接还原铁矿石及其碳沉积行为

焦炉煤气改质后可用于生产直接还原铁, 为炼钢提供优质的原料. 利用热重分析法, 研究了H₂ 与CO 物质的量比(H₂/CO)、温度对铁矿石球团矿还原速率及其碳沉积速率的影响. 实验结果表明: H₂ 的还原能力大于CO, 且随着混合气体中H₂ 含量的增加, 铁矿石球团矿的 还原速率增大; 当H₂/CO 比大于8/2 时, 增加H₂ 含量对还原速率影响减小; 在铁矿石还原 后期出现碳沉积, 且碳沉积速率随着H₂ 含量的增加而减小; 低温易于碳沉积, 但当温度高于 850 °C 时, 碳沉积得到抑制.     

Cu-磺化酞菁钴负载型活性炭的制备及其对PH3的催化氧化净化

以工业4号活性炭(AC4)为载体,采用浸渍法制备Cu-磺化酞菁钴(CoSPc)负载型活性炭,考察不同制备条件对其催化氧化净化PH3性能的影响,并采用N2物理吸附(N2-BET)、扫描电镜(SEM)、能量色散谱仪(EDS)、X线光电子能谱(XPS)等手段对改性活性炭进行表征.研究结果表明:当Cu2+浓度为0.1 mol/L,干燥温度为110℃,焙烧温度为350℃时改性炭对PH3的催化氧化净化效果最好；与以往研究的Cu2+改性活性炭相比,Cu-CoSPc负载型活性炭对PH3具有更好的净化脱除性能.     

活性炭选择性催化还原NOx

采用活性炭作催化剂,NH3为还原剂,进行活性炭脱硝机理的实验研究.分别考察了烟气组分、温度、活性炭的比表面积及不同材质对NOx去除率的影响.结果表明:活性炭作为单纯的吸附剂,其NO吸附容量较小,O2的加入使吸附容量增大,NH3与O2同时存在则可达到最佳去除效果,H2O的存在不利于活性炭的催化作用;温度在200℃时,活性...     

玉米芯活性炭的制备及储气性能

天然气、氢气、二氧化碳等气体的吸附研究在洁净气体代油燃料的强化存储、温室气体减排、大气治理等方面具有重要意义,其重点内容是高效吸附材料的开发．以玉米芯为原料,采用磷酸活化法制备了含有较高中孔比例的活性炭,其比表面积达到1,610,m2/g,孔容为1.72,cm3/g,中孔体积达到1.14,cm3/g,占孔容的66％．测定了H2、N2、CH4和 CO2在该吸附剂上的吸附等温线．在0.4,MPa 时,CO2对 CH4的选择性达到2.76,对 N2的选择性达到7.63,对 H2的选择性达到42.31,具有良好的分离应用前景．测定了水存在条件下甲烷在该活性炭上的吸附等温线,由于孔尺寸有利于甲烷水合物的生成,因此甲烷吸入量较在干燥吸附剂上提高了82％．根据克劳修斯-克拉佩龙方程计算了甲烷水合物的生成焓为-64.37,kJ/mol．     

三维大孔氮化碳材料的制备及其血液相容性

以粒径640 nm的单分散二氧化硅胶体晶体为模板,由四氯化碳和乙二胺回流加热制备出氮化碳的前驱物;将其填入模板的缝隙中,在氮气中热处理,形成氮化碳/二氧化硅的复合物;用氢氟酸除去二氧化硅模板,制备出三维大孔氮化碳材料. 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射 (XRD)、选区电子衍射(SAED)、元素分析、红外光谱(FT-IR)、X射线光电子能谱(XPS),对其形貌结构、元素组成、键合状态进行了形貌和结构的表征. 采用部分凝血活酶时间(APTT)、凝血酶原时间(PT)和凝血酶时间(TT)对其体外抗凝血活性作了初步的评价,发现制备的大孔氮化碳对血液不会造成促凝,说明其可能成为一种新的血液相容性材料.     

过氧化氢改性活性炭对三甲胺废气的吸附

对煤质柱状活性炭进行H2O2改性,测试了H2O2改性前后活性炭的比表面积和含氧官能团,研究了其对三甲胺的静态吸附量、动态穿透曲线、脱附活化能。结果表明,经氧化改性后活性炭的表面含氧官能团、比表面积均有明显提高,其中以体积分数为15%的H2O2溶液浸渍1.5h后的活性炭最佳。其对三甲胺的吸附量达到440.9mg/g,较改性前提高了281.5%。对三甲胺的动态吸附穿透时间由10min提高到35min,脱附活化能由11.461kJ/mol提高到15.663kJ/mol,改性后活性炭的吸附性能得以提高。     

多壁碳纳米管负载镧掺杂氢氧化铁纳米胶粒修饰碳纤维簇电极对CO2的光电催化还原研究

通过溶胶法制备了氢氧化铁溶胶纳米粒子及镧掺杂氢氧化铁溶胶纳米粒子,多壁碳纳米管负载后,化学修饰在碳纤维簇电极上,制备出多壁碳纳米管负载镧掺杂氢氧化铁纳米胶粒修饰碳纤维簇电极,该电极对CO_2有光电催化还原作用。多壁碳纳米管修饰后增加了电极的表面积,氢氧化铁纳米胶粒修饰后还原电流变大增强了电催化还原功能,镧掺杂后起始电位正移增加了光催化还原功能。以MOPAC2012提供的PM7半经验分子轨道方法在设计的铁-氧-氯构成的氢氧化铁分子簇模型上进行半经验分子轨道计算,通过对计算结果的热力学,能级,分子轨道组成以及光谱分析表明,氢氧化铁溶胶纳米粒子及其镧掺杂对CO_2有光电催化还原行为。所设计的分子簇模型是具有热力学稳定的结构,镧掺杂加强了其稳定性。氢氧化铁分子簇具有较好的电子转移性,镧掺杂降低了其费米能级高度,有利于光催化,与实验结果相对应。且催化后的CO_2在键长、分子结构以及红外光谱都发生了较大变化,并具有碳酸的前体结构,实现了对CO_2分子的活化和光电化学催化还原。     

淀粉基活性炭的制备及在超级电容器中的应用

以淀粉为原料,分别采用H₃PO₄活化法和物理-化学复合活化法制备活性炭,并将制备的活性炭组装成超级电容器。研究了制备工艺对活性炭孔结构及电容特性的影响;通过氮气吸附和SEM方法表征了淀粉基活性炭的孔结构和表面形貌,通过循环伏安曲线、恒流充放电、交流阻抗实验考察了其电化学性能。结果表明,比表面积与比电容并没有线性关系;物理-化学复合活化法在温度为850 ℃、活化时间为2h条件下,制备的淀粉基活性炭比表面积为1438 m²/g,比电容为150 F/g。     

应用活性炭在燃烧后捕获二氧化碳的研究

从燃烧后大型固定二氧化碳点源捕获分离二氧化碳,如燃烧化石燃料的发电厂,水泥和钢铁厂,能减少操作成本并提高效率。利用活性炭分离吸附二氧化碳操作简单和成本低廉。而且,许多副产品及废物都可以作为活性炭的来源。因此,活性炭分离吸附二氧化碳的技术有远大前途。