Effects of iron oxide on crystallization behavior and spatial distribution of spinel in stainless steel slag

Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.

In-situ electrochemical study on the eff ects of Fe(Ⅲ)on kinetics of pyrite acidic pressure oxidation

Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.

Finite Element Analysis of Large Size Chromium Oxide Green Bodies During Firing

To prevent dense chromium oxide covers from cracking during firing,such as internal cracking,surface cracking and fracture,the firing process of dense chromium oxide products was simulated,and the performance parameters at several specific temperatures before and after densification of chromium oxide green bodies were tested.The temperature difference and the stress difference of chromium oxide green bodies were calculated by Finite Element Software at heating and cooling rates of 10,20,30 and 40℃·h^(-1),respectively.The results show that large temperature difference and thermal stress difference are the main causes of internal cracking,surface cracking and fracture of the brick.Suitable heating rates reduce or avoid internal cracking of the brick.When the heating rate is 30℃·h^(-1) below 1450℃and 10℃·h^(-1) above 1450℃,the temperature difference and the thermal stress difference in the brick are below 4℃and 4 MPa,respectively,and there is no internal crack in the brick after firing.The initial cooling stage is the key stage that causes cracking or fracture of bricks.When the cooling rate is 20℃·h^(-1) above 1450℃,the thermal stress difference in the brick is less than 4 MPa,which can significantly reduce the surface cracks and fracture of the brick.

Oxidation of As^Ⅲ by Several Manganese Oxide Minerals in Absence and Presence of Goethite

Oxidation of As^Ⅲ by three types of manganese oxide minerals affected by goethite was investigated by chemical analysis, equilibrium redox, X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Three synthesized Mn oxide minerals of different types, birnessite, todorokite, and hausmannite, could actively oxidize As^Ⅲ to Asv, and greatly varied in their oxidation ability. Layer structured birnessite exhibited the highest capacity of As^Ⅲ oxidation, followed by the tunnel structured todorokite. Lower oxide hansmannite possessed much low capacity of As^Ⅲ oxidation, and released more Mn^2＋ than birnessite and todorokite during the oxidation. The maximum amount of Asv produced during the oxidation of As^Ⅲ by Mn oxide minerals was in the order： birnessite （480.4 mmol/kg） 〉 todorokite （279.6 mmol/kg） 〉 hansmannite （117.9 mmol/kg）. The oxidation capacity of the Mn oxide minerals was found to be relative to the composition, crystallinity, and surface properties. In the presence of goethite oxidation of As^Ⅲ by Mn oxide minerals increased, with maximum amounts of Asv being 651.0 mmol/kg for birnessite, 332.3 mmol/kg for todorokite and 159.4 mmol/kg for hansmannite. Goethite promoted As^Ⅲ oxidation on the surface of Mn oxide minerals through adsorption of the Asv produced, incurring the decrease of Asv concentration in solutions. Thus, the combined effects of the oxidation （by Mn oxide minerals）-adsorption （by goethite） lead to rapid oxidation and immobilization of As in soils and sediments and alleviation of the As^Ⅲ toxicity in the environments.

Factors Affecting Cr(Ⅲ) Oxidation by Manganese Oxides

The high oxidation ability of manganese oxides or soils was used to study effects of pH and coatingon Cr(Ⅲ) oxidation. The results indicated that Cr(Ⅲ) oxidation peaked in pH 4.0-6.5. The amount andrate of Cr(Ⅲ) being oxidized by uncoated δ-MnO2 were larger than those by Fe oxide- or CaCO3-coatedone. Inorganic Cr(Ⅲ) was more easi1y oxidized by MnO2 than organic complex Cr(Ⅲ) due to differentsurface affinities. Precipitated Cr(Ⅲ) and adsorbed Cr(Ⅲ) might be transferred onto MnO2 surface andthen oxidized to Cr(VI).

基于金纳米粒子-纳米氧化铈-石墨烯复合物修饰电极对环境水体中As(Ⅲ)的检测

先通过滴涂法制备纳米氧化铈-石墨烯(CeO_(2)-Gr)复合物修饰玻碳电极(GCE),再在含氯金酸(HAuCl_(4))的缓冲溶液中,采用循环伏安法将Au(Ⅲ)还原到CeO_(2)-Gr表面,从而制得AuNPs/CeO_(2)/Gr/GCE。采用电化学阻抗谱法(EIS)对修饰电极进行电化学特性表征。研究了AuNPs/CeO_(2)/Gr/GCE快速、准确测定水环境中As(Ⅲ),采用差分脉冲溶出伏安法,探讨了氧化铈与石墨烯质量比、金纳米粒子沉积圈数、沉积时间和沉积电位及干扰离子等对测定结果的影响,并确定检测As(Ⅲ)的优化实验条件。在最优条件下,该电化学传感器对As(Ⅲ)具有良好的电流响应,其溶出伏安峰电流与As(Ⅲ)浓度的线性范围为13.35~387.15μmol/L,检出限为4.74μmol/L。在不同干扰离子存在的情况下,传感器对As(Ⅲ)的选择性较好。为了评估传感器的实际应用能力,以实验室自来水为样本进行As(Ⅲ)加标检测,加标回收率为90.5%~99.2%,表明该电化学传感器具有监测As(Ⅲ)的应用潜力。

Cr(Ⅲ)对锰氧化菌P.putida MnB1活性及功能的影响规律与机制

三价铬(Cr(Ⅲ))与锰氧化菌在环境中通常伴同存在,锰氧化菌介导生成的锰氧化物是Cr(Ⅲ)的主要天然氧化剂,探究Cr(Ⅲ)对锰氧化菌活性和功能的影响对于阐明环境中的锰循环和铬的迁移转化行为具有重要意义。以锰氧化模式菌Pseudomonas putida MnB1为研究对象,通过批实验探究了Cr(Ⅲ)对MnB1活性与功能的影响及其机制。结果表明,Cr(Ⅲ)浓度高于0.05 mmol/L时会造成MnB1的显著死亡,且Cr(Ⅲ)浓度越高杀菌作用越显著,当Cr(Ⅲ)高于0.02 mmol/L时会推迟锰的生物氧化,当Cr(Ⅲ)浓度高于0.2 mmol/L时完全抑制锰的生物氧化。机制研究表明,Cr(Ⅲ)诱导产生的胞内活性氧和Cr(Ⅲ)颗粒引起的细胞膜通透性改变共同影响了MnB1的生长代谢和功能。研究结果为认识锰的生物地球化学循环和铬的迁移转化行为提供了新的理论依据。

Eu(Ⅲ) complexes involving 1,3,5-triazine diphosphine oxides

The 1,3,5-triazine diphosphine oxide ligands with donor-acceptor properties formed strong complexes with europium（Ⅲ） ion in acetonitrile. Spectrophotometric titrations and mass spectra indicated that two ligands coordinated to one europium ion. The stability constants varied from 11.64 to 14.60 （log 13）. Binary complexes exhibited rather weak luminescence in solution. 1,3,5-triazine diphosphine oxides engaged as co-ligands in Eu（Ⅲ） （2-thenoyltrifluoroacetonate）3 complex contributed to the overall photoluminescence and allowed for excitation with longer wavelengths than the parent complex.

Preparation of hexagonal and amorphous chromium oxyhydroxides by facile hydrolysis of K_xCrO_y

The hydrolysis process and mechanisms of unique as-prepared KCrO2 and K3 CrO4 were systematically investigated. The characterization results of XRD, IR and SEM show that the hydrolysis reaction can be realized at a low reaction temperature of 80 ℃ and a reaction time of 24 h. Moreover, the greyish-green α-CrOOH with a hexagonal plate-like morphology and a large size of 10 μm is formed via the hydrolysis of the single-phase hexagonal KCrO2, while the green sol-gel of amorphous Cr(OH)3 with a lumpy aggregate morphology is generated through the hydrolysis of a cubic K3 CrO4. It is a facile and rapid method to synthesize pure-phase chromium oxyhydroxide via the above hydrolysis.

不同Mn/Fe比例天然含铁锰矿的As(Ⅲ)吸附性能与机制

水体中的砷主要以亚砷酸(As(Ⅲ))形态存在.金属氧化物常用于水体砷的去除,但其对As(Ⅲ)的亲和力较弱,导致水体砷很难去除,因此,寻求高效、廉价、绿色的除As(Ⅲ)材料具有显著的环境意义.天然含铁锰矿是一种高效的砷吸附剂,由于自然形成条件复杂,其不同含铁锰矿对As(Ⅲ)的去除性能存在较大差异.本研究以两种不同Mn/Fe比例的天然含铁锰矿(NFM-L、NFM-H)为研究对象,评估其对As(Ⅲ)的吸附性能,并结合XPS、XRD等光谱学表征手段探究其砷的去除机制.实验结果表明,NFM-L的Fe含量是NFM-H的5.61倍,其As(Ⅲ)的最大吸附量(24.82 mg·g^(−1))与吸附速率亦显著高于NFM-H(18.94 mg·g^(−1)),NFM-L和NFM-H对As(Ⅲ)的等温吸附曲线更符合Freundlich模型.影响因子实验表明,溶液pH值对NFM-L的影响更大,共存离子H_(2)PO_(4)^(−)能够显著抑制两种材料对As(Ⅲ)的吸附,但是材料粒径对As(Ⅲ)去除的影响较小.光谱学表征发现,两种矿物吸附砷后结构并未发生明显变化,但锰氧化物能将As(Ⅲ)氧化为As(V),从而显著提高了铁锰矿对砷的吸附能力.

Aluminum(Ⅲ) triflate-catalyzed selective oxidation of glycerol to formic acid with hydrogen peroxide

Glycerol is a by-product of biodiesel production and is an important readily available platform chemical.Valorization of glycerol into value-added chemicals has gained immense attention.Herein,we carried out the conversion of glycerol to formic acid and glycolic acid using H2O2 as an oxidant and metal(Ⅲ)triflate-based catalytic systems.Aluminum(Ⅲ)triflate was found to be the most efficient catalyst for the selective oxidation of glycerol to formic acid.A correlation between the catalytic activity of the metal cations and their hydrolysis constants(Kh)and water exchange rate constants was observed.At 70 ℃,a formic acid yield of up to 72% could be attained within 12 h.The catalyst could be recycled at least five times with a high conversion rate,and hence can also be used for the selective oxidation of other biomass platform molecules.Reaction kinetics and 1H NMR studies showed that the oxidation of glycerol(to formic acid)involved glycerol hydrolysis pathways with glyceric acid and glycolic acid as the main intermediate products.Both the [Al(OH)x]^n+ Lewis acid species and CF3SO3H Brosted acid,which were generated by the in-situ hydrolysis of Al(OTf)3,were responsible for glycerol conversion.The easy availability,high efficiency,and good recyclability of Al(OTf)3 render it suitable for the selective oxidation of glycerol to high value-added products.

Reduction of chromium oxides in stainless steel dust

The recovery of metal oxides from stainless steel dust using C（graphite）, SiFe, and Al as reductants was investigated under various conditions. The apparent distribution ratio of Cr（L Cr ′^m/s ） in the recovered metal and residual slag phases was defined as the major performance metric. The results show that the recovery ratio of metals increases as the ratio of CaO ：SiO2 by mass in the residual slag increases to 1.17. The residual content of metals in the slag decreases as the Al2O3 content of the slag is increased from approximately 8wt% to 10wt%. The recovery ratio of Cr increases with increasing L Cr ′^ m/s , and a linear relationship between L Cr ′^m/s and the activity coefficient ratio of CrO in the slag and the recovered metal phase is observed. The combination of C and SiFe or Al as the reducing agents reveals that Si is the more effective coreductant.

Cr(Ⅲ) removal from simulated solution using hydrous magnesium oxide coated fly ash： Optimization by response surface methodology (RSM)

Hydrous magnesium oxide coated fly ash （MFA） has environmental remediation potential by providing a sub- strate for the adsorption of aqueous Cr（Ⅲ）. Aqueous Cr（Ⅲ） adsorption onto MFA was examined as a function of MFA dosage, pH and initial Cr（Ⅲ） concentration with the Box-Behnken approach used for experimental design and optimization using response surface methodology （RSM）. pH and dosage （dosage and concentration） have significant interactive effects on Cr（Ⅲ） adsorption efficiency. Analysis of variance shows that the response surface quadratic model is highly significant and can effectively predict the experimental outcomes. Cr（Ⅲ） removal effi- ciency of 98% was obtained using optimized conditions of MFA dosage, pH and initial Cr（Ⅲ） concentration of 1,5 7 g. L- 1, 4.11 and 126 mg. L- 1, respectively. Cr（Ⅲ） adsorption onto MFA is mainly attributed to the interaction between Or（Ⅲ） and the functional group --OH of the hydrous magnesium oxide, in all probability caused by chemisorptions. The results of this study can conduce to reveal the interactions between Cr（Ⅲ） pollutant and MFA characteristics, posing important implications for the cost-effective alternative adsorption technology in the treatment of heavy metal containing wastewater.

Effect of partial pressure of reactive gas on chromium nitride and chromium oxide deposited by arc ion plating

The effects of reactive gas partial pressure on droplet formation, deposition rate and change of preferred orientation of CrN and Cr2O3 coatings were studied. For CrN coatings, as nitrogen partial pressure increases, the number and size of droplets increases, the deposition rate initially increases obviously and then slowly, and the preferred orientation of CrN changes from high-index plane to low-index one. For Cr2O3 coatings, with the increase of oxygen partial pressure, the number and size of droplets decreases, the deposition rate decreases and the (300) becomes the preferred orientation. These differences are ascribed to the formation of CrN (with a lower melting point) and Cr2O3 (with a higher melting point) on the surface of Cr target during the deposition of CrN and Cr2O3. Complete coatings CrN or Cr2O3 film can be formed when reactive gas partial pressure gets up to 0.1 Pa. The optimized N2 partial pressure for CrN deposition is about 0.1?0.2 Pa in order to suppress the formation of droplets and the suitable O2 partial pressure for Cr2O3 deposition is approximately 0.1 Pa for the attempt to prevent the peel of the coating.

Effect of Atmosphere on Sintering Behavior of Chromium Oxide Materials

The chromium oxide materials were prepared using Cr2O3 micropowder as main starting material, TiO2 micropowder as sintering aid, polyvinyl alcohol as binder, by a series of processes such as slurrying, spraying granulation, machine moulding and cold isostatic pressing, and firing at 1 500 ℃ for 3 h in air （ oxygen partial pressure was 2. 1× 10^4 Pa ）, industrial nitrogen （ oxygen partial pressure was 1×10^3 Pa ） , pure nitrogen （ oxygen partial pressure was 10 Pa） , high purity nitrogen （ oxygen partial pressure was 0.1 Pa ） , and carbon cake embedded atmosphere （ oxygen partial pressure wtas 2.3×10-12 Pa ）. Effects of oxygen partial pressures on the sintering behavior of Cr2 O3 materials were investiga- ted. The results show that （ 1 ） for 3 wt% TiO2-doped specimeas, there is a substantial dependence of sintering on oxygen partial pressure （0. 1 Pa - 2. 1 ×10^4 Pa ） , and the bulk density increases and apparent porosity decreases with oxygen partial pressure decreasing; （2） even if the oxygen partial pressure is 0. 1 Pa, the specimen without TiO2 cannot reach densification sintering; （3） under very low oxygen partial pressure of carbon embedded atmosphere, Cr2O3 materials containing TiO2 or not can attain denzification.

Preparation and Characterization of Plasma-Sprayed Ultrafine Chromium Oxide Coatings

Ultrafine chromium oxide coatings were prepared by plasma spraying with ultrafine feedstock. Processing parameters of plasma spraying were optimized. Optical microscope （OM） was used to observe the microstructure of the ultrafine chromium oxide coatings. Scanning electron microscopy （SEM） was used to observe the morphology and particle size of ultrafine powder feedstock as well as to examine the microstructure of the chromium oxide coating. In addition, hardness and bonding strength of the ultrafine chromium oxide coatings were measured. The results showed that the optimized plasma spraying parameters were suitable for ultrafine chromium oxide coating and the properties and microstructure of the optimized ultrafine chromium oxide coating were superior compared to conventional chromium oxide wear resistant coatings.

Effect of Chromium Powder on Sintering Property of Chrome Oxide Materials

The specimens were prepared using Cr2O3 micropowder, TiO2 micropowder and chromium powder as starting materials, PVA as binder, after spraying granulation and cold isostatic pressing, firing at 1 450 ℃ for 3 h in standard nitrogen and oxygen control atmosphere （ oxygen partial pressure was 1 010 Pa and 10. 1 Pa, respectively）. Effects of chromium powder （ mass percent were 0, 0. 5% , 1.0% , 1.5% and 2.0% , respectively） on sintering behaviors of Cr2O3 materials were researched. The results show that： adding 0. 5% chromium powder can obviously decrease the oxygen partial pressure in the specimens. Meanwhile, because the expansion caused by the oxidation reaction is small, Cr2O3 materials could realize the densifieation sintering under 1 010 Pa and 10. 1 Pa of oxygen partial pressure. The chromium powder addition in Cr2O3 materials shouldn＇t be excessive, otherwise, the expansion reaction occupies a dominant position, which deteriorates the properties of the materials.

Use of Chromium Oxide and Alkane Indicator Methods for Determination of Feed Intake for Grazing Sheep

This experiment was carried out to determine feed intake and digestibility of grazing sheep on pasture. A total of 14 animals randomly divided into two groups with seven animals each group were used in the experiment. Digestibility of pastures was determined using two types of markers-alkane （C32-C36） and chromium oxide. Dry matter intake （DMI） was 717.22 g/d based on chromium oxide method in the experiment, while according to alkane method, DMI was 965.93 g/d and 1,051.07 g/d for C32 and C36, respectively. In conclusion, pastures met 74%-81% of crude protein （CP） and 57%-61% of energy requirements of lambs grazing on Yuzuncu Yil University pasture, who are mid-quality and 4-7 month-old with a 275 g/d expected daily gain. It was calculated that when 628-693 g/d of barley is given, both CP and metabolizable energy （ME） requirements of animals can be met.

Comparative Study of Removal of Hexavalent Chromium from Water Using Metal Oxide Nanoparticles

Hexavalent chromium is one of the important heavy metals found in water and wastewater. The hexavalent form of chromium is considered to be a human carcinogen because of its mutagenic and carcinogenic properties. This work has focused on the comparison of copper oxide nanoparticles and aluminium oxide nanoparticles for the removal of chromium(VI) from water. The cooper oxide nanoparticles (CuNP) and aluminium oxide nanoparticles (AlNP) were synthesised by sol gel method. Both the adsorbents were evaluated for the adsorption capacity using Langmuir and Freundlich adsorption model. The CuNP and AlNP were characterized for X-ray diffraction and SEM. The study indicated that the AlNP showed better removal as compared to CuNP and can be further explored as potential adsorbent for hexavalent chromium removal.

Fe(Ⅲ)/2,6-吡啶二羧酸活化高碘酸盐强化染料脱色的效能与机制

有色染料是环境中非常重要的污染源之一,严重威胁着水生生态环境和人类健康。由于其难以被天然降解,且传统的污水处理工艺亦无法实现其高效去除,因此急需开发绿色、高效的水处理工艺进行有色染料污染控制。发现Fe(Ⅲ)/2,6-吡啶二羧酸(2,6-PDA)可高效活化高碘酸盐(PI)实现亚甲基蓝(MB)这一典型染料的高效降解。实验结果表明,该体系在Fe(Ⅲ)浓度为10μmol/L、2,6-PDA浓度为10μmol/L和PI浓度为200μmol/L时,可在pH 3.0条件下使5 mg/L MB降解率在120 s内大于97%。该方法依托高级氧化原理和配位强化策略,利用PI对有色染料进行降解,为目前染料废水治理提供了新思路从而有效地修复了污染水体。