Effect of rare earth addition on Cu-Fe/AC adsorbents for phosphine adsorption from yellow phosphorous tail gas

Phosphine(PH3) is a highly toxic air pollutant,commonly produced in phosphorous chemical industry.But it has received less research attention due to its handling difficultly.CO is the main content of the phosphorous chemical industry tail gas,the concentration of which is always more than 80 vol.%,and it can be the feed gas to produce various valuable products such as formate,oxalate,and methanol and so on.But,PH3 is one of the important barriers,which is harmful to the following chemical process.In order to make use of the tail gas,PH3 should be removed firstly,and CO should be covered in the whole purified procedure at the same time.In this work,the modified activated carbon(MAC) was used as the adsorbent to separate PH3 from the mixture tail gas.Series of MAC adsorbents were prepared for the adsorption of PH3,which loaded Cu-Fe and Ce(La),or separately.The PH3 adsorption capacities,chemical and physical properties of MAC were all investigated.The results showed that over 99% PH3 adsorption efficiency was achieved when used MAC adsorbents.The removal efficiency and PH3 adsorption capacity of the Cu-Fe-Ce/AC(20:1:0.4) were both much higher than those modified activated carbons.The maximum PH3 adsorption capacity was 71 mg of PH3/g of MAC on the Cu-Fe-Ce/AC,which were much higher than literature data using CuO only for adsorbing hydride gases.     

Effect of zinc and cerium addition on property of copper-based adsorbents for phosphine adsorption

A series of copper-based activated carbon (AC) adsorbents were prepared in order to investigate the effect of Zn, Ce addition on Cu-based AC adsorbent for phosphine (PH3) adsorption removal from yellow phosphorous tail gas. N2 adsorption isotherm and X-ray diffrac-tion (XRD) results suggested that the addition of Zn could increase the adsorbent ultramicropores, decrease the adsorbent supermicropores and the adsorbent average pore diameter. Therefore it enhanced the PH3 adsorption capacity. Appropriate amoun...     

Models for the adsorption of aurocyanide onto activated carbon. Part II: Extraction of aurocyanide ion pairs by polymeric adsorbents

The adsorption of aurocyanide onto activated carbon has been known but not fully understood for many years. This is due to the difficulty involved in studying the nature of the adsorbed gold cyanide species on activated carbon by conventional techniques of chemical investigation such as infrared and ultraviolet-visible spectroscopy. A novel approach using model systems was adopted by the authors to shed further light on the adsorption mechanism. This study reports on the extraction of gold cyanide by polymeric adsorbents and ion-exchange resins and demonstrates that, as in the case of ion-pair solvent extraction (Part I), the adsorptive behaviour of Au(CN)₂⁻ in the presence of various cations onto polymeric adsorbents is analogous to the adsorptive behaviour onto activated carbon (Part III). The effect of the cation is rationalized in terms of the type of ion pair viz., [Mⁿ⁺] [Au(CN)₂⁻]_n formed between the Au(CN)₂⁻ anion and the Mⁿ⁺ cation in the adsorption medium, and which is subsequently adsorbed.     

Reactive phosphide inclusions in commercial ferrosilicon

The goal of this work was to determine the origin of phosphine gas (PH₃), which has been reported to be generated from wet, commercial ferrosilicon alloys containing ∼75 wt pct Si. Based on previous work, it is suspected that PH₃ evolves when phosphides present within the alloy react with atmospheric moisture or water. Reactive phosphides have been identified in synthetic ferrosilicon alloys, which contain higher amounts of phosphorus than are typically present in commercial alloys. Therefore, reactive phosphides in commercial FeSi75 alloys are expected to be important to the evolution of PH₃ from these alloys. To identify the role of reactive phosphides in the evolution of PH₃ from commercial FeSi75 alloys, the microstructures of four commercial and two synthetic FeSi75 ferrosilicon alloys were investigated. Reactive phosphides were observed in each of the commercial alloys and characterized with respect to composition, morphology, and location within the microstructure. The phosphides observed in all of the commercial alloys contained aluminum, calcium, and magnesium. The phosphides had inclusion-like morphologies and were located on the silicon/ζ (high-temperature FeSi₂) interfaces at microcracks. The microstructural features observed support the hypothesis that atmospheric moisture penetrates ferrosilicon, reacting with the phosphide inclusions to produce PH₃. A possible mechanism describing the spontaneous crumbling sometimes observed in ferrosilicon alloys is also presented.     

氢化钛粉烧结Ti-6Al-4V性能研究

研究了以氢化钛粉与铝钒合金粉为原料,在冷等静压机压制成型后分别采用真空烧结和气氛烧结制备Ti-6Al-4V合金,并对制备的Ti-6Al-4V合金进行相对密度、微观组织及力学性能进行分析。结果表明:在真空条件或气氛条件下烧结制备Ti-6Al-4V合金的相对密度均大于98%,力学性能满足ASTM B348要求;与真空烧结相比,气氛烧结制备的Ti-6Al-4V合金晶粒尺寸较小,力学性能在真空烧结的基础上提高了8%~10%。     

The rate of formation of SiO by the reaction of CO or H2 with silica and silicate slags

The rate of formation of SiO(g) by the reaction of CO and H₂ with silica or silicate slags containing SiO₂, CaO, and A1₂O₃ has been measured. The rate with hydrogen for both pure silica and silica in slags is controlled by gas phase mass transport. The rate changed with flow conditions, sample size, and gas properties as predicted by the appropriate mass transfer equations. In particular, the rate is faster in H₂-He than in H₂-Ar gas mixtures with the same hydrogen pressure, which proves conclusively the rate is controlled by gas phase mass transport. The rate of formation of SiO by the reaction of silica with CO did not change with flow conditions or particle size and the rate was the same in CO-He and CO-Ar with the same pressure of CO. In addition, the calculated rate with CO for mass transfer is considerably faster than was observed. These observations strongly indicate the rate is controlled by chemical kinetics on the surface. Similar results were obtained for the rate of reaction of CO with silica in slags and the rate was found to be proportional to the activity of SiO₂ and CO pressure. The present results are discussed in relationship to silicon transfer in slag-metal reactions.     

The kinetics of S35 exchange between SO2/CO/CO2 gas mixtures and copper sulfide melts at 1523 K

The kinetics and mechanisms of oxidation of copper sulfide melts have been investigated using a radioisotope exchange technique. Copper sulfide melts were doped with S³⁵. The transfer of the radioisotope between the melt and SO₂/CO/CO₂ gas mixtures in chemical equilibrium with the melt was monitored by analyzing the changes in radioactivity of the gas. Analysis of the results indicates that the rate-limiting chemical reaction involves the formation of an activated complex SO, and the rate of exchange of the sulfur isotope at 1523 K is described by the relationshipR = 6.4(±2) (P _CO /P _CO2 )P _SO2 g atom S m⁻² s⁻¹. formerly Research Assistant, University of Queensland formerly Postdoctoral Fellow, University of Queensland     

高磷铁矿脱磷技术现状及磷资源化提取新方法

 为了提高磷铁矿作为炼铁原料的使用率,对高磷铁矿中磷元素的降低和脱除技术（选矿法、化学浸出法、生物浸出法、高温脱磷法）的特点及发展现状进行了综合评述,并从磷的资源化利用的角度探讨其提取与利用的可能性。介绍了一种基于湿法酸浸-生物吸附方法提取高磷铁矿或高温脱磷渣中磷资源新工艺技术,对其基本原理、工艺流程与技术特点进行了讨论。该提磷新方法的最大优势在于可以从pH值为1～2的酸浸溶液中直接选择性地吸附脱磷,使酸液得以循环使用,而磷也可解吸成高纯度的磷酸盐得以回收,吸附剂本身则可以多次循环使用。     

Models for the adsorption of aurocyanide onto activated carbon. Part III: Comparison between the extraction of aurocyanide by activated carbon,polymeric adsorbents and 1-pentanol

The factors that influence the adsorption of aurocyanide onto activated carbon, such as cation type, are examined, and compared with previous work using the model systems of 1-pentanol and polymeric adsorbent resins. The effect of the nature of the cation is rationalized in terms of the type of ion pair viz., [Mⁿ⁺] [Au(CN)₂⁻]_n, formed between the Au (CN)₂⁻ anion and the Mⁿ⁺ cation in the adsorption medium, and subsequently adsorbed onto the carbon surface. In a study of pyrolysed polymeric adsorbents, the temperature of activation is confirmed to have a profound influence on the adsorption of aurocyanide. X-ray diffractometry shows this to be related to the formation of a graphitic-type structure with a preponderance of micropores. The mechanism of adsorption is further clarified by E.S.R. spectroscopy, which indicates that a specific interaction between the adsorbed ion pair and the condensed aromatic structure is also probably occurring.     

Equilibrium Adsorption of Phenol-, Tire-, and Coal-Derived Activated Carbons for Organic Vapors

Adsorption isotherms for alkane, aromatic, and ketone vapors were determined for activated carbon fiber cloth, tire-derived activated carbon and coal-derived activated carbon adsorbents. Physical and chemical properties of the vapors and adsorbents were used to interpret these results that were obtained from 20 to 50°C, with a more limited data set at 125 and 175°C and relative pressures between 0 and 0.99. Fitted isotherms using the Freundlich and Dubinin–Radushkevich adsorption models had mean total relative errors <5.6 and 9.2% for the microporous and mesoporous/macroporous adsorbents, respectively, at the temperature range from 20 to 50°C. The predictive direct quantitative structure activity relationship model had mean total relative errors <9.7 and 61% for the microporous and mesoporous/macroporous adsorbents, respectively, at the temperature range from 20 to 50°C without requiring experimental input.     

Kinetics of chlorination and carbochlorination of molybdenum trioxide

Kinetics of chlorination of MoO₃ with Cl₂-air, Cl₂-N₂, and Cl₂-CO-N₂ gas mixtures have been studied by nonisothermal and isothermal thermogravimetric measurements, between ambient temperature and 900 °C. Between 500 °C and 700 °C, the chlorination reaction of MoO₃ with Cl₂-N₂ gas mixture has an apparent activation energy of about 165 kJ/mole, reflecting that a chemical reaction is the rate-controlling step. The reaction order with respect to Cl₂ partial pressure is about 0.75. The apparent activation energy for carbochlorination with Cl₂-CO-N₂ gas mixture is about 83 kJ/mole, between 400 °C and 650 °C. The carbochlorination of MoO₃ was controlled by the chemical reaction, probably affected by the pore diffusion regime. The maximum reaction rate is obtained by using a Cl₂-CO-N₂ gas mixture, having a Cl₂/CO volume ratio equal to about 1. The total apparent reaction order with respect to Cl₂ + CO in Cl₂-CO-N₂ gas mixture is about 1.5 for a Cl₂/CO ratio equal to 1. Laboratoire Environnement et Minéralurgie, associated with the Centre National de la Recherche Scientifique, Mineral Processing and Environmental Engineering team.     

Different Approaches for the Development of Low-Cost CO2 Adsorbents

Different carbon materials were tested as precursors for the production of CO2 adsorbents. The chemical modification of the surface of the prepared adsorbents was studied by means of three different approaches: impregnation with amines, electrophilic aromatic substitution, and heat treatment in the presence of ammonia. The samples were chemically characterized and the porous texture was evaluated from the N2 adsorption isotherms at ?196°C. The CO2 adsorption capacities of the adsorbents at 25 and 100°C were evaluated in a thermogravimetric analyzer. In general, the incorporation of basic nitrogen functionalities enhanced the CO2 capture capacities of the modified carbons, but this increase depended on the textural properties of the support and the surface modification methodology. CO2 adsorption capacities of up to 111?mg CO2/g at room temperature were attained. All the tested samples were completely regenerated when subjected to heat treatment at 100°C under inert atmosphere.     

Kinetics of carbochlorination of chromium (III) oxide

Kinetics of the carbochlorination of Cr₂O₃ has been studied with Cl₂+CO gas mixtures between 500 °C to 900 °C using thermogravimetric analysis. The apparent activation energy is about 100 kJ/mol. Mathematical fitting of the experimental data suggests that the shrinking sphere model is the most adequate to describe the carbochlorination mechanism of chromium oxide and that is controlled by the chemical reaction. In the temperature range of 550 °C to 800 °C, the reaction order is about 1.34 and is independent of temperature. Changing the Cl₂+CO content from 15 to 100 pct increases the reaction rate and does not affect the reaction mechanism. Similarly, changing the ratio of Cl₂/(Cl₂+CO) from 0.125 to 0.857 does not modify the carbochlorination mechanism of Cr₂O₃. In these conditions, the reaction rate passes through a maximum when using a chlorinating gas mixture having a Cl₂/(Cl₂+CO) ratio of about 0.5.     

Mercury Adsorption Properties of Sulfur-Impregnated Adsorbents

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 μg?Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.     

Adsorption on Carbon and Zeolite of Pollutants from Flue Gas during Incineration

The volatile organic compound, polycyclic aromatic hydrocarbon, dioxin, and metallic components released from incineration threaten human health. These pollutants, appearing in a molecular state, cannot be effectively removed by baghouse and electrostatic precipitators through capture and filtration mechanisms. Previous studies indicate that activated carbon is conventionally used to remove organic compounds from gas at low temperatures (less than 30°C). However, the adsorption characteristics of organic compounds from a gas phase at high temperatures (over 120°C) are seldom mentioned. Moreover, the complex compositions of flue gas cause the adsorption characteristics of organic compounds and heavy metals on adsorbent tubes to be more complicated. This research examines the adsorption characteristics of organic compounds and heavy metals at various incineration conditions. The evaluated parameters include: (1) the operating temperatures; (2) the characteristics of adsorbents (activated carbon and zeolite); and (3) waste compositions and the presence of heavy metals. The results indicate that activated carbon has a high adsorption capacity compared with zeolite.     

Models for the adsorption of aurocyanide onto activated carbon. Part I: Solvent extraction of aurocyanide ion pairs by 1-pentanol

Factors influencing the adsorption of gold cyanide onto activated carbon are well known, but there is currently no consensus of opinion on the actual mechanism of extraction. This situation has arisen mainly because activated carbon is not readily amenable to conventional techniques of chemical investigation such as infrared and ultraviolet-visible spectroscopy. This study reports on a novel approach using a model system in which the analogous behaviour of the extraction of gold cyanide by ion-pair solvent extraction is demonstrated. The effect of the nature of the cation on gold extraction by activated carbon is explained in terms of the type of ion pair, viz., [Mⁿ⁺][Au(CN)₂⁻]_n, formed between the Au(CN)₂⁻ anion and the cation Mⁿ⁺ present in the adsorption medium.     

Effect of Na2O on the Reduction of Fe2O3 Compacts with CO/CO2

Compacts of Fe₂O₃ and Fe₂O₃ doped with varying amounts of Na₂O were isothermally reduced at several temperatures, using CO/CO₂ mixed gas in a vertical resistance furnace. To determine the effect of Na₂O on the reduction of Fe₂O₃ compacts, the mass loss due to oxygen removal was continuously recorded, from which the reduction rate and rate constant were obtained. Na₂O was found to retard the reduction of Fe₂O₃ compacts. The apparent activation energy (E _a) of reaction and the mathematical relationship for pore gas diffusion suggested that the reduction behavior at the initial stages was controlled by a combination of pore gas diffusion and interfacial chemical reaction. At the intermediate and late stages of reduction, pore gas diffusion was the sole contributing factor. Morphological examination of the reduced compacts showed the formation of a liquid phase during the reduction process, which appeared to lower the rate of reaction.     

改性兰炭烟气SO2吸附材料的制备及其再生性能

利用活性炭（焦）等吸附剂将烟气中的污染物分离出来是一种有效的烟气治理与资源化方式。兰炭作为一种廉价半焦碳素材料,是一种有潜力代替现有商用活性焦的多孔材料。本文采用陕西兰炭作为研究对象,研究炭化时间、炭化温度、黏结剂添加量等改性工艺对所制备的吸附剂性能的影响,考察了微观形貌变化,利用X射线光电子能谱（XPS）探究在吸附解吸过程中的表面官能团的变化。结果表明,炭化温度对耐磨强度、耐压强度指标影响显著,炭化时间对饱和脱硫值和穿透脱硫值影响显著;在煤焦油添加比例50%,700 ℃炭化20 min,900 ℃活化60 min条件下制得改性兰炭参数为:耐磨强度95.81%,抗压强度536.1 N·cm?1,每克兰炭饱和脱硫值45.71 mg,每克兰炭穿透脱硫值23.45 mg;经历多次吸脱附过程第一次失活时,表面被大面积刻蚀,孔隙与小颗粒增多。兰炭吸附剂失活后可以通过二次活化的方式提高其吸附性能,但衰减速度比新改性兰炭要快。二次失活后,在酸蚀刻、水蒸气扩孔等共同作用下致使骨架结构过度烧蚀而坍塌;改性兰炭表面含氧基团的量和构成比例会影响吸附性能。含氧与含碳基团的比值与吸附性能相对应,含氧基团比例越高,吸附性能越差。二次活化再生改变了各含氧基团所占比例,令C=O显著下降,O?C=O显著增加,C?O变化不大。O?C=O官能团尽管含氧,但可能对吸附抑制作用不显著。本研究将为工业烟气治理提供一种新型吸附剂的制备方法,同时也为兰炭表面改性以及二氧化硫吸附解吸机制的研究提供参考。      

High-Temperature Oxidation of Alloy 617 in Helium Containing Part-Per-Million Levels of CO and CO<Subscript>2</Subscript> as Impurities

The objective of this study was to determine the mechanisms of carburization and decarburization of alloy 617 in impure helium. To avoid the coupling of multiple gas/metal reactions that occurs in impure helium, oxidation studies were conducted in binary He + CO + CO₂ gas mixtures with CO/CO₂ ratios of 9 and 1272 in the temperature range 1123 K to 1273 K (850 °C to 1000 °C). The mechanisms were corroborated through measurements of oxidation kinetics, gas-phase analysis, and surface/bulk microstructure examination. A critical temperature corresponding to the equilibrium of the reaction 27Cr + 6CO ↔ 2Cr₂O₃ + Cr₂₃C₆ was identified to lie between 1173 K and 1223 K (900 °C and 950 °C) at CO/CO₂ ratio 9, above which decarburization of the alloy occurred via a kinetic competition between two simultaneous surface reactions: chromia formation and chromia reduction. The reduction rate exceeded the formation rate, preventing the growth of a stable chromia film until carbon in the sample was depleted. Surface and bulk carburization of the samples occurred for a CO/CO₂ ratio of 1272 at all temperatures. The surface carbide, Cr₇C₃, was metastable and nucleated due to preferential adsorption of carbon on the chromia surface. The Cr₇C₃ precipitates grew at the gas/scale interface via outward diffusion of Cr cations through the chromia scale until the activity of Cr at the reaction site fell below a critical value. The decrease in activity of chromium triggered a reaction between chromia and carbide: Cr₂O₃ + Cr₇C₃ → 9Cr+3CO, which resulted in a porous surface scale. The results show that the industrial application of the alloy 617 at T > 1173 K (900 °C) in impure helium will be limited by oxidation.     

低阶煤一步法制备活性炭的脱硫脱硝性能

 活性炭法是能实现多种污染物综合控制的烟气治理技术,可同时处理烧结过程中产生的二氧化硫和氮氧化物等有害物质,但由于活性炭较高的生产和使用成本,限制了其在烧结烟气多污染物净化领域的推广应用。以低阶煤为基炭,氧化球团为活化剂,利用低阶煤热解和气化反应与铁氧化物还原之间的耦合作用,一步完成低阶煤炭化和活化,制备活性炭(SF AC),并与商品活性炭(ZJ AC)在产品工业分析、比表面积、碘吸附值、脱硫脱硝性能和再生活性炭吸附性能等方面进行综合比较。结果表明,SF AC的碘吸附值、比表面积分别为695.13 mg/g、370.42 m2/g,而ZJ AC仅530.54 mg/g、157.50 m2/g,单独脱硫时SF AC、ZJ AC的穿透硫容分别为368.11 mg/g、73.58 mg/g,单独脱硝时SF AC、ZJ AC的穿透硝容分别为250.39 mg/g、14.99 mg/g,前者较后者具有更优的吸附性能;就再生性能而言,SF AC、ZJ AC的脱硫脱硝性能均出现下降,但前者的脱硫脱硝性能更优;与单独脱硫、脱硝相比,两种活性炭同时脱硫脱硝时脱硫性能均提高,脱硝性能却降低,采用NH₃低温催化还原可改善脱硝性能差的问题。