铁矿粉烧结过程CO与NO协同控制技术研究现状

钢铁工业是我国最大的工业污染物排放源之一。为实现烧结烟气多污染物超低排放目标,特别是NOx、CO减排,建立全过程、一体化的污染物协同控制技术体系迫在眉睫。本文分析了铁矿粉烧结过程CO、NO的生成机理及其影响因素,明确了烟气CO、NO排放主要取决于燃料中C、N的氧化及其产物CO二次氧化和NO还原,阐述了燃料赋存状态、CaO与Fe2O3等催化作用对燃料燃烧和CO、NO生成与二次反应的影响规律,提出烧结过程多反应并行体系的反应机理与控制机制的深入研究与烧结工艺参数优化,将为烧结烟气CO、NO协同控制技术的研发提供支撑。     

O2/N2与O2/CO2气氛下Fe2O3与K2CO3对无烟煤催化燃烧反应性的影响

利用综合热分析仪研究了O2/N2与O2/CO2气氛下Fe2O3与K2CO3对无烟煤催化燃烧反应性的影响。结果表明,在O2/CO2气氛下,Fe2O3与K2CO3均可以催化无烟煤粉的燃烧,但其催化作用要弱于O2/N2气氛,且在低氧气浓度的O2/CO2气氛下对Fe2O3与K2CO3的抑制作用大于高氧气浓度。氧气浓度为20%~80%时,K2CO3在O2/N2气氛下催化煤粉前期燃烧使燃烧由反应控制转变为扩散控制,Fe2O3则只在氧气浓度为20%时能改变煤粉前期燃烧的控制步骤;而Fe2O3与K2CO3在O2/CO2气氛下均只能在氧气浓度为20%时改变煤粉前期燃烧的控制步骤,由反应控制转变为扩散控制。     

CO及CO-H_2气体还原铁氧化物反应表观活化能的评估

搜集并评估了用CO及COH2气体还原铁的各类氧化物的反应表观活化能。分析了反应动力学条件与机理和表观活化能的关系。得出:在气体内扩散、界面化学反应及固态铁离子扩散控速条件下,反应3CO(G) Fe2O3(S)→2Fe(S) 3CO2(G)的表观活化能分别为8.0～28.0kJmol,50.0～75.0kJmol及≥90.0kJmol,两个环节混合控速时的表观活化能则处于这两个环节分别控速时的表观活化能之间。界面化学反应控速时,用CO将Fe2O3还原为Fe3O4的表观活化能处于同一机理条件下将Fe2O3还原为Fe的表观活化能范围内;用COH2气体还原铁氧化物过程的表观活化能处于相应条件下,分别以CO,H2还原铁氧化物的表观活化能之间。     

CaO—SiO_2—Al_2O_3—X渣中FeO还原率的研究

美国马萨诸塞州的麻省理工学院材料工程系进行了该项研究。试验是在 172 3K温度下 ,用 Fe—C熔滴还原 Ca O— Si O2 —Al2 O3渣中的 Fe O,考察它的还原率。试验时 ,将 2 g重 Fe— C熔滴滴到数量比其大得多的上述熔融渣中 ,熔滴中碳与渣中的 Fe O发生还原反应 ,析出 CO气体 ,通过测定 CO的量来确定 Fe O的还原率。同时 ,还将少量的金属氧化物 (如 Ti O2 或 Nb2 O5 等 )加入渣中 ,生成 Ca O— Si O2 — Al2 O3— X渣 ,并把Fe— C熔滴与不活泼金属 (如钼 )接触 ,考察还原反应的情况。试验中 ,采用了 X射线对整个反应过程定时成象…     

CO还原Fe2O3过程中金属铁析出的微观行为

 通过原位观察和同步热分析的方式,研究气固两相界面还原反应时金属铁析出形态、矿相结构演变过程,明确金属铁的析出形态与显微结构、黏结特性之间的关系。结果表明,CO气氛下Fe2O3还原时金属铁主要以纤维状生成的铁晶须为主,还原速率是决定这种形态差异的主要原因;在Fe2O3→Fe3O4→FeO中只会因晶格转变产生体积大小变化,且伴有裂纹和孔洞的发生,没有铁晶须生成;在FeO→Fe中出现铁晶须形核和生长,且铁晶须是100%的纯金属铁。要避免铁晶须生成,就要在FeO→Fe转变时抑制铁原子的定向迁移。     

高炉喷补料中Fe2O3含量对其抗CO破坏能力的研究

 以自行开发的适用于高炉中上部使用的喷补料为基料，通过添加Fe2O3粉改变料中的Fe2O3含量，研究了Fe2O3含量对高炉喷补料抗CO破坏能力的影响，初步分析了产生破坏作用的机理。结果表明，随着Fe2O3含量的增加和侵蚀时间的延长，喷补料的气孔率和质量变化微弱，而以耐压强度为代表的力学性能指标急剧降低，因此降低喷补料中Fe2O3含量有利于提高抗CO破坏能力。     

钛铁矿磁化焙烧分离的热力学分析

为了探讨钛铁矿以Fe3O4和TiO2分离路线的可能性,对钛铁矿低温下的氧化与还原热力学进行了分析研究.结果表明:若通过直接磁化焙烧的方法,氧气能够将FeTiO3氧化成Fe3O4,但实际操作会难于控制反应条件,易过氧化成Fe2O3和Fe2TiO5;使用CO2和H2O气体将FeTiO3氧化生成Fe2O3和Fe2TiO5的反应更容易发生,而非生成Fe3O4,因此这两种气体也无法直接将钛铁矿磁化;若通过间接磁化焙烧的方法,先用氧气或空气将FeTiO3氧化,而后无需较高浓度的CO以及较低的温度即可以将FeO3和Fe2TiO5还原成Fe3O4.根据上述结果,提出钛铁矿分离钛与铁的新路线:将钛铁矿通过氧化和磁化,再通过磁选的方式得到铁精矿粉和钛渣.     

铁碳合金钢锭凝固时CO宏观气泡的生成

以前,森-美和野村等人曾作为基础研究,在铸锭条件下研究了CO气泡的生成,对于铁在单向凝固时CO气泡的生成作了一系列的研究,考察了CO宏观气泡的生成机理,决定了气泡生成的临界成分。此外,橋浦和森氏等人在铁的凝固速度为5毫米/分的定速单向凝固条件下,研究了CO气泡的生成和消失,研究并比较了CO气泡生成与消灭的机理。因为这些试验都是在定速凝固、且凝固速度很小的条件下进行的,所以,有必要在近似铸锭或连铸的凝固条件下进行研究。本研究就是在这样的凝固条件下,求铁凝固时生成CO气泡的C、O临界成分。为了研究CO气泡的生成机理,把所定的C、O浓     

PbSO4-ZnO-C体系在Na2CO3熔盐中的反应行为

考察了PbSO4-ZnO-C体系中各组分在Na2CO3熔盐中的反应行为,揭示了PbSO4固硫还原炼铅的反应机理。结果表明：在873~1 123 K的温度范围内,PbSO4首先和Na2CO3反应生成PbO和Na2SO4,PbO和Na2SO4再分别被还原成金属Pb和Na2S;温度大于1 123 K时,Na2S和ZnO反应生成ZnS和Na2O,Na2O再和CO2反应生成Na2CO3。Na2CO3在PbSO4-C-ZnO固硫还原熔炼体系中不仅是充当反应介质,改善反应体系的传热、传质和动量传递效果,同时也是主要反应物之一;ZnO在反应过程中不仅是固硫剂,同时也是Na2CO3熔盐的再生剂。     

用CO还原BRC3热轧带钢表面氧化铁皮的研究

采用SEM和XRD等方法对BRC3热轧带钢表面氧化铁皮进行了研究,结果表明:BRC3热轧带钢表面氧化铁皮由Fe2O3外层、Fe3O4中间层及FeO内层组成,在邻近基体的FeO层内有少量的Fe3O4析出.在CO高温还原过程中,BRC3热轧带钢表面氧化铁皮中的氧化物首先全部转变为FeO,然后再被还原,最终形成大部分亮白色的多孔状金属铁及小部分未被还原的灰黑色铁的氧化物.实验表明:在750℃,CO流量为3L/min,反应时间为180s的条件下,CO还原氧化铁皮的效果最好;而在相同的温度及反应时间的条件下,CO的流量越大,还原氧化铁皮的效果越好.     

Effects of the pH-controlled hemoglobin vesicles by CO2 gas

The hemoglobin vesicle (HbV) is a red cell substitute encapsulating purified concentrated Hb in a phospholipid vesicle. In order to improve the oxygen carrying capability of HbV, the pH value of the Hb solution should be adjusted to 7.0 in the HbV preparation, and then the pH value should be adjusted to 7.4 where HbV functions as an oxygen carrier, because the maximum value of [Hb]/[Lipid] was obtained in which the pH of the Hb solution was 7.0, and the metHb formation rate was suppressed in the pH 7.4. Generally, the pH control of the inner aqueous phase of HbV is difficult by changing the pH in the outer phase. We could control the pH of the Hb solution from 7.4 to 7.0 by dissolving CO2 into the Hb solution, and after the preparation of HbV, the pH of HbV is changed to 7.4 by reducing the pressure. The resulting pH-controlled HbV by CO2 gas showed a high [Hb]/[Lipid] value of 1.7 with a low rate of metHb formation.     

CO2对焦炭高温气化影响及微观结构分析

??In order to improve the metallurgical properties of coke in blast furnace smelting and reduce the melting loss of the material by CO2 to reduce the coke ratio?? the effect of CO2 on coke gasification in blast furnace was simulated in laboratory. The changes and specific surface areas of coke under different melting loss conditions were studied and calculated. The results shows that the specific surface area of coke is always increasing when the CO2 concentration is lower. When the CO2 volume fraction is high?? the specific surface area first increases and then decreases. Fourier transform infrared analysis shows that with the increase of CO2 volume concentration?? the macrocyclic aromatics in coke decrease?? and a large amount of gas is generated and volatilized from coke?? accompanied by the formation of other salts. Therefore?? under the condition of constant CO2 volume concentration?? with the increase of reaction time?? the specific surface area of coke increases?? the microstructure changes and the vibration peak of some groups shifts. As a result?? the coke is pulverized and the strength is lowered.     

转炉应用CO2技术

 通过对转炉顶吹CO2的热力学分析,结合实验室模拟转炉顶吹O2＋CO2混合气体试验结果,确立了CO2在转炉中应用的关键参数。得出在转炉中顶吹纯CO2虽可脱碳,但温降较大,顶吹CO2供气强度为3.0 m3/(t·min)时,钢液温降速率为15.1 ℃/min;通过喷吹O2＋CO2混合气体可实现温度平衡,但CO2配比的最大理论比例为79.1%;随着混合气体中CO2比例增大,吹炼终点钢液碳氧积降低,当[φ(CO2)∶][φ(O2)＝1][∶]1时可控碳氧积为(25～32)×10－8。     

Wound healing and soft tissue effects of CO2, contact Nd: YAG and combined CO2-Nd: YAG laser beams on rabbit trachea

Rabbit trachea was used as an experimental model to study tissue effects and healing of full-thickness tracheal lesions produced by CO2, contact Nd: YAG and combined, coaxial CO2-Nd: YAG (Combo) laser beams. Two power settings (10 W and 16 W) were used with CO2 and contact Nd: YAG lasers. Three different CO2/Nd:YAG power ratios (1:1, 1:2 and 1:4) and power settings (12 W 15 W and 16 W) were used with the Combolaser. Histological specimens for light and transmission electron microscopy were prepared immediately and 1, 3, 5, 7, 14 and 21 days postoperatively. The wound with the most precise and fastest healing was produced by contact Nd: YAG laser. CO2 laser produced a moderate amount of charring and the largest amount of coagulated tissue with a slightly prolonged healing period. In the acute phase, tissue defects produced by the Combolaser with power ratios 1:1 and 1:2 resembled the CO2 laser lesions but with slightly less charring. The power ratio 1:4 diminished the cutting properties of the beam considerably. During the healing period the Combolaser produced the most intensive inflammation and granulation tissue formation resulting in delayed regeneration of the lesion. In transmission electron micrographs the most severe damage to chondrocytes was seen after using the Combolaser. These findings indicate that the Combolaser produces deeper tissue damage than CO2 or contact Nd:YAG laser. However, the Combolaser appears to be suitable for tracheobronchial operations, owing to its good simultaneous cutting and haemostatic properties.     

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.     

Effects of human and experimental cancer on the conversion of 14C tripalmitin to 14CO2

14C Tripalmitin was administered intraperitoneally to control mice and to mice bearing subcutaneous Krebs-2 carcinoma. The rate of excretion of 14CO2 was studied. The presence of a tumor induced a greater than 80% suppression of the formation of 14CO2 within 24 hours from the implantation of the tumor, thus allowing unambiguous identification of the tumor-bearing mice. When cancer patients were studied, along with normal volunteers and patients with non-neoplastic diseases, 14CO2 excretion data could be used to identify the cancer patients with an overall accuracy of 84%.     

The rate of CO bubble nucleation at oxide metal interfaces within liquid iron alloys

Baker, Warner, and Jenkins found that levitated droplets of Fe-0.8 pet C alloys exploded when decarburized at 1660°C, whereas during the present investigation, the drops remained intact during decarburization at temperatures above 1850°C. Therefore, the object of this work was to determine whether heterogeneous nucleation of CO bubbles at an iron-iron oxide interface could occur at 1900°K but could not occur at 2200°K. An equation was developed to calculate the nucleation rate of CO bubbles at an iron-iron oxide interface in iron at 1900°K containing 0.8 pct C and in iron at 2200°K containing 0.1 pct C. The results of the calculation showed that an iron-iron oxide interface could not serve as a site for CO bubble nucleation. Therefore, a new mechanism is postulated in which cavities swept into the levitated droplet from the surface serve as nuclei for CO bubble formation instead of nuclei formed at the iron-iron oxide interface.     

转炉炉气CO分析在炼钢过程中的应用

通过优化用于回收转炉煤气的煤气检测仪，将所检测数据以实时线状图传至炉前操作室，根据煤气中CO的变化情况来判断溢渣、喷溅、返干等状况，并及时作出调整。详细列举了几种比较典型的CO曲线走势图，分别阐述了曲线的形成原因、过程以及造成的影响，给出了及时调整以及解决的方法，有效地保证了转炉冶炼的顺利进行，也有利于降低成本。     

CO2 binding by Baralyme in three different carrier gases

The absorptive properties of Baralyme and Sodasorb for CO2 in a container were studied by measuring the lifetime T0.5 of the unit, i.e., the time until the exit concentration of CO2 reaches 0.5%. The container size, the inlet gas flow rate, and the inlet CO2 concentration were varied. The experiments were repeated with either He, N2, or SF6 as the inert gas to evaluate the effect of increased gas density due to hyperbaric conditions on scrubber performance. It was found that T0.5 is best described by an exponential function of the type b (ttr)a, where ttr is the transit time of the gas through the container. The exponent a equals about 1.5 and varies relatively little. The constant b, however, is strongly dependent on inert gas density and on CO2 concentration in the inlet gas; it is independent of container size and gas flow rate. In addition, the amount of absorber reaching up to time T0.5 was measured in all conditions. It is strongly dependent on CO2 concentration; however, surprisingly it is nearly independent of inert gas properties. These results are compared with a mathematical model of scrubber behavior that is based on the chemical reaction rate of an imaginary absorber. The model neglects possible effects of CO2 diffusion in the gas phase, of ash formation, and of heat produced by the reaction. Differences between our experimental data and the model are analyzed as a function of these effects. The results give some simple predictive equations for the lifetime and the amount of absorber reacting.     

CO/CO2 potentiometric titrations of carbon monoxide dehydrogenase from Clostridium thermoaceticum and the effect of CO2

Acetogenic carbon monoxide dehydrogenases catalyze the reversible oxidation of CO to CO2 and the synthesis of acetyl-coenzyme A, utilizing two novel Ni-Fe-S active sites (the C- and A-clusters, respectively) and an [Fe4S4]2+/1+ cluster (the B-cluster) that serves to transfer electrons. Enzyme samples were titrated under equilibrium conditions using various partial pressures of CO in Ar and CO2 atmospheres. EPR signal intensities from each cluster were analyzed as a function of potential using the Nernst equation. The presence of CO2 raised the reduction potentials of the A-, B-, and C-clusters, and it appeared to increase the strength of CO (substrate for acetyl-CoA synthesis) binding to the reduced A-cluster. Carbon dioxide also appeared to stabilize an intermediate EPR-silent state of the C-cluster and alter the saturation/relaxation properties of the reduced B-cluster. Simulations assuming n values (number of e- involved in reduction) larger than appropriate for the individual reactions generally fit better to the titration data than those which assumed the appropriate n, indicating positive redox cooperativity. Carbon dioxide did not inhibit 1,10-phenanthroline from removing the labile Ni from the A-cluster, but it did inhibit the CO/acetyl-coenzyme A exchange activity, probably by causing CO to bind more tightly to the A-cluster. Taken together, these results indicate a significant CO2-dependent conformational change affecting the properties of all three clusters and both subunits. Since the enzyme operates in vivo in a CO2 environment, the CO2-induced conformation may be mechanistically important.