硫杂质对焦反应性的影响及其机理(英文)

采用以低杂质沥青焦模拟石油焦和外掺杂的方式,研究硫杂质元素对焦反应性的影响,并通过XRD、SEM和EDS等检测手段探讨其作用机理。结果表明:在无其他杂质元素干扰的情况下,硫实际上是一种对焦的空气和CO2反应性都具有明显催化性的杂质元素。其催化作用可能是通过在焦的空气和CO2反应过程中分别引发有机硫→H2S→SO2→COS和单质硫(S x)→SO2和有机硫→H2S→COS→S x→C2S→COS两组可部分循环并具有增加碳耗和增大焦比表面积作用的反应体系来实现的。     

提高炼焦煤密度试验研究

用日本栗田工业株式会社提供的密度提高剂及其实验设备,对焦化厂的炼焦配煤进行了密度提高试验,试验证明添加密度提高剂后,配合煤的密度提高了4.23%～4.61%,小焦炉试验焦炭质量变化不明显。     

不锈钢电弧炉粉尘直接还原回收工艺研究

电弧炉粉尘巳被列为有害废物，直接还原回收粉尘中有价金属不仅可保护环境，而且可充分利用宝贵的金属资源。采用中频感应电炉模拟电弧炉冶炼工艺进行了A、B、C和D系列实验研究。通过气体成分的检测、钢锭和炉渣的成分分析，了解工艺参数对还原过程的影响，认为电弧炉粉尘直接还原回收工艺切实可行，不影响钢产品质量，为该新工艺的生产实践提供了依据。     

焦炭过滤床电炉粉尘捕集特性的模拟研究

以超细二氧化硅微粒为模拟粉尘,研究了在冷态焦炭过滤床条件下的电炉粉尘捕集特性：即在固定床的实验条件下,当气流速度一定时,平衡状态下静态捕集量在过滤床纵轴方向上的分布状态变化较小;当焦炭颗粒以一定速度下移时,随粉尘供给速率的增大,整体的静态捕集量也随之增加,从上部到下部静态捕集量呈渐增趋势。本实验条件下,在综合考虑捕集量、捕集速率和捕集效率的基础上,气流速度应小于0.65 m/s。     

钢铁厂副产低压煤气采样制样的方法探讨

研发一种钢铁厂副产低压煤气采样 制样的新方法,用于低压煤气检测。将无空气干扰采样与充氦气增压制样方法相结合,实现低压煤气组分的精准检测。通过对低压煤气中存在的气体(N2、CO2、H2和CO)采样 制样 检测,增压前后的数据差异不显著,相对标准偏差不大于 4.93%,充气增压最佳混合时间1 h,验证该方法可行。将该方法应用于实际低压煤气组分检测中,得到气体成分结果具有较高的准确性,且操作简单,可重复性高,为钢铁行业高炉、转炉、焦炉的气体组分检测提供技术支持。     

Bi2S3-ZnO-Na2CO3体系热力学分析及应用

对Bi2S3-ZnO-Na2CO3低温熔盐体系进行热力学分析,计算了在700～1 500 K温度下体系中各反应的标准吉布斯自由能变化值(ΔG TΘ),并绘制了相应的ΔG TΘ—T图。热力学分析结果表明,在700～1 100 K温度范围内,Bi2S3中的Bi会被C还原成金属Bi进入金属相中,S将以ZnS形式进入固体物渣中。根据分析结果,在700～1 100 K温度下,以Na2CO3等钠盐为熔剂、ZnO为固硫剂、粉煤为还原剂,开展了验证试验。试验得到了直收率达98%的粗铋,S几乎100%以ZnS的形式固定在渣中,与热力学分析结果一致。     

Equilibria in the gas system S-O-C between 550 and 1100°C

Equilibria in the S-O-C gas system have been calculated, for a variety of starting values of CO, CO₂, and SO₂ between 550–1100° C, assuming the existence of 10 gaseous species. It is shown that the species COS, SO₃, CS, and SO may form in concentrations sufficiently high that values of sulfur and oxygen partial pressures, calculated from the initial values of CO, CO₂, and SO₂, are in error. Results are given for three sets of initial compositions and are available for 39 more.     

Structural, optical and chemical analysis of zinc sulfide thin film deposited by RF-mganetron sputtering and post deposition annealing

Zinc sulfide (ZnS) thin films were deposited by radio-frequency (RF) magnetron sputtering. The effects of the process parameters such as deposition time and RF-power, as well as of post deposition annealing under oxygen containing atmospheres, on the material properties of ZnS films have been investigated. X-ray diffraction analysis reveals out that the as-deposited ZnS films preferred (002) hexagonal wurtzite and (111) cubic zinc blend (111) at 28.60°, while a thicker ZnS film has additional hexagonal wurtzite (100), (110), and (200) planes coexisting with the preferred oriented-planes, suggesting that the thickness is dependent on the growth of ZnS. After annealing, ZnO phases were detected, indicating island-like grain growth on the surface of the ZnS film. By increasing the deposition time and the RF power, the optical band gap energy (E_g) of the ZnS film changes from 4.13 to 3.87 eV, indicating the presence of lower E_g with thicker ZnS film. The lower E_g (～3.27 eV) value of the annealed films is attributed to the ZnO transition. Unlike bulk ZnS material (Zn/S～1.08), deposited ZnS thin film has Zn-rich and S-deficient composition (Zn/S～1.28). However, the Zn/S ratio is closer to the ideal value when there is a longer deposition time or higher RF-power.     

大牛地气田含硫气井腐蚀监测

根据大牛地含硫气井生产特点,室内采用化学分析方法分别对D1、D2两口气井的气样、水样、天然气中H2S含量、腐蚀产物等进行取样检测分析,现场采用挂片腐蚀失重法对试验井进行离线监测,计算油管腐蚀速率.结合两种常用气井腐蚀监测技术确定出试验井主要存在腐蚀类型为H2S气体引起的酸性腐蚀及高矿化度腐蚀.     

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 炼焦装炉煤水分是焦化企业一项重要的控制指标,与焦炉热工操作密切相关。人工检验水分存在费时、费力和测量频次有限等缺点。新型微波水分仪可在线测量装炉煤水分,具有测量准确、运行稳定、免维护等优点。微波实时测量装炉煤水分试验的成功,对于提高焦炉热工操作水平具有重要意义。     

Method for Identifying Areas of Sulfidation on Water-Wall Tubes in Coal-Fired Boilers

In Japan, pulverized-coal-fired thermal power plant boilers are operated with a high two-stage combustion ratio to reduce NOx emissions. This combustion ratio forms a strongly reducing atmosphere containing H₂S at the burner zone. Water-wall tube materials, such as low-alloy steel, sulfidize severely in such an atmosphere. In the past few years, wastage of the tubes observed in limited areas. However, the sulfidation area tends to extend and/or to shift along with changes in combustion conditions and coal properties. As a result, large-area inspections are necessary to identify the sulfidation areas. Several methods for identifying sulfidation areas have been developed, but these methods have various drawbacks, including (a) long inspection times to adequately assess large areas and (b) a need for descaling, which can act to accelerate tube wastage. Accordingly, a new approach is required for quick identification of sulfidation areas in large commercial boilers without any need for wall descaling. Toward this end, we investigated coal ash chemistry, scale structure/composition, and combustion conditions at several pulverized-coal-fired boilers in Japan. The results show that severe sulfidation occurs in areas where coal-ash deposits contain a comparatively high Zn content. In a reducing atmosphere with sufficient sulfur potential, only a limited amount of Zn contained in coal is sulfidized to form ZnS. At the combustion temperature (about 1300 °C), ZnS is present as a gaseous phase. It presumably solidifies on the tube surface, the temperature of which is about 500 °C. Continuous deposition of ZnS acts to increase the Zn content in the coal ash on tube surfaces. A relatively high level of Zn on the tube surface can be an “indicator” for a sulfidation area. With this as an indicator, the entire region of actual boilers can be easily evaluated without descaling and within several hours by the use of a handheld X-ray fluorescence analyzer.     

用闪锌矿制备ZnS-ZnO异质结及其NO2气敏特性

将闪锌矿纯矿物通过焙烧工艺制备成ZnO前驱体,随后添加Na2S·9H2O实现对ZnO前驱体的硫化,从而制备出ZnS-ZnO异质结材料,采用XRD、SEM、FTIR等检测手段对其进行结构表征。结果表明,制备出的ZnS-ZnO异质结材料呈颗粒状,尺寸在80 nm左右,且具有较大的比表面积。ZnS-ZnO异质结材料对NO2气体具有良好的响应和恢复特性,并在工作温度250℃时获得最大灵敏度,且灵敏度与NO2气体浓度符合指数函数关系。在相同检测条件下,与单一ZnO材料相比,ZnS-ZnO异质结材料呈现出工作温度低、灵敏度高、响应和恢复时间短等优异特性。在ZnS与ZnO晶界处所形成的n-n型异质结结构是改善气敏特性的关键因素。     

Die Verzunderung von Eisen zwischen 700 und 900 °C in CO/CO2-Gemischen mit kleinen Zusätzen von COS,SO2 und H2S

Scaling of iron between 700 and 900°C in CO/CO₂mixtures with minor additions of COS, SO₂ and H₂S Scaling of iron in CO/CO, mixtures containing less than 1.6% COS, H₂S or SO₂follows initially a linear kinetic law. The transition from the linear to the parabolic law is displaced toward shorter periods with increasing sulfur contents in the gas and with decreasing temperature. At 800 and 900°C the rate of the reaction between iron and the sul-fur compound in the gas is controlled by the mass transfer in the gas phase. In this conditions the reaction rates with COS and H₂S are practically identical, while the reaction with SO₂yields al-most double the weight increase because in this case not only sulfur, but also part of the oxygen of SO₂ react with iron. At 700°C there is a transition of the control mechanism in CO/CO₂C/S mixtures with increasing COS contents, namely from control by mass transfer in the gas phase to control by the phase boundary reaction. Some consequences concerning the heating of steel in technical furnaces are discussed.     

脱酸塔底换热器腐蚀原因分析及改进措施

AS脱硫工艺利用焦炉煤气中的氨作为脱硫剂,洗涤吸收煤气中的硫化氢,该工艺流程短、设备数量少、能耗低。但普遍存在的问题是生产设备和工艺管道的腐蚀严重。针对脱酸塔底换热器使用中出现的腐蚀情况,分析原因并提出了相应的改进措施。     

Thermal Recycling of Waelz Oxide Using Concentrated Solar Energy

The dominating Zn recycling process is the so-called Waelz process. Waelz oxide (WOX), containing 55–65% Zn in oxidic form, is mainly derived from electric arc furnace dust produced during recycling of galvanized steel. After its wash treatment to separate off chlorides, WOX is used as feedstock along with ZnS concentrates for the electrolytic production of high-grade zinc. Novel and environmentally cleaner routes for the purification of WOX and the production of Zn are investigated using concentrated solar energy as the source of high-temperature process heat. The solar-driven clinkering of WOX and its carbothermal reduction were experimentally demonstrated using a 10 kW_th packed-bed solar reactor. Solar clinkering at above 1265°C reduced the amount of impurities below 0.1 wt.%. Solar carbothermal reduction using biocharcoal as reducing agent in the 1170–1320°C range yielded 90 wt.% Zn.     

用贫瘦煤代替瘦煤的炼焦实践

针对煤炭资源日益紧张的形势,通过对贫瘦煤的性质分析以及40kg小焦炉实验,成功开发出低价贫瘦煤代替部分瘦煤炼焦,投入到生产实践中后,焦炭质量得到改善,并且经济效益显著。     

焦炉装煤冒烟的原因分析及解决办法

针对承钢焦化厂4.3m焦炉在装煤过程中冒烟严重的问题,经过分析,确定了装煤技术改进和设备改造方案,实施后取得了良好的效果。     

拦焦车台车辊道的改造设计与实践

针对承钢焦化厂4.3m拦焦车台车辊道运行中存在问题,通过分析与研究,提出了切合实际的改造方案,改造后运行状况良好,延长了设备检修周期。     

The microwave processing of electric arc furnace dust

An ideal treatment for electric arc furnace (EAF) dust is to cost-effectively process the dust on site to generate high-value products. Microwave heating has the potential to be the ideal approach. In this study, testing was conducted to evaluate the feasibility of treating EAF dust under microwave radiation to produce iron metal and zinc metal instead of zinc oxides as co-products. Microwave processing time and fixed carbon addition amounts were investigated. Different carbons with high fixed carbon contents were also tested and no significant influence was observed. Products of both metallic zinc-rich particles and metallic iron-rich residuals exhibited high purities, which satisfy recycling feedstock requirements.     

Effect of annealing on the conversion of ZnS to ZnO nanoparticles synthesized by the sol-gel method using zinc acetate and thiourea

A systematic study is presented on the conversion of zinc sulfide to zinc oxide nanoparticles as a function of annealing temperature. Zinc acetate dihydrate (Zn(CH₃COO)₂.2H₂O) and thiourea (NH₂CSNH₂) are used as precursors to synthesize ZnS and then ZnO. The aqueous solution of the precursor was refluxed at 90 °C for over 12 h. The synthesized complex was then annealed at 300 °C, 500 °C, 700 °C, and 900 °C in air for one hour. From elemental analyses, it was found that the as-synthesized powder is a mixture of ZnS and ZnO, which annealing later converts to the zinc oxide phase only. The morphological observations revealed spherical particles of various sizes (20 nm to 300 nm) while increasing the annealing temperatures. A drastic change in the vibration bands is noticed with annealing. Photoelectron peaks related to sulfur and carbon are observed for synthesized powder, whereas, these peaks disappeared when annealed at 500 °C.