二氧化碳气氛下的焦炭高温耐压强度研究

在实验室条件下,研究在N2、CO2以及50%N2+50%CO2混合气氛下的焦炭高温耐压强度,考察温度和碳素溶损反应程度对焦炭高温耐压强度的影响。结果表明,随温度、CO2浓度以及碳素溶损反应程度的增加,焦炭的高温耐压强度降低,内部溶损反应程度小的焦炭,有利于维持焦炭在高温段的耐压强度。     

富钙废渣配煤对焦炭溶损反应的影响

将1%富钙碱渣配入焦煤中制备焦炭,采用自制小型垂直固定床反应器研究了900~1200℃下所得焦炭的溶损反应过程. 结果表明,碳素溶损率小于15%时焦炭的溶损反应速率基本不变,碳素溶损率大于15%时溶损反应速率逐渐减小. 焦炭反应后的比表面积随碳素溶损率增加先增大后减小,在溶损率约为15%时最大. 配入富钙碱渣提高了焦炭的溶损反应速率,增大了焦炭的反应性,溶损温度越高,溶损速率增幅越大. 用随机孔模型描述了焦炭的溶损反应动力学过程,基础焦炭和添加1%碱渣的焦炭的溶损反应表观活化能分别为132.15和103.81 kJ/mol.     

焦炭反应性及反应后热性质及其检测方法

通过焦炭反应性(CRI)和反应后强度(CSR)在模拟高炉内焦炭热性质中存在问题的分析,提出了CRI和反应后热性质(PRTP)及其检测方法,指标包括溶损反应开始温度、溶损速率、等溶损率后强度、反应后热处理性和热处理后强度. 7种高炉用焦炭的CRI和CSR及CRI-PRTP的实验研究和分析显示,几种焦炭的反应初始温度有较大差别,最大相差44℃. 焦炭D的CSR为74.1,但较高的CSR主要是其低CRI造成的,用等溶损率后强度能够更好地评定焦炭抵抗溶损劣化的能力. 焦炭A的溶损-热处理后与等溶损率后强度相比,降低幅度达到了7.1%. 研究证明,用CRI-PRTP评定焦炭热性质可行.     

灰分对焦炭溶损反应起始温度的影响

通过灰分添加实验得到不同灰分含量的焦炭,研究了灰分对焦炭溶损反应起始温度的影响。随着灰分的增加,焦炭的溶损反应起始温度逐渐降低,焦炭灰分由1.63%增加至20%时,溶损反应起始温度由941.6℃降低至927.7℃;Fe2O3、Ca O、Mg O对焦炭溶损反应起催化作用,而Si O2和Al2O3对焦炭溶损反应的影响较小。     

溶损反应动力学对焦炭溶损后强度的影响

为了分析溶损反应动力学行为对焦炭反应后强度的影响,在1 050℃～1 300℃的范围内,对三种典型焦炭进行了等温溶损反应实验.当焦炭的溶损失重率为25%时停止反应,通过I型转鼓检测焦炭的溶损后强度.结果表明,不同反应性的焦炭发生最严重的劣化梯度反应时的温度不同,高反应性焦炭为1 100℃左右,低于其他两种焦炭.虽然高反应性焦炭发生最严重的劣化梯度反应后的强度很低,但改变反应温度使反应速率加快或减慢都能使高反应性焦炭的反应后强度显著地提高.     

H2O和CO2对焦炭溶损反应动力学的研究

采用自制高温气固相反应连续测定装置,研究了900~1100℃下,CO2,H2O及其混合气体与焦炭的溶损反应. 结果表明,焦炭与H2O反应的溶损率远高于其与CO2反应后的溶损率,前者是后者的2~5倍. 相比与CO2的反应,焦炭与H2O的反应在颗粒外围更为剧烈,且不易在中心部位生成大的串孔及裂纹. 900℃时,与CO2、H2O反应开始的焦炭的主要气化方式分别为微孔生成、小孔扩张;1100℃时,分别为小孔扩张、微孔生成. 随着混合气体中H2O含量的增加,焦炭的溶损率不断增加. 当[H2O]/[CO2]=5/5和7/3时,焦炭与混合气体的共气化过程中均产生了明显的交互作用. 用缩核反应模型描述了焦炭与H2O和CO2气化反应的结果,得反应活化能分别为154.47和214.77 kJ/mol.     

矿物质催化焦炭溶损反应动力学

研究了 1 1种矿物质对焦炭溶损反应的催化动力学 .结果表明 ,具有正催化作用的氧化物 ,随其量增加 ,起始反应温度提前 ,反应的活化能降低 ;具有负催化作用的氧化物 .随其量增加 ,起始反应温度延迟 ,反应的活化能升高 ;频率因子随活化能同方向变化 ,且所研究的大多数矿物质 ,其催化溶损反应的活化能与频率因子之间存在良好的补偿效应 ;催化作用强的氧化物使反应具有较小的反应级数 ,但反应级数基本不随氧化物量变化而变化     

氧化铁对焦炭溶损反应的影响

在井式硅钼棒电炉中对焦炭溶损反应性进行研究,考察了反应条件(CO₂流量、反应时间)并重点研究负载氧化铁对焦炭溶损反应性的影响;通过扫描电子显微镜(SEM)和电子能谱(EDS)对反应前后负载氧化铁的焦炭进行分析,探究氧化铁负载方式对焦炭溶损反应影响差异的原因,并进一步分析比较其影响机理。结果表明:焦炭溶损反应性随CO₂流量和反应时间的增加而增大;以吸附法和添加法负载氧化铁对焦炭溶损反应均有促进作用,氧化铁吸附负载量存在一个饱和点(1%),超过该点后氧化铁吸附负载量对焦炭溶损反应性影响甚微;吸附法负载氧化铁对焦炭溶损反应性的影响大于添加法。SEM分析表明:添加法的部分铁氧化物被焦炭气孔壁基质包裹而无法发挥作用,吸附法的氧化铁均匀分布在焦炭表面使其能提供更多有效催化活性中心;且添加氧化铁时铁氧化物参与成焦,影响焦炭结构从而对焦炭溶损反应产生影响,吸附氧化铁则是影响焦炭溶损反应的催化作用,两种负载方式下氧化铁的影响机理不同。     

不同配比碱金属化合物对焦炭反应性的影响

通过将一定粒度焦炭浸入不同配比碱金属化合物（K2CO3＋Na2CO3）溶液的方法在实验室制得焦样,用热重天平对焦样进行了焦炭反应性实验及SEM扫描电镜和能谱分析。研究结果表明,不同配比碱金属K、Na复合催化剂催化效果不同,K2CO3对焦炭溶损反应的催化作用贡献较大,焦炭溶损反应主要催化作用时间为前10min,浸碱焦炭试样中K、Na含量随碱溶液中K、Na含量增加而增加。     

碱土金属Ca的添加方式对焦炭溶损反应的影响

采用前置法和后置法制备添加碱土金属Ca的焦炭.考察不同反应温度下,CO_2对焦炭溶损行为的影响,并运用比表面积测定仪、X射线衍射仪和扫描电子显微镜表征焦炭的微观结构.结果表明:添加碱土金属Ca可以提高焦炭的反应性.当温度达到1 200℃时,后置法焦炭的反应性和反应后强度均高于前置法焦炭的反应性和反应后强度.用随机孔模型模拟了焦炭溶损反应动力学过程,后置法制备的焦炭溶损反应活化能较前置法制备的焦炭溶损反应活化能低.添加碱土金属后的焦炭微晶结构有序性、微晶尺寸和反应前后的比表面积均发生变化.     

Effect of pore diffusion on reactivity of lump coke

The gasification of fine-grained and lump coke in CO₂ atmosphere was measured in a laboratory reactor. Owing to the effect of pore diffusion, the reactivity of lump coke at 1050 °C was found to be considerably lower than that of fine-grained coke at otherwise the same conditions. The diffusion effect is more significant for cokes produced by a stamping method than for cokes from top charges. To express the gasification of lump coke, a simplified mathematical model considering the effect of pore diffusion on gasification rate was adopted. Kinetic parameters were determined from experiments with fine-grained coke, while effective diffusivity was evaluated from experiments with a single coke particle. The model fits experimental data of lump coke well. The relation between reactivity and textural characteristics was also examined: the correlation between effective diffusivity and the fraction of largest pore volume was found.     

Enhanced hydrodesulphurization of cokes deposited on iron ore by air gasification

The influence on air-gasification of cokes deposited on iron ores were studied in under successive desulphurization at 750 °C under atmospheric hydrogen. Gasification promoted by steam (water: 40 μl min⁻¹) at 350 °C for 125 min gasified 21% of the coke and allowed 25% oxidative desulphurization (based on sulphur in the coke) during the gasification and enhanced the successive hydrodesulphurization level up to 63% giving a total desulphurization of 88%. This level is comparable with that achieved after grinding. Gasification at higher temperatures, which burned more coke, was less effective in enhancing hydrosedulphurization. Gasification increases the access of hydrogen molecules to sulphur atoms in the coke. Gasification, which increases the surface area of the coke and removes the sulphur preferentially, is discussed in terms of reactivity.     

Effect of coal blending ratio on CO<Subscript>2</Subscript> coke gasification

Coke gasification is largely influenced by the raw coal, catalyst, and blending ratios, pore structure, and specific surface area of the raw coal. In this study, several properties of cokes related to their reactivity were measured using coke reactivity test apparatus (CRTA), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Brunauer-Emmet-Teller (BET) surface area analysis, and energy dispersive X-ray spectroscopy (EDS) to investigate the characteristics of coke gasification. The results indicated that the reactivity of coke in the temperature range from 950 to 1,050 °C was affected by the type of coke and its specific surface area rather than the general properties of the coke, although the overall reactivities at the other temperatures were uniform. EDS analysis showed that the catalyst acted on the reactivity of cokes at low temperatures, whereas the BET analysis indicated that the reactivity at high temperature was influenced by the specific surface area.     

新型煤气化载能材料的质量研究

利用自行设计的新型煤气化炉,实现了不同碳质原料的气化实验.分析了气化对载能材料的纯度、晶体形态及产量的影响,研究了烟煤的高温孔隙结构和焦炭的高温表面碳微粉对6H-SiC多型含量的影响,指出气化对载能材料质量无影响,烟煤高温孔隙率高、断面结构复杂及烟煤焦炭的高温表面碳微粉是造成6H-SiC多型含量高的主要原因.     

Comparison of steam-gasification characteristics of coal char and petroleum coke char in drop tube furnace

The steam-gasification reaction characteristics of coal and petroleum coke (PC) were studied in the drop tube fur-nace (DTF). The effects of various factors such as types of carbonaceous material, gasification temperature (1100–1400 °C) and mass ratio of steam to char (0.4:1, 0.6:1 and 1:1 separately) on gasification gas or solid products were investigated. The results showed that for al carbonaceous materials studied, H2 content exhibited the larg-est part of gasification gaseous products and CH4 had the smal est part. For the two petroleum cokes, CO2 content was higher than CO, which was similar to Zun-yi char. When the steam/char ratio was constant, the carbon con-version of both Shen-fu and PC chars increased with increasing temperature. When the gasification temperature was constant, the carbon conversions of al char samples increased with increasing steam/char ratio. For al the steam/char ratios, compared to water gas shift reaction, char-H2O and char-CO2 reaction were further from the thermodynamic equilibrium due to a much lower char gasification rate than that of water gas shift reaction rate. Therefore, kinetic effects may play a more important role in a char gasification step than thermodynamic ef-fects when the gasification reaction of char was held in DTF. The calculating method for the equilibrium shift in this study wil be a worth reference for analysis of the gaseous components in industrial gasifier. The reactivity of residual cokes decreased and the crystal layer (L002/d002) numbers of residual cokes increased with increasing gasification temperature. Therefore, L002/d002, the carbon crystallite structure parameter, can be used to evaluate the reactivity of residual cokes.     

Enhancements in nickel-catalyzed hydrogasification of carbon by surface treatments

A pitch coke was given 4 types of pretreatment to modify the surface state; air oxidation, heatingquenching, steam treatment and hydrogen treatment. The treated cokes were impregnated with nickel and gasified in an atmospheric hydrogen flow. The catalytic reactivity of the pitch coke was enhanced by these pretreatments. Several properties of pretreated cokes were compared and it seemed that highly hydrophilic or acidic surfaces of carbon were unfavorable to metal-catalyzed hydrogasification. The reactivity enhancement was ascribed to an increase in the hydrogen adsorption capacity of nickel on the pretreated coke. The oxygen-containing surface groups are presumed to inhibit the spillover of atomic hydrogen from nickel to carbon. The effect of 1 type of pretreatment. heating-quenching, seems to relate to the expansion in pore volume.     

Study of the reaction of cokes with KOH under nitrogen

Five cokes of increasing content of anisotropic carbon were prepared. Polished surfaces of these cokes were characterized by optical microscopy in terms of components of optical texture. These surfaces were reacted with KOH at 873, 1073 and 1273 K in an inert atmosphere for 2 h and the resultant topography monitored by scanning electron microscopy (SEM). The extent of potassium take-up by coke particles was measured and the diffusion of potassium was detected by EDAX. Microstrength testing was made on the cokes before and after reaction with the alkali. Coke reactivity measurements were obtained for untreated and treated cokes. Results indicate that in an inert atmosphere the alkali reacts preferentially on the prismatic edges of anisotropic carbon and that the rates of reaction increase with increasing temperature. Potassium is able to diffuse into the interior of the more anisotropic coke particles and this casues weakening of the coke. The reactivity measurements indicate that for the more anisotropic cokes the effect of potassium as a catalyst in the solution-loss reaction is more pronounced than for the least anisotropic coke. These conclusions suggest that metallurgical coke in the blast furnace in the presence of alkali materials can lose strength by direct reaction over and above considerations of gasification processes.     

Gasification rate analysis of coal char with a pressurized drop tube furnace

Two coal chars were gasified with carbon dioxide or steam using a Pressurized Drop Tube Furnace (PDTF) at high temperature and pressurized conditions to simulate the inside of an air-blown two-stage entrained flow coal gasifier. Chars were produced by rapid pyrolysis of pulverized coals using a DTF in a nitrogen gas flow at 1400°C. Gasification temperatures were from 1100 to 1500°C and pressures were from 0.2 to 2 MPa. As a result, the surface area of the gasified char increased rapidly with the progress of gasification up to about six times the size of initial surface area and peaked at about 40% of char gasification. These changes of surface area and reaction rate could be described with a random pore model and a gasification reaction rate equation was derived. Reaction order was 0.73 for gasification of the coal char with carbon dioxide and 0.86 for that with steam. Activation energy was 163 kJ/mol for gasification with carbon dioxide and 214 kJ/mol for that with steam. At high temperature as the reaction rate with carbon dioxide is about 0.03 s⁻¹, the reaction rate of the coal char was controlled by pore diffusion, while that of another coal char was controlled by surface reaction where reaction order was 0.49 and activation energy was 261 kJ/mol.     

锯木屑在超临界水中气化制氢过程的主要影响因素

以锯木屑混合羧甲基纤维素钠（CMC）为反应原料,利用连续管流反应器,在反应器外壁面温度稳定在650 ℃条件下,对反应压力在17.5～30 MPa,反应停留时间在14.4～50 s,浓度范围为4%～9%（质量分数）的湿生物质浆液进行了超临界水气化制氢实验研究,讨论了气化过程的主要参数压力、温度、反应停留时间以及物料浓度对气化结果的影响.锯木屑在超临界水中接近完全气化,生成气体产物的主要成分是H₂、CH₄、CO、CO₂以及少量的C₂H₄和C₂H₆,气化产物中的H2含量可以超过40%.同时,实现了气化反应液体产物的循环利用.