高炉熔渣组分对煤-CO_2气化反应性的影响

利用STA409PC综合热分析仪以等温热重法对高炉熔渣组分对煤焦-CO_2气化反应性的影响进行了研究,主要考察了SiO_2、MgO、CaO及Al_2O_3对气化反应的影响。实验结果表明:CaO对高炉熔渣中煤焦的气化反应具有催化作用,但是气化反应温度达到一定值时,CaO组分含量的变化对气化反应速率的影响可以忽略不计;Al_2O_3对高炉熔渣煤焦的气化反应具有一定阻碍作用,且这种阻碍作用与气化反应温度有一定的关系;MgO对气化反应具有一定的催化作用,在本实验的研究范围内,当MgO组分含量在8%~10%变化时,煤焦的气化反应速率随MgO组分含量的增加而增加;当MgO组分含量在10%~12%变化时,煤焦的气化反应速率随MgO组分含量的增加而降低;SiO_2在气化反应过程中既没有起到催化气化的作用,也没有阻碍气化反应的进行,但这没有考虑SiO_2对熔渣流动性的影响。     

焦炭体系下二氧化碳重整甲烷制取合成气

利用连续流动固定床反应器,研究了不同煤种制得的焦炭及反应器的操作参数对CH4和CO2转化率的影响,并用比表面孔径测定仪和扫描电镜对反应前后焦炭进行表征.研究结果表明:采用的几种样品中,灰分含量最低的铜川煤焦催化活性最好;但是在不同焦炭上反应气转化行为相似,初始转化率比较高,30 min后降低至一个相对平稳的阶段;较低的反应气流速和较高的反应温度有利于反应气的转化;焦炭粒径在0.53 mm以下适合进行动力学研究;反应后焦炭比表面积有所降低,反应过程中部分焦炭发生了气化.     

生物油催化裂解的动力学分析

以CaO·MgO混合物为催化剂,采用热重分析法探讨了混合物中MgO含量对生物油催化裂解反应速度和最终残留率的影响.实验结果显示,生物油的热重变化过程可以分为室温～200℃范围内的挥发阶段和200～520℃范围内的热裂解阶段.在热裂解阶段中,反应速率常数和温度的关系可以用Ardaenius方程式表示.在MgO含量为50%的CaO·MgO混合物的催化作用下,生物油热裂解反应活化能从无催化剂时的20.9kJ/mol降低到16.5kJ/mol,最终相对残留率降低到0.75.MgO含量为38.7%的煅烧白云石是有效的生物油裂解催化剂.     

钾盐对煤焦-CO_2气化反应特性的影响

利用法国Setaram公司生产的TGA92型热重分析仪,比较钾基、钙基、铁基催化剂对煤焦-CO2气化反应的影响,发现钾基催化剂催化效果最好.在反应温度900~1050℃范围内,利用自行建造的小型固定床试验装置研究了气化温度、钾盐催化剂含量、形成焦炭的原煤煤质对煤焦与CO2的气化反应活性的影响.试验结果表明,反应温度对气化过程影响显著,提高气化温度,煤焦与CO2的气化反应速率急剧增加,转化率显著提高;不同配煤比的原煤制得的焦炭,在气化过程中表现出不同的反应特性,弱黏结性的气煤表现出良好的抗碱能力.     

添加剂对垃圾焚烧炉飞灰熔融特性的影响

将SiO2、CaO和Al2O3按不同比例与垃圾焚烧炉飞灰均匀混合,对混合后试样的熔融特性进行实验研究。结果表明:当添加剂加入量在15%左右时,试样的灼烧减量基本趋于稳定,添加量过高或过低试样灼烧减量波动均很大。适量(15%左右)的加入3种添加剂时,SiO2可使试样达到更好的熔融效果,CaO不利于试样的熔融,Al2O3可提高试样的硬度和致密性。添加剂对熔融试样的重金属分布有显著影响,添加SiO2、CaO均能促使Cr、Ni固溶在熔融体中,且SiO2含量增加有助于As的挥发;而CaO可抑制As挥发。Al2O3除对Ni固溶有正面影响外,对Cr、As、Cu的固溶有负面影响。     

典型农业生物质催化气化反应动力学特性研究

以CaO、MgO和Fe2O3为催化剂,用程序升温热重法对典型农业生物质催化气化特性及反应动力学进行了研究.利用均相反应模型和缩核反应模型对转化率与温度的关系进行了拟和计算,得到了谷壳样在4种不同二氧化碳气化条件下热解阶段及焦炭气化阶段的活化能和指数前因子.结果表明,在820～1000℃区间内,添加CaO的谷壳样表观活化能比谷壳的大;而添加MgO和Fe2O3的谷壳样表观活化能与谷壳的相比,分别下降了32.6%和17.9%以上,可以看出3种催化剂催化活性大小顺序为MgOFe2O3CaO,活化能区间范围为15.25～123.74kJ/mol.研究表明在低温区间(热解阶段),反应机理更趋向于均相反应模型,而在高温区间(气化阶段),反应机理更趋向于缩核反应模型.最后给出了谷壳在热解阶段及焦炭气化阶段的反应动力学方程.     

钾盐对煤焦-CO2气化反应特性的影响

利用法国Setaram公司生产的TGA92型热重分析仪，比较钾基、钙基、铁基催化剂对煤焦-CO2气化反应的影响，发现钾基催化剂催化效果最好．在反应温度900—1050℃范围内，利用自行建造的小型固定床试验装置研究了气化温度、钾盐催化剂含量、形成焦炭的原煤煤质对煤焦与CO2的气化反应活性的影响．试验结果表明，反应温度对气化过程影响显著，提高气化温度，煤焦与CO2的气化反应速率急剧增加，转化率显著提高；不同配煤比的原煤制得的焦炭，在气化过程中表现出不同的反应特性，弱黏结性的气煤表现出良好的抗碱能力。     

生物油热解及燃烧特性分析

对由木粉热解所得的生物油样品分别进行了氮气与氧气气氛下不同升温速率的热重分析试验.结果表明:生物油的热解分为两个阶段,第一阶段为生物油中低沸点有机物的挥发以及各组分间反应生成各类产物的过程,第二阶段为各种重组分的裂解过程;生物油的燃烧分为3个阶段,即前期的挥发与裂解和最后焦炭的燃烧过程.提高升温速率使氮气气氛中生物油样品的初始失重温度、失重峰值温度及对应的最大失重速率均有所增大,且在较高升温速率(20℃min)下,较少含炭残余物形成.随升温速率升高,生物油着火温度提高,最终失重率无变化.最后根据热重数据对热解与燃烧各段反应进行了动力学拟合.     

基于活性炭的微波辐射CO_2重整CH_4的研究

以木质活性炭为催化剂,在微波加热实验台上进行了CO2重整CH4的实验研究,考察了活性炭的升温特性,比较了CH4裂解、CH4/CO2重整和CO2气化反应中反应气转化率,分析了反应温度、CH4与CO2物质的量比值和空气流速对重整反应的影响,测试了活性炭的催化活性.结果表明,微波辐射下活性炭床层温度迅速升高;重整反应中CH4转化率高于裂解反应,而CO2转化率低于气化反应;提高反应温度、减小CH4与CO2物质的量比值和降低空气流速均利于提高CH4和CO2转化率,同时降低合成气中H2与CO物质的量比值;初始阶段活性炭表现出较好的催化活性,40 min后活性炭迅速失活.     

影响烧结过程最初液相形成的因素分析

试验考察添加SiO2、Al2O3和MgO对铁酸盐黏结相(20%CaO-80%Fe2O3)最初液相熔化行为的影响,同时考察对于最初液相形成矿石中脉石含量与CaO的关系。试验结果表明:矿石中的SiO2和Al2O3脉石成分对烧结过程中最初熔体的形成都有抑制作用,但从熔化温度区间考察,2%~6%SiO2的添加可以显著减小熔体的熔化时间,而不同含量Al2O3和MgO的添加都会增加熔体的熔化时间;同时随着矿石中脉石含量的增加,形成最低液相的CaO含量也在增加。     

Hydrogen synthesis from biomass pyrolysis with in situ carbon dioxide capture using calcium oxide

Hydrogen (H₂) and other gases (CO₂, CO, CH₄, H₂O) produced during the pyrolysis of cellulose, xylan, lignin and pine (Pinus radiata), with and without added calcium oxide (CaO), were studied using thermogravimetry-mass spectrometry (TG-MS) and thermodynamic modeling. CaO improved the H₂ yield from all feedstocks, and had the most significant effect on xylan. The weight loss of and gas evolution from the feedstocks were measured over the temperature range 150-950 °C in order to investigate the principle mechanism(s) of H₂ formation. Without added CaO, little H₂ was produced during primary pyrolysis; rather, most H₂ was generated from tar-cracking, reforming, and char-decomposition reactions at higher temperatures. When CaO was added, significant H₂ was produced during primary pyrolysis, as the water-gas shift reaction was driven toward H₂ formation. CaO also increased the formation of H₂ from reforming and char gasification reactions. Finally, CaO increased the extent of tar cracking and char decomposition, and lowered their onset temperatures. The production of H₂ from pine over the course of pyrolysis could be modeled by summing the H₂ evolutions from the separate biomass components in relevant proportions.     

CaO-Al2O3-MgO三元渣对钢液洁净度影响的研究

由于Al的烧损,炉渣中w（Al2O3）明显增加,w（CaO）明显降低,而w（MgO）降低幅度不大.通过CaO-Al2O3-MgO渣系对钢液洁净度影响的实验表明,钢液中硫含量基本呈先降低后增加的趋势,钢液中氮和氧的含量基本呈降低的趋势,与溶解速率实验的结果基本相符,炉渣成分为50％CaO-45％Al2O3-5％MgO时脱氧速率常数最大.     

Ni、Fe负载CaO催化剂作用下生物油模化物水蒸气催化重整制氢研究

采用浸渍法制备Ni/CaO、Fe/CaO、Ni-Fe/CaO催化剂,用于生物油模化物乙酸水蒸气催化重整反应.对反应前后催化剂进行BET、H2-TPR、CO2-TPD、XRD等表征.通过比较3种催化剂重整反应性能得出Ni/CaO催化剂具有最佳性能.进一步研究在Ni/CaO催化剂参与下反应温度、水碳比(S/C)、液时空速(...     

Kinetic characterizations of biomass char CO2-gasification reaction within granulated blast furnace slag

The reactions of biomass char CO₂-gasification within granulated blast furnace slag (BFS) were systematically conducted by the non-isothermal program using a thermogravimetric analyzer. At the same time during reaction proceeded, the conversion of biomass char CO₂-gasification reaction increased with the increasing heating rate. However, at the same temperature during reaction proceeded, the conversion of biomass char CO₂-gasification reaction decreased with the increasing heating rate. The granulated BFS could be used as a catalyst in the biomass char CO₂-gasification reaction and its catalytic effect became more obvious with the increasing content of BFS in the mixture. The A₄ model (nuclei production (m = 4) model) selected through the novel two-step method firstly proposed in the study was the best match with all the gasification reactions. The activation energy was from 52.75 kJ/mol to 64.42 kJ/mol and was lower with the increase of heating rate and the content of BFS in the mixture. The kinetic equations of biomass char CO₂-gasification reaction within granulated BFS were developed through the selected model and calculated kinetic parameters.     

循环流化床锅炉飞灰特性研究

CFB锅炉飞灰的化学成分以及物理特性和煤粉炉有所不同.研究讨论了CFB锅炉飞灰和煤粉炉飞灰的区别.在实验中发现CFB锅炉飞灰中SiO2、Al2O3、TFeO、CaO、MgO的含量随着粒度的变化而有规律地变化.随着粒度的减小,飞灰中SiO2的含量逐渐降低,而Al2O3、TFeO、CaO、MgO含量则逐渐升高.在实验的基础上对铁元素存在形式进行了理论上的分析,得出在CFB锅炉和煤粉炉的燃煤飞灰中,铁元素因为运行工况的不同其存在形式不同,进而呈现出颜色上的差异.CFB锅炉飞灰含碳量高,比电阻低.     

Effect of ash on dielectric properties and micro-structure of high alkali coal at different temperature pyrolysis

The effect of ash on dielectric properties and micro-structure of high alkali coal at different temperature pyrolysis was studied, so as to provide theoretical basis for coal deep processing by microwave. An acid-washed method was adopted to remove ash in Zhundong coal for preparing coal chars at 700 °C–1300 °C. X-ray diffraction analysis was used to characterize the microcrystal structure. The thermal stability was characterized by thermogravimetric analyzer, and the dielectric properties were measured by a vector network analyzer. The results showed that when the pyrolysis temperature was below 1100 °C, the presence of ash hindered the development of carbon structure in raw coal char. The main reason is that the alkali metal oxides (K₂O and Na₂O) in the ash promoted the solution loss reaction during pyrolysis. The structure of the original carbon layer was damaged, thereby the graphitization degree, thermal stability and dielectric properties of raw coal char were weaker than the ash-free coal char. When the pyrolysis temperature reached 1300 °C, the minerals were completely melted. The reaction of phase transition of SiO₂ in ash played a catalytic role on raw coal char structure, resulting in tighter arrangement of adjacent carbon layers. The raw coal char showed stronger dielectric properties and thermal stability.     

Experimental study of Ni/MgO catalyst in carbon dioxide reforming of toluene,a model compound of tar from biomass gasification

An experimental study of Ni/MgO solid solution catalyst in CO₂ reforming of toluene was conducted in this paper. Experimental parameters were reduction temperature, reaction temperature, CO₂/toluene mole ratio, and toluene feed rate.     

烟气中水分对循环流化床受热面上CaO碳酸化特性的影响

为探讨循环流化床炉内受热面上飞灰的沉积特性,在热重分析仪上对有无水分条件下CaO在受热面上的碳酸化特性进行了研究,得到CaO的碳酸化反应速率和最终转化率.结果表明:水分对CaO的碳酸化进程有很大影响;当模拟烟气中存在水分时,CaO呈现出更快的碳酸化反应速率和更高的转化率,且随着温度的降低(由700℃降低到400℃),碳酸化反应得以改善的程度更加明显;温度越低,水分在CaO碳酸化反应中所起的作用越重要.最后,对该现象的反应机理进行了讨论.     

Hydrogen production from sorption enhanced steam reforming of ethanol using bifunctional Ni and Ca-based catalysts doped with Mg and Al

This work evaluated the performance of nickel-based catalysts supported on CaO and CaO–MgO–Al₂O₃ in the sorption enhanced steam reforming of ethanol (SESRE) aiming the production of high purity H₂. The catalysts were prepared by sol-gel method and characterized by different methods: Temperature programmed reduction (TPR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) with chemical element mapping, N₂ physisorption and CO₂ capture capacity determined by thermogravimetric analysis (TGA). XRD analysis showed that the predominant phases were CaO, MgO, CaCO₃, Ca(OH)₂ and NiO in the calcined samples and Ni⁰ in the reduced and passivated samples. TPR profiles indicated that all catalysts presented a high degree of reduction (Ni/CaMgAl-68 > Ni/CaMgAl-79 > Ni/Ca), although Ni/CaMgAl-X samples presented high reduction temperatures indicating the formation of NiAl₂O₄. The addition of MgO and Al₂O₃ to CaO was very beneficial since the deactivation coefficients, calculated by the TGA data modeling, decreased by a factor of 3.8 for Ni/CaMgAl-79 and by a factor of 4.3 for Ni/CaMgAl-68 when compared to the Ni/Ca catalyst. The catalytic tests in the SESRE showed that Ni/CaMgAl-79 catalyst had the best performance since it had the longest high purity hydrogen production time. In the pre-breakthrough period, the H₂ mole fractions were close to 90% for all samples during all reaction cycles. After the reaction-regeneration cycles, the average crystallite size of CaO estimated by XRD increased around 38, 6 and 35% for Ni/Ca, Ni/CaMgAl-79 and Ni/CaMgAl-68, respectively. Thus, adding a dopant to the sorbent material proved to be an effective strategy to obtain a more stable catalyst capable to produce hydrogen of high purity.