褐煤低温热解特性研究

在固定床反应器中,采用GC、GC/MS、FTIR、SEM和TG等手段考察了褐煤低温热解产物的生成特性及其反应机理。结果表明:低温热解气在600℃时生成速率最大,达100 mL/min,主要为CO、CO_2、H_2、CH_4、C_2H_4和C_2H_6等气体。焦油在600℃时产率最大,主要由烷烃、芳烃、酚类及少量烯烃、环烷烃、含氧和含氮化合物组成。热解后褐煤H/C和O/C减小,表面结构从致密变成疏松的泡沫状。     

典型炼焦高硫煤热解过程中硫迁移规律研究

选择一种山西肥煤(YX)、新西兰1/3焦煤(NXL)和一种山西焦煤(JX)为研究对象,模拟工业炼焦条件,在水平管式炉中制备了300℃~1 000℃的半焦,用化学分析法分析了原煤及不同温度下半焦中的形态硫含量的变化,并用XRD考察了热解过程中煤中硫铁矿晶型的转变.结果表明,三种煤中的全硫都随热解温度的升高而降低,随着变质程度的升高,全硫降低最大的温度区间向高温偏移.除YX外,其他两种煤中的硫酸盐硫随温度的变化不明显;三种煤中的硫铁矿先分解成FeS1-x,当温度超过600℃,FeS1-x进一步分解为FeS;三种煤中的有机硫变化无明显的规律.     

褐煤与稻壳共热解过程中氢的迁移及分布特征研究

为考察外加富氢物质对低阶煤热解焦油产率及质量的影响规律,阐明低阶煤与外加富氢物质共热解作用机理,以锡林浩特褐煤(XL)和稻壳(DK)为原料,在铝甑干馏炉中进行低温共热解,通过比较单独热解与共热解产物产率及氢分布的实际值与理论值,研究锡林浩特煤与稻壳共热解过程中氢的迁移及分布特征。结果表明:锡林浩特煤与稻壳共热解过程中发生了协同作用,稻壳木质素中的甲氧基与锡林浩特煤热解产生的自由基结合,使焦油中含甲氧基的酚类物质增多。锡林浩特煤与稻壳共热解对水和气体产物的形成存在正协同作用,与理论值相比,转移到水和气体产物中的氢分别增加了1.22%~3.33%和1.16%~2.39%;而转移到焦油中的氢降低了1.00%~3.53%。稻壳中碱金属及碱土金属元素(AAEMs)不仅加剧稻壳中焦油的二次裂解,也促进锡林浩特煤中焦油的二次裂解,导致气体中C_2~C_4烃产率增加,使氢从焦油中转移到气体产物中。     

粗煤气环境下褐煤热解过程中CH_4逸出规律研究

现对鄂尔多斯褐煤在粗煤气环境下快速热解气化过程中CH_4生成逸出规律进行研究。研究了温度、压力、气氛对CH_4生成特性的影响。在H_2/CO/N_2气氛下,CO歧化反应较CO甲烷化反应易进行;煤加压热解过程中CH_4总产量随温度升高而增大,700 ℃时达到最大,该变化规律主要受H_2/CO/N_2气氛中CO甲烷化反应控制。在H_2/CO_2/N_2混合气氛中,水煤气变换逆反应远比CO_2甲烷化反应容易进行,特别是在温度升至700 ℃后,前者反应CO_2转化率远远超过后者,煤热解CH_4总产量随着温度升高而增大,在800 ℃时达到最大,之后略有减少,该变化规律主要受水煤气变换的逆反应控制。实验表明,在粗煤气环境中,700 ℃是煤热解最佳反应温度。     

褐煤热解特性及热解动力学研究

采用非等温热重法对白音华褐煤热解特性进行了实验研究,考察了升温速率和粒度对白音华褐煤热解特性的影响,同时对其热解动力学进行了分析。结果表明：升温速率是影响褐煤热解的主要因素,粒度对褐煤的热解也有一定的影响。利用Coats-Redferm积分法确定了褐煤热解低温段的动力学参数。     

褐煤低温热解特性研究

研究了褐煤进行低温热解时,热解温度对热解气相产物的影响,分析了褐煤低温热解产生的低温煤焦油的基本组成。结果表明,热解温度对煤气的组成产生一定的影响。热解气中可燃组分H2、CH4和CO最大含量可达27．92％、31．14％和17．21％;低温煤焦油烷烃含量可达33．84％,芳烃含量达16．73％,酚类含量为11．89％。     

褐煤低温热解特性研究

研究了褐煤进行低温热解时,热解温度对热解气相产物的影响,分析了褐煤低温热解产生的低温煤焦油的基本组成.结果表明,热解温度对煤气的组成产生一定的影响.热解气中可燃组分H2、CH4和CO最大含量可达27.92％、31.14％和17.21％;低温煤焦油烷烃含量可达33.84％,芳烃含量达16.73％,酚类含量为11.89％.     

传热特性对褐煤热解过程的影响研究

利用氮气作为对流气体,在温度为450℃、气体流量为0~10 L/min的条件下,对褐煤的热解过程进行了实验研究;在一维拟均相模型上,利用热解数据对煤的导热系数进行了计算;结果表明,5~10 L/min的气体流量可在一定程度上促进热解炉内的传热,增加煤的导热系数;气体温度一定,且小于热解终温时,增大气体流量450~500℃时的热解时间会增加。     

小麦秸秆热解过程中硫的迁移规律研究

利用X射线光电子能谱(XPS)、热解-气质联用(Py-GC/MS)和热重-红外联用(TG-FTIR)系统研究了小麦秸秆中的硫元素进入热解炭、油、气三相产物的迁移转化行为。结果表明,小麦秸秆中的硫主要为有机硫(28.33%)和无机硫酸盐(71.67%);有机硫在低于450℃就已经完全释放;41.46%～48.13%的硫保留在热解炭中,主要包括硫酸盐(55.27%～75.52%)、噻吩硫(21.78%～34.13%)和金属硫化物(2.70%～11.22%);7.16%～11.24%的硫进入热解油中,主要是2-甲硫基苯并噻唑;600℃还发现了噻吩硫的生成。热解气中含硫化合物的主要成分为H₂S、SO₂和COS,主要的释放温度区间为200～400℃。     

印尼褐煤快速热解试验研究

为考察神雾快速热解炉的产品产率及产品性质,将神雾蓄热式快速热解工业炉型按一定比例缩小,在实验室自建的快速热解小试试验装置上,考察了热解温度对热解产物产率的影响,并对产物性质进行分析。结果表明,印尼褐煤快速热解最佳反应温度为590℃,印尼褐煤油收率为9.91%,高达格金含油率的95%,快速热解装置油收率较高。与固定床热解煤焦油相比,快速热解煤焦油的密度、黏度、凝点和残炭含量均较低。模拟蒸馏结果表明,快速热解煤焦油中汽油馏分为2%,柴油馏分为44%,重油馏分为54%。印尼褐煤快速热解气中的主要组分是CH4和H2,热值较高。     

喷动载流床中温度对霍林河褐煤快速热解产物的影响

在喷动载流床反应器内对霍林河褐煤的快速热解进行了研究,并对该煤的热解机理进行了初步分析。考察了在500～850℃范围内温度对热解产品产率分布及气体和液体产品具体组成的影响。分别利用气相色谱和色质联用仪来分析气体和液体产物的组成。实验结果表明,气体总产率及CO、H2和C1～5烃类的产率随热解温度的提高而增大;在热解温度为650℃时,液体产率最高,在煤粉粒径为0.125～0.18mm,液体产品的总产率可达23%,其中正己烷可溶物的产率可达30%以上,沸点340℃前馏分也达30%以上。液体产品中酚类产品较多;温度对液体产品的组成有极大的影响。     

Gas evolution during rapid,low-temperature pyrolysis of a North Dakota lignite

Low-temperature pyrolysis of low-rank coals is proposed as a possible technique for producing high-heating value solids. Results are presented showing gas yields and char compositions from low-temperature pyrolysis of a lignite at very short residence times. Tar evolution is observed even at temperatures less than 570K coinciding with the first release of CO₂, presumably from carboxyl groups.     

Effect of lignite addition and steam on the pyrolysis of Turkish oil shales

Steam was found to be a more effective sweep gas than nitrogen at low velocities in fixed-bed pyrolysis of Goynuk oil shale but, at higher velocities and in fluidized-bed pyrolysis, the differences were considerably less marked. Relatively small but significant synergistic effects were observed between lignites and the two oil shales investigated — Goynuk and Seyitomer — under static retorting conditions. These effects were more pronounced with large concentrations of oil shales but disappeared in fluidized-bed pyrolysis, where conversions are considerably higher because mass transfer limitations largely disappear.     

褐煤及其热解产品利用现状

为了提高褐煤利用率,介绍了国内褐煤资源的储量形态、分布。分析了目前褐煤的利用途径,包括共伴生资源的利用、直接燃烧、干燥脱水与成型、气化、液化、制水煤浆与热解。并进一步分析了褐煤热解气、液、固产品的利用方向。提出了褐煤半焦利用的新方法,即利用半焦干法气化,或将半焦和热解废水等制成水煤浆,通过湿法气化制得合成气,再通过甲烷化催化剂将合成气制成甲烷,或将合成气通过费托合成制成汽油柴油。     

乌拉盖褐煤热解特性及反应动力学参数研究

为获得较好的褐煤半焦制备工艺参数,研究了不同制备条件(热解终温、升温速率、原煤粒径、热解气氛)下制得的乌拉盖褐煤半焦的燃烧性能和燃烧动力学参数。结果表明,热解终温对半焦品质的影响最大,热解升温速率、原煤粒径和热解气氛对半焦燃烧特性的影响不显著。热解终温由350℃升至600℃时,反应指数RI由235℃升至292℃,半焦着火性能变差;燃尽指数Cb由4.68升至6.15,半焦燃尽性能变差;爆炸指数Kd由2.54降至0.46,半焦爆炸倾向性变低;反应活化能由44.4 k J/mol升至63.4 k J/mol,半焦燃烧动力学特性变差。热解终温为520℃时制得的半焦反应指数、燃尽指数、爆炸指数和反应活化能分别为265℃,5.34、0.80和53.2 k J/mol,属于易着火、易燃尽、中等爆炸燃料,燃烧特性良好。     

Effect of lignite pyrolysis conditions on calcium oxide dispersion and subsequent char reactivity

A demineralized North Dakota lignite was loaded with 2.9 wt% Ca by ion exchange. Chars were prepared by pyrolysis in N₂ at 1275 K and residence times between 0.3 s and 1 h. Major differences were observed in their subsequent reactivities in 0.1 MPa air. X-ray diffraction analysis was carried out to obtain information on the state and dispersion of the Ca species on the various chars. The results clearly indicate that CaO is the predominant species responsible for catalysis of lignite char gasification. It is concluded that pyrolysis residence time also has a profound effect on CaO dispersion. Thus, a correlation was established between a fundamental physical property (catalyst dispersion) and the observed gasification behaviour of lignite chars prepared under different pyrolysis conditions.     

Pyrolysis and hydropyrolysis of Louisiana lignite

Pyrolysis and hydropyrolysis kinetics of five samples of Louisiana lignite have been studied in an atmospheric pressure TG system as a function of heating rate and atmosphere. Final pyrolysis temperature was always 800 °C. The total volatile yield (dry basis) was 33.5–43.8wt%. For all lignites the volatile yield in hydrogen was greater than that obtained in nitrogen at similar conditions. However, variation in heating rate produced an opposite result in the two atmospheres with volatile yield increasing with heating rate in nitrogen but decreasing in hydrogen. Results have been analysed using the distributed activation energy pyrolysis model and parameters compared to similar studies using North Dakota and Montana lignites.     

褐煤经四氢化萘处理后的结构及热解-气化特性分析

在小型反应釜上采用非极性有机溶剂四氢化萘(tetrahydronaphthalene, THN)对内蒙古锡林郭勒褐煤进行脱水,获取了不同温度下的脱水试样,运用傅里叶红外光谱(Fourier transform infrared spectroscopy,FT-IR)分析技术对比研究了在不同脱水温度下煤样中有机官能团的变化,通过FT-IR谱图的分峰拟合计算,对脱水煤样的化学结构变化特征进行半定量分析,并结合热重(thermal gravity analysis/differential thermal gravity,TG/DTG)和实验室固定床反应器(fixed bed reactor)考察了不同脱水温度下煤样的热解气化特性和热解气相产物分布规律,并对脱水煤样在最大失重速率区间的动力学参数进行了计算。试验结果显示:四氢化萘溶剂对褐煤的脱水提质是有效的,150~200℃时C O开始分解,而此时芳香环上的C C仍然相对稳定。随着脱水温度的升高,芳香类氢含量先减小后增大,脂肪类氢含量先增大后减小,芳香度和芳香碳在脱水温度范围内逐渐增大。煤样的脱水温度升高,热解气相产物H₂、CH₄、CO累积产率增大,CO₂累积产率减小;脱水煤样热解活化能随着脱水温度的升高而升高,进而导致脱水温度较高煤样热解失重率降低。     

A model of devolatilization behavior in lignite pyrolysis with solid heat carriers

To elucidate the influence of the process conditions on pyrolytic products, the interactions between transport phenomena and pyrolysis kinetics are quantitatively analyzed at the level of a single coal particle. A comprehensive mathematical model is formulated to predict intraparticle multiphysics and devolatilization behaviors; the model contains two correlative one-dimensional unsteady heat conservation equations and ternary mass conservation equations in conjunction with the simplified dusty-gas model. Moreover, a multistep kinetic model of coal devolatilization is adopted to predict the generating rates of the lumped pyrolytic products. Validation of the model against experimental and literature data showed that can predict the transient temperature profiles of a coal particle and the yields of volatiles. Finally, the effects of the main process conditions on the intra- and extra-temperature history of lignite during pyrolysis with solid heat carriers are analyzed. The interactions between physical transport and the pyrolysis reaction are also examined.