复合流化床低阶煤热解制备兰炭的工艺条件

以不同粒径范围的新疆准东煤为原料,在耦合下部流化床和上部输送床的复合流化床中热解制备兰炭,考察了热解温度、过量氧气系数、气化温度、煤颗粒停留时间等对热解产物分布和热解半焦性质的影响. 结果表明,随过量氧气系数、气化温度和颗粒平均停留时间增加,气体产率升高,半焦和焦油产率降低;半焦的比表面积随气化温度升高而增大,而随过量氧气系数增大先增大后减小. 当煤从下部流化床进料时,在过量氧气系数0.11、流化床气化温度850℃、输送床热解温度750℃、流化床内煤颗粒停留时间90 s的操作条件下,可制备出固定碳含量超过83%(w)、挥发分含量低于9%(w)的兰炭.     

稻草及热解半焦颗粒流化特性

研究了稻草及不同温度热解半焦颗粒在内径100 mm、高1000 mm的有机玻璃流化床中的流化特性. 结果表明,稻草颗粒无法单独流化,而其热解半焦颗粒可单独流化;半焦颗粒的最小流化速度随粒径增大而增大,与床层高度无关,筛分粒径为0.45~0.9, 0.18~0.45, 0.125~0.18 mm的半焦颗粒的最小流化速度分别为0.19, 0.16, 0.14 m/s;300~550℃温度范围内稻草热解半焦颗粒的流化特性无明显区别;半焦与稻草颗粒混合流化时,稻草颗粒不大于20%(w)时床层有较好的流化质量,混合颗粒的最小流化速度都随混合颗粒中稻草含量增大而增大.     

沉降炉中生物质热解产物的脱硝特性

利用连续沉降炉模拟白酒糟循环流化床解耦燃烧再燃区的反应气氛,研究各因素对半焦、焦油和热解气脱硝效率(比脱硝效率)的影响. 结果表明,反应温度由800℃升至1050℃,热解产物比脱硝效率均增大;半焦和焦油达到最佳比脱硝效率所需的停留时间为3.4 s;随反应气中NO浓度由400′10-6(j)增加到1000′10-6(j),热解产物比脱硝效率均呈降低趋势,但NO绝对还原量却呈增加趋势;随反应气中O2浓度增加,半焦比脱硝效率增大,热解气比脱硝效率降低,焦油比脱硝效率呈先增加后减少的趋势,在O2浓度为1.6%(j)时达最大,为60.1%. 在本研究的反应条件下,焦油比脱硝效率最好,热解气次之,半焦效果较差.     

褐煤半焦热解温度对其加氢制甲烷活性的影响

利用固定床热解炉在不同热解温度(400~900℃)下制得热解半焦,采用BET和XRD分析手段对不同热解温度的褐煤半焦理化性质进行表征。在高温高压(800℃、4 MPa)条件下,利用固定床反应器对呼伦贝尔褐煤半焦试样进行直接加氢制甲烷的研究。结果表明,呼伦贝尔褐煤半焦在高温高压加氢制甲烷的最优热解温度为600℃;热解温度在600~800℃的半焦加氢反应碳转化率可达82%,产品气中CH_4的质量分数约96%;在400~800℃,半焦比表面积由8 m2/g增大到182 m~2/g,半焦加氢反应碳转化率随比表面积的增大而增加,当热解温度高于800℃,半焦中碳结构的晶面间距d002减小,堆垛高度L002明显增大,d002/L002从0.472迅速减小为0.365,石墨化程度加深,导致其加氢反应碳转化率迅速下降。     

霍州煤氧化性气氛下热解预脱硫及硫的变迁

利用流化床反应系统对霍州原煤在氧气浓度(体积分数)分别为2.5%,5.5%和8.5%O2-N2混合气,热解温度分别为400℃,500℃,600℃,700℃和800℃,热解停留时间为20min的条件下进行了热解预脱硫的研究.结果表明,在氧气浓度为5.5%,热解温度为700℃时的脱硫效果最佳,脱硫率可达70%以上.而且,与惰性气氛下热解相比,半焦产率没有明显降低.当继续加大氧气浓度或升高热解温度时,虽然脱硫率有所增加,但是半焦产率却大大降低,且半焦产率的降幅要大于脱硫率的升幅.通过热解质谱(PY-MS)实验表明,在1%O2-He气氛下,SO2和CO2在500℃以前的逸出趋势基本相同,这说明氧气在低温时对不稳定有机硫中的C-S键能够选择性断裂,此时煤中的C-C键不受影响;随后CO也开始逸出,使得它们的逸出趋势稍微发生了变化,最后这三个峰基本在同时达到了最大,这是由于随着温度的升高,C-S键被氧气选择性断裂的同时,C-C键也大量参与到了反应中来,使氧气由原来的过量变得相对不足,从而使得部分碳转化为CO.     

碳氧官能团对煤焦低温还原NO的影响

在450℃对神木煤制半焦还原NO进行研究,采用Raman、FT-IR、XPS等分析方法探究了半焦脱硝影响因素与其表面碳氧官能团的关系。结果表明：热解制焦温度、烟气中氧气浓度以及负载金属对脱硝效果的影响都与半焦表面碳氧官能团有关,降低热解温度、增大氧气浓度、负载金属均有利于增加C—O官能团。采用XPS表征对金属负载半焦表面的碳氧官能团进行分析,发现热力学相对稳定的C—O官能团含量与脱硝指标之间存在明显的线性关系(R²>0.96)。研究进一步揭示了热力学稳定的C—O官能团在半焦脱硝过程的重要地位。     

半焦制备烟气脱硫用成型活性焦的研究

以流化床反应器所制得的半焦为基质 ,高温煤焦油为黏结剂 ,制备了烟气脱硫用成型活性焦 ,考察了制备条件对活性焦性能的影响 .实验表明 :最适宜的炭化温度为 70 0℃ ,活化温度为85 0℃ ,活化 H2 O浓度为 75 % .活化温度、水蒸气浓度过低 ,活化反应速度慢 ,而活化温度、水蒸气浓度过高 ,容易造成孔的烧失 ,使得比表面积、微孔面积和微孔孔容都下降 ,相应的硫容也下降 .延长活化时间虽有扩孔和造孔的作用 ,比表面积和微孔面积都增加 ,但是硫容却没有太大的变化 .由于是以具有一定初孔半焦为基质 ,活化时间较短 ( 2 0 min～ 30 min) .制得的活性焦可以达到商业活性焦的性能指标 ,满足实际使用要求 .     

半焦催化裂解煤焦油试验研究

为了提高褐煤热解制得半焦对焦油的催化裂解效果,采用煤热解制备的半焦催化裂解煤热解过程中产生的煤焦油。采用两段式固定床反应器,在反应器上段放置煤样热解,下段放置半焦催化剂催化裂解上段产生的焦油。研究了制焦温度、半焦用量、经O_2活化后半焦对焦油催化裂解效果的影响。结果表明,增加褐煤的制焦温度,焦油产率明显下降,褐煤900℃制备的活化半焦1 g时的焦油产率仅6.3%,提高半焦制焦温度有利于焦油中的大分子芳香类物质催化裂解成少环物质和小分子气体组分;增加半焦用量对焦油脱除效果作用不明显,焦油产率缓慢减少。与未活化半焦相比,O_2活化后的半焦对焦油的脱除效果更好。半焦的比表面积及孔隙分析(BET)表明,活化后半焦的比表面积更大,且孔隙更丰富;能谱分析(EDS)发现,活化后半焦表面金属元素总量高于未活化半焦。     

热解温度和脱灰处理对褐煤半焦孔结构的影响及分形分析

采用低温氮气吸附法分析了胜利褐煤在低温(350℃~600℃)热解过程中孔结构的变化,研究了热解温度及脱灰处理对半焦的平均孔径、比表面积和孔径分布等孔结构参数的影响,并利用FHH(Frenkel-Halsey-Hill)模型,分别在相对压力为0~0.50和0.50~0.95内计算了不同的分形维数D_1和D_2,用以表征煤样的分形特征.结果表明:在热解过程中,半焦的比表面积与孔容积具有相同的变化趋势,与平均孔径呈相反的变化趋势;当热解温度高于500℃时,脱灰褐煤转化为半焦的过程中孔结构变得更为发达,比表面积和微孔孔容明显增大,孔径区间在0.45nm~1.58nm及2.65nm~10.00nm内的孔数量明显增加;FHH模型分析表明,半焦内存在两种变化趋势相反的分形维数D_1和D_2.D_1可以描述450℃之前脱灰褐煤半焦微孔表面的粗糙程度,D2可以反映出整个热解过程中脱灰褐煤的中孔孔容粗糙程度.     

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。     

Low-temperature air oxidation of caking coals. 1. Effect on subsequent reactivity of chars produced

The effect of preoxidation of two highly caking coals in the temperature range 120–250 °C on weight loss during pyrolysis in a N₂ atmosphere up to 1000 °C and reactivity of the resultant chars in 0.1 MPa air at 470 °C has been investigated. Preoxidation markedly enhances char reactivity (by a factor of up to 40); the effect on char reactivity is more pronounced for lower levels of preoxidation. For a given level of preoxidation, the oxidation temperature and the presence of water vapour in the air used during preoxidation have essentially no effect on weight loss during pyrolysis and char reactivity. An increase in particle size of the caking coals reduces the rate of preoxidation as well as subsequent char reactivity. Preoxidation of caking coals sharply increases the surface area of the chars produced. Compared to heat treatment in a N₂ atmosphere, pyrolysis in H₂ of either the as-received or preoxidized coal results in a further increase in weight loss and a decrease in subsequent char reactivity.     

低阶煤低温热解半焦在模拟高炉喷吹条件下的燃烧性能

采用自制固定床热解装置在隔绝空气的条件下制备神木长焰煤热解终温分别为400℃、450℃、500℃及550℃的热解半焦,利用管式沉降炉模拟高炉喷吹条件研究神木长焰煤低温热解半焦的燃烧性能,并考察了热解终温、半焦喷吹粒径以及燃烧反应温度对半焦燃烧性能的影响。研究表明：低温热解半焦的燃烧性能优于实验所选用无烟煤的燃烧性能,半焦的燃烧性能与其燃料比之间存在负相关关系,即燃料比越高,燃烧性能越差;降低热解终温、减小半焦喷吹粒径以及提高燃烧反应温度均能改善半焦的燃烧性能,当热解终温为400℃、喷吹粒径100～200目、燃烧反应温度为1100℃时半焦的燃尽度最佳为96%。本实验半焦制备及燃烧条件与现有低温热解和高炉喷吹工艺相符,且热解半焦各项性能均符合喷吹用煤指标。     

煤拔头中低温快速热解烟煤半焦的孔隙结构

利用喷动载流床模拟煤拔头工艺,在550, 650, 750和850℃热解温度下对大同烟煤进行热解得到拔头半焦. 采用氮吸附法对该烟煤及其半焦的孔隙结构进行了研究. 结果表明,拔头半焦的孔隙发达度都弱于原煤;由低到高4个热解温度下挥发分析出率(Y)依次为7.89%, 21.79%, 22.12%, 39.33%,中孔尺寸随Y增加而减小,微孔和大孔尺寸及总孔体积和总孔比表面积基本随Y增加而增加;550℃时挥发分的析出对孔隙结构的发展无明显有利影响. 从原煤到半焦(热解温度由低到高),样品满足BET吸附等温式的相对压力范围依次为0.101~0.351, 0.093~0.201, 0.072~0.152, 0.032~0.053, 0.058~0.108,BET比表面积与NLDFT总孔比表面积变化趋势一致.     

The effect of coal particle size on pyrolysis and steam gasification

For future power generation from coal, one preferred option in the UK is the air-blown gasification cycle (ABGC). In this system coal particles sized up to 3 mm, perhaps up to 6 mm in a commercial plant, are pyrolysed and then gasified in air/steam in a spouted bed reactor. As this range of coal particle sizes is large it is of interest to investigate the importance of particle size for those two processes. In particular the relation between the coal and the char particle size distribution was investigated to assess the error involved in assuming the coal size distribution at the on-set of gasification. Different coal size fractions underwent different changes on pyrolysis. Smaller coal particles were more likely to produce char particles larger than themselves, larger coal particles had a greater tendency to fragment. However, for the sizes investigated in this study ranging from 0.5 to 2.8 mm, the pyrolysis and gasification behaviour was found not to vary significantly with particle size. The coal size fractions showed similar char yields, irrespective of the different char size distributions resulting from pyrolysis. Testing the reactivity of the chars in air and CO₂ did not reveal significant differences between size fractions of the char, nor did partial gasification in steam in the spouted bed reactor. From the work undertaken, it can be concluded that pyrolysis and gasification within the range of particle sizes investigated are relatively insensitive to particle size.     

The devolatilisation of millimetre sized coal particles at high heating rate: the influence of pressure on the structure and reactivity of the char

Most studies on the influence of pressure on the combustion of coal particles have shown that for a constant oxygen concentration, an increase of pressure leads to a decrease of combustion rate. Among the different phenomena, which can explain this behaviour, the influence of the devolatilisation pressure on the structure and reactivity of the char formed may be important. The aim of this paper was to obtain a quantitative characterisation of the physical and chemical structure of chars formed during pyrolysis under a large range of pressure. Experiments of single coal particle pyrolysis were conducted in a laser reactor with pressure ranging from 0.014 to 2.1 MPa in a nitrogen atmosphere. As expected, an increase of pressure lead to a decrease of the volatile matter yield, which can be related to the secondary reactions of volatile matter. A characterisation of the char was performed by gas adsorption methods: nitrogen adsorption, carbon dioxide adsorption and active surface area (ASA) measurement. True and apparent densities, porosities and swelling of the particles were also investigated. Although the volatile matter yield decreases, the porosity and the swelling of the char increases with increasing pyrolysis pressure. We observed an increase in surface area and microporosity with increasing pressures up to 0.6 MPa. The ASA surface also increases in this temperature range, but the ratio of ASA to CO₂ surfaces shows that the intrinsic reactivity of the surface decreases with increasing pyrolysis pressure.     

热解温度对生物质和煤成焦特性的影响

以麦秆、橡树木屑和华亭烟煤为原料,研究热解产物的理化特性并讨论燃料种类和热解温度对其的影响.采用BET、SEM-EDS、XRD和TGA对其进行分析表征.结果表明:在600~1 000 ℃的温度范围内,煤焦的比表面积和孔隙容积随热解温度增加而增大,而木屑焦的变化不明显,麦秆焦在800 ℃时比表面积和孔隙容积最大,更高温度则发生烧结;焦样中C元素含量随热解温度升高而增加,而H元素和O元素随之降低,麦秆焦的着火特性优于木屑焦和煤焦.木屑焦和煤焦的着火特性随热解温度升高而变差,而麦秆焦在800 ℃具有最佳的着火特性.     

半焦基催化剂裂解煤热解产物提高油气品质

利用上段热解下段催化的两段固定床反应器,针对府谷煤研究了半焦和半焦负载Co催化剂对煤热解产物的催化裂解效果。结果表明,半焦和半焦负载钴对热解产物催化裂解后,热解气收率增加,焦油收率降低,但焦油中沸点低于360℃的轻质组分含量提高,轻质焦油收率基本保持不变或略有增加。与煤在600℃直接热解相比,在热解和催化温度均为600℃,采用煤样质量20%的半焦为催化剂时焦油中轻质组分质量含量提高了约25%,轻质组分收率基本不变,热解气体积收率增加了31.2%;在热解温度600℃,催化温度500℃时,采用煤样质量5%的半焦负载钴催化剂,焦油中轻质组分质量收率和含量分别提高了约8.8%和28.8%,热解气体积收率增加了21.5%。煤热解产物的二次催化裂解的总体效果是将焦油中重质组分转化为轻质焦油和热解气。     

热解条件对煤焦气化活性影响的研究进展

简述了原煤性质与温度、压力和热解气氛等热解条件对煤焦结构和气化反应活性的影响;参考该领域的国内外研究成果,分析了热解条件影响煤焦气化反应活性的机理.由于实验设备和研究方法的差异,对温度和压力等热解条件对煤焦气化反应活性影响的评价不尽相同,但总体来讲,热解终温越高、停留时间越长、升温速率越快、热解压力越大,煤焦的气化反应活性越低;热解过程中,原煤性质的差异也会影响煤焦的结构和气化反应活性.煤焦的石墨化应该是导致煤焦气化反应活性下降的主要原因,因此,热解条件的改变,特别是温度和压力的改变对煤焦石墨化进程的影响值得进一步研究.     

Rapid pyrolysis of Canadian coals in a miniature spouted bed reactor

A 25 mm diameter bench scale pyrolyser unit was constructed to study atmospheric pressure rapid pyrolysis of coal. Coals with particle size below 250 microns were injected continuously into a bed of sand spouted with nitrogen. Gas, liquid and char yields were determined as functions of temperature, coal feed rate and particle size. Gas compositions, tar yield and solvent fractionation results, and char proximate analyses are presented for six coals as functions of the pyrolysis temperature. Pyrolysis liquids from low rank coals contained significant amounts of water and were high in hexane solubles. Hexane and benzene soluble fractions are dependent on coal type and pyrolysis conditions.