Influence of heating rate on reactivity and surface chemistry of chars derived from pyrolysis of two Chinese low rank coals

A series of char samples were derived from pyrolysis of two typical low-rank coals in China （Shengli lig- nite and Shenmu bituminous coal） at low, medium and fast heating rates, respectively, to the same pyrol- ysis temperature 750℃. Then these chars were characterized by means of thermogravimetric analysis and Fourier transform infrared spectrometer with the aim to investigate the influence of heating rate in pyrolysis process on gasification reactivity and surface chemistry of them. Besides, a homogeneous model was used to quantitatively analyze the activation energy of gasification reaction. The results reveal that Shengli lignite and its derived chars behave higher gasification reactivity and have less content of oxygen functional groups than Shenmu coal and chars. Meanwhile, chars derived from Shengli lignite at 50℃/min and Shenmu coal at 200℃/min have the greatest gasification reactivity, respectively. The oxygen functional groups in Shengli lignite are easily thermo-decomposed, and they are less affected by the heating rate, while that in Shenmu coal have a significant change with the variation of heating rate. In addition, there is no good correlation between the change of oxygen functional groups and that of the gasification reactivity of the derived chars from pyrolysis at different heating rates.

Mechanism of oxidation of low rank coal by nitric acid

The pretreatment of low rank coal with nitric acid oxidation can promote its bio-liquefaction. However, the detailed mechanism of which remains an unresolved problem. In the present work, the characteristics of Fushun coal before and after oxidation by nitric acid were investigated combined with elemental composition, pore volume and pore size, Zeta potential, FT-IR, and 13C solid NMR spectrum analysis. The results show that the inorganic substance inlaid in coal are dissolved by ni- tric acid, which results in the decrease of coal ash content and increase of pore volume and pore size. Furthermore, there exist obvious chemical reactions between nitric acid and the functional groups of coal including aromatic ring carboxylation, side chain alkyl of aromatic ring oxidation and aromatic ring nitration. Among these reactions, some led to the increase in content of carboxyl, aliphatic carbon connected with O and humic acid carbon, while others caused the reduction of aromaticity, methyl carbon, substituted aryl carbon and side chain.

Resistivity response to the porosity and permeability of low rank coal

Laojunmiao coal samples from the eastern Junggar basin were studied to understand the relationship between coal resistivity and the physical parameters of coal reservoirs under high temperatures and pressures.Specifically,we analysed the relationship of coal resistivity to porosity and permeability via heating and pressurization experiments.The results indicated that coal resistivity decreases exponentially with increasing pressure.Increasing the temperature decreases the resistivity.The sensitivity of coal resistivity to the confining pressure is worse when the temperature is higher.The resistivity of dry coal samples was linearly related to φ~m.Increasing the temperature decreased the cementation exponent(m).Increasing the confining pressure exponentially decreases the porosity.Decreasing the pressure increases the resistivity and porosity for a constant temperature.Increasing the temperature yields a quadratic relationship between the resistivity and permeability for a constant confining pressure.Based on the Archie formula,we obtained the coupling relationship between coal resistivity and permeability for Laojunmiao coal samples at different temperatures and confining pressures.

Carbon monoxide adsorptive capability of low rank coal's maceral

The centrifugal separation with gravity experiment was made for getting every pure macerals like inertinite and vitrinite,and the isothermal adsorption tests of pure mac- eral are carried out at 30,40,50,55,60,65℃,respectively,after analyzing the proximate element and maceral of coal samples,which was aimed to study the CO adsorptive capa- bility of every maceral of low rank coal at difference temperature and pressure.The results show that the adsorption isotherm of CO can be described by Langmuir equation because it belongs to the Type I adsorption isotherm at low temperature(T≤50℃),and the tem- perature effect on coal adsorption is greater than of pressure in lower temperature and pressure area;what's more,the relationship is linear between the coal adsorption quantity of CO and the pressure at high temperature(T>50℃),it can be described by Henry equation(Q=KP),which increases with pressure.Both temperature and pressure has great influence on CO adsorptive capability of low rank coals,especially the temperature's effect is so very complex that the mechanism need to study further.At the same time,the volatile matter,inertinite,oxygen-function groups and negative functional groups are high popu- larly in low rank coal samples,especially,the content of hydroxide(-OH) has great influ- ence on CO adsorption in that the inertinite has stronger effect than vitrinite on adsorptive capability of low rank coal samples,the result is same to the research on CH4 adsorption.

Investigation of Low Rank Coal Gasification in a Two-Stage Downdraft Entrained-Flow Gasifier

Low-rank coal contains more inherent moisture, high alkali metals (Na, K, Ca), high oxygen content, and low sulfur than high-rank coal. Low-rank coal gasification usually has lower efficiency than high-rank coal, since more energy has been used to drive out the moisture and volatile matters and vaporize them. Nevertheless, Low-rank coal comprises about half of both the current utilization and the reserves in the United States and is the largest energy resource in the United States, so it is worthwhile and important to investigate the low-rank coal gasification process. In this study, the two-stage fuel feeding scheme is investigated in a downdraft, entrained-flow, and refractory-lined reactor. Both a high-rank coal (Illinois No.6 bituminous) and a low-rank coal (South Hallsville Texas Lignite) are used for comparison under the following operating conditions: 1) low-rank coal vs. high-rank coal, 2) one-stage injection vs. two-stage injection, 3) low-rank coal with pre-drying vs. without pre-drying, and 4) dry coal feeding without steam injection vs. with steam injection at the second stage. The results show that 1) With predrying to 12% moisture, syngas produced from lignite has 538 K lower exit temperature and 18% greater Higher Heating Value (HHV) than syngas produced from Illinois #6. 2) The two-stage fuel feeding scheme results in a lower wall temperature (around 100 K) in the lower half of the gasifier than the single-stage injection scheme. 3) Without pre-drying, the high inherent moisture content in the lignite causes the syngas HHV to decrease by 27% and the mole fractions of both H2 and CO to decrease by 33%, while the water vapor content increases by 121% (by volume). The low-rank coal, without pre-drying, will take longer to finish the demoisturization and devolatilization processes, resulting in delayed combustion and gasification processes.

Pore Characteristics of Vitrain and Durain in Low Rank Coal Area

The low rank coalbed methane (CBM) has great potential for exploration and development in China, but its exploitation level is low at present stage. The pores are the storage space of CBM, so recognizing its structural characteristics has very important practical significance for the development of CBM. The samples of No. 4 and upper No. 4 coalbed in Dafosi were selected to carry out the analysis of mercury injection test, nitrogen adsorption test and scanning electron microscopy to study the different lithotypes of the pore structure, pore throat distribution and fracture character of low rank coal reservoir. The results showed that micropore of low rank coal in Dafosi relatively developed and the pore volume of vitrain was equivalent to durain. The pore throat of durain was larger than vitrain, the connectivity was better and the fissures were more developed. The percolation capacity and reservoir performance of upper No. 4 coal was better than No. 4 coal. Generally, the potential of exploration and development of upper No. 4 coal in the study area was better than that of No. 4, and the developed area of durain was more beneficial for the development of CBM.

Swelling Measurements of a Low Rank Coal in Supercritical CO₂

Coal swelling in the presence of water as well as CO2 is a well-known phenomenon, and these may affect the permeability of coal. Quantifying swelling effects is becoming an important issue to verify the suitability of particular coal seams for CO2-enhanced coal bed methane recovery projects. In this report, coal swelling experiments using a visualization method in the CO2 supercritical conditions were conducted on crushed coal samples. The measurement apparatus was designed specifically for the present swelling experiment using a visualization method. Crushed coal samples were used instead of block coal samples to shorten equilibrium time and to solve the problem of limited availability of core coal samples. Dry and wet coal samples were used in the experiments because there is relatively limited information about how the swelling of coal by CO2 is affected by water saturation. Moreover, some coal seams are saturated with water in initial reservoir conditions. The maximum volumetric swelling was around 3% at 10 MPa for dry samples and almost half that at the same pressure for wet samples. The wet samples showed lower volumetric swelling than dry ones because the wet coal samples were already swollen by water. Experimental results obtained for swelling were comparable with other reports. Our visualization method using crushed samples has advantages in terms of sample preparation and experimental execution compared with the other methods used to measure coal swelling using block samples.

Investigation of drying characteristics of low rank coal of bubbling fluidization through experiment using lab scale

Lignite is a low rank coal which is evenly distributed throughout the world and accounts for 45% of the total coal reserves. As it has a higher moisture content, its moisture content must be reduced in order to utilize it in power plant. In the present work, experiments on lignite has been done using a lab scale fluidized-bed reactor. Drying lignite through fluidized-bed reactor has a higher drying rate because there is good contact between particles and gas in the fluidized-bed reactor. Fluidized-bed drying can use air of 1.5 times of the minimum fluidizing velocity performance at bubbling fluidized-bed. Experiments have been performed on coal particle sizes of 0.3-1 mm, 1-1.18 mm and 1.18-2.8 mm, with operating temperatures being 100℃, 125℃ and 150℃, respectively. It is found that fluidization has a higher drying rate due to the heat transfer rate through air velocity. Hence, moisture content in lignite can be dried to a desired value with a time interval of 10 rain. The experiment through fluidized-bed reactor is expected to be useful for saving money and time.

The mechanism and products for co-thermal extraction of biomass and low-rank coal with NMP

The high-value utilization of low-rank coal would allow for expanding energy sources,improving energy efficiencies,and alleviating environmental issues.In order to use low-rank coal effectively,the hypercoals(HPCs)were co-extracted from two types of low-rank coal and biomass via N-methyl-2-purrolidinone(NMP)under mild conditions.The structures of the HPCs and residues were characterized by proximate and ultimate analysis,Raman spectra,and Fourier transform infrared(FT-IR)spectra.The carbon structure changes within the raw coals and HPCs were discussed.The individual thermal dissolution of Xibu(XB)coal,Guandi(GD)coal,and the biomass demonstrated that the biomass provided the lowest thermal dissolution yield Y1 and the highest thermal soluble yield Y2 at 280℃,and the ash content of three HPCs decreased as the extraction temperature rose.Co-thermal extractions in NMP at various coal/biomass mass ratios were performed,demonstrating a positive synergic effect for Y2 in the whole coal/biomass mass ratios.The maximum value of Y2 was 52.25wt% for XB coal obtained with a XB coal/biomass of 50wt% biomass.The maximum value of Y2 was 50.77wt% for GD coal obtained with a GD coal/biomass of 1:4.The difference for the optimal coal/biomass mass ratios between XB and GD coals could be attributed to the different co-extraction mechanisms for this two type coals.

Co-pyrolysis characteristics and interaction route between low-rank coals and Shenhua coal direct liquefaction residue

To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer and a fixed-bed reactor. GC–MS, FTIR, and XRD were used to explore the reaction mechanisms of the various co-pyrolysis processes. Based on the TGA results, it was confirmed that the tetrahydrofuran insoluble fraction of DLR helped to catalyze the conversion reaction of lignite. Also, the addition of DLR improved the yield of tar in the fixed-bed, with altering the composition of the tar. Moreover, a kinetic analysis during the co-pyrolysis was conducted using a distributed activation energy model. The co-pyrolysis reactions showed an approximate double-Gaussian distribution.

催化剂对煤热解焦油品质的调控及其表面积炭行为的分析

以催化剂为核心和焦油提质为目的的低阶煤热解技术是保障国家能源安全和实现“双碳”目标的煤炭清洁高效转化技术。鉴于煤焦油品质调控和催化剂表面积炭行为的复杂性,阐述了金属、金属氧化物、天然矿物质、分子筛和炭基催化剂对煤和热解挥发物的催化作用及其对热解产物分布和组成的影响,并对比分析了各类催化剂的优缺点。探讨不同催化剂物理化学性质的区别及其与催化性能之间的关系,结合煤及热解挥发物中C—C、C—H、C=C、—OH、C=O、C—O和—COOH等化学键的断键行为,揭示了不同催化剂的作用机制。在此基础上,针对催化过程中存在的焦油产率低及提质效果差的问题,提出了利用金属尤其是过渡金属改性催化剂活化热解体系中的内部小分子氢供体和外部固体/气体氢供体对重质组分裂解碎片原位供氢的方法,实现焦油产率的提高及焦油品质的改善。同时,针对催化剂易积炭失活问题,分析了积炭的物理化学性质和组成以及积炭形成的原因。从催化剂设计及热解反应体系出发,分析了多种有效抑制积炭的途径,如多级孔与金属活性位点的组合效应、双金属改性调控Brønsted和Lewis酸性位点的比例、酸碱双功能催化剂的开发以及引入H_(2)O、CH_(4)、C_(2)H_(6)和CH_(3)OH等富氢小分子调控挥发物组成等,以期为低阶煤催化热解技术的发展提供理论基础。

矿物分选中低阶多孔煤的药剂吸附及表征实验设计

该实验以低阶多孔煤为实验材料,首先采用工业和元素分析、扫描电镜和孔隙测试等方法分析煤样基础性质,然后使用复配药剂W-1对其进行吸附改性,再通过红外光谱、X-射线光电子能谱和接触角对改性机理进行表征,并借助等离子体发射光谱测试方法计算药剂在煤样表面的吸附量。实验结果表明,实验煤样表面极性基团丰富、孔隙结构发达、亲水性强、不易分选;药剂吸附改性后的煤样疏水性得到大幅优化。该实验设计遵循逐步深化原则,帮助学生强化思维训练,提升基础理论知识掌握和实践操作能力。

多段移动床干馏炉集气结构的优化研究

为考察移动床干馏炉内部集气结构对串气率的影响,以陕北低阶碎煤为试验对象,搭建移动床冷态试验装置,在不同进气流量下测定各层气量的流量分配比例,研究在不同位置增设集气结构对气体分布的影响。结果表明:气体经布气伞进入移动床后,有10%的气量无法通过集气主伞流出,而从卸料口泄漏导致串气。在布气伞下部0.6 m和1.2 m处、集气主伞上部0.6 m处分别增设一层集气伞,均可以降低串气比例。同时在上部与中部或中部与下部增加两层集气伞时,可以使串气率降低为0。当中部集气伞与主伞内的压差由0 Pa增加至80 Pa时,串气率由2.80%升高至5.22%,设计炉内结构时应考虑降低沿程阻力损失或者加设集气通道。

烟气干法熄焦在低阶煤热解工艺中的应用研究

以烟气为干法熄焦介质,可以回收半焦热量用于原煤的干燥,从而提高热解系统热效率。通过中试考察了烟气流量、停留时间对半焦温度的影响,分析了热解工业装置冷却段运行数据。结果表明,采用烟气干法熄焦,半焦显热回收率达到93.8%,影响冷却效果的主要因素是烟气流量,其次是半焦入口温度。

基于热重-质谱分析的榆木/低阶煤共热解特性研究

为了研究烘焙对共热解行为的影响,以榆木(E)、250℃烘焙后榆木(E_(T250))和低阶煤(L)为原料,利用热重-质谱联用分析仪(TG-MS)进行榆木/低阶煤不同质量比例下(1∶1、1∶3、3∶1)的共热解实验。TG分析结果表明,相比E和E_(T250),L热解需要更高的温度和更长的时间;但当将生物质与低阶煤共热解后,共热解所需的温度和时间都随着生物质质量比的增加而减小;在共热解过程中,E与L的失重特性曲线相互影响,而E_(T250)在热解过程中与L的失重特性基本一致,说明经250℃烘焙后榆木与低阶煤的品质相似。

高、低阶煤孔隙结构差异性及其对甲烷吸附特性的影响研究

采集沁水盆地高阶煤、二连盆地低阶煤,采用氮气、二氧化碳吸附法对煤基质纳米级吸附孔隙进行测试,分析高低阶煤的储气特征,从而确定影响高、低阶煤煤层气开发的关键因素。研究结果发现,高、低阶煤的比表面积相似,高阶煤的比表面积均值为215.33 m~2/g,可吸附甲烷49.53 cm~3/g;低阶煤的比表面积均值为212.17 m~2/g,可吸附甲烷48.96 cm~3/g。高、低阶煤储气主要为吸附气,占总储气量的99%以上,高阶煤储气主要是微孔吸附气,占总储气量的99.71%;低阶煤不同孔隙均有贡献,微孔最多,占比47.33%,其次是中孔,占比32.644%,大孔最少,占比19.69%。地层水侵入对低阶煤储气量影响大于高阶煤,平衡水条件下,高阶煤可储气量43.46 cm~3/g,低阶煤可储气量33.89 cm~3/g;受微孔特性影响,高阶煤储层储气量较高,但易储难逸,因此煤层气开采的关键问题是疏导微孔吸附气;受中、大孔及亲水性强影响,低阶煤储气量较低,且易储易散,勘察储气聚集区是低阶煤煤层气开发的首要工作。

油酸和Span80协同煤油对低阶煤的浮选强化及分子模拟计算

低阶煤表面含有较多含氧基团,可浮性差,采用传统煤油捕收剂不仅药剂消耗大,而且分选效果差。复配捕收剂可以选择性地作用于矿物表面,从而提升浮选效果。以内蒙古色连二矿选煤厂低阶煤为研究对象,考察了传统捕收剂煤油的作用效果,并在此基础上引入含氧有机药剂油酸和Span80与其复配,考察复配药剂对低阶煤浮选的强化作用,并对其作用机理进行分析。结果表明:煤油-油酸和煤油-Span80复配药剂对实验煤样浮选均有促进作用。捕收剂用量为4000 g/t,起泡剂用量为800 g/t时,煤油-Span80复配药剂对应的精煤产率为83.17%,精煤灰分为11.78%,尾煤灰分为69.15%,可燃体回收率达到93.48%,浮选完善指标为42.18%。与煤油和煤油-油酸复配药剂相比,煤油-Span80复配药剂可显著提升尾煤灰分和可燃体回收率,达到了较为理想的分选效果。机理研究结果显示,油酸和Span80与煤油复配,可显著降低药剂在矿浆中的分散粒径,提高其与颗粒的接触概率;同时,油酸和Span80与煤作用,掩蔽了煤样表面的亲水基团,改善了煤样疏水性,使其更易在煤粒表面铺展。模拟计算发现油酸和Span80药剂的前线轨道能隙小于正十二烷(煤油)的前线轨道能隙,煤油-油酸和煤油-Span80复配药剂与煤表面的相互作用能大于正十二烷(煤油)与煤表面的相互作用能,表明复配药剂更具活性,更容易与煤表面发生吸附。

低阶煤不同宏观煤岩组分孔隙发育特征及甲烷吸附/解吸性能差异

目的针对煤储层非均质性较强,不同宏观煤岩组分由于物质成分和孔隙结构差异导致煤层气吸附解吸性能和气水运移特征迥异的问题,方法以黄陇煤田彬长矿区延安组低阶煤为研究对象,采集并分离镜煤和暗煤组分,综合运用显微组分测定、元素分析、压汞、低温液氮吸附、吸附解吸试验等测试方法,研究低阶镜煤和暗煤的孔隙发育特征差异和对甲烷吸附/解吸性能的影响。结果结果表明:(1)镜煤的镜质组质量分数、挥发分及H,O,N,S元素质量分数高于暗煤的,而惰质组、壳质组、矿物、灰分、固定碳和C元素质量分数低于暗煤的。(2)煤样孔隙度为2.92%~10.29%,总体孔隙较发育,暗煤孔隙度略高于镜煤的,孔喉更粗,大孔更发育,连通性更好。镜煤BET比表面积和BJH总孔容均略大于暗煤的,微孔更发育,且多以半封闭型和墨水瓶型孔隙为主。(3)镜煤微小孔更发育,比表面积更大,吸附能力更强。结论煤中甲烷吸附/解吸过程普遍存在解吸滞后现象,暗煤孔隙连通性相对较好,解吸滞后程度低于镜煤的,理论解吸效率高于镜煤的。研究结果可为彬长矿区低阶煤煤层气储层物性认识提供参考。

基于ReaxFF MD模拟的低阶煤热解产物演化规律及反应机理

热解是实现煤炭资源清洁高效利用的重要途径,深入认识煤热解过程中挥发分自由基的变化规律对调控热解产物至关重要,但实验方法难以捕捉其细节。本文选用经典的褐煤分子模型,结合反应分子动力学(ReaxFF MD)模拟探究了低阶煤热解过程中挥发分自由基的演化规律及反应机理。ReaxFF MD模拟结果表明,挥发分产物的收率随升温速率的增大而增加,较高的升温速率抑制了气体产物的生成、提高了焦油产物的收率,但焦油的重质化严重。含氧官能团的裂解是煤热解的触发机制,热解过程主要分为活化(800~1200K)、热解(1200~2400K)和缩聚(2400~2800K)三个阶段。在高温缩聚阶段,焦油片段之间更容易交联,进而发生缩聚反应形成焦炭,并伴随着气体生成,导致焦油收率降低,气体和焦炭产率增加。因此,改善焦油收率和品质的关键是促进焦油片段的裂解,抑制其缩聚。分析了气相产物的形成机理,CO_(2)主要来自羧基和酯基的裂解;甲氧基侧链和桥键裂解形成·CH_(3)和·CH_(2)自由基并捕获·H,最终形成CH_(4)分子;焦油的二次热解和缩聚释放大量·H和H_(2),·H之间进一步反应生成H_(2);而煤中的硫醚结构与含氮支链裂解后,进而被·H自由基稳定为H_(2)S和NH_(3)。这些从分子层面获得的机理认识,可为实验或工业调控热解产物提供重要的参考依据。

低阶煤热溶萃取物的配煤炼焦性能

目前,使用黏结性添加物进行配煤炼焦,降低焦/肥煤的使用比例,是焦化行业降本增效的重要途径。国内外学者已经在实验室阶段初步证明了低阶煤热溶萃取物替代焦/肥煤炼焦的可行性,工业化应用需要开展大规模的萃取物炼焦实际验证。基于此,本文搭建了低阶煤热溶萃取装置,并与多家焦化厂展开合作,完成了萃取物替代焦/肥煤的小焦炉实验验证。结果表明:萃取物取代20%肥煤或10%焦煤时能够明显降低焦炭的灰分,保持焦炭冷热性能基本不变。并且萃取物在炼焦过程中有72%~77%的留存率,不会造成焦炭产量的明显降低。因此,本研究明确了低阶煤热溶萃取物取代焦/肥煤炼焦方案的可行性,为焦化行业的降本增效提供了新选择,并进一步推动了低阶煤热溶萃取技术的工业化进展。