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 lignite and Shenmu bituminous coal) at low, medium and fast heating rates, respectively, to the same pyrolysis temperature 750 °C. 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 °C/min and Shenmu coal at 200 °C/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.

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.

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.

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.

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.

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.

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.

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。

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。

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。

二连盆地富气凹陷低阶煤煤层气成因及成藏机制

内蒙古低阶煤煤层气资源丰富,煤层气成因与成藏机制研究对低阶煤煤层气资源选区评价至关重要。以二连盆地重点富气凹陷低阶煤煤层气为研究目标,利用煤层气组分、碳/氢同位素、煤层水水质、氢/氧同位素及放射性同位素^(3)H和^(14)C测试等多种实验手段,分析煤层气、水地球化学特征,揭示低阶煤煤层气成因来源及成藏机制。结果表明,二连盆地煤层气组分以甲烷为主,均为干气,其中甲烷体积分数随埋深增加而增大,CO_(2)体积分数随埋深增加呈先增加后降低趋势,在300~500 m范围出现高值区。甲烷碳、氢同位素普遍偏轻,δ^(13)C(CH_(4))分布在-70.3‰~-48.0‰,δD(CH_(4))分布在-285.5‰~-189.0‰,δ^(13)C(CO_(2))在-37.6‰~1.94‰变化。煤层水化学类型主要为HCO_(3)-Na型和Cl·HCO_(3)-Na型,现今煤层水体环境较为稳定,水动力较弱,煤层水表观年龄在1020~47490 a,主要来源于第四纪大气降水,没有或较少有现今地表水补给。二连盆地煤层气主要为原生生物成因气,混有少量早期热成因气,随着埋深加大,地层环境和产甲烷古菌类型发生变化,生物甲烷生成途径发生转变。其中吉尔嘎朗图凹陷早期以乙酸发酵产气为主,晚期转变为CO_(2)还原产气为主,并混有少量低熟热成因气;巴彦花和霍林河凹陷微生物产气途径均以乙酸发酵为主,其中霍林河凹陷还混有少量甲基发酵型生物气。研究区具有适合生物气生成的低地温、低矿化度和低热演化程度的“三低”煤层条件,其中,吉尔嘎朗图凹陷属于地堑式浅部厚煤层生物气成藏模式,巴彦花和霍林河凹陷属于半地堑式中深部承压区水力封堵生物气成藏模式。寻找适合生物成因气形成和富集的有利目标区,应是二连盆地煤层气未来勘探开发的重点方向,也是二连盆地低阶煤煤层气增储上产的现实保障。

甲烷气氛下铁基催化剂对低阶煤温和液化的影响

针对煤直接液化的高温高压苛刻反应条件和高昂的氢气成本问题,通过降低煤液化反应温度、压力和更换供氢气氛等方法来优化工艺过程。选用四种铁基催化剂研究低阶煤在甲烷气氛下温和液化的反应特性,研究结果表明:神华黑山长焰煤HS在温度350℃、初始压力3 MPa的甲烷气氛下液化产物为轻质气体、液化油和沥青质;以FeSO_(4)为催化剂时沥青质的产率最高达到8.03%,并将煤液化的转化率提升了6.10%;以FeS为催化剂时油气产率提升了3.48%;助剂硫元素的加入对煤液化反应总转化率的提升有着重要作用;Fe粉、Fe+S和FeS催化剂的加入有助于提升煤液化油中单环芳烃的含量。

SHMP与PAM协同强化低阶煤泥浮选研究

为改善低阶煤泥的浮选效果,采用六偏磷酸钠(SHMP)和聚丙烯酰胺(PAM)来协同强化低阶煤泥的浮选,探究了SHMP、PAM及SHPM+PAM对低阶煤泥浮选效果的影响。基于接触角和Zeta电位测试分析了改善低阶煤泥浮选效果的机理。研究结果表明,在SHPM用量为600 g/t、CPAM用量为80 g/t时,精煤产率和可燃体回收率分别为60.83%和93.27%,相比于单一SHPM或CPAM,精煤产率分别提高了6.82个百分点和1.88个百分点;可燃体回收率分别提高了9.63个百分点和12.89个百分点。经SHPM+CPAM作用后,煤粒表面的接触角提高了31°,Zeta电位的绝对值提高了17.22 mV。

低阶煤和生物质水热碳化特性及水热炭功能化改性研究进展

低阶煤中大量含氧官能团赋予其强亲水性,导致孔隙表面吸收大量水分,从而增加运输成本,能源转化效率降低,因此低阶煤的清洁低碳高效转化备受关注。水热碳化反应能耗较低,可直接处理高含水率有机固体物质,是一种绿色低碳高效经济的低阶煤提质技术;而生物质作为可代替化石燃料的可再生能源,水热碳化也可大幅提高其利用率。低阶煤与生物质共水热碳化时,二者会产生一定的协同效应,相较于单一水热碳化具有更高的产率和碳保留率。对水热炭进行功能化改性,可以进一步丰富其孔隙结构,增加材料表面的官能团,进而制备出性能优异的功能性炭材料,用于CO_(2)和SO_(2)等气体吸附。综述了低阶煤和生物质单独水热碳化及共水热碳化特性,分析生物质水热碳化主要影响因素;同时对水热炭活化改性和掺杂改性方法进行了总结,比较了氮、硫掺杂及硫氮共掺杂方式、掺杂机制及改性水热炭应用范围。此外,还对改性水热炭对CO_(2)和SO_(2)吸附性能等进行了综述,探讨了多孔炭表面吸附CO_(2)和SO_(2)的机理;最后对低阶煤和生物质共水热碳化以及水热炭低成本制备气体吸附剂等未来发展方向进行了展望。

低阶煤催化加氢裂解可溶物的结构分析

采用水热合成法制备了CuFeO_(2)催化剂,并将其应用于低阶煤的催化加氢裂解,将所得反应混合物利用石油醚进行萃取。采用气相色谱质谱联用仪(GC/MS)分析可溶物的组成和结构特征。结果表明:水热合成法制备的CuFeO_(2)催化剂是纳米级的CuFeO_(2)颗粒;GC/MS检测到的化合物可以划分为4个族组分,分别为脂肪烃、芳烃、含氧化合物和含氮化合物,其中芳烃的相对含量最高。研究结果对于低阶煤在温和条件下的清洁高效转化具有一定的理论指导作用。

月桂酸甲酯强化低阶煤浮选的作用机制

为了探究月桂酸甲酯对低阶煤浮选的强化作用机制,以月桂酸甲酯为捕收剂,对宁东某低阶煤泥进行了浮选实验、浮选速度实验和浮选动力学分析,并与正十二烷进行对比。研究结果表明:月桂酸甲酯比正十二烷处理后煤样的可燃体回收率和浮选速率常数分别提升10.01%和1.84%;红外光谱分峰拟合分析表明,与正十二烷相比,月桂酸甲酯作用后精煤的极性官能团含量减少了8.69%,脂肪烃和芳香烃含量升高了8.69%。这说明月桂酸甲酯有效覆盖了低阶煤表面含氧官能团位点,并将自身C—C/C—H暴露出来,导致煤样疏水性增加,从而提高低阶煤的可燃体回收率和浮选速率常数,这是月桂酸甲酯强化低阶煤浮选的主要作用机制。