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.

Effect of the benzene ring of the dispersant on the rheological characteristics of coal-water slurry:Experiments and theoretical calculations

In this study,low-rank coal-water slurry(LCWS)was prepared using polyoxyethylene dodecylphenol ether(PDPE)and polyoxyethylene lauryl ether(PLE),respectively.A combination of experiments and simulations was used to investigate the pulping properties and microscopic mechanism of the LCWS samples prepared using the two agents,so as to explore the influence of benzene ring on the performance of dispersant.The results of the LCWS preparation experiments revealed that the pulp-forming performance of PDPE exceeded that of PLE.When LCWS concentration is 62%,64%,and 66%,the apparent viscosity corresponding to PDPE is 247.80,504.17,and 653.10 mPa·s,and the apparent viscosity corresponding to PLE is 548.10,1470.61,and 1549.98 mPa·s,respectively.The C_(1000)(When the apparent viscosity is 1000 mPa·s,the corresponding concentration of LCWS is defined as C_(1000))values of PDPE and PLE are 67.60%and 62.95%,respectively.In addition to the van der Waals forces and hydrogen bonds between the PDPE and/or PLE molecules and coal,the benzene rings of PDPE presentπ-πstacking effect with the aromatic rings of coal.That could facilitate and strengthen the adsorption of PDPE on coal,which would be conducive to further improving the dispersion of coal particles.The two dispersants have no significant difference in effect on the pyrolysis of LCWS.The simulation results indicated that the times for PDPE and PLE molecules to reach flat adsorption state on coal are approximately 290 and 565 ps,respectively.The self-diffusion coefficient(D)of the PDPE and PLE on coal is 3.16 x 10^(-6)and6.57×10^(-6)m~2/s,respectively,and their interaction energies with coal are 785.71 and 648.60 kcal/mol,respectively.The results of the simulation calculations demonstrated that PDPE adsorbed on coal easier than PLE,and its binding is more stable than that of PLE owing to theπ-πstacking effect,which is conducive to uniform dispersion of coal in solution.The simulation results confirmed the experimental results.

Blended coals for improved coal water slurries

Three coal samples of different ranks were used to study the effect of coal blending on the preparation of Coal Water Slurry (CWS). The results show that by taking advantage of two kinds of coal, the coal concentration in slurry made from hard-to-pulp coal can be effectively improved and increased by 3%–5% generally. DLT coal (DaLiuTa coal mine) is very poor in slurryability and the stability and rheology of the resulting slurry are not very good. When the amount of easily slurried coal is more than 30%, all properties of the CWS improve and the CWS meets the requirements for use as fuel. Coalification, porosity, surface oxygenic functional groups, zeta potential and grindability have a great effect on the performance of blended coal CWS. This leads to some differences in performance between the slurry made from a single coal and slurry made from blended coal.

Cation exchange for mercury and cadmium of xanthated,sulfonated,activated and non-treated subbituminous coal,commercial activated carbon and commercial synthetic resin:effect of pre-oxidation on xanthation of subbituminous coal

A subbituminous coal was oxidized with air at 150℃on a fixed bed for 4 h and xanthated with carbondisulfide in a basic solution,at 30 or 5-10℃.This xanthated coal was evaluated for the removal of Hg^(2+)and Cd^(2+)from 7,000 mg/L aqueous solutions;metal concentrations were detemmined by atomic absorption spectrometry.The ionexchange of the xanthated coal was compared against those of the original subbituminous coal,a sulfonated subbituminouscoal,activated carbon,commercial activated carbon,and commercial synthetic resin.The commercial synthetic resinshowed the highest exchange capacity(concentration factor 98%)followed by the xanthated coal(concentration factor 96%).The retention of cadmium on the sulfonated subbituminous coal was lower(exchange capacity 0.56 meq/g)thanthat of xanthated coals(1.85±0.09 meq/g).Our xanthated coal showed a better Cd^(2+)removal(8l%o against 15%)than anon preoxidized 40-h-xanthated coal,which shows that oxidation of coal increased the amount of oxygenated groups whichenhanced xanthation.

The Influence of CO on the Carbon Isotopic Composition of CH_4 in Closed Pyrolysis Experiment With Coal

A low-mature coal (R o=0.4%, from the Manjia’er depression, Tarim Basin, China) was subjected to closed system pyrolysis, in sealed gold tubes, under isothermal temperature conditions. The carbon isotopic compositions of the pyrolyst fractions (hydrocarbon, CO 2, CO, etc.) at two temperature points (350°C and 550°C) were measured. The results showed that δ 13C CH 4 value is generally heavier at 350°C than that at 550°C, because the high abundance of CO generated at low temperature would greatly influence δ 13C CH 4 value, and the retention time of CO in gas chromatograph is close to that of CH 4. But CO is formed through chemical reaction of the oxygen-containing functional group -C=O, e.g. lactones, ketones, ether, etc. at low temperature, while CO 2 comes mainly from decarboxylization. The carbon isotopic composition of coal gas from Lanzhou Coal Gas Works was definitely different from that of thermally pyrolysed products from coal. The δ 13C CH 4 value of coal gas was abnormally heavier than δ 13C CO. At the same time, the reversed sequence ( δ 13C 1> δ 13C 2) of δ 13C 1 and δ 13C 2 happened. The bond energy of free ions generally decides the sequence of generation of hydrocarbon fractions according to the chemical structure, whereas the stability of pyrolysate fractions and their carbon isotope fractionation are affected by the C-C bond energy.

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。

Coalbed methane enrichment model of low-rank coals in multi-coals superimposed regions: a case study in the middle section of southern Junggar Basin

The Middle Jurassic Xishanyao Formation in the central section of the southern Junggar Basin has substantial amounts of low-ranked coalbed methane(CBM)recourses and is typically characterized by multi superimposed coal seams.To establish the CBM enrichment model,a series of experimental and testing methods were adopted,including coal maceral observation,proximate analysis,low temperature nitrogen adsorption(LTNA),methane carbon isotope determination,porosity/permeability simulation caused by overburden,and gas content testing.The controlling effect of sedimentary environment,geological tectonic,and hydrogeological condition on gas content was analyzed in detail.The results demonstrate that the areas with higher gas content(an average of 8.57 m3/t)are mainly located in the Urumqi River-Santun River(eastern study area),whereas gas content(an average of 3.92 m3/t)in the Manasi River-Taxi River(western study area)is relatively low.Because of the combined effects of strata temperature and pressure,the gas content in coal seam first increases and then decreases with increasing buried depth,and the critical depth of the inflection point ranges from 600 m to 850 m.Affected by the changes in topography and water head height,the direction of groundwater migration is predicted from south to north and from west to east.Based on the gas content variation,the lower and middle parts of the Xishanyao Formation can be divided into three independent coalbearing gas systems.Within a single gas-bearing system,there is a positive correlation between gas content and strata pressure,and the key mudstone layers separating each gas-bearing system are usually developed at the end of each highstand system tract.The new CBM accumulation model of the multi-coals mixed genetic gas shows that both biological and thermal origins are found in a buried depth interval between 600 m and 850 m,suggesting that the coals with those depths are the CBM enrichment horizons and favorable exploration regions in the middle section of the southern Junggar Basin.An in-depth discussion of the low-rank CBM enrichment model with multi-coal seams in the study region can provide a basis for the optimization of CBM well locations and favorable exploration horizons.