Qualitative and quantitative ATR-FTIR analysis and its application to coal char of different ranks

This paper analyzes the coal to char stages of char formation of six coals of different ranks by using Fourier transform infrared coupled w ith attenuated total reflectance(ATR-FTIR).The chars w ere obtained by coal pyrolysis carried out at temperature range of 450~700℃.The data obtained show s the pragmatic disappearance of the aliphatic hydrogen content w ith increasing char formation temperature.Numerical evaluation of the spectra enabled the determination of aromaticity,fa.The aromaticity w as found to be betw een 0.66~0.79 for lignite,0.75~0.90 for sub-bituminous,0.84~1.00 for low volatile bituminous,0.83~1.00 for high volatile bituminous,0.94~1.00 for semi-anthracite,and 0.97~1.00 for anthracite respectively.With increasing rank of coal samples,spectra exhibit rising aromaticity and enhanced condensation of aromatic rings,w hereas the aliphatic chain lengths decrease.

Comparison of kinetic models for isothermal CO_2 gasification of coal char–biomass char blended char

This study investigated the isothermal gasification reactivity of biomass char （BC） and coal char （CC） blended at mass ratios of 1：3, 1：1, and 3：1 via isothermal thermogravimelric analysis （TGA） at 900, 950, and 1000℃ under CO2. With an increase in BC blending ra- tio, there were an increase in gasification rate and a shortening of gasification time. This could be attributed to the high specific surface area of BC and the high uniformity of carbon structures in CC when compared to those in BC. Three representative gas-solid kinetic models, namely, the volumetric model （VM）, grain model （GM）, and random pore model （RPM）, were applied to describe the reaction behavior of the char. Among them, the RPM model was considered the best model to describe the reactivity of the char gasification reaction. The activa- tion energy of BC and CC isothermal gasification as determined using the RPM model was found to be 126.7 kJ/mol and 210.2 kJ/mol, re- spectively. The activation energy was minimum （123.1 kJ/mol） for the BC blending ratio of 75%. Synergistic effect manifested at all mass ratios of the blended char, which increased with the gasification temperature.

Simulation of coal char gasification using O_(2)/CO_(2)

The authors proposed an integrated gasification fuel cell zero-emission system.The coal char gasification is discussed using high temperature and concentration of CO_(2) produced by solid oxide fuel cells and oxy-fuel combustion.The gasification is simulated by Aspen plus based on Gibbs free energy minimization method.Gasification model of pulverized coal char is computed and analyzed.Effects of gas flow rate,pressure,preheating temperature,heat losses on syngas composition,reaction temperature,lower heating value and carbon conversion are studied.Results and parameters are determined as following.The optimum O_(2) flow rate is 20 kg/h.The reaction temperature decreases from 1645 to 1329℃when the CO_(2)flow rate increases from 0 to 5 kg/h,the CO_(2) flow rate should be operated reasonably;lower heating value reduces and reaction temperature increases as the pressure increases;compared to the CO_(2) preheating,O_(2) preheating has greater influence on reaction temperature and lower heating value.

Changes in char reactivity due to char-oxygen and char-steam reactions using Victorian brown coal in a fixed-bed reactor

This study was to examine the influence of reactions of char–O2and char–steam on the char reactivity evolution.A newly-designed fixed-bed reactor was used to conduct gasification experiments using Victorian brown coal at800 °C. The chars prepared from the gasification experiments were then collected and subjected to reactivity characterisation(ex-situ reactivity) using TGA(thermogravimetric analyser) in air. The results indicate that the char reactivity from TGA was generally high when the char experienced intensive gasification reactions in 0.3%O2in the fixed-bed reactor. The addition of steam into the gasification not only enhanced the char conversion significantly but also reduced the char reactivity dramatically. The curve shapes of the char reactivity with involvement of steam were very different from that with O2 gasification, implying the importance of gasifying agents to char properties.

Reaction Kinetic Equation for Char Combustion of Underground Coal Gasification

Based on the quasi-steady-state approximation, the dynamic equation of char combustion in the oxidation zone of underground coal gasification (UCG) was derived. The parameters of the dynamic equation were determined at 900℃ using a thermo-gravimetric (TG) analyzer connected to a flue gas analyzer and this equation. The equation was simplified for specific coals, including high ash content, low ash content, and low ash fusibility ones. The results show that 1) the apparent reaction rate constant increases with an increase in volatile matter value as dry ash-free basis,2) the effective coefficient of diffusion decreases with an increase in ash as dry basis, and 3) the mass transfer coefficient is independent of coal quality on the whole. The apparent reaction rate constant, mass-transfer coefficient and effective coefficient of diffusion of six char samples range from 7.51×104 m/s to 8.98×104 m/s, 3.05×106 m/s to 3.23×106 m/s and 5.36×106 m2/s to 8.23×106 m2/s at 900℃, respectively.

Experimental Study on Chemical Looping With Oxygen Uncoupling Using Copper Based Oxygen Carrier and Different Volatiles Contained Coal Chars

采用溶胶一凝胶法制备CuO／CuAl204氧载体，研究了该氧载体在N2气氛下的释氧性能，发现氧载体774℃时开始释氧，且随着温度的升高氧气含量不断升高。随后，在流化床反应器中研究了挥发分含量不同的6种煤焦的化学链氧解耦燃烧（chemicalloopingwithoxygenuncoupling，CLOU）特性，结果表明，挥发分含量的增加和温度的升高均会加速煤焦燃烧，煤焦中碳元素转化率达到95％所需要的时间随着挥发分含量及温度的升高不断减少，相应的碳的平均转化率也不断增加；然而，较高的挥发分含量和反应温度都会导致CO2捕集率的下降。对于挥发分含量低的高平煤焦和东欢坨煤焦，C02捕集率超过99％，而对于挥发分高的胜利褐煤焦，C02捕集率不足95％。

The influence of particle size on the thermal performance of coal and its derived char in a Union stove

For low-income communities in South Africa,coal is the most common solid fuel which is burnt in a variety of devices,including imbaulas and cast-iron stoves.The present work was conducted with the aim of determining the effect of the fuel particle size on the performance of coal,typically sourced in low-income households in townships in South Africa,and to subsequently compare the performance with a feed char of a common cast iron stove.Four fuel particle sizes of 15,20,30,and 40 mm,as well as a composite of the sizes were tested at 550C,against their untreated coal analogues to evaluate the thermal performance of each fuel.The thermal performance assessment metrics are ignition time,water boiling time,heat transfer and combustion efficiencies,while CO and CO_(2)emissions were measured for the calculations of CO/CO_(2)ratios.Ignition times were found to decrease from coals to chars and to decrease with increasing particle size.The effects of fuel type on the water boiling time were only observed in the later stages of the burn cycle,with the char boiling a 2 L batch of water in an average 24 min,while the coals reported an average boiling time of 20 min.Heat transfer efficiencies showed no significant variation with fuel type or particle size,with the average efficiency for the coals and that of the chars being around 66%.The fuels’performance was better gauged by the combustion efficiency,which was found to improve marginally from the coal fuels to the chars,and to increase with increasing particle size.Results from this testwork could contribute to the performance inventories from the combustion of domestic coal mined in South Africa in a typical cast iron stove which is used in informal settlements.

Kinetic and thermodynamic investigations of CO2 gasification of coal chars prepared via conventional and microwave pyrolysis

This study examined an isothermal CO2 gasification of four chars prepared via two different methods,i.e.,conventional and microwave-assisted pyrolysis,by the approach of thermogravimetric analysis.Physical,chemical,and structural behaviours of chars were examined using ultimate analysis,X-ray diffraction,and scanning electronic microscopy.Kinetic parameters were calculated by applying the shrinking unreacted core(SCM)and random pore(RPM)models.Moreover,char-CO2 gasification was further simulated by using Aspen Plus to investigate thermodynamic performances in terms of syngas composition and cold gas efficiency(CGE).The microwave-induced char has the largest C/H mass ratio and most ordered carbon structure,but the smallest gasification reactivity.Kinetic analysis indicates that the RPM is better for describing both gasification conversion and reaction rates of the studied chars,and the activation energies and pre-exponential factors varied in the range of 78.45–194.72 kJ/mol and 3.15–102,231.99 s−1,respectively.In addition,a compensation effect was noted during gasification.Finally,the microwave-derived char exhibits better thermodynamic performances than the conventional chars,with the highest CGE and CO molar concentration of 1.30%and 86.18%,respectively.Increasing the pyrolysis temperature,gasification temperature,and CO2-to-carbon molar ratio improved the CGE.

High temperature dephosphorization behavior of monazite concentrate with charred coal

Dephosphorization behavior of monazite concentrate with charred coal at high temperature was investigated.It is found that the roast temperature is the main factor for the dephosphorization of the monazite.The high dephosphorization efficiency can be reached at the temperatures ranging from 1 200 to 1 400°C.When the monazite pellets,made by pressing mixture of the monazite,charred coal and water into mould,were roasted at 1 400°C for 2 h,98%of phosphorus was removed from the monazite pellets.The roast time has little effect on the dephosphorization efficiency.Meanwhile,the particle size of the charred coal also has great influence on the dephosphorization efficiency of the monazite,and it is better to control particle size around 150μm,while Fe and Fe2O3 have neglectable effect on the dephosphorization of the monazite.

Effect of Particle Size on Gasification Reactivity of Different Rank Coal Chars

In the current research process of coal rank char gasification reaction in China, it is found that particle size has different influence on the gasification reactivity of coal char of different ranks. Therefore, monodisperse pulverized coal was prepared from eight kinds of coal chars of different ranks in entrained-flow gasifier. The particle size and gasification temperature of coal char were analyzed for these samples. The degree of influence of carbon dioxide gasification reaction. Through research and analysis, the performance differences of these samples under different carbon conversion rates were compared, and the sample reaction under high carbon conversion rates was discussed. The experimental results show that the orderliness of the microcrystalline structure of coal char is directly proportional to the rank of coal, while the gasification activity of coal char is inversely proportional to the rank of coal. Therefore, for different coal ranks, the influence of coal char particle size on coal char gasification reaction is different. According to the experiments, smaller coal char size and higher gasification temperature can promote the reactivity of higher-order coal gasification. In order to clarify the correlation between particle size and gasification reactivity of coal chars with different ranks, this paper discussed this issue.

Spectroscopic Elucidation of the Links between Char Morphology and Chemical Structure of Coals of Different Ranks

In this investigation, SAXS and XRD were used to investigate both the physical and chemical changes in six coals of different ranks subjected to heat treatment. The specific surface area which gives an indication of the reactivity of the coal (measures surface area available for reaction) was determined to be in the range of 70.04 - 260.40 m2/cm3 particle volume for lignite from 450°C - 700°C. The specific surface area was determined to be in the range of 51.58 - 239.00 m2/cm3 particle volume for sub-bituminous;440.60 - 241.70 m2/cm3 particle volume for light volatile bituminous;452.71 - 247.73 m2/cm3 particle volume for high volatile bituminous;349.11 - 347.52 m2/cm3 particle volume for semi-anthracite and 333.60 - 125.34 m2/cm3 particle volume for anthracite respectively. On the other hand, the aromaticity was determined in the range of 0.66 - 0.76 for lignite;0.67 to 0.80 for sub-bituminous;0.91 - 0.97 for light volatile bituminous;0.93 - 0.99 for high volatile bituminous;0.96 - 1.00 for semi-anthracite and 0.96 to 0.99 for anthracite respectively. The porosity, pore size distribution associated with SAXS and the other crystallite parameters identified with XRD were also determined. Links between the physical and chemical parameters were established.

Investigation on the catalytic effects of AAEM during steam gasification and the resultant char reactivity in oxygen using Shengli lignite at different forms

The purpose of this study is to investigate the catalytic effects of alkali and alkaline earth metallic species （AAEM） on char conversion during the gasification in steam and the changes in ex-situ char reactivity in oxygen after the gasification in steam using different forms （i.e. H-form, Na-form） of Shengli brown coal. The surface area, AAEM concentration and carbon crystallite of chars were obtained to understand the change in char reactivity. It was found that not only Na concentration and carbon structure were the main factors governing the char reactivity in the atmosphere of steam and oxygen, but also they interacted each other. The presence of Na could facilitate the formation of disordering carbon structure in char, and the amorphous carbon structure would in turn affect the distribution of Na and thus its catalytic performance. The surface area and pore volume had very little relationship with the char＇s reactivity. Addi- tionally, the morphology of chars from different forms of coals were observed using scanning electron microscope （SEM）.

Investigation into characteristics of the char bed in the melter gasifier through tuyere probing

Tuyere coke probing was conducted at the Baosteel Corex Plant in order to gain a better understanding of the structure of the char bed in the melter gasifier （ MG ）. After screening, the specimens were observed by an optical microscope to determine the mechanism of the char bed formation. X-ray diffraction （XRD） was used to clarify the degree of graphitization and infer thermal history of coke. The results show that the amount of powder coming from lump coal in the burden is much more than that from coke. Based on this, measures for improving the char bed＇ s permeability are proposed.

Comparison on Non-isothermal Oxidation between Spent Catalytic Cracking Catalysts and Coal

Oxidation of coke deposited on spent catalytic cracking catalysts was compared with that of coal and coal char via the non-isothermal oxidation means, i.e. the thermal-gravimetric analysis （TGA） and the differential thermal analysis （DTA）. Oxidation kinetic parameters were further investigated by model-fitting methods. The test results showed that the oxidation of spent catalysts was a quite mild process, while coal and coal char experienced sharp weight loss during oxidation. The temperature for commencement and termination of oxidation increased in the following order： coal〈coal char〈spent catalysts, and the oxidation of the three tested materials displayed a self-catalytic nature, with their largest oxidation rate appearing at a weight percent of 24.96%, 34.21% and 57.93%, respectively. The oxidation of spent catalysts obeyed a random nucleation model for the first-order reaction, with Ea=206.13 kJ/mol and lgA=10.10, and the oxidation of coal could be a diffusion-controlled reaction mechanism, with Ea=161.61 kJ/mol and lgA=7.74, while the oxidation of coal char also obeyed a random nucleation model for the first-order reaction, with Ea= 149.36 k J/mol and lgA=7.89.

不同处理方法对煤焦上甲烷裂解制氢性能的影响

在小型石英管固定床上,考察甲烷在小龙潭(XLT)褐煤焦以及处理煤焦:水洗煤焦、HCl-HF洗煤焦及硝酸洗煤焦上的裂解反应性能。结果表明,XLT煤焦上甲烷的初始转化率为64.7%,水洗煤焦和硝酸洗煤焦上甲烷初始转化率明显提高,分别为78.5%、72.4%,而经HCl-HF处理后,甲烷初始转化率下降到54.1%,煤焦的催化活性降低。随着反应时间的不断增加,甲烷裂解转化率和氢气收率逐渐降低,说明不同煤焦在反应过程中逐渐失活。通过扫描电子显微镜和比表面积测定仪对反应前后不同煤焦进行表征,BET数据表明,甲烷裂解后煤焦的比表面积和微孔容降低,平均孔径增大,分析其原因是反应生成的积炭堵塞煤焦的微孔。SEM结果显示甲烷裂解后,煤焦表面上有明显的积炭生成,最终导致煤焦催化活性逐渐降低。

淖毛湖煤加氢热解产物特性及半焦气化反应性

在加压固定床反应器中进行淖毛湖煤在常压和1.5 MPa氢气和氮气中的热解试验,利用多种表征方法对比研究了氢气和氮气下的热解产物产率和组成及半焦结构的变化,并利用热重分析研究热解半焦的CO_(2)气化反应性。结果表明:与常压N_(2)中热解相比,煤在加压的H_(2)中热解可有效提高热解气体中CH_(4)和C_(2)~C_(3)的产率,在800℃热解CH_(4)和C_(2)~C_(3)的体积产率分别由53.5和16.6 mL/g增至345.6和20.8 mL/g。焦油和轻质焦油产率也有效提升,在600℃下,与常压N_(2)中热解相比,1.5 MPa H_(2)中煤热解的焦油产率由19.3%升至22.8%,焦油中脂肪烃含量由35.5%降至14.8%,单环芳烃含量由8.3%增至28.9%,轻质焦油质量分数和产率分别升至95.0%和21.8%。半焦的N_(2)吸附和拉曼光谱分析结果表明,煤在加压H 2中热解得到半焦的比表面积和孔体积由常压氮气下的40 m^(2)/g和0.05 cm^(3)/g增至289 m^(2)/g和0.16 cm^(3)/g,孔结构显著发展,有利于半焦的CO_(2)气化反应进行;而半焦的石墨化程度及大芳香环比例增加,不利于半焦气化反应;但由热重分析得到的加压加氢热解半焦的CO_(2)气化反应性明显提高,表明孔结构对半焦CO_(2)气化反应性起主要作用。

《医学衷中参西录》药物炮制撷英

张锡纯《医学衷中参西录》中有关药物炮制的内容非常丰富,在药物的净制方面,主要有麻黄去节、桂枝去皮、蜈蚣去头、竹茹的入药部位等;在药物的切制方面,主要有茯苓切片、用隔纸焙代替植物叶片使乳香、没药去油、五味子捣碎、石类药物轧细等;在矿物药炮制方面,主要有石膏、代赭石、赤石脂均宜用生品不需煅制,朱砂人工合成者不宜入药,并列举了玄明粉与黑锡丹的制作方法;动物药的炮制方面,龙骨、牡蛎、石决明、水蛭、全蝎均主张用生品,并列举了血余炭的制作方法;毒性药物的炮制方面,主要有鸦胆子不可使皮破并宜装入龙眼肉中吞服,市售半夏要漂去矾味并阐述了制作半夏的方法,拟定了马钱子新的减毒增效炮制方法;药物炒炭方面,除血余炭外,鲜用炒炭药物;药物发酵方面,认为麦芽虽为脾胃之药,而实善舒肝气;酒曲调气破癥的作用较神曲强,但是神曲性更平和,更适于健胃消食。

CO_(2)和H_(2)O气化反应对富氧气氛煤热解和焦炭燃烧影响进展

富氧燃烧技术作为一种具有广阔前景的燃煤电站CO_(2)减排技术,对实现可持续发展的能源目标具有重要意义。由于CO_(2)和H_(2)O物理性质和气化反应的影响,煤在富氧气氛中的转化过程可能明显异于空气气氛。通过分析已有文献发现,CO_(2)对煤热解过程中挥发分的析出率和焦炭的物理结构和化学性质有一定影响,但较少学者关注CO_(2)和H_(2)O混合气体物性的作用。在煤或焦炭燃烧过程中,CO_(2)的高比热和低氧扩散速率对燃烧反应有明显抑制作用,但可能是由于H_(2)O浓度差异的原因,目前对CO_(2)和H_(2)O混合气体物性在燃烧过程中的影响机制还有争议,尤其是缺少加压下的数据。对于气化反应的影响,目前研究表明,CO_(2)单气化和CO_(2)/H_(2)O共气化提高了煤热解时挥发分轻质气体的产率,但焦炭产率却有所降低,而压力增加强化了这一影响。此外,气化作用下的煤焦可能由于表面积增加而提高了反应活性,其表面官能团结构也因气化而发生改变。关于煤或焦炭燃烧反应,目前普遍认为CO_(2)气化在温度较高和氧气浓度较低时可促进燃料碳消耗,H_(2)O的加入则进一步加速了这一过程。随着环境压力的升高,CO_(2)气化反应在燃料碳消耗中占比逐渐增大,但对于加压下CO_(2)/H_(2)O共气化的影响鲜有涉及。本研究总结了富氧气氛中CO_(2)和H_(2)O气化作用下的煤热解和焦炭燃烧行为,为今后富氧燃烧技术的发展提供了理论参考。