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.

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.

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％。

Thermogravimetric Analysis of Coal Char Combustion Kinetics

Four chars prepared from pulverized coals were subjected to non-isothermal and isothermal combustion tests in a thermogravimetric analysis （TGA） device. Three different test methods, i. e. , non-isothermal single heat- ing rate （A）, non-isothermal multiple heating rate （B）, and isothermal test （C）, were conducted to calculate the ki- netic parameters of combustion of coal char. The results show that the combustion characteristics of bituminous coal char is better than that of anthracite char, and both increase of heating rate and increase of combustion temperature can obviously improve combustion characteristics of coal char. Activation energies of coal char combustion calculated by different methods are different, with activation energies calculated by methods A, B and C in the range of 103.12-- 153.77, 93.87--119.26, and 46.48--76.68 kJ/mol, respectively. By using different methods, activation energy of anthracite char is always higher than that of bituminous coal char. In non-isothermal tests, with increase of combus- tion temperature, the combustion process changed from kinetic control to diffusion control. For isothermal combus- tion, the combustion process was kinetically controlled at temperature lower than 580 ℃ for bituminous coal char and at temperature lower than 630 ℃ for anthracite char.

Non-isothermal study of gasification process of coal char and biomass char in CO_2 condition

Non-isothermal method was used to study gasification characteristics of three coal chars and one biomass char.Four chars were made from anthracite coal（A）,bituminous coal（B）,lignite coal（L）,and wood refuse（W）,respectively.The gasification process was studied by random pore model（RPM）,unreacted core model（URCM）and volumetric model（VM）.With an increase in metamorphic grade,the gasification reactivity of coal char decreased,and the gasification reactivity of biomass char was close to that of low metamorphic coal char.With an increase in heating rate,the gasification of all samples moved towards high temperature zone,and the whole gasification time decreased.It was concluded from kinetics analysis that the above-mentioned three models could be used to describe the gasification process of coal char,and the RPM fitted the best among the three models.In the RPM,the activation energies of gasification were193.9,225.3 and 202.8 kJ/mol for anthracite coal char,bituminous coal char and lignite coal char,respectively.The gasification process of biomass char could be described by the URCM and VM,while the URCM performed better.The activation energy of gasification of wood refuse char calculated by the URCM was 282.0 kJ/mol.

Gasification reactivity and kinetic parameters of coal chars for non-isothermal steam gasification

The gasification reactivity and kinetic parameters of coal chars for non-isothermal steam gasification were investigated.One kind of lignite and three kinds of bituminous coals were used as the samples,and their coal ranks follow the ascending order:XB<KL<ZJ<GD.As characterized by the comprehensive gasification index,the gasification reactivity of coal chars follows the descending order:XB>KL>ZJ>GD.Through systematically analyzing factors affecting gasification reactivity,it was ascertained that the gasification reactivity is mostly determined by the carbonaceous structure.The gasification reactivity is inversely proportional to the coal rank,and the higher the coal rank,the lower the gasification reactivity.A new kinetic model was proposed to calculate the kinetic parameters,in which the reaction order was considered as an unknown kinetic parameter.The reaction order n follows the ascending order:XB<KL<ZJ<GD,which are n=1.00,n=1.34,n=1.83,and n=2.63,respectively.It is proved that the reaction order is proportional to the coal rank,and the higher the coal rank,the higher the reaction order.

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.

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.

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.

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.

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.

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。

煤焦颗粒群异相反应特性的数值模拟研究

煤焦异相反应是煤粉燃烧区别于气体燃料燃烧或液体燃料燃烧的特征之一,其反应过程占整个煤粉燃烧时间约90%,对煤粉高效燃烧至关重要。通常情况下,煤粉颗粒以稠密相而非以稀疏相或单颗粒形式进入炉膛,颗粒间的相互作用会影响煤焦异相反应,因此,深入开展煤焦颗粒群异相反应行为研究对于煤的高效利用十分必要。采用准稳态的数值模拟方法研究煤焦颗粒群的异相反应行为,对比分析了煤焦单颗粒和煤焦颗粒群的反应特性,相比于煤焦单颗粒,煤焦颗粒群燃烧峰值温度升高约300 K,颗粒表面温度降低约100 K,碳消耗速率降低56%~65%,说明颗粒间作用影响了煤焦颗粒的燃烧反应进程。对3种典型分散形式下煤焦颗粒群燃烧反应特性进行研究,随着颗粒间距的增加,各分散形式的煤焦氧化反应占比增加0.22%~2.20%,碳消耗速率随之增大9.8%~26.1%,较大颗粒间距有利于O_(2)分子在颗粒间的扩散,促进了氧化反应以及煤焦消耗。探究了不同反应气氛下煤焦颗粒群的燃烧反应特性,相比于空气气氛,高CO_(2)和H_(2)O气氛下燃烧群峰值温度增加4%~30%,颗粒表面温度升高0.5%~3.7%,其中30%O_(2)/70%H_(2)O工况的碳消耗速率最大,较空气气氛高80%。综合对比,各颗粒间作用、颗粒间距和反应气氛工况下3种颗粒群分散形式的煤焦燃烧碳消耗速率依次为:形式C>形式B>形式A(形式A:颗粒群呈正方形分散;形式B:颗粒群呈正菱形分散;形式C:颗粒群呈正三角形分散),因此颗粒与气流之间的扰乱作用对煤焦的消耗产生不可忽视的影响。

加压流化床Co-Ca催化煤焦加氢气化反应动力学

煤催化加氢气化是极具发展潜力的煤制天然气技术,包括煤催化加氢热解和煤焦催化加氢气化2个步骤,其中煤焦催化加氢气化的反应速率远小于煤催化加氢热解的反应速率,是整个气化过程的速率控制步骤,因此建立适宜的煤焦催化加氢气化反应动力学对该技术的应用具有重要的意义。在小型加压流化床中,研究了Co-Ca催化煤焦加氢气化过程中煤焦颗粒密度和孔隙结构随碳转化率的变化规律,发现随反应进行煤焦颗粒密度减小,孔隙总比表面积与反应速率线性相关,表明Co-Ca催化煤焦加氢气化反应符合随机孔模型的特征。通过调控反应温度、氢分压和Co负载量,获得了煤焦中碳转化率的变化规律。结果表明:650~850℃反应仍处于动力学控制阶段;反应温度超过750℃后,反应速率显著提升,进一步提升温度至850℃时,碳转化率由650℃时的16.32%增至95.32%。随氢分压升高,碳转化率增大,氢气分压由0.6 MPa增至2.5 MPa时,碳转化率由19.49%提高至94.11%。随Co催化剂负载量由1%提高至3%,碳转化率持续提升,继续增加Co负载量至5%,碳转化率变化较小。采用扩展随机孔模型,引入经验参数c和p对试验数据进行分析,得到煤焦催化加氢气化反应的活化能为122.7 kJ/mol,反应级数为1.54。模型预测的反应速率值与试验值之间的平均偏差为4.81%。