煤焦反应活性影响因素探讨

总结了前人在热处理对煤焦反应活性的影响方面的研究结果，并得到如下的结论：热处理过程使得煤焦中碳结构排列有序化及具有催化能力的矿物质组分烧结或熔融，从而导致了煤焦反应活化能增加，反应活性下降，煤焦反应活性可以用低温下其对氧的化学吸附量来表征，使用分布活化能模型能较好地考察煤焦本征反应活性在反应过程中的变化。     

高钠煤及其洗煤的气化反应研究

以60%水蒸气和40%N2作为气化剂,采用热重方法,在850 C～950 C条件下,研究了澳大利亚高盐煤、水洗煤以及不同浓度酸洗后的煤在所制得的快速低温热解焦的水蒸气气化反应特性.同时,用N2作为吸附剂测定了几种煤焦的比表面积.结果表明:水洗煤焦和0.01 mol/LHCl洗煤焦气化反应活性最高,原煤焦次之,0.1 mol/L HCl洗煤焦和0.5 mol/L HCl洗煤焦的活性较低.洗涤过程会导致煤焦孔径的扩大,煤焦的比表面积减小.原煤焦的活化能较高,而洗涤煤焦的活化能降低.     

神木煤焦与流化床气化带出细粉的CO2气化特性

为了研究煤焦与流化床气化带出细粉的CO_2气化特性,采用热重分析仪考察了不同气化温度和CO_2分压对神木煤焦与细粉气化行为的影响。结果表明,固定CO_2分压提高气化温度或固定气化温度提高CO_2分压都能加快神木煤焦和细粉气化反应的进行,缩短达到一定碳转化率所需时间;神木煤焦和细粉的反应速率随碳转化率的增大均先快速增大到最大值,而后缓慢降低;神木煤焦和细粉的CO_2气化反应活化能均随碳转化率的升高而增大,在相同的碳转化率下,神木煤细粉的反应活化能大于神木煤焦。与神木煤焦相比,神木煤细粉的CO_2气化反应活性较低。     

煤焦燃烧特性及反应活性探究

中国褐煤资源丰富,然而由于褐煤自身特点使其应用受到了极大的限制。针对中国褐煤应用最广的途径———燃烧,借助热重分析仪对不同热解终温的褐煤半焦及热解终温为1273 K的褐煤半焦与原煤的混合燃料的燃烧特性进行了分析。并利用Coats-Redfern法进行了燃烧动力学的分析,通过求得的表观活化能表征煤焦的燃烧反应活性。研究发现：热解终温越高,煤焦的燃烧特性越差;掺混褐煤有助于提高其半焦的燃烧特性,而掺混燃料的燃烧稳定性几乎和原煤无差别,且随着掺混比例的增加,混合燃料的活化能逐渐增大,越不易点燃,掺混半焦对燃料的燃烧特性和反应活性都有影响。相同制备条件下的烟煤半焦和褐煤半焦的燃烧动力学参数尤其是活化能相差很大,可见煤焦的燃烧反应活性与煤种有关。     

碱金属对煤热解和气化反应速率的影响

通过对原煤、酸洗原煤、负载碱金属的酸洗原煤在800～1050℃热解制得焦样,用X射线衍射技术考察了碱金属对煤焦微晶结构的影响,在加压热天平（PTGA）上考察了煤样的热解过程,以及焦样的二氧化碳气化活性。结果表明：碱金属对煤的热解和气化阶段都有影响。在热解阶段,碱金属的存在抑制了煤焦的石墨化进程,降低了热解反应活化能,促进了热解反应的进行;在气化阶段,作为催化剂的碱金属,降低了气化反应活化能,延长了反应速率达到最大值的时间。修正的随机孔模型可以较好地描述煤焦-CO₂的气化反应过程。     

TPR法研究煤焦—CO_2气化反应──（Ⅰ）碳化条件和掺加金属催化剂对气化反应性的影响

改变碳化条件和掺加金属催化剂，制备了十几个煤焦样品。用ＸＲＤ测定了未载金属煤焦的碳微晶尺寸。用ＴＰＲ法测定了上述煤焦的ＣＯ_２气化反应性，用Ｆｒｅｅｍａｎ－Ｃａｒｒｏｌｌ方法计算得到了反应活化能Ｅ和指前因子Ａ。结果表明：碳化条件越剧烈，煤焦的气化活性越低。掺加不同量的钙催化剂，煤焦的气化活性得到不同程度的提高，同时ＤＴＧ曲线有明显的变化。这些现象可从碳化条件对煤焦气化活性的影响，以及钙对煤焦ＣＯ_２气化的催化作用等方面来解释。     

贵州老矿煤焦加压CO2气化反应动力学研究

为解析我国高灰熔融性煤的气化特性及动力学,采用Cahn Thermax 500加压热重分析仪,研究了1种典型贵州高灰熔融性煤焦在加压下与CO_2气化反应的特性及动力学,采用混合反应模型对实验数据进行处理,求取动力学参数。实验结果表明:气化温度越高,煤焦的反应速率越快;在0.5～3MPa压力范围内,气化压力越高,煤焦的反应速率越快;气化剂中CO_2浓度越高,煤焦与CO_2气化反应的速率越快。1 MPa下,老矿精煤快速焦与CO_2的反应活化能介于255.82～304.96 kJ/mol之间;2MPa下,反应活化能介于205.83～248.34 kJ/mol之间,2MPa下的反应活化能低于1MPa下的反应活化能。     

等温热重分析法对煤焦反应动力学特性研究

针对工业气化炉二级旋风分离器的气化后半焦,同时选取京能烟煤在1173K,1273K和1373K三个温度下快速热解焦炭作为比较,在TGA/SDTA851e型热重分析仪上,对四种经历不同热过程的焦炭进行等温热重实验,实验温度范围为773K～1023K,研究煤焦燃烧反应动力学特性及其影响因素.煤焦制取方式和热解温度的不同决定了煤焦反应性的不同,在这四种煤焦中,气化半焦JC的反应性最小,而京能烟煤三种热解煤焦的反应性随着热解温度的升高而减小.随着燃烧温度和氧含量的升高,煤焦的反应速率在增大.同时,用半转化率法确定了煤焦燃烧的转捩温度和各个反应区域的活化能,在化学反应动力区,JC,JN-1,JN-2和JN-3活化能分别为115kJ/mol,57kJ/mol,70kJ/mol和97kJ/mol,与等转化率法所求得的平均活化能相近.随着煤焦转化率的增大,反应越来越困难,活化能也在增大,而且煤焦燃烧反应离开化学反应动力区的转捩温度也在升高.     

煤焦CO_2气化的热重分析研究 （Ⅰ）等温热重研究

运用等温热重技术，对三种不同煤化度的煤焦，在９５０～１４００℃温度区内进行了ＣＯ_２气化研究，考察了这三种煤焦在不同气化温度下的活性变化，并对动力学计算的结果进行了讨论，研究发现，气化温度对煤焦气化速率的影响程度不同，１１００℃以下反应为。动力学控制阶段，１１００℃以上逐步过渡为扩散控制阶段，在高的气化温度下，反应速率增大，表现活化能值降低。     

半焦对富含甲烷气体转化制备合成气的作用（Ⅳ）理论分析半焦表面含氧官能团的催化机理

运用密度泛函理论方法研究了煤焦表面典型含氧官能团与甲烷的作用机理,分析了煤焦含氧官能团上氧的电荷分布、Fukui指数和变形密度等参数.结果表明,煤焦表面含氧官能团＼中,内酯和酸酐中 C=O结构上氧的电荷相对较大,为化学反应的活性位点.在煤焦与甲烷的反/＼应中,内酯和酸酐中 C=O上的氧为申烷活化脱氢的活性位置.甲烷进攻内酯氧反应的动力学计/算显示,反应活化能为94.50 kJ/mol,与实验值96 kJ/mol吻合.     

生物质玉米芯热解机理研究

利用热重分析方法对生物质玉米芯在不同条件下热解行为进行了详细研究 ,得出了影响热解过程的因素及热解动力学参数 (如表观活化能、反应级数及指前因子等 ) .结果表明 ,所选保护气的种类对热解过程基本上不产生影响 ;同在较低的气体流速下进行热解相比较 ,在较高的流速下进行热解 ,发生分解反应需要较高的起始分解温度、最大分解速率的温度及较高的反应活化能 ,反应级数也大 ;随着加热速率的增大 ,发生分解反应的最大分解速率的温度向高温处移动 ,但反应的活化能降低 ,反应级数减小 .在实际的热解过程中 ,采用快速加热、低流速的惰性保护气进行热解 ,有利于利用热解过程的各种产物 .     

苯并环丁烯封端的聚酰亚胺树脂的流变行为研究

用旋转流变仪研究了苯并环丁烯封端的聚酰亚胺树脂体系固化过程中的化学流变行为,用动态和静态两种方法分析了其固化过程,发现存在三个固化阶段,用Arrhenius方程确定了固化前的表观物理粘流活化能为195.9kJ/mol.并用Roller法确定固化反应过程中表现化学粘流活化能和表现固化反应活化能,分别为148.2kJ/mol和161.2kJ/mol.结果表明,在整个固化成型工艺温度范围内,苯并环丁烯封端的聚酰亚胺树脂的粘度特性符合Roller模型方程,通过该模型可较好地预测该树脂在固化过程中的粘度特性.     

可发泡性酚醛树脂的合成研究

考查了可发泡性酚醛树脂的合成条件,如反应时间、温度和催化剂用量等对树脂活性、物理以及酚醛泡沫塑料容重和表观品质的影响,结果表明:催化剂用量越大,树脂粘度越大,泡沫固化时间越长;反应时间介于65～95min,泡沫塑料容重和表观品质较好;用加热板测定了合成的可发泡性树脂的固化速度,并求出固化反应活化能。     

EFFECTS OF SELECTED CATALYSTS ON KINETIC PARAMETERS OF THE CARBON-STEAM REACTION

A comparison has been made between the catalytic effects of two groups of elements on the steam gasification of carbon: the alkaline earths and noble transition metals of Group VIII. Spectroscopically pure graphite was selected as a model carbon because it consists of well-defined crystals with a large number of atoms located in basal planes, which, without a catalyst, are of low reactivity. Moreover, foreign atoms which can enhance or inhibit catalysis are eliminated. Local overheating is prevented by the endothermic reaction with steam.

It is not possible to distinguish unambiguously reaction-rate increases associated with a lowering of the activation energy and those caused by an increase of the reaction-site density. Thus conclusions about the mode of catalyst action are by necessity tentative. However, evidence from electron micrographs, in connection with elemental maps and theoretical calculations indicates that catalysis in the case of alkaline earths can be explained essentially by an increase of the reaction-site density. A close contact between these catalysts and the carbon surface is preserved during the reaction. In contrast, metals of Group VIII have a tendency to coalesce and to become isolated from the graphite surface. Here a lowering of the activation energy is a distinct possibility due to intercalation of these metals and weakening of the C-C bonds which are to be severed in the carbon gasification.     

EFFECTS OF SELECTED CATALYSTS ON KINETIC PARAMETERS OF THE CARBON-STEAM REACTION

A comparison has been made between the catalytic effects of two groups of elements on the steam gasification of carbon: the alkaline earths and noble transition metals of Group VIII. Spectroscopically pure graphite was selected as a model carbon because it consists of well-defined crystals with a large number of atoms located in basal planes, which, without a catalyst, are of low reactivity. Moreover, foreign atoms which can enhance or inhibit catalysis are eliminated. Local overheating is prevented by the endothermic reaction with steam.

It is not possible to distinguish unambiguously reaction-rate increases associated with a lowering of the activation energy and those caused by an increase of the reaction-site density. Thus conclusions about the mode of catalyst action are by necessity tentative. However, evidence from electron micrographs, in connection with elemental maps and theoretical calculations indicates that catalysis in the case of alkaline earths can be explained essentially by an increase of the reaction-site density. A close contact between these catalysts and the carbon surface is preserved during the reaction. In contrast, metals of Group VIII have a tendency to coalesce and to become isolated from the graphite surface. Here a lowering of the activation energy is a distinct possibility due to intercalation of these metals and weakening of the C-C bonds which are to be severed in the carbon gasification.     

煤燃烧时形态硫的析出及钙基添加剂的作用

在固定床反应器上进行了大同烟煤以及添加钙基固硫剂的样品在不同氧气浓度、不同升温速率下的燃烧实验.对所得到的SO₂逸出曲线采用Gaussian拟合,得到了各形态硫燃烧形成SO₂的温度范围以及影响形态硫逸出的反应条件.结果表明：随着升温速率增加,各形态硫燃烧释放SO₂的温度向高温区移动.氧气浓度升高,各形态硫燃烧释放SO₂的温度提前,而且它们之间的温度间隔缩小.加入的钙基添加剂中,CaO和Ca(OH)₂具有较高的固硫能力,而CaCO₃由于与SO₂反应困难,在低温阶段没有固硫效果;相反,由于它的催化作用,在低温阶段甚至促进了SO₂的释放.机械搅拌法和超声搅拌法加入的Ca (OH)₂由于高分散性,表现出比机械混合更好的固硫效果,其中超声的作用尤其明显.实验证明,固硫中间体CaSO₃在进一步燃烧形成CaSO₄的过程中会释放出一定量的SO₂.     

Kinetic studies of graphon and coal-char reaction with NO and O2: direct non-linear regression from TG curves

The reactions of carbonaceous materials (graphon and coal-char) with NO, O₂ and NO+O₂ were investigated by a thermogravimetric analysis (TGA). A method of direct non-linear regression of the kinetic equation was applied for a simultaneous calculation of the apparent activation energy, frequency factor and reaction order from a single TG curve of carbon gasification in various atmospheres. It was proven that the proposed calculation method is applicable for the calculation of kinetic parameters from overlapping processes. Calculations from TG curves of the above reactions demonstrate that NO-carbon and (NO+O₂)-carbon reactions contain two processes, while O₂-carbon is a single process. The reaction order of O₂-carbon is approximate 0.5, while the reaction orders of NO-carbon or (NO+O₂)-carbon reaction are dependent on the process and type of carbon. Graphon shows higher apparent activation energy than coal-char due to the pore structure and uncatalysed effects.     

纤维表面冷等离子体处理对其表面性能的影响

本文采用冷等离子体技术来处理碳纤维、芳纶纤维与聚酯纤维，处理后纤维表面活性基团、浸润量与浸润速度增大，而接触角与浸润过程活化能降低，说明纤维浸润性是得到了很大的改善。     

非等温动力学研究煤的着火特性

以乌煤和自洗蒙古煤为原料,采用TG-DTG法,应用非等温动力学方法研究了升温速率和粒径对煤着火特性的影响,并得出两种煤燃烧过程的动力学参数.根据煤燃烧产物释放特性指数R的大小来确定煤的燃烧性能.在实验条件下得出以下结论:1)乌煤在升温速率较低时,挥发分释放特性指数R值大,燃烧特性好,对煤着火有利;而升温速率对自洗蒙古煤的燃烧性能影响不大;2)乌煤:粒径0.2 mm～0.3 mm失重量最大,粒径小于0.15 mm和0.15 mm～0.2 mm失重量基本一致.自洗蒙古煤:粒径0.2 mm～0.3 mm失重量最小,粒径小于0.15 mm失重量和0.15 mm～0.2 mm失重量基本一致;3)通过对两种煤燃烧过程的动力学分析,得出乌煤燃烧过程的活化能高于自洗蒙古煤.     

Plasmonic energy transformation in the photocatalytic oxidation of ammonium

The plasmonic transformation of light into energy for a chemical reaction is demonstrated in the endothermic oxidation of ammonium ions. The plasmonic heating effect physically triggers a platinum thin film, which becomes an active catalyst for the plasmonic catalytic reaction. The amount of chemical energy consumed in the plasmonic photocatalytic reaction was less than that in the normal chemical process. A homogeneous, condensed, pinhole-less 8 nm platinum thin film fabricated via plasma-enhanced atomic layer deposition served as a medium that transformed the energy in two steps.