煤焦加压水蒸气催化气化反应特性及甲烷释放规律研究

以内蒙褐煤焦为研究对象,K_2CO_3为催化剂,在小型加压固定床上考察了反应温度、操作压力和水碳比对煤焦水蒸气气化反应过程中碳转化率、反应速率和甲烷浓度及其累计流量的影响。结果表明,随着反应温度的增加,碳转化率和反应速率显著增加,甲烷浓度及其累计流量也增加,表明甲烷化反应在600~700℃内仍受动力学控制。操作压力的提高,碳转化率和反应速率呈先增加后减小的变化趋势,而甲烷的浓度逐渐增加,其累计流量由常压下的2.4 mL逐渐增加至3.5 MPa下的43.2 mL。随着水碳比的增加,碳转化率和反应速率大幅增加,但是甲烷的浓度逐渐降低,甲烷的累计流量受反应速率和反应平衡的共同影响,呈先增加后减小的趋势。     

煤焦加压水蒸气催化气化反应特性及甲烷释放规律研究

以内蒙褐煤焦为研究对象,K_2CO_3为催化剂,在小型加压固定床上考察了反应温度、操作压力和水碳比对煤焦水蒸气气化反应过程中碳转化率、反应速率和甲烷浓度及其累计流量的影响。结果表明,随着反应温度的增加,碳转化率和反应速率显著增加,甲烷浓度及其累计流量也增加,表明甲烷化反应在600⁷00℃内仍受动力学控制。操作压力的提高,碳转化率和反应速率呈先增加后减小的变化趋势,而甲烷的浓度逐渐增加,其累计流量由常压下的2.4 mL逐渐增加至3.5 MPa下的43.2 mL。随着水碳比的增加,碳转化率和反应速率大幅增加,但是甲烷的浓度逐渐降低,甲烷的累计流量受反应速率和反应平衡的共同影响,呈先增加后减小的趋势。     

微波辐射下污泥残渣催化甲烷裂解制氢

采用石英管固定床反应器,在微波加热条件下分别研究了不同功率、气氛条件、粒径以及进口甲烷浓度对污泥残渣催化甲烷裂解反应的影响。结果表明,污泥残渣对甲烷裂解反应具有良好的催化活性;增加微波功率和减小粒径均能够有效提高甲烷转化率;污泥残渣在不同气氛条件下表现出不同的温度特性,其中氮气和氢气氛围内的温度明显高于甲烷气氛中,表明甲烷裂解过程中气氛条件是影响反应进行的因素之一;进口甲烷浓度越高,甲烷的转化率越大。反应前后污泥残渣电镜扫描分析及物性参数的比较表明,甲烷裂解后产生的大量积炭覆盖在污泥残渣表面,导致比表面积降低、平均孔径增大,表明污泥残渣活性降低的原因可能与积炭覆盖表面,导致甲烷分子无法与活性中心接触所致。     

介质阻挡放电微等离子体分解二氧化碳研究

二氧化碳既是主要的温室气体之一,也是包含碳和氧的资源,把相对惰性的CO₂转化为易于利用的CO是其利用的方法之一。采用介质阻挡微等离子体反应器通过单变量和正交实验探究了反应器参数(放电区长度、放电间距、介质厚度)和工艺参数(输入功率、放电频率和停留时间)对CO₂分解为CO的转化率和能量效率的影响规律。研究结果表明,影响CO₂转化率的大小顺序依次为：放电间距>放电长度>输入功率≈停留时间>介质厚度>放电频率;输入功率60.0 W、放电频率9.0 kHz和停留时间1.5 s、放电区长度60 mm、放电间距0.5 m、介质厚度1.6 mm时,CO₂的转化率为10.6%,能量效率为4.1%。     

直流电弧等离子体甲烷二氧化碳重整反应

采用一种简单结构的直流电弧反应器,在无催化剂存在的条件下,高效率地实现了毫秒级甲烷二氧化碳的重整反应,产物选择性好,并且在反应过程中几乎没有积炭生成。在恒定输入功率(170W)的条件下考察了气体总流量和二氧化碳/甲烷摩尔比对反应结果的影响。提高反应气体的输入能量密度可以提高甲烷和二氧化碳的转化率,并且能够有效地抑制副产物的生成。当二氧化碳/甲烷摩尔比为1时,二氧化碳转化率为89.8%,甲烷转化率为96.3%,氢气和一氧化碳的选择性分别为99.6%和99.3%。二氧化碳过量可显著促进甲烷的转化以及同时获得合成气的高选择性。采用比能耗对该过程的能量利用效率进行了分析,以期指导反应条件优化以提高过程的能量利用效率。     

煤焦中灰成分对甲烷裂解的影响

利用煤焦作为催化剂,采用小型石英管固定床为反应装置,对甲烷在煤焦、脱灰煤焦、煤灰以及石英砂床层上在温度为1123 K下的裂解反应进行了较为详细的研究。甲烷在脱灰煤焦上和新鲜的褐煤焦上的转化率和氢气收率有一定的差别。煤灰作为催化剂时,甲烷初始转化率和氢气初始收率分别为9.81%和8.14%。表明煤焦中的灰成分对甲烷裂解有一定的影响。随着反应时间的增加,甲烷的转化率和氢气的收率都逐渐降低。通过扫描电子显微镜和比表面积测定仪对反应前后的褐煤焦、脱灰煤焦进行了表征。甲烷裂解后煤焦比表面积、微孔容都明显降低,平均孔径增大。说明甲烷裂解生成的积炭堵塞煤焦的微孔。SEM照片显示甲烷裂解后积炭覆盖在煤焦的表面,使煤焦的催化活性逐渐降低。     

焦油热解反应模拟研究

为了考察焦油的热解情况,基于芳香族化合物的热解反应及其动力学参数,构建以萘、甲苯、苯酚的混合物作为焦油模型化合物的热解模型,考察温度、压力、停留时间以及气氛对焦油热解过程的影响。结果表明,随着温度、停留时间以及压力的增加,焦油热解的转化率呈现不同程度的增加。在900～1100℃之间,焦油转化速率基本恒定;停留时间达到6 s、压力增至1 MPa以后,焦油转化速率逐渐降低。不同的反应气氛对焦油热解过程也有着不同影响,CO_2和水蒸气对焦油热解过程有着促进作用,水蒸气的促进作用更加显著,且水蒸气对抑制积炭形成有着显著效果;CO对焦油热解过程影响很小;H_2对焦油热解过程有抑制作用。     

太阳能甲烷干重整复杂反应体系的热化学储能特性

基于热力学第一和第二定律对太阳能甲烷干重整复杂反应体系的热力学特性进行建模分析,研究该体系在不同太阳光照强度时的反应器温度响应及热化学储能特性,以及副反应和各部分能量损失对整个体系能量效率的影响规律。通过平衡常数法计算反应器平衡状态时的物质组成,并进而利用热力学模型计算不同条件下入口气转化率、选择性、功效率和能量转换效率的变化规律。结果表明：进料比n(CO₂)/n(CH₄)的升高有助于提高甲烷转化率、选择性、功效率和能量转换效率;反应器温度的变化对系统热化学储能特性的影响显著,在较低温区（923～1123K）,副反应较多,且随着温度的升高副反应逐渐受到抑制,积炭减少,功效率和能量转换效率逐渐升高,并在1123K时达到峰值;温度继续升高（>1123K）,反应器辐射损失显著增加,导致功效率和能量转换效率随温度升高而降低;高温区（>1200K）,副反应受到抑制,复杂反应体系的系统效率同单一反应体系趋于一致,副反应基本对系统性能无影响。     

煤基合成气甲烷化反应过程的热力学计算与分析

建立了煤基合成气甲烷化反应过程基于吉布斯自由能最小法的热力学计算模型。考察了温度、压力对CO,CO_2单独及同时甲烷化反应的影响,探讨了原料气脱碳处理后,CO_2摩尔分数对CO转化率、CH_4选择性、CH_4产率及积炭的影响。结果表明,低温高压有利于甲烷化反应。在多数情况下CO转化率要高于CO_2,尤其是温度低于600℃时,CO甲烷反应比CO_2更容易发生;随着温度进一步升高,CO_2转化率明显上升,而CO转化率迅速下降。另外,当原料气中CO_2摩尔分数低于2.44%时对积炭无影响,对CH_4的选择性和产率降幅小于10%,在脱碳工艺中可以不予脱除。     

熔铁催化剂超临界相费托合成的研究

在固定床反应器上进行了熔铁催化剂在超临界介质存在条件下的费托合成,并与气相费托合成进行对比。结果表明,由于超临界介质具有类似气体的传质速率和类似液体的溶解能力和热容,减小了催化剂床层过热,减少了催化剂床层积炭,增加了合成气在催化剂表面浓度,促进了产物的脱附,使CO转化率提高,α-烯烃选择性和C5＋选择性增加,甲烷选择性减小。实验考察了温度、压力、合成气比例、合成气空速对超临界相费托合成反应的影响。发现当反应温度或压力低于介质的临界温度及压力时,反应性能迅速下降,说明介质仅在其临界点以上才表现出优良的超临界性能。其他反应条件对超临界相费托合成反应性能的影响类似气相费托合成。     

Conversion of methane through dielectric-barrier discharge plasma

Methane coupling to produce C₂ hydrocarbons through a dielectric-barrier discharge (DBD) plasma reaction was studied in four DBD reactors. The effects of high voltage electrode position, different discharge gap, types of inner electrode, volume ratio of hydrogen to methane and air cooling method on the conversion of methane and distribution of products were investigated. Conversion of methane is obviously lower when a high voltage electrode acts as an outer electrode than when it acts as an inner electrode. The lifting of reaction temperature becomes slow due to cooling of outer electrode and the temperature can be controlled in the expected range of 60°C–150°C for ensuring better methane conversion and safe operation. The parameters of reactors have obvious effects on methane conversion, but it only slightly affects distribution of the products. The main products are ethylene, ethane and propane. The selectivity of C₂ hydrocarbons can reach 74.50% when volume ratio of hydrogen to methane is 1.50.     

甲烷与正丁烷微小尺度催化燃烧性能比较

对微圆管内甲烷和正丁烷在Pt/ZSM-5上的催化燃烧进行实验研究,获得并分析了二者的稳燃范围、产物浓度、壁温分布和壁面散热等燃烧性能。发现在富燃条件下甲烷和正丁烷能够在大当量比下实现催化自稳燃烧。相同流量下正丁烷稳燃当量比范围宽于甲烷,贫燃范围在0.4附近。流量由200 ml·min^-1增大至1000 ml·min^-1,甲烷和正丁烷转化率出现大幅下降。在实验范围内,正丁烷和甲烷的转化率差异不大。化学当量比条件下随流量增大,正丁烷的转化率在600 ml·min^-1开始高于甲烷。甲烷和正丁烷能够在散热比例高达70%的情况下自稳催化燃烧且转化率在95%以上。相同流量下,与甲烷相比,正丁烷催化燃烧的壁温、散热功率和散热比例都更高。整体来看,正丁烷催化稳燃范围较甲烷略宽,两者转化率曲线相近,放热功率和壁面散热功率相差较小,正丁烷在必要时可作为甲烷的替代燃料。     

Direct nonoxidative conversion of methane to hydrogen and higher hydrocarbons by dielectric barrier discharge plasma with plasma catalysis promoters

Direct nonoxidative conversion of methane to hydrogen and hydrocarbons was achieved at atmospheric pressure and 120°C using nonthermal plasma sustained by plasma catalysis promoters (PCPs). Reactors had two different electrode configurations. Methane conversion correlated well with the specific energy density (SED). Methane conversion was independent of plasma power, flow rate, electrode configuration, or the type of PCPs. Hydrogen selectivity (ca. 60%) was dependent significantly on PCP and electrode configuration. The ethane/ethylene molar ratio increased from 0 to 0.15 with increasing SED. When the SED value was below ca. 100 kJ/L, ethylene was the only C₂ hydrocarbon. These results are similar to the recently reported nonoxidative catalytic methane conversion at ca. 1000°C. Therefore, these results represent process intensification in methane conversion. PCPs underwent structural and chemical changes but their performances are not affected during an 80‐h experimental period. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4418–4429, 2017     

Conversion of methane through dielectric-barrier discharge plasma

Methane coupling to produce C₂ hydrocarbons through a dielectric-barrier discharge (DBD) plasma reaction was studied in four DBD reactors. The effects of high voltage electrode position, different discharge gap, types of inner electrode, volume ratio of hydrogen to methane and air cooling method on the conversion of methane and distribution of products were investigated. Conversion of methane is obviously lower when a high voltage electrode acts as an outer electrode than when it acts as an inner electrode. The lifting of reaction temperature becomes slow due to cooling of outer electrode and the temperature can be controlled in the expected range of 60°C–150°C for ensuring better methane conversion and safe operation. The parameters of reactors have obvious effects on methane conversion, but it only slightly affects distribution of the products. The main products are ethylene, ethane and propane. The selectivity of C₂ hydrocarbons can reach 74.50% when volume ratio of hydrogen to methane is 1.50. __________ Translated from Petrochemical Technology, 2007, 36(11): 1099–1103 [译自: 石油化工]     

The simultaneous activation of methane and carbon dioxide to C2 hydrocarbons under pulse corona plasma over La2O3/γ-Al2O3 catalyst

The pulse corona plasma has been used as an activation method for reaction of methane and carbon dioxide, the product was C₂ hydrocarbons and by-products were CO and H₂. Methane conversion and the yield of C₂ hydrocarbons were affected by the carbon dioxide concentration in the feed. The conversion of methane increased with increasing carbon dioxide concentration in the feed whereas the yield of C₂ hydrocarbons decreased. The synergism of La₂O₃/γ-Al₂O₃ and plasma gave methane conversion of 24.9% and C₂ hydrocarbons yield of 18.1% were obtained at the power input of plasma was 30 W. The distribution of C₂ hydrocarbons changed by using Pd-La₂O₃/γ-Al₂O₃ catalyst, the major C₂ product was ethylene.     

A kinetic study on the conversion of methane to higher hydrocarbons in a radio-frequency discharge

This study investigated methane conversion with direct current discharge at low pressure in a radio frequency. The main gaseous products of the reaction were ethane, ethylene, acetylene and propane. This study was concentrated on the influence of discharge conditions on the conversion of methane to higher hydrocarbons. Reaction temperature, electron density and mean residence time were calculated from experimental data and mathematical relations. The maximum conversion of the methane was about 45% with the pure methane as a reactant. Ethane was the main product when the reaction occurred in the glow discharge. Ethane selectivity decreased with the increase of the gas temperature. The kinetics of reactions was also analyzed from possible reaction equations and various rate constant data. Consequently, the dissociation constant and the density of radicals could be obtained at any experimental conditions.     

Plasma methane conversion using dielectric-barrier discharges with zeolite A

Experimental investigation on plasma methane conversion in the presence of carbon dioxide using dielectric-barrier discharges (DBDs) has been conducted. Zeolite A has been applied to inhibit the formation of carbon black and plasma-polymerized film during such plasma methane conversion. A co-generation of syngas, light hydrocarbons and liquid fuels has been achieved. The conversions and selectivities are determined by the CH₄/CO₂ feed ratio, residence time and input power. Compared to the use of zeolite X within the DBDs, plasma methane conversion with zeolite A leads to a higher selectivity of light hydrocarbons (C₂–C₄).     

Decomposition of CH4 over supported Ir catalysts

The decomposition of methane and its conversion into higher hydrocarbons have been investigated on supported Ir catalysts. The effects of temperature, flow rate and support materials have been examined. The interaction of CH₄ with iridium has been observed at as low a temperature as 473 K. As a result, hydrogen, a small amount of ethane and surface carbonaceous species were produced. With increase of the temperature, the extent of the decomposition significantly increased. At 773 K, the initial conversion varied between 2.0–5.0%, which decreased to low values in a short reaction time. Taking into account the dispersion of Ir, the most effective sample in the decomposition of CH₄ was Ir/MgO. By means of Fourier transform infrared spectroscopy adsorbed CH₃ was identified as a reaction intermediate of methane decomposition. Temperature programmed reactions revealed that the reactivity of surface carbon produced in the decomposition of CH₄ depends on the nature of the support. Hydrogenation of the most reactive carbonaceous species led to the production of aliphatic hydrocarbons up to six carbon atoms.     

利用介质阻挡放电水蒸汽重整甲烷的转化率

Conversion of methane by steam reforming was carried out by means of dielectric-barrier discharge. A systemic procedure was employed to determine the suitable experimental conditions. It was found that one of the plasma generators can match the system best. A higher power input can always bring a higher conversion, but the selectivity to C2H6 decreased from 52.48% to 39.43% as the power increased from 20W to 49W. When discharge distance was 4 mm, selectivities to almost all main products reached the max. The inner electrode made of stainless steel and the outer electrode with aluminum foil were one of the best options which can obviously enhance the conversion of methane. A larger flow rate always resulted in a lower conversion of methane. In the most time, 19.93% steam promoted conversion of methane.