利用催化加氢热解技术提取沉积 有机质中生物标志化合物

利用催化加氢热解技术提取了高演化沉积有机质中共价键结合的生物标志化合物,探讨了干酪根催化加氢热解反应机理,并考察了反应产物分布和影响反应的关键变量.实验表明,程序升温固定床催化加氢热解反应条件:温度上限为520℃,升温速率为5℃/min,氢压大于10MPa,氢气流量为5L/min,分散型催化剂为MoS₂(Mo的质量分数为1%).实验结果表明,催化加氢热解对提取高产率、结构重排少的干酪根中共价键结合的生物标志化合物有独特作用,该方法可以应用于有机地球化学领域.     

氢气预处理对煤加氢热解脱硫的影响

在固定床反应器中,研究了氢气预处理对兖州煤和大同煤加氢热解脱硫的影响.煤样首先在200～400 ℃,2 MPa,氢气体积流量1 L/min下预处理30 min,再在650℃,2MPa,氢气体积流量1 L/min下进行加氢热解20 min.研究结果表明:同直接加氢热解相比,氢气预处理会降低半焦和水的收率,同时会使焦油收率和脱硫率增加.在直接加氢热解中,大同煤和兖州煤半焦中硫的质量分数分别是2.07%和1.07%;而经适宜的氢气预处理后,其硫的质量分数分别降至1.93%和0.55%,对兖州煤和大同煤而言,其适宜的预处理温度分别为250℃和350℃.     

Comparative reactivities of coal asphaltenes during hydropyrolysis

Comparisons have been drawn in the relative reactivities of three coal asphaltenes during hydropyrolysis. All were derived from hydrogen donor-solvent extracts of bituminous coal, but had different hydrotreatment histories and different carbon contents (87.1, 91.9 and 90.8 wt% for asphaltenes 1, 2 and 3, respectively). The hydropyrolyses were carried out in the presence of CoO–MoO₃ catalyst and gaseous hydrogen at 8.7 MPa. For two of the asphaltenes (1 and 2) systematic comparisons were made for different reaction times at 425°C; for all three asphaltenes comparisons were made for l h of hydropyrolysis at 425°C. The general pattern of asphaltenes conversion indicated that more pentane-soluble product was produced from asphaltene isolated from straight coal extract (asphaltene 1). For the asphaltenes isolated from hydrotreated extracts, the extent of conversion to liquids was limited when the carbon content was high (asphaltene 2) although the pattern of conversion was similar in the other hydrotreated asphaltene (asphaltene 3). The aliphatic content of the liquid products formed was low, and the distribution of hydrogenated species in the highly aromatic liquid products indicated that complete hydrogenation of the polyaromatics produced in pyrolysis is difficult. Altogether the aliphatics made up ≈ 10 wt% of the asphaltene 1 hydropyrolysate. Aromatic hydrocarbons made up 90% of the liquid product. Phenanthrene, pyrene and anthracene were prominent, and the largest component in the mixture was phenanthrene which, together with other polyaromatics such as fluoroanthene, dominated the liquid product.     

Sulfur transformation during rapid hydropyrolysis of coal under high pressure by using a continuous free fall pyrolyzer☆

The behavior of sulfur transformation during rapid hydropyrolysis of coal was investigated using a pressurized, continuous free fall pyrolyzer under the conditions of temperature ranging from 923 to 1123 K and hydrogen pressure up to 5 MPa. The yields of sulfur converted to gas, tar and char were determined, together with the analyses of sulfur form distributions in coals and chars. The results showed that the decomposition of inorganic sulfur species was affected only by the temperature, while the increases in temperature and hydrogen pressure obviously enhanced the removal of organic sulfur from coal. The extent of organic sulfur removal was proportional to the coal conversion, depending on coal type. A significant retention of gaseous sulfur products by the organic matrix of the char was observed during hydropyrolysis of a Chinese coal above 1023 K, even under the pressurized hydrogen atmosphere. The kinetic analysis indicates that the rate of organic sulfur removal from coal was 0.2th-order with respect to the hydrogen pressure, and the activation energy for total sulfur removal and organic sulfur removal is 17-26 and 13-55 kJ/mol, respectively. The low activation energies suggest that the transformation and removal of sulfur from coal might be controlled by the diffusion and/or thermodynamic equilibrium during hydropyrolysis under the pressurized conditions.     

煤加氢热解高效转化及过程脱硫脱氮效应

系统考察了煤非催化加氢热解反应特性及过程脱硫脱氮效应，通过调整工艺条件，煤加氢热解的焦油收率视煤种不同可高达５０％￣７０％，占煤热解总转化率的７０％￣８０％，表现出很高的选择性，而不同煤种热解过程的氢利用效率对氢压的变化均存在一个峰值压力。煤热解的过程总脱硫率可高达７０％以上，煤中几乎所有硫铁矿硫被脱除殆尽，残留在热解半焦中的微量硫的形态分布主要表现为硫酸盐硫，热解半焦为洁净固体燃料，而热解焦油的     

煤加氢热解脱硫作用及硫分析方法的研究

选取两种高硫煤进行加氢热解脱硫作用的研究．应用有机元素分析仪选择合适的标样与条件测定其原料、固态和液态产物中的硫含量达到了理想的分析精度．研究表明，加氢热解具有高效脱硫作用，但煤种不同其脱硫率、硫分布规律也有所不同．     

Thermobalance hydropyrolysis of a bituminous coal sample and its macerals vitrinite and exinite: structural analysis of the relevant tars

Thermobalance hydropyrolysis experiments are carried out on a highly volatile coal sample and its main macerals, vitrinite and exinite. The results are discussed according to the characterization of the tars using ultrasound solvent extractions, extrography, liquid chromatography, capillary gas chromatography and mass spectrometry.     

煤在H2/Ar等离子体热解过程中脱氮脱硫的研究

对几种中国煤在H₂/Ar等离子体热解过程中的脱氮脱硫进行了实验研究，结果表明:煤中氮在H₂/Ar等离子体热解过程中主要以HCN形式存在，也有少量氮转化为NH₃，脱氮率最高达50%；HCN的产率随煤种和输煤速率的变化而变化，NH₃的产率随输煤速率的增大变化不大，与煤种没有一定的对应关系；HCN的产率大于煤常规加氢热解，而NH₃产率(<1.5%)则相反；煤中氧含量较高时，HCN和NH₃的产率较低；煤中硫转化生成的H₂S产率随输煤速率的变化而变化，脱硫率最高达60%左右，煤等离子体热解反应后得到的焦样n(N)/n(C)和n(S)/n(C)都小于原煤.      

Zncl2 catalyzed flash hydropyrolysis of +525°C pitch from cold lake bitumen

Flash hydropyrolysis experiments have been performed on the vacuum bottoms fraction of Cold Lake bitumen, using zinc chloride as a catalyst. Milligram size samples of vacuum bottoms resid were heated rapidly (120–400°C/s) by passing a large electric current through the reactor tube. The variables studied included temperature, heating rate, catalyst/pitch ratio, vapour phase residence time and pressure. Temperature and catalyst/pitch ratio caused major changes in yields. In contrast pressure had little effect. It was found that high conversions could be obtained at hydrogen pressures which are much lower than those normally used in catalytically hydrocracking residual oils.     

Mineral matter effects on the rapid pyrolysis and hydropyrolysis of a bituminous coal: 2. Effects of yields of C3-C8 hydrocarbons

Effects of minerals on yields of C₃-C₈ volatiles from rapid pyrolysis of a Pittsburgh Seam bituminous coal were investigated. Whole, demineralized, and mineral-treated samples of pulverized coal were heated in 101 kPa He or 6.99 MPaH₂ at 1000 K s⁻¹ to temperatures of up to 1300 K. Yields of C₃, C₄–C₆, and C₆–C₈ hydrocarbon gases were determined as a function of time-temperature history. Calcium minerals decrease yields of all three fractions in pyrolysis under He atmosphere but have little effect on hydropyrolysis. Kaolinite reduces yields in pyrolysis, but increases them in hydropyrolysis. Other minerals, notably FeSO₄, have varying effects on product yields depending on run conditions.