Mixed reforming of heptane to syngas in the Ba0.5Sr0.5Co0.8Fe0.2O3 membrane reactor

Fuel cells are recognized as the most promising new power generation technology, but hydrogen supply is still a problem. In our previous work, we have developed a LiLaNiO/γ-Al₂O₃ catalyst, which is excellent not only for partial oxidation of hydrocarbons, but also for steam reforming and autothermal reforming. However, the reaction needs pure oxygen or air as oxidant. We have developed a dense oxygen permeable membrane Ba_0.5Sr_0.5Co_0.8Fe_0.2O₃ which has an oxygen permeation flux around 11.5 ml/cm² min at reaction conditions. Therefore, this work is to combine the oxygen permeable membrane with the catalyst LiLaNiO/γ-Al₂O₃ in a membrane reactor for hydrogen production by mixed reforming of heptane. Under optimized reaction conditions, a heptane conversion of 100%, a CO selectivity of 91–93% and a H₂ selectivity of 95–97% have been achieved.     

气相色谱法测定工业纯苯中微量正庚烷含量

选用合适的色谱柱,重新建立气相色谱分析方法,准确测定工业纯苯中微量正庚烷含量,满足公司原料分析计划的检测要求。通过选择色谱柱型号,改变柱温、载气流速等参数,优化气相色谱条件,使杂质组分达到最佳分离。采用色谱柱为CP7773毛细管柱,氮气为载气,分流比为20∶1,运用程序升温模式,外标法测定正庚烷含量。得到线性回归方程为y=1.011x+0.666,相关系数r=0.999,标准偏差小于0.4(n=8),平均回收率为99.80%~101.20%。     

正庚烷HCCI燃烧下芳香烃及多环芳烃形成的多维数值研究

将发动机多维CFD程序KIVA-3V与化学动力学程序CHEMKIN III相耦合,对正庚烷HCCI燃烧下芳香烃(苯)与多环芳烃(萘、菲及芘)的生成及演变规律进行了详细分析.发动机以正庚烷为燃料,其化学反应采用了正庚烷的燃烧与分解、多环芳烃生成的详细反应机理.结果表明在缸内混合气着火前,A1(苯)的质量浓度场较不均匀,在缸中心区域A1质量浓度较高,而在边界层及缝隙区则相对较低;然而在缸中心区域及缝隙区,A2(萘)、A3(菲)与A4(芘)的质量浓度场较低,而在边界层区则相对较高.在缸内混合气着火后,在缸中心区域及边界层区,A1～A4质量浓度较低,而在缝隙区则相对较高.混合气着火后短暂时间内为A1～A4生成的高峰期,在经历高峰期后A1～A4质量平均浓度迅速降低.同时,在排气门打开(120°CA ATDC)时,在这4种芳香烃与多环芳烃中,苯的排放量最高,萘其次,而芘的排放量则最低.     

SEPARATION OF AROMATIC AND ALIPHATIC HYDROCARBONS WITH IONIC LIQUIDS

Naphtha cracker feeds may contain 10-25 wt% aromatic compounds. Removal of these aromatic compounds from the feed to the cracker would offer several advantages: higher capacity, higher thermal efficiency, and less coke formation. In this work, we investigated the separation of toluene from heptane by extraction with ionic liquids.

Several ionic liquids are suitable for extraction of toluene from toluene/heptane mixtures. The selectivities for the aromatic/aliphatic hydrocarbon separation with all ionic liquids tested increase with decreasing aromatic content in the feed. The toluene/heptane selectivities at 10% toluene in the feed at T = 40°C and 75°C with several ionic liquids ([emim]HSO₄, [mmim] methylsulfate, [emim] ethylsulfate, [bmim]BF₄, [emim] tosylate, [mebupy]BF₄, and [mebupy] methylsulfate) are a factor of 1.5-2.5 higher than those obtained with sulfolane, which is a conventional solvent for the extraction of aromatic hydrocarbons from a mixed aromatic/aliphatic hydrocarbon stream. The three most suitable ionic liquids from the ionic liquids tested for the separation of aromatic and aliphatic hydrocarbons are [mebupy]BF₄, [mebupy]CH₃SO₄, and [bmim]BF₄ and at 75°C also [emim] tosylate. The ionic liquid [mebupy]BF₄ is selected for further testing in our extraction pilot plant.

Because ionic liquids have a negligible vapor pressure, evaporating the extracted hydrocarbons from the ionic liquid phase could achieve the recovery of the ionic liquid. A conceptual process scheme for the extraction has been set up. Preliminary calculations show that both the investment costs and the energy costs will be considerably lower with ionic liquids than with sulfolane as the solvent.     

丁二烯在庚烷溶剂和镍基催化剂系统内的聚合行为

通过一系列聚合试验,对丁二烯在庚烷溶剂和镍基催化剂系统内的聚合行为进行了研究。认为：（１）该聚合的特点是快引发、慢增长、逐步加成、无终止;（２）诱导期外,聚合速度与单体浓度为一级关系;（３）增长链端的浓度不变。     

Effects of the ambient temperature and initial diameter in droplet combustion

Results are presented from transient numerical simulations of combustion of an isolated heptane (n-_C7H16${\mathrm{C}}_7{\mathrm{H}}_{16}$) droplet in nearly quiescent ambient air. The focus is on the effects of environment temperature and droplet size on the combustion characteristics. Droplet sizes range from 10 μm to 1 mm, environment temperatures range from 800 K to 1600 K, and pressure is 1 atm.     

塔里木盆地塔中地区原油轻烃组成特征及其意义

塔里木盆地塔中地区原油总体上相对富含链烷烃,贫芳烃,苯的含量很低,正己烷和己烷含量较高,处于高成熟阶段,所经历的最高温度为115~128℃,除个别井原油表现为高K1值外,其他样品K1值与M ango所做的结论一致。     

Steady-state modeling and bifurcation behavior of circulating fluidized bed membrane reformer-regenerator for the production of hydrogen for fuel cells from heptane

The production of hydrogen for fuel cells by steam reforming of heptane is investigated in a Circulating Fluidized Bed Membrane Reformer-Regenerator (CFBMRR) system (A.I.Ch.E. Journal 49(5) (2003) 1250). Palladium based hydrogen permselective membranes are used for hydrogen removal and dense perovskite oxygen permselective membranes are used for oxygen introduction. A series of pseudo-steady-state simulations show that when the catalyst is not regenerated, the circulating nickel reforming catalyst deactivates quickly and the “half catalyst activity life” for efficient production of hydrogen is quite short, especially at high temperatures. Efficient continuous catalyst regeneration can keep the catalyst activity high (∼1.0). With continuous catalyst regeneration, autothermal operation for the entire adiabatic reformer-regenerator system is achievable when the exothermic heat generated from the catalyst regenerator is sufficient to compensate for the endothermic heat consumed in the riser reformer. This type of autothermal operation becomes less likely at high steam to carbon feed ratios. This is due to the fact that carbon deposition rate decreases leading to the decrease of autothermal circulating feed temperature and energy-based hydrogen yield (adiabatic hydrogen yield in autothermal reformer-regenerator system). Multiplicity of the steady states for the reformer is possible for this configuration. With the steam to carbon feed ratio as the bifurcation parameter, multiplicity occurs between the two bifurcation points 1.444 and 2.251 mol/mol. In this multiplicity region, the energy-based hydrogen yield at the upper steady state with high regenerator output temperature is surprisingly the lowest one. While it is the highest one at the lower steady state with low regenerator output temperature. The maximum energy-based hydrogen yield is about 15.58 moles of hydrogen per mole of heptane fed at the lower steady-state when steam to carbon feed ratio is very close to the bifurcation value of 1.444 mol/mol. After removing the sweep gas steam by downstream cooling and de-humidification, the product hydrogen from steam reforming of hydrocarbons can be used for fuel cells with high purity (∼100%).     

Selective formation of light olefin by n-heptane cracking over HZSM-5 at high temperatures

The catalytic cracking of n-heptane has been performed over HZSM-5 catalysts with various Si/Al ratios at 723-923 K to form light olefins selectively. The HZSM-5 zeolites with various acid site densities exhibited almost the same selectivity at the same conversion. The ethylene + propylene selectivity increased, while the propylene/ethylene ratio decreased with an increase in reaction temperatures. It is found that a high temperature is required to obtain a high ethylene + propylene yield. The highest ethylene + propylene yield obtained in this study was 59.7 C-% with a propylene/ethylene ratio of ca. 0.72 at 99.6% conversion over HZSM-5 (Si/Al = 31) at 923 K. Moreover, it is concluded from the selectivities and activation energies that the monomolecular cracking is predominant at a high temperature as 923 K.     

塔中北斜坡原油轻烃组成及地球化学特征

塔中北斜坡原油为低硫、低蜡的典型腐泥型母质来源的原油，其苯含量低，正己烷和环己烷含量较高，正庚烷含量高，二甲基环戊烷含量极低，说明藻类和细菌是主要的烃源。该斜坡原油的Mango轻烃参数K1值主要分布在1左右，平均值为1.11，除个别井（塔中24井）K1值偏离较大之外，基本上与Mango所做结论一致；K₂值普遍较低，平均值为0.21，为典型的海相油特征；原油庚烷值大于30%，异庚烷值也大于2.0，表明原油已处于高成熟阶段。