Isomerization of n-hexane over mono- and bimetallic Pd–Pt catalysts supported on ZrO2–Al2O3–WOx prepared by sol–gel

The catalytic performance of mono- and bimetallic Pd (0.6, 1.0 wt.%)–Pt (0.3 wt.%) catalysts supported on ZrO₂ (70, 85 wt.%)–Al₂O₃ (15, 0 wt.%)–WO_x (15 wt.%) prepared by sol–gel was studied in the hydroisomerization of n-hexane. The catalysts were characterized by N₂ physisorption, XRD, TPR, XPS, Raman, NMR, and FT-IR of adsorbed pyridine. The preparation of ZrW and ZrAlW mixed oxides by sol–gel favored the high dispersion of WO_x and the stabilization of zirconia in the tetragonal phase. The Al incorporation avoided the formation of monoclinic-WO₃ bulk phase. The catalysts increased their S_BET for about 15% promoted by Al₂O₃ addition. Various oxidation states of WO_x species coexist on the surface of the catalysts after calcination. The structure of the highly dispersed surface WO_x species is constituted mainly of isolated monotungstate and two-dimensional mono-oxotungstate species in tetrahedral coordination. The activity of Pd/ZrW catalysts in the hydroisomerization of n-hexane is promoted both with the addition of Al to the ZrW mixed oxide and the addition of Pt to Pd/ZrAlW catalysts. The improvement in the activity of Pd/ZrAlW catalysts is ascribed to a moderated acid strength and acidity, which can be correlated to the coexistence of W⁶⁺ and reduced-state WO_x species (either W⁴⁺ or W⁰). The addition of Pt to the Pd/ZrAlW catalyst does not modify significantly its acidic character. Selectivity results showed that the catalyst produced 2MP, 3MP and the high octane 2,3-dimethylbutane (2,3-DMB) and 2,2-dimethylbutane (2,2-DMB) isomers.     

Evidence for non-site-isolation in ZSM-5 from ion-exchange and catalytic studies

Ion exchange of HZSM-5 samples with alkali metal cations, using metal chloride solutions, results in partially exchanged zeolites, MHZSM-5, M = Li, Na, K or Cs. The degree of exchange is found to increase with increasing ionic radius of the cations. The catalytic properties of the alkalized zeolites were evaluated using the reaction conditions under which the catalytic activity of the HZSM-5 samples in terms of n-hexane cracking is proportional to the aluminium content. From the residual catalytic activity exhibited by the Na-, K- and CsHZSM-5 samples it is concluded that each of the larger Na⁺, K⁺ and Cs⁺ ions is influencing more than one AlO ₄ ^– tetrahedron, implying that the aluminium sites in ZSM-5 are not isolated. The ion-exchange results are then interpreted in terms of non-isolated aluminium sites. The ion-exchange and catalytic properties of the zeolites as a function of aluminium content are also discussed.     

固定化脂肪酶催化菜籽油合成蜡酯

以菜籽油、鲸蜡醇为原料,采用实验室自制的固定化Candidia sp.99-125脂肪酶分别在有机溶剂和无溶剂体系下合成了蜡酯,在两种体系下对影响蜡酯合成的各种因素进行了比较研究,研究表明:以正己烷为反应介质,在40℃条件下反应12h,油醇摩尔比1∶2,酶量15%(质量分数,上同),水含量7.5%,蜡酯产率可达85.87%;无溶剂体系中在50℃条件下反应20h,油醇摩尔比1∶1.5,蜡酯产率可达80.68%。通过流加鲸蜡醇可以提高酶的使用寿命。     

正己烷裂解反应自由基模型的理论研究

采用量子化学法研究了模型化合物正己烷裂解过程,并计算其动力学参数。依据自由基理论,建立由216个基元反应组成的正己烷裂解反应自由基模型,用CBS-QB3法计算链引发和终止反应动力学参数,用MPW1B95/6-311+G(2d,2p)法计算链增长反应动力学参数。根据动力学参数计算结果,忽略相对不重要的反应,将模型简化为160个基元反应。模拟计算表明,在相同的裂解条件下,简化模型模拟结果与完整模型模拟结果一致,各组分相差不大于0.1%wt;建立的动力学模型对主要产物收率预测较好,与实验值相差小于0.7%wt,可正确地预测正己烷裂解产物的组成和各组分含量沿反应管长度的分布,为进一步研究复杂的烃裂解过程提供了基础。     

正己烷在ZnNi／HZSM—5上微波芳构化

研究了常规加热和微波辐射两种加热方法对正己烷在ZnNi/HZSM-5催化剂上的芳构化反应的影响。考察了温度、空速对反应性能的影响,并利用XRD对ZnNi/HZSM-5催化剂作了表征。结果表明,金属锌和镍高度分散于HZSM-5沸石中,微波辐射对分子筛结构的影响很小。与常规加热反应相比,要达到相同的芳烃收率,在微波加热条件下能使反应温度降低约100℃左右。在一定程度上提高反应温度可以获得较高的总芳烃收率和BTX收率,亦能明显地改变BTX中各组分的相对选择性。改变空速能显著影响总芳烃收率和BTX收率,在常规加热和微波加热条件下的最佳空速分别为1.5h-1和1.0h-1。讨论了正己烷在微波辐射下ZnNi/HZSM-5上的芳构化反应机理。正己烷首先裂解为C03+C=3,一部分烯烃齐聚、环化生成芳烃,另一部分烯烃则经氢转移或加氢生成烷烃,C03和C04在锌和镍活性中心上直接脱氢二聚环化生成芳烃。     

顶空-气相色谱法测定食用油中苯和正己烷的残留量

采用顶空-气相色谱法测定食用油中苯和正己烷的残留量。选择顶空进样器的平衡温度和平衡时间分别为120℃和30 min;采用FID检测器,HP-5毛细管柱分离,顶空进样。重点考察了方法的线性、重复性、回收率和仪器的精密度。结果表明:苯和正己烷的线性范围分别为1.26~12.64μg、0.92~9.28μg,线性方程分别为Y=12.453X+11.15(r=0.999 6)、Y=82.56X+59.466(r=0.999 7);苯和正己烷的检出限分别为0.063 0、0.046 4μg/mL,加标回收率分别为96.2%(RSD=1.91%)、93.8%(RSD=1.63%)。该方法灵敏度高,定量准确,具有简单实用的特点,适合食用油中苯和正己烷的残留检测。     

正己烷在CGG-Ⅱ催化剂上非临氢异构化条件的考察

在石油工业中,作为提高汽油辛烷值的重要手段,烷烃异构化己经引起了广泛的关注.以正己烷为原料,采用CGG-Ⅱ催化剂,在WFD-3030微型反应器中进行异构化反应,考察在非临氢常压条件下,空速、温度等反应条件对正己烷异构化反应的影响.结果表明:随着反应温度的升高,正己烷的转化率提高,液体收率下降;随着空速(WHSV)的提高,正己烷的转化率降低,液体收率增加.在本实验条件范围内,正己烷异构化最佳反应条件为反应温度为380℃,质量空速为8 h-1,正己烷的转化率为71.85%,液体收率为80%,反应产物的研究法辛烷值为47.0,马达法辛烷值为46.8,与原料相比,辛烷值提高了25个单位.     

二噁类的紫外光降解——八氯代二苯并二噁和八氯代二苯并呋喃

运用多功能光化学反应仪,对八氯代二苯并二和呋喃(OCDD和OCDF)在正己烷中的紫外光解特性进行了研究.结果表明,OCDD及OCDF的降解主要是通过脱氯反应,OCDD在正己烷溶液中脱氯反应优先发生在侧位(2-,3-,7-,8-)上,而OCDF的光解脱氯反应优先发生在邻位(1-,4-,6-,9-)上.同时OCDD和OCDF在正己烷中的光解反应符合一级反应动力学.增加汞灯功率,可加快OCDF在正己烷溶液中的光解速度.     

Aromatization of n-Hexane Under Microwave Irradiation

Abstract

The aromatization of n-hexane over HZSM-5 and ZnNi/HZSM-5 catalysts has been investigated using two different heating methods: microwave irradiation (MW) and conventional heating (CH). The results indicate that the aromatics and BTX yields under MW are higher than those under CH. n-Hexane aromatization mechanism under MW was similar to that under CH at the temperature below 673 K. However, the mechanism of n-hexane aromatization was different at the temperature from 673 K to 753 K. The higher the reaction temperature is, the more condensed-nucli aromatics are produced. Therefore, MW requires the lower reaction temperature when equal yields of aromatics and BTX are obtained.