Mg改性L分子筛负载Pt重整催化剂的制备及其石脑油芳构化性能

为克服常规氧化铝型重整催化剂氯离子流失及对设备产生腐蚀等问题，通过离子交换法制备了Mg²⁺改性的L分子筛，采用浸渍法制备了不含氯离子的Pt/MgL重整催化剂，对分子筛载体进行了XRD、N₂吸附-脱附、NH₃-TPD和Py-IR等表征，并以硫含量0.50μg/mL工业精制石脑油为原料在固定床微反装置上评价了催化剂重整芳构化性能。结果表明，Mg²⁺离子交换对L分子筛的骨架结构没有破坏，Mg²⁺的存在提高了载体的酸量和酸强度，Mg²⁺改性的Pt/MgL催化剂重整芳构化性能明显提高，适当强酸性对L分子筛重整催化剂芳构化反应起到显著的促进作用。     

正庚烷异构化催化剂研究进展

阐述了当前正庚烷异构化所用的负载型催化剂和过渡金属碳化物和氧化物催化剂的研究进展,对催化剂性能的影响因素及对策进行了分析与讨论。正庚烷异构化催化剂中,研究较多的是以SAPO、HZSM-5和Y、B型分子筛为载体的贵金属催化剂,其中SAPO分子筛载体的性能较优,Pt比Pd具有更好的催化性能,非贵金属／分子筛催化剂的活性比贵金属／分子筛催化剂相差较大。过渡金属Mo、W的碳化物和氧化物也具有较好的正庚烷异构化性能,与碳氧化物或碳化物相比,部分还原氧化物催化正庚烷异构化活性和选择性要高得多,其活性甚至高于传统的Pt/USY双功能催化剂。展望了正庚烷异构化催化剂的研究方向和意义。     

正丁烷异构化催化剂的制备及其反应的研究

制备了一系列担载贵金属Pt的分子筛催化剂，评价了不同载Pt量对催化剂活性的影响。分子筛Pt含量的变化对反应结果影响很大，确定了载Pt量为催化剂总量的0．2％Pt/HZSM-5催化剂，能使正丁烷转化率＞40％，异丁烷选择性＞80％，同时考虑了反应温度，反应压力和H2／nC4^0对正丁烷异构化反应转化率及选择性的影响，结果表明：反应温度350－450℃，反应压力1．0－2．0MPa;H2/nC40－1．3等工艺条件较适合于正丁烷异构化反应，担载贵金属Pt的分子筛型催化剂对正丁烷异构化反应是一种很理想的催化剂。     

无溶剂合成多级孔ZSM-5分子筛及丙烷芳构化反应性能研究

以无溶剂合成方法,利用生物质多糖海藻酸钠制备了具有多级孔道结构的ZSM-5分子筛。采用XRD、SEM、TEM、FT-IR和N2吸附-脱附等多种表征技术对合成分子筛进行了表征,探究了海藻酸钠的添加量对分子筛形貌、孔结构、比表面积等物化性质的影响。结果表明,通过添加海藻酸钠制备的ZSM-5分子筛是具有丰富的多级孔结构,其添加量显著影响分子筛的形貌和孔结构,进而影响其在丙烷芳构化反应中的稳定性和芳构化选择性。该分子筛经Zn改性后用于丙烷芳构化反应,显示出良好的催化性能,其中样品Zn/ZSM-5-SA-16.7的丙烷转化率最初达87.2%,反应进行24 h后,丙烷转化率仍能达到50%以上,并且保持了较高的芳烃选择性（接近60%）。引入介孔结构有利于提高微孔分子筛内有机大分子的扩散速率和催化剂活性位的可接近性,降低副反应的发生,进而提高催化剂的选择性和反应稳定性。     

分子筛负载铂催化剂上四氢萘加氢裂解反应行为

四氢萘是多环芳烃加氢转化的产物或者中间体,其加氢裂解行为和规律的研究在重芳烃转化和脱除领域有着重要的意义。采用等体积浸渍法制备得到了氧化铝负载贵金属(Pt,Ir和Pd)催化剂和酸性分子筛(MOR和ZSM-5)负载铂双功能催化剂,考察了它们催化四氢萘加氢裂解的反应行为。氧化铝为载体时金属催化剂表面主要发生加氢及脱氢反应,其中金属Pt表现出最高的加氢和脱氢活性。双功能催化剂上四氢萘发生加氢裂化、异构化、氢转移及烷基化等复杂反应,金属Pt通过氢溢流作用提高了分子筛Br?nsted酸活性从而提高催化剂加氢裂解活性和选择性,但过量金属Pt会加剧苯环加氢而不利于单环芳烃的生成。分子筛孔道的限域作用对四氢萘的反应活性及产物分布有重要影响,相比Pt/ZSM-5催化剂,Pt/MOR表现出更高的裂解活性及异构化选择性。Pt/MOR催化剂上四氢萘加氢裂解主要通过异构-裂解路径进行,异构化活性及异构体构型决定了裂解活性及产物的分布。     

C_4液化气芳构化制芳烃催化剂的研究

在HZSM-5（SiO2/Al2O3=38）分子筛上,经金属改性制备了碳四液化气芳构化催化剂,并对催化剂进行了表征。在100 mL固定床实验装置上,考察了金属改性对催化剂物化性质、芳构化活性以及稳定性的影响,结果表明,金属改性能显著提高催化剂芳构化活性,由Zn和Ga共同改性的HZSM-5分子筛酸性分布更加合理,并能进一步促进碳四液化气芳构化制芳烃催化剂活性和稳定性的提高。     

Pd/KL催化剂高效催化苯酚选择性加氢制环己酮的研究

以KL分子筛为载体,采用浸渍法制备了Pd/KL负载型催化剂,对比了不同载体的钯负载型催化剂的苯酚选择性加氢反应及反应条件等对其催化活性和产物选择性的影响。结果表明,催化剂载体性质对该反应的催化性能具有较大的影响,载体表面碱性较强时,催化剂表现出更高的催化活性;由于KL分子筛载体中特殊的阳离子分布(孔道中必须存在K⁺),使分子筛表面呈碱性,因此表现出优异的催化性能。在反应温度为60℃、反应时间为6 h时,其苯酚转化率可达96. 1%,环己酮选择性达到94. 4%。     

正十二烷在Pt/ZSM-22和Pt/ZSM-23上的加氢异构反应性能

采用常规水热合成法合成了ZSM-22和ZSM-23分子筛,进而制备了分别含有上述分子筛的催化剂,并借助XRD、SEM、NH3-TPD和Py-IR表征了这两种分子筛和催化剂的结构和酸性,同时以正十二烷为模型化合物,采用固定床反应器研究了Pt/ZSM-22和Pt/ZSM-23催化剂上正十二烷加氢异构反应性能。结果表明,在这种模型反应基础上,催化剂的反应活性和选择性主要取决于催化剂的酸量和酸强度以及酸分布,相对而言,ZSM-22分子筛催化剂由于其弱酸和中等强度酸的含量较高,具有更佳的异构化选择性。     

铂负载AlPO-5催化剂的制备及其甘油催化氧化性能研究

采用水热合成法制备磷酸铝分子筛AlPO-5,并通过焙烧处理得到AlPO-5分子筛多孔材料,以浸渍法和沉淀法分别制备了Pt负载型AlPO-5催化剂,通过粉末XRD、TEM、氮气吸附-脱附等手段对制备的催化剂进行了对比表征,研究了负载方法对Pt团簇分散度以及粒径尺寸的影响。以Pt/AlPO-5作为催化剂,研究了其对甘油的催化氧化性能,系统考察了Pt负载量、还原方法和反应时间对甘油转化率和产物选择性的影响。实验结果表明,由浸渍法制备的催化剂对甘油的转化率和甘油醛的选择性较高,甘油醛的选择性最高可达到63.46%。甘油醛作为起始反应产物,其高选择性与较大尺寸的Pt纳米团簇有关。     

Pt/ZSM-5分子筛催化甲苯甲醇烷基化反应的积炭失活与再生研究

负载型Pt/ZSM-5分子筛具有较高的选择性和稳定性，是潜在的甲苯甲醇烷基化高效催化剂。负载Pt可有效提高催化剂的稳定性，但由于积炭引起的失活不可避免且失活后的催化剂活性和稳定性难以恢复，且积炭再生过程中的放热会引起金属颗粒烧结。因此，提出了一种水蒸气混合低浓度氧气再生催化剂的方法，考察了再生前后催化剂的催化性能，并结合多种表征方法对再生前后催化剂的物化性质进行了研究。结果表明，该方法能有效消除Pt/ZSM-5分子筛孔道内的积炭，催化剂的选择性与活性得到恢复，稳定性达到新鲜催化剂的90%以上。     

n-Octane aromatization on Pt-containing non-acidic large pore zeolite catalysts

Platinum catalysts supported on the potassium-form of different large-pore zeolites (i.e. K-LTL, K-BEA, K-MAZ, and K-FAU) have been tested for n-octane aromatization at 500 °C. All catalysts were prepared by the vapor phase impregnation (VPI) method. It was found that the Pt/K-LTL catalyst exhibit a better aromatization performance than the other zeolite catalysts. However, due to secondary hydrogenolysis, the C8 aromatics produced inside the zeolite are converted to benzene and toluene. By contrast, a non-microporous Pt/SiO₂ catalyst did not present the secondary hydrogenolysis. Therefore, despite a lower initial aromatization activity, Pt/SiO₂ results in higher selectivity to C8 aromatics than any of the other zeolite catalysts. All fresh catalysts were characterized by hydrogen chemisorption and FT-IR of adsorbed CO. In addition, the residual acidity of the supports was analyzed by temperature programmed desorption (TPD) of ammonia. In agreement with previous studies, it was found that after reduction at either 350 or 500 °C, the Pt/K-LTL showed much higher Pt dispersion than other catalysts. It is known that the structure of L zeolite can stabilize the small Pt clusters inside the zeolite channel. By contrast, FT-IR indicated that a large fraction of platinum clusters were located outside the zeolite channels in the case of Pt/K-BEA and Pt/K-MAZ catalysts.     

Sulfur- and water-tolerance of Pt/KL aromatization catalysts promoted with Ce and Yb

Different Pt/KL catalysts containing rare earth (RE; Ce and Yb) promoters were prepared by two techniques, incipient wetness impregnation (IWI) and vapor phase impregnation (VPI). The catalysts were tested for the activity and the selectivity of n-hexane aromatization to benzene under clean, sulfur-containing, and water-containing feeds at 500 °C. It was observed that the catalysts prepared by the VPI technique exhibited much higher activity and selectivity than those prepared by IWI. It was also found that although under clean conditions, the addition of Ce or Yb caused a decrease in activity, in the presence of sulfur the addition of Ce and to a lesser extent Yb, significantly inhibited catalyst deactivation.

The influence of water in the feed was investigated by contacting the catalysts for 1 h to a feed containing 3 mol.% water. After this treatment, all the catalysts exhibited a significant activity loss. This loss was more pronounced for the catalyst prepared by the VPI method. The catalyst prepared by IWI already had suffered a significant deactivation before the water treatment, so the activity drop was not so pronounced. The sample prepared by VPI not only showed a drop in activity immediately after the water treatment but it became more susceptible to deactivation afterwards. By contrast, the Ce-promoted catalyst showed a more stable activity after the water treatment.

All catalysts were characterized before and after reaction by a number of techniques. In agreement with previous studies, FT-IR of adsorbed CO and chemisorption results indicated that the VPI method resulted in higher Pt dispersion than that obtained by the IWI method. After reaction in the presence of sulfur, the Ce-promoted Pt/KL catalyst showed a higher resistance to metal agglomeration and a lower rate of coke formation than the unpromoted Pt/KL. On all the catalysts, the amount of carbon deposits was greater in the presence of sulfur and after exposure to water vapor than under the reaction with clean feeds. This difference is explained in terms of metal particle growth and location in the zeolite.     

Effect of halogen anion on hexane aromatization activity of Pt/KL catalysts

Potassium salts were added to the catalyst prepared by ion exchange of KL with [Pt(NH3)₄]Cl₂ and the effect of their counter anion on the activity and selectivity for hexane aromatization was studied. The catalyst to which KF was added showed the highest activity and selectivity for benzene formation; methylcyclopentane and hydroisomerization products were negligible. Although the catalyst with KCl added also exhibited excellent performance, the catalysts with KBr or KI added gave rise to low hexane conversion and benzene yield. Infra-red spectra of adsorbed CO revealed that the presence of the low frequency C-O stretching band is closely related to catalytic performance of the Pt/KL series catalysts. The electron-rich Pt site formed through the interaction with KF or KCl may be responsible for the high activity and selectivity for hexane aromatization.     

Influence of Cesium in Pt/NaCsβ on the Physico-Chemical and Catalytic Properties of the Pt Clusters in the Aromatization ofn-Hexane

Various Pt/NaCsβ catalysts with decreasing Na/Cs ratios and a Pt/KL sample taken as a reference catalyst for aromatization ofn-hexane, have been prepared by exchange of NaCsβ and KL zeolites in a Pt tetraammine solution then calcination and reduction. The increase of the Cs content in the NaCsβ zeolitic support results in a decrease of the cyclohexane adsorption and Pt exchange capacities. The Pt/Csβ and Pt/KL samples show similar behaviors which strongly differ from those of the Na-containing Pt/NaCsβ samples in terms of (i) reducibility of the Pt ions after calcination, (ii) shape of the FTIR spectra of CO adsorbed on the Pt clusters after reduction, and (iii) catalytic activity of these clusters in the conversion ofn-hexane. In particular, the selectivity to aromatization is much higher on the Pt/Csβ and Pt/KL catalysts than on the Na-containing Pt/NaCsβ ones. The reasons for the specific behaviors of the Pt/Csβ and Pt/KL samples are discussed.     

EFFECT OF ZEOLITE CRYSTALLITE SIZE ON Pt/KL CATALYSTS USED FOR THE AROMATIZATION OF n-OCTANE

The effects of varying zeolite crystallite size in n-octane aromatization over Pt/KL have been studied on a series of catalysts. Various KL zeolites were synthesized via microwave-hydrothermal treatment, which allows for good control of crystallite morphology. Zeolites with different crystallite sizes were prepared by varying aging time (17–24 h), amount of barium (0–445 ppm), and seeding (0–8 wt%). The results showed that higher aging time resulted in smaller zeolite crystallite size, whereas the addition of barium resulted in larger crystallite size. Moreover, the addition of seeding reduced the crystallite size from 1.47 to 0.94 μm. Pt supported on different zeolite catalysts (Pt/KL) was prepared by vapor phase impregnation (VPI). The fresh catalysts were characterized by DRIFTS of adsorbed CO and volumetric hydrogen chemisorption. The results indicated that Pt clusters are well dispersed inside the zeolite channel in all the catalysts prepared. The aromatization of n-octane was tested on the different catalysts at 500°C and atmospheric pressure. It was found that the catalytic activity of all catalysts dropped rapidly after about 200 min on stream due to coke plugging inside the pore of the KL zeolite. It was also observed that less ethylbenzene (EB) and o-xylene (OX) were obtained as the conversion increased because both EB and OX are converted to smaller molecules such as benzene, toluene, etc., by secondary hydrogenolysis. Furthermore, the EB/OX ratio increases with zeolite crystallite size due to an enhanced preferential conversion of the larger OX molecules compared to the narrower EB as their path through the pores is restricted.     

EFFECT OF ZEOLITE CRYSTALLITE SIZE ON Pt/KL CATALYSTS USED FOR THE AROMATIZATION OF n-OCTANE

The effects of varying zeolite crystallite size in n-octane aromatization over Pt/KL have been studied on a series of catalysts. Various KL zeolites were synthesized via microwave-hydrothermal treatment, which allows for good control of crystallite morphology. Zeolites with different crystallite sizes were prepared by varying aging time (17-24 h), amount of barium (0-445 ppm), and seeding (0-8 wt%). The results showed that higher aging time resulted in smaller zeolite crystallite size, whereas the addition of barium resulted in larger crystallite size. Moreover, the addition of seeding reduced the crystallite size from 1.47 to 0.94 μm. Pt supported on different zeolite catalysts (Pt/KL) was prepared by vapor phase impregnation (VPI). The fresh catalysts were characterized by DRIFTS of adsorbed CO and volumetric hydrogen chemisorption. The results indicated that Pt clusters are well dispersed inside the zeolite channel in all the catalysts prepared. The aromatization of n-octane was tested on the different catalysts at 500°C and atmospheric pressure. It was found that the catalytic activity of all catalysts dropped rapidly after about 200 min on stream due to coke plugging inside the pore of the KL zeolite. It was also observed that less ethylbenzene (EB) and o-xylene (OX) were obtained as the conversion increased because both EB and OX are converted to smaller molecules such as benzene, toluene, etc., by secondary hydrogenolysis. Furthermore, the EB/OX ratio increases with zeolite crystallite size due to an enhanced preferential conversion of the larger OX molecules compared to the narrower EB as their path through the pores is restricted.     

L沸石催化剂的改性及其在正十二烷临氢异构化中的应用

对KL沸石处理后得到了不同的HL沸石,再对其筛选,负载0.4%铂后得到了Pt/HL沸石。经过400℃氢气还原后,将该催化剂与0.4%Pt(质量分数)/SAPO-11分别进行了正十二烷临氢异构化反应并对其产物进行了比较。该反应在温度360℃,压力1MPa,空速1h-1,H2/C12(物质的量比)为9.13的不锈钢反应管中进行。通过实验我们发现Pt/HL沸石有一定的异构化活性;在相同的反应条件下一交一焙的0.4%Pt/HL与0.4%Pt/SAPO-11相比,前者有着更高的转化率,但异构化产物产率和单支链产物选择性较低。     

Role of pore size analysis in development of zeolite reforming catalyst

Effect of preparation variables on the aromatization activity of Pt/KL catalysts was studied. The aromatic content as well as C₅⁺ liquid yields were greatly influenced by the nature of binder material used in catalyst preparation. Detailed characterization of the catalysts indicated that two factors, namely (1) nature of binder and (2) size and volume of pores, influenced the catalytic activity. Among the catalysts studied the one prepared by MgO doped basic binder exhibited better performance. Pt loading was also observed to influence the pore volume and aromatization activity of the catalysts, where the catalyst exhibited decrease in pore volume above 0.4 wt.% Pt loading.     

On the role of gallium for the aromatization of lower paraffins with Ga-promoted ZSM-5 catalysts

Aromatization of butane or propane was conducted with a series of ZSM-5 catalysts. A small amount of oxygen in the feed promoted butane conversion to aromatic hydrocarbons on H-ZSM-5. It suggests that if hydrogen atoms on the zeolite surface are removed effectively, H-ZSM-5 exhibits a high selectivity for aromatic hydrocarbons. A hybrid catalyst composed of the physical mixture of Ga/SiO₂ and H-ZSM-5 showed comparable activity and aromatic selectivity to those of the Ga-supported ZSM-5 zeolite, whereas the Ga/SiO₂ itself exhibited little catalytic activity for the paraffin conversion and olefin aromatization. The excellent promotional effect of Ga/SiO₂for aromatics formation was observed only when it was intimately contacted with H-ZSM-5. These results suggest that the supported Ga promotes the zeolite-catalyzed aromatization of lower paraffins by promoting hydrogen desorption via the ‘reverse spillover’ effects.