粘结剂对HZSM-5芳构化催化剂的性能影响研究

The effect of different binders on light hydrocarbon aromatization performance of the HZSM-5 catalyst was investigated.Physicochemical properties of the catalysts,such as the specific surface area,pore volume and acidity,etc.,were characterized to correlate with their aromatization performance data.The results showed that the pore structure of Al2O3 could significantly affect the catalyst performance.As the accessible pore diameter of the catalyst increased from 8.0 nm to 9.0 nm,the light aromatics yield increased by 2.7 percentage points,while the operating time of the catalyst nearly doubled.In addition,catalysts prepared with SiO2 and aluminum phosphate was more active and stable than that prepared with Al2O3,of which the light aromatics yield enhanced 6-8 percentage points and the run length,or seivice eife run length nearly doubled.     

Modeling of flow of oil-in-water emulsions through porous media

Formation and flow of emulsions in porous media are common in all enhanced oil recovery techniques.In most cases,oil-in-water(O/W) emulsions are formed in porous media due to oil-water interaction.Even now,detailed flow mechanisms of emulsions through porous media are not well understood.In this study,variation of rate of flow of O/W emulsions with pressure drop was studied experimentally,and rheological parameters were calculated.The pressure drop increases with an increase in oil concentration in the O/W emulsion due to high viscosity.The effective viscosity of the emulsion was calculated from the derived model and expressed as a function of shear rate while flowing through porous media.Flow of O/W emulsions of different concentrations was evaluated in sand packs of different sand sizes.Emulsions were characterized by analyzing their stability,rheological properties,and temperature effects on rheological properties.     

Influence of catalyst support structure on ethene/decene metathesis and coke formation over WO3/SiO2 catalyst

8wt%WO3/SiO2 metathesis (disproportionation) catalysts with different pore structures were prepared by the incipient-wetness-impregnation method. The as-synthesized catalysts were characterized by N2 adsorption-desorption, scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (DRS) and scanning transmission electron microscopy-high-angle annular dark field (STEM HAADF). The results of STEM HAADF showed that WO3 species were not uniformly distributed on the SiO2 support. The experimental results of 8wt%WO3/SiO2 performance in ethene/decene metathesis revealed that the catalytic effect of 8wt%WO3/SiO2 catalyst and coke formation over it were closely related to the support pore structure: The 8wt%WO3/SiO2 catalyst with a more complicated pore structure showed better catalytic performance but the coke deposition rate was also faster.     

二次重建法制备具有大孔容高比表面的大孔-介孔γ-Al2O3

Through improving the aging process during synthesis of the support, γ-Al2O3 with large pore volume and high surface area was synthesized by a facile secondary reforming method. The synthesis parameters, such as the reaction temperature, the first aging temperature and the second aging temperature, were investigated. The textural properties of γ-Al2O3 were characterized by means of N2 adsorption-desorption isotherms, X-ray powder diffractometry(XRD), scanning electron microscopy(SEM), Fourier transform infrared(FTIR) spectroscopy and thermogravimetry(TG). The experimental results indicated that AACH and amorphous AlOOH were the precursors of alumina, which were formed via precipitation from solutions after reaction of aluminum sulphate with ammonium hydrogen carbonate. The precursor nanocrystallites grew and re-assembled during the secondary reforming process, which resulted in an increased pore size and pore volume and a decreased bulk density. The as-synthesized γ-Al2O3 materials featured meso/macroporosity, large pore volume(2.175 cm3/g), high surface area(237.8 m2/g), and low bulk density(0.284 g/mL).     

固相研磨法合成MgO-Al2O3/ZSM-5及其丙烷脱氢催化反应性能的研究

Solid-state grinding is a simple and effective method to introduce guest species into the channels of microporous materials through filling.The structure and the surface acidity of the materials were obtained from BET isotherms and NH3-TPD, respectively.XRD, UV-vis, UV diffuse-reflectance, and TEM were used to characterize the phases, and the morphology, respectively.The clustered layers of MgO-Al2O3phases were formed in the internal pore surface and were highly dispersed inside the channels of the ZSM-5 host.So the volume of MgO-Al2O3/ZSM-5 composite was larger than the ZSM-5 zeolite itself and some mesoporous channels appeared when Mg/Al species entered the channels.Meanwhile, new acid sites emerged in MgO-Al2O3/ZSM-5 composite and the acid amount of the sample changed.The improved Pt dispersion and the increased acid content would cause the increase of propane conversion and the modification of selectivity during the reaction.     

Experimental Study on the Characteristics of CO_2 Hydrate Formation in Porous Media below Freezing Point

Porous medium has an obvious effect on the formation of carbon dioxide hydrate. In order to study the characteristics of CO2 hydrate formation in porous medium below the freezing point, the experiment of CO2 hydrate formation was conducted in a high-pressure 1.8-L cell in the presence of porous media with a particle size of 380 μm, 500 μm and 700 μm, respectively. The test results showed that the porous medium had an important influence on the process of CO2 hydrate formation below the freezing point. Compared with porous media with a particle size of 500 μm and 700 μm, respectively, the average hydrate formation rate and gas storage capacity of carbon dioxide hydrate in the porous medium with a particle size of 380 μm attained 0.016 14 mol/h and 65.094 L/L, respectively. The results also indicated that, within a certain range of particle sizes, the smaller the particle size of porous medium was, the larger the average hydrate formation rate and the gas storage capacity of CO2 hydrate during the process of hydrate formation would be.     

Effect of Carrier Processing Temperature on Its Properties for Adsorption of Active Metals

The influence of the carrier pseudo-boehmite (PB), which was impregnated with a Ni-Mo-P solution under over-saturation conditions and treated at different temperatures, on its property for adsorption of active metals (Ni, Mo) was studied. The results showed that the amount for adsorption of active metal was decreased with an increasing treatment temperature of the carrier. After phase transition of the carrier PB to γ-Al2O3, its capacity for adsorption of active metals was significantly reduced. The difference in properties for adsorption of active metals (Ni, Mo) by PB dried at 120 ℃ and γ-Al2O3 calcined at 600 ℃ was studied in detail. The results suggested that the ability of the PB carrier to adsorb metals was higher than that of the γ-Al2O3 carrier. Especially, the ratio of chemically adsorbed metals on the PB support was much higher than γ-alumina. The chemical adsorption sites on the PB carrier were proved to be much more than those on the γ-Al2O3 carrier. Ni and Mo chemical adsorption sites differed a lot on the carrier possibly because of the difference in chemical adsorption sites.     

Preparation and Characterization of Zeolite Beta with Low SiO_2/Al_2O_3 Ratio

Zeolite beta with a low SiO2/Al2O3 ratio was synthesized by a novel two-step process.The synthesized sample was characterized with XRD,SEM,FTIR,and N2 adsorption-desorption and solid-state MAS NMR.The results showed that aluminium species were inserted into the framework of zeolite beta.The BET surface area,volume,and particle size of the zeolite beta sample decreased with decreasing SiO2/Al2O3 ratio.Our process was proved an efficient route to synthesize zeolite beta with a low SiO2/Al2O3 ratio.     

Influence of Crystal Size of USY Zeolite on Performance of Hydro-upgrading Catalysts

The effect of crystal size of USY zeolite on the performance of hydro-upgrading catalysts for treating catalytically cracked(FCC) LCO(light cycle oil) was studied.Three W-Ni catalysts supported on USY zeolites with different crystal sizes and Al2O3 were prepared by impregnation method.The catalysts were characterized by XRD and BET methods,and evaluated in a micro-reactor using tetralin as the model compound and in an 100-mL hydrogenation test unit using FCC LCO as the feedstock.By contrast,catalyst made from smaller crystal-size USY zeolite had higher external surface area and shorter pore length,having more hydrogenation activity sites and short contact time of reactant molecules with acidity sites.The evaluation results showed that the catalyst prepared on the basis of small crystal-size USY zeolite had higher tetralin conversion and better hydro-upgrading performance for treating FCC LCO.     

Two-Stage Hydrogenation Modification of C_9 Petroleum Resin over NiWS/γ-Al_2O_3 and PdRu/γ-Al_2O_3 Catalysts in Series

Hydrogenation modification is one of the most important ways to produce high-quality petroleum resin.The colorless C9 petroleum resin(C9PR) was obtained by two-stage catalytic hydrogenation over NiWS/γ-Al2O3 catalyst and PdRu/γ-Al2O3 catalyst connected in series.Via the hydrogenation reaction,aromatic rings in C9PR were converted to alicyclic rings,and its color was reduced from Gardner color grade No.11 to Gardner color grade No.0.The optimum Ni/W atomic ratio was found to be close to 0.23,while the optimum Pd/Ru atomic ratio was close to 3.80.The TEM results showed that the morphology and size of sulfide or metal particles of the two kinds of catalysts remained almost unchanged after the reaction was carried our for 1 204 hours,attesting to their good catalytic stability.     

钼基改性催化剂的制备及其催化氧化脱硫性能研究

采用自组装的方法合成了氧化硅,考察了硅源浓度、模板剂用量及陈化时间对氧化硅介孔结构的影响。以氧化硅为载体,采用等体积浸渍法制备了钼基负载型催化剂,并加入柠檬酸、硝酸镧、硝酸铈对其进行改性。在温和条件下,以双氧水为氧化剂,考察了不同改性催化剂对减压馏分油（VGO）的催化氧化脱硫性能,并优化了催化氧化脱硫条件。结果表明：氧化硅的最佳合成条件为硅源浓度0.68 mol/L、CTAB/TEOS摩尔比0.22、陈化时间2 h;催化剂脱硫活性由大到小的顺序为Ce-MoO3/SiO2＞CA-MoO3/SiO2＞MoO3/SiO2＞La-MoO3/SiO2;以Ce-MoO3/SiO2为催化剂时,最佳催化氧化脱硫条件为氧化温度70 ℃、O/S摩尔比8、氧化时间2 h、催化剂的加入量（w）15%,此条件下VGO脱硫率达到64.8%。     

助剂引入对γ-Al2O3性质及其负载催化剂性能的影响

采用NaAlO2-CO2法制备了γ-Al2O3,在制备过程中分别引入助剂SiO2,B2O3,P2O5,SiO2-B2O3,SiO2-P2O5,考察了不同助剂对γ-Al2O3性质及其负载催化剂性能的影响。结果表明,助剂能有效增加γ-Al2O3孔容和比表面积,其中复合助剂SiO2-P2O5的效果最为显著。助剂对γ-Al2O3热稳定性有很大影响。引入助剂能提高γ-Al2O3的总酸量及B酸含量。     

混合氧化物载体对反应吸附剂Ni/ZnO的影响

The effect of mixed oxide support on the performance of the reactive adsorption desulfurization (RADS) for Ni/ZnO was invested by using thiophene in model gasoline in a fixed bed reactor. A series of oxide supports of Ni/ZnO was synthesized by co-precipitation method and characterized by XRD, N2-adsorption, TPR and NH3-TPD. It was found that the desulfurization capacity of Ni/ZnO is enhanced greatly when active components were supported on proper mixed oxide. Ni/ZnO supported on oxides exhibits much higher desulfurization efficiency and sulfur adsorption capacity than unsupported Ni/ZnO and the synthesized Ni/ZnO-SA adsorbent exhibits the highest efficiency for thiophene removal. The higher desulfurization activity and sulfur capacity of Ni/ZnO supported on SiO2-Al2O3 with small particle size, high specific surface area and large pore volume promotes the highly dispersion of active metal phase and the transfer of sulfur to ZnO with lower mass transfer resistance. γ-Al2O3 can weaken the interaction of active phases and SiO2 as well as increasing greatly the amount of weak acid. Therefore, these oxides have a great influence on the structure and chemical properties of the catalyst.     

颗粒/整体式催化剂双层床反应器中甲烷氧化偶联反应性能

用5%Na2WO4-2%Mn/SiO2颗粒催化剂和3%Ce-5%Na2WO4-2%Mn/SBA-15/Al2O3/FeCrAl金属基整体式催化剂,构建了一种颗粒/整体式新型双层床新型甲烷氧化偶联催化反应器,评价了双层床反应器中甲烷氧化偶联反应性能,重点考察了催化剂床层高度、原料气的流向方式、反应温度、烷氧比、进料流量等与反应性能的关系。结果表明,颗粒催化剂床层高度为15mm、整体式催化剂床层高度为50mm,原料气先通过颗粒床层再通过整体式床层的方式下,具有最好的反应性能,甲烷转化率为38.4%时,乙烯选择性可达41.5%,比单床层催化剂的综合性能有明显提高。     

超大孔分子筛的合成研究

以氧化铝和硅酸钠为骨架的铝硅源，十六烷基三甲基溴化铵（ＣＴＭＡＢ）为模板剂，用水热法全成超大孔ＭＣＭ－４１分子筛，并对合成过程的主要影响因素进行了考察，结果表明晶化温度过低，形成ＭＣＭ－４１分子筛速度慢，温度，过高，会破坏模板分子之间形成胶棒的内聚力，形成ＭＣＭ－４１分子筛还需适当的ＣＴＭＡＢ／Ｈ２Ｏ，碱度，Ｈ２Ｏ／ＳｉＯ２等条件，否则会降低结晶度甚至于生成其它杂晶。     

SiO2掺杂对V-Mo/TiO2催化剂脱硝性能的影响

采用共沉淀法制备不同SiO₂掺杂量的TiO₂-SiO₂复合载体,采用浸渍法在这些复合载体上负载活性组分V₂O₅和MoO₃,制备不同SiO₂掺杂量的V-Mo/TiO₂-SiO₂催化剂 (VMTS)。运用XRD,SEM,BET,H₂-TPR等分析手段对催化剂的理化性能进行表征,结果表明：随着SiO₂掺杂量的增加,VMTS催化剂的XRD谱图中不仅出现了SiO₂衍射峰,而且出现了锐钛矿型TiO₂的衍射峰,表明活性组分V₂O₅和MoO₃含量相对较低,主要以非晶态或微晶态形式存在;掺杂SiO₂的催化剂H₂-TPR还原峰向低温方向移动,同时比表面积和孔体积增大,孔径减小;与其他催化剂相比,SiO₂与TiO₂的质量比为0.2∶1的催化剂VMTS-(0.2∶1)具有最佳的氧化还原能力。脱硝效率评价结果表明：VMTS-(0.2∶1)催化剂具有最佳的烟气脱硝效率,烟气中通入SO₂时,VMTS催化剂烟气脱硝效率下降幅度均低于未掺杂SiO₂的催化剂,VMTS-(0.2:1)催化剂烟气脱硝效率下降幅度最小,说明掺杂SiO₂有利于催化剂抗硫性能的提高。     

氟离子存在下合成的β沸石的物化和催化性能

在氟离子存在下,用ＴＥＡＢｒ－ＮａＯＨ作模板剂,通过水热晶化法合成了β沸石,用ＸＲＤ,ＩＲ,ＤＴＡＴＧ,ＳＥＭ和ＴＥＭ等研究了其物化性能,测定了对苯的异丙基化反应的摧化性能,结果表明,合成的β沸石硅源利用率高,颗粒度大,热稳定性高。     

负载型纳米Pt催化剂的制备及其催化合成对氨基苯酚

针对硝基苯加氢合成对氨基苯酚(PAP)反应,于反相微乳液体系中,采用重新分散沉积负载法和改进的微乳-溶胶凝胶负载法制备了不同Pt粒径的Pt/SiO2催化剂,考察了Pt粒径对反应活性及选择性的影响。实验结果表明,采用改进的微乳-溶胶凝胶负载法制备的Pt/SiO2催化剂,Pt粒子在载体表面分散得更均匀,且粒径较小。在Pt/SiO2催化剂制备过程中加入一定量的草酸及改变H2PtCl6溶液浓度,均对Pt粒径有一定的调控作用。以制备的不同Pt粒径的Pt/SiO2为加氢反应催化剂、以S2O82-/ZrO2固体酸为重排反应催化剂进行硝基苯加氢合成PAP反应。实验结果表明,随Pt粒径的减小,硝基苯转化率及PAP的选择性均明显提高,当Pt粒径为5.1nm时,PAP的选择性最高,为48.5%。     

采用NaAlO2-CO2连续中和法制备拟薄水铝石

采用NaAlO2-CO2连续中和方式制备拟薄水铝石,研究了连续中和-母液老化和连续中和-净水老化2种工艺的规律,探讨了不同中和pH值、老化方式、老化温度以及老化时间对产物性质的影响。采用XRD、BET、XRF、TEM等手段表征了产物的晶相、相对结晶度、晶粒尺寸、孔结构、比表面积、杂离子含量以及晶粒的形貌和堆积方式。结果表明,连续中和与间歇中和工艺反应规律相似,但连续中和工艺更易生成丝钠铝石;采用连续中和-净水老化工艺可有效避免丝钠铝石的生成;随着中和pH值下降,拟薄水铝石晶粒堆积更加致密,其焙烧所得?-Al2O3的孔容和比表面积均有所降低,最可几孔直径增大。