The prevulcanization precipitation liquid was prepared by self-assembly with thiocarbamide,citric acid and polyethylene glycol-200.The two-stepped presulfurization Mo-Ni/Al2O3 catalysts were prepared by in-situ precipitation method and characterized by BET,XRD,FT-IR of CO adsorbed,XPS,and TEM.The hydrogenation performances of the prepared catalyst were evaluated with micro fixed bed reactor and with the directly in-situ presulfurization catalyst as reference.The results showed that the two-stepped presulfurization Mo-Ni/Al2O3 already achieved 74.8％ of sulfidity after the first step of presulfurization (ex-situ presulfurization).The additions of polyethylene glycol-200 and thiocarbamide made an improvement of the pore properties of the catalysts.The biggest specific surface of 198 cm2/g was obtained when the mass fraction of thiocarbamide reached 20％ of Mo and Ni oxides in the catalyst,at the same time,the active metal dispersion was better and the sulfidity was 2.60 percentage points higher than the reference catalyst.The hydrodesulfurization (HDS),hydrodenitrogenation (HDN) and hydrodearomatization (HDA) rates of 40 h hydrotreating for FCC diesel fraction over the two-stepped presulfurization Mo-Ni/γ-Al2O3 catalyst were 2.28 percentage points,1.94 percentage points and 3.46 percentage points higher than those over the reference catalyst,respectively.

The macromolecule templates are removed from macropores alumina nano material by using different solvents.The extracted supports are characterized by gravimetric,element,SEM and BET.Meanwhile,the oil phase products are analyzed by the gel chromatography (GPC) and infrared (IR).The results showed that the removal rate of templates reached 86.81％,and that of carbon,hydrogen and nitrogen is 80.44％,81.67％ and 62.83％ when the petrol-ethanol as extraction solvent,respectively.The calcinated macropores alumina support has a pore volume of 1.24 mL/g,a surface area of 253.3 m2/g and a pore diameter of 17.4 nm.According to SEM images,the removed templates supports are formed many meso/macro-porous structures.The Mw and Mn of RHP is 14 384 g/mol and 2 545,and the dispersion coefficient Mw/Mn is 5.65 when the mass ratio of PIBSA and TEA is 12 ∶ 1.The results that confirmed the templates are macromoleclar polymer and the molecular weight distribution are relatively wide range.The templates can be recycled and utilization because IR spectra further confirmed that the templates and oil phase product are the same structure.This research is accorded to green environmental protection.

This article focuses on several exiting self-assembly synthesis method,and introduces application progresses in biological medicine,battery application,membrane separation,and catalytic materials.Expounds the advantages and importance in modern technology.The development and application of self-assembly technology in medicine,chemical and catalytic field are prospected.

A series of TiO2-Al2 O3 compound supports FAT1 ~FAT5 were prepared by adding different concentration of TiO 2 to macroporous alumina ,which was formed by nano self-assembly method .When the concentration of TiO2 are different,the properties of compound supports were characterized by BET ,XRD, TEM and NH3-TPD,and then compared with nano self-assembly alumina support FAT0.Results showed that the biggest specific surface area was 331.68 m2/g for FAT3,as well as the uniform pore ,which pro-duce the most perfect crystal structure of TiO 2 and Al2 O3 .With the increasing concentration of TiO 2 ,Ti-Al bond formed gradually ,and the TiO2 dispersed uniformly on Al 2 O3 surface.Moreover, the acid amount of 17.47 mL/g was higher for FAT3,a weak and mid strong acid amount were occupied 93.6%of the total acid,which to the benefit of hydrogenation reaction smoothly .Therefore,TiO2 played an important role of improving the pore structure ,crystal structure and surface acidity of nano self-assembly support Al 2 O3 . So,the compound support had the most favorable pore structure and surface acid for catalytic hydrogena -tion activity when the concentration of TiO 2 reached 50%.

模板法在纳米材料的合成过程中已成为一种非常重要的技术.利用其结构导向、骨架填充、平衡和匹配电荷等作用,可以达到精确地调控纳米材料孔道的大小、形状及结构的目的.本文主要对模板剂的种类进行了详细的分类,重点介绍了硬模板法和软模板法在合成纳米材料过程中的现状及特点,并具体介绍了模板剂在合成纳米生物材料及纳米催化剂、电化学、化工合成等方面的应用;阐述了模板法在介孔材料合成过程中的重要性,指出了目前模板剂方法存在的优缺点;提出了模板剂在超分子功能材料、光化学反应及催化工业等方面应用的纳米材料合成中的发展趋势和良好前景.

A novel self-assembled catalyst, FA-Z30, possessing a mesoporous/macroporous structure is prepared and applied to FCC diesel hydrodesulfurization (HDS). The catalyst has 54 % of the total pore volume lying within 30–60 nm pores, greater than 26 % of the continuous phase. This indicates interconnected pores. N2 adsorption data show a bimodal structure with pores ranging between 30–60 nm and <10 nm. Textural properties of the catalyst show that the pore volume is 0.78 cm g–1 having a specific surface area of 181 m2 g–1 with a most probable pore diameter of 20 nm. The catalyst possesses a low active metal concentration of ~154.9 g L–1 per unit volume and a low bulk density of ~0.50 g cm–3. X-Ray diffraction, high resolution transmission electron microscopy, and X-ray photoelectron spectroscopy show improved active metal dispersion with an average MoS2 layered slab number of 3–7, having lengths ranging from 5 to 10 nm. Molybdenum sulfide sulfidity at 75 % is higher than the commercial catalyst, FCB, at 62 %. The activity and stability of HDS and hydrodenitrification (HDN) are improved, as is aromatics saturation (HDAr) reflected by limited coke formation. Average conversion rates of HDS, HDN, and HDAr are 95, 97, and 67 % at 100 h on stream for FA-Z30, respectively, and their respective rates of 6.1, 6.3, and 4.3 % per unit volume of active metal is twice that of the commercial catalyst. The low bulk density of FA-Z30 improves the utilization rate and relative activity of the active metals. FA-Z30 is a promising catalyst for FCC diesel hydrogenation.

采用纳米自组装方法以钼镍铵溶液作为浸渍液制备贯穿性介孔Mo-Ni-NH3/γ-Al2O3催化剂.利用BET比表面积测试法(BET)、CO吸附原位红外、X射线衍射(XRD)、透射电子显微镜(TEM)等表征手段,考察了表面活性剂、助溶剂种类、用量在自组装过程中对催化剂的分散性及孔结构的影响.结果表明,改性后催化剂TOP-3的孔性质最好,其比表面积为183 m2.g-1,孔容为0.46 m3·g-1,平均孔径为10.11 nm,且孔道在10 ～ 30 nm处高度集中,高达35.63％;红外CO原位吸附结果证明了Mo2+,Mo4+和Ni2+活性中心的存在,且均以线式吸附态吸附CO;从XRD分析可发现催化剂NOP-3、NOP-4在2θ=15.9°,20.8°,22.2°和30.8°处出现了Al2(MoO4)3的(111),(102),(021),(312)4个晶面的特征衍射峰,而TOP系列催化剂的特征峰弥散,说明TEA与OP-20复配可以改善金属的分散性.TEM表征结果证明了15 ～ 20 nm贯穿性多孔结构的存在,且分散均匀.此结构有利于大分子扩散,适合于重油加氢处理.

Using self-assembled nano alumina with the large aperture and low bulk density as support,the nanoassembly bimetallic Mo-Ni agents are used to prepare the supported Mo-Ni-P diesel hydrogenation catalysts by coimpregnation method. The pore structures of the catalysts are characterized by the BET method. The optimal experimental conditions are obtained by examining the desulfurization rate in the fixed-bed microreactor: 6. 5 MPa of the pressure,370℃ of temperature,1. 5 h- 1of the space velocity and 700 ∶ 1 of hydrogen to oil. Meanwhile,the 40 hours of hydrogenation performance of the catalysts with different metal proportions are evaluated. The results show that better hydrogenation effect can be achieved when the mass ratio of Mo / Ni is 5 ∶ 1. The average desulfurization rate,denitrification rate and dearomatic saturation rate are 95. 92%,97. 84% and 73. 50%,respectively.

The macropore alumina catalysis material FA-06 was prepared by nano self-assembly technique which has a pore volume of 1.39 cm(3).g(-1), a specific surface area of 297 m(2).g(-1), most probable pore size of 32.4 nm and a porosity of 81.85%. High concentration pore size distribution of 10 similar to 30 nm and 30 similar to 60 nm which percentages are 35.61% and 40.88%, respectively. GPC showed that the dispersion and relative molecular weight of RHP are controlled by the amount of PIBSA, which is the formation material of RHP, in order to control the pore sizes. From TEM and SEM, the results showed that the diameters of nano aluminum hydroxide rods are 250 similar to 300 urn, and the lengths are 600 similar to 800 nm. After calcinating at 550.0 degrees C, the nano alumina rods had the diameter of 150 similar to 300 urn, the length of 400 similar to 600 nm. XRD results of burned nano self-assembly aluminum hydroxide showed that gamma-Al2O3 be formed completely from three types of precursor of nano self-assembly aluminum hydroxide by burning process. Combining with data of TG, the gamma-Al2O3 is folioed completely due to the decomposition of pseudoboehmite at temperature of 605.0 degrees C, and the total weight loss reaches 61.88%. Based on the above experimental results, the molecular self-assembly and nano self-assembly formation process of reverse supersoluble micelle, aluminum hydroxide and macropore alumina were simulated. Moreover, the formation mechanism of NSA of nano self-assembly macropore alumina with penetrable pores was presented.

A new method was put forward to increase the amount of loading active metal by the silicon modification. The pore properties of silicon modified third nano self-assembly macroporous Mo-Ni/γ-Al2O3 catalytic materials were characterized by mercury porosimetry and N2 adsorption method. It is shown that the catalytic materials have pore volume of 0.66~0.90 cm3?g-1, specific surface area of 122~175 m2?g-1, and the pore size distribution reaches up to 69.08% at the range of 30~100 nm by the mercury porosimetry. The results show that the amount of loading active metal are increased, the amount of unit volume active metal and the bulk density are decreased by the silicon modification;The catalytic performance of hydrodesulfurization and hydrodecarbonresidue is better when the hydrogenation reaction tends to stable after 200 h.

以汽油-无水乙醇混合溶液为萃取剂,采用萃取-焙烧法脱除介孔氧化铝载体的模板剂,借助元素分析仪、物理吸附仪、傅里叶变换红外光谱仪(FTIR)、凝胶渗透色谱仪等仪器,考察了模板剂的脱除情况、载体的孔性质及相应的分子扩散.结果表明,采用萃取-焙烧法能脱除几乎全部的模板剂,并且C,N,H残留量少;萃取焙烧后载体6 ～ 20 nm的孔分布占71.2％,孔集中度高.经FTIR定性分析油相产物,确定与模板剂具有相同的官能团组成,为同一物质.由凝胶渗透色谱分析可知,油相产物的Mn,Mw分别为1 036,4 054,与渣油平均相对分子质量相当,渣油大分子可以很好地在大孔氧化铝载体中扩散.

利用不同共浸剂制备纳米自组装催化剂,用BET、XRD和H2-TPR手段考察催化剂中活性金属的分散状态、晶型及其还原性质.结果表明,活性金属在催化剂中的分散状态与催化剂中活性金属的晶型、催化剂的还原性能以及加氢活性密切相关.当催化剂中的活性金属呈单层分散时,八面体配位Mo物种的数量最高,此时催化剂的还原性能和加氢活性最好;当活性金属在载体表面的分散状态变差时,催化剂中八面体配位Mo物种数量逐渐减少,同时催化剂的还原性能和加氢活性也随着变低.

运用低温氮气吸附法、X射线光电子能谱法(XPS)、红外光谱一氧化碳原位吸附等方法对根据3次纳米自组装机理制备的大孔主客体纳米催化材料进行表征分析.结果表明,主客体催化材料的物性较优异;红外光谱的分析结果表明,一氧化碳在主客体催化材料表面的吸附主要表现为线式一氧化碳吸附态,共浸剂含量的增加有助于活性组分钼与载体之间发生强相互作用和催化材料的变换活性;而XPS则印证了活性金属钼在氧化态时以正六价的形式存在而硫化态则以正四价或低价钼的形式存在;并可知当共浸剂的含量由基准+20增加到基准+30后,催化材料中四价钼的比例由73.63％增加到80.01％;加氢评价表明催化材料FA70-Z30的HDS、HDN、HDAr转化率可达81.3％、47.6％、55.8％,其具有较好的抑制结焦和加氢性能.

A kind of alumina with large pore volume and framework structure has been prepared by using secondary nanoscale self-assembly process. It can be used as the catalyst support. The Mo-Ni-P nanoscale self-assembly alumina catalysts are prepared by adding surfactant A and B in order to modify the loading methods of dual activity metal on the alumina supports. The result shown that from the BET characteriza-tion,as for the system catalysts A,the most pore volumes and specific surface areas are 0. 49 cm3 / g and 211 cm2 / g,respectively,and the pore distribution between 10 ~ 60 nm accounted for more than 50% . That of B system,are 0. 41 cm3 / g and 202 cm2 / g,the pore distribution between 6 ~ 30 nm accounted for 55. 72% . Furthermore,the pore distribution are more than 10% at 0 ~ 6 nm and 60 ~ 100 nm. By analy-zing the result,the active of catalysts which have been absorbed by MNP has increased greatly,and these MNP nanoscale catalysts can be used in residue hydrotreating aspects.

Secondary nano self-assembly alumina was prepared by nano self-assembly owns the properties of large pore volume ,high specific surface area and low bulk density .Adopt this carrier ,a macroporous host-guest catalyst was prepared by third nano self-assembly .The desulfurization ,denitrification and aromatics saturation rate of the catalyst could be as much as 66.7% ,34 .6% and 77 .1% ,which showed a high performance of active metal per unit volume .In order to explain the high activity of macroporous host-guest catalyst ,a resonance absorption hydrogen spillover mechanism was proposed in this paper . Based on the double resonance-double precession-resonance movement model of introverted principle of the resonance field ,it explains the high hydrogenation activity of active components (transition metal elements as Mo ,Ni etc .) well ,especially for macroporous host-guest catalyst .

Adopting secondary nano self-assembly method to prepare macroporous catalyst(0106 ,1227)with small stacking density and high metal loading ,the distribution of pore volume centralized from 30 nm to 100 nm ,which accounts for 11% , 28% .The first activity of two kinds of nano self-assembly catalyst(0106 ,1227) was investigated with Zhenhai FCC diesel oil as feed at reaction temperatures of 360 ℃ ,reaction pressure of 7 MPa ,hydrogen-oil volume ratio of 600 ,volume space velocity oh 1 .5 h-1 in a fixed bed micro reactor of 10 mL ,and with reference agent as a contrast .The experimental results show that the two kinds of nano self-assembly catalyst (0106 ,1227)has higher activity of hydrodesulfurization ,hydro-denitrificationand aromatics saturation than the reference catalyst .The sulfur mass fraction of FCC diesel oil feedstock could be reduced from 12 400 μg/g to 483 ,283 μg/g which the highest desulfurization rate of 96 .10% and 97.71% ;the nitrogen mass fraction of FCC diesel oil feedstock could be reduced from 1 507 μg/g to 35 .7 ,14 μg/g which the highest denitrification rate of 97.63% and 99.00% ;the highest aromatics saturation rate of 67 .99% and 68 .88% ,while only to 537 ,64 .6 μg/g and 94.57% ,95 .54% , 65.65% over the reference catalyst .

The big pore host-guest catalysis material FA-40 was prepared with the secondary nano-assembly Al2O3 support by third nano-assembly technique which has a pore volume of 0.78 cm(3)center dot g(-1), a specific surface area of 114 m(2)center dot g(-1), average pore diameter of 27 nm, a structure of double peak pore of 6.0 nm and 40 nm, high concentration pore size distribution of 10 similar to 100 nm, a low stacking density of 0.56 g center dot cm(-3) and a concentration of metal as high as 35.70%. The results of the XRD and TEM showed that the active metal uniformly dispersed and existed in form of the microcrystal nano bulk phase which has < 2 nm diameter on the guest surface. Using the poor quality FCC diesel as stock feed, Hydrogenation performance of the different catalysts has been evaluated after 20 h the hydrogenation treating. The results. showed that the conversion in desulfurization, denitrification and aromatics saturation for FA-40 were 94.4%, 95.5%, 67.9% and 77.6%, 52.3%, 28.7%. Compared with F-5, increased by about 20%, 80% and 140%, respectively. Stability experiments for a long period of 300 h have been shown that FA-40 was better catalyst for hydrogenation performance.

采用二次纳米自组装法合成催化剂的堆积密度较低、金属负载量较高.FNMC和FA-28的比表面积分别为50 m2/g和170 m2/g.说明金属在FNMC上小孔堵塞和大孔金属大量聚集,而在FA-28上是多层分散的并形成纳米粒子.通过XRD和TEM的表征得到催化剂的晶相结构、微观形貌和金属分散,证明了BET的结论.活性评价结果表明,催化剂FNMC在渣油加氢处理上脱硫、脱氮、脱金属和脱残炭率分别为48.80％、20.08％、44.15％和31.34％,约为参比剂FCB的50％,而FA-28对催柴加氢处理的脱硫、脱氮及芳烃转化率分别为93.33％、95.34％和65.84％,约为FCB的2倍.

Using the Super-Solubilization Nanometer Self-Assembly method, bulk Ni-Al2 O3 catalyst is prepared with nickelnitratehexahydrate as the precursor and urea as precipitation agent,the mixture of the surfactant-gather isobutylene maleic acid triethanolamine esters and petroleum hydrocarbon-150SN as template agent.The Ni-Al2 O3 catalysts were characterized by TEM and TPR,and reaction mechanism of precipitation was studied.The results indicate that nanosized Ni-Al2 O3 bulk catalyst has a crystalline form with not only spherical shape,but also nanorod and nanometer silk,etc.Particles prepared by this method have good dispersion and uniform size,and narrow diameter distribution is observed between 10~50 nm.The Ni-Al2 O3 reduced by hydrogen also has a crystalline form,and nanostructure of reduced Ni-Al2 O3 is more orderly than before.Particles size after reduction is still in the nanoparticles scope.TPR results show that there are two reduction peak appeared in the structure of nanometer bulk Ni-Al2 O3 catalyst,and the low-temperature peak is NiO,high temperature reduction peak attributes to spinel structure which produced by the interaction of nickel and aluminum oxide.