丙烷选择氧化用VPO/SiO_2催化剂的研究

对比研究了VPO和VPO/SiO2 催化剂的结构、表面元素氧化态、还原性及其对丙烷选择氧化反应的催化性能 .与VPO催化剂相比 ,VPO/SiO2 催化剂具有较大的比表面积 ;VPO主要以 (VO) 2 P2 O7的形式高度分散于SiO2 表面 ;VPO/SiO2 催化剂的还原温度较低 ;VPO/SiO2 催化剂与丙烷的相互作用较强 ;在反应条件下 ,VPO/SiO2 催化剂的活性较高 ,但产物丙烯的选择性较低 ,并有丙烯醛等C3含氧化合物生成 .这可能是由于VPO/SiO2 催化剂表面的V与Si发生了相互作用之故 .随着VPO担载量的增加 ,VPO/SiO2 催化剂的比表面积减小 ;催化剂的还原温度略有升高 ,可还原的晶格氧量增加 ;催化剂表面与丙烷的相互作用增强 ;丙烷转化率升高而丙烯选择性降低 ,丙烯醛选择性在 5 %VPO/SiO2 催化剂上最高 .这可能是由于随着VPO担载量的增加 ,催化剂表面晶格氧的密度增大所

丙烷选择氧化用VPO/SiO_2催化剂的研究

对比研究了VPO和VPO/SiO2 催化剂的结构、表面元素氧化态、还原性及其对丙烷选择氧化反应的催化性能 .与VPO催化剂相比 ,VPO/SiO2 催化剂具有较大的比表面积 ;VPO主要以 (VO) 2 P2 O7的形式高度分散于SiO2 表面 ;VPO/SiO2 催化剂的还原温度较低 ;VPO/SiO2 催化剂与丙烷的相互作用较强 ;在反应条件下 ,VPO/SiO2 催化剂的活性较高 ,但产物丙烯的选择性较低 ,并有丙烯醛等C3含氧化合物生成 .这可能是由于VPO/SiO2 催化剂表面的V与Si发生了相互作用之故 .随着VPO担载量的增加 ,VPO/SiO2 催化剂的比表面积减小 ;催化剂的还原温度略有升高 ,可还原的晶格氧量增加 ;催化剂表面与丙烷的相互作用增强 ;丙烷转化率升高而丙烯选择性降低 ,丙烯醛选择性在 5 %VPO/SiO2 催化剂上最高 .这可能是由于随着VPO担载量的增加 ,催化剂表面晶格氧的密度增大所

Preparation and Characterization of Sinter-Resistant RhSm2O3/SiO2 Catalyst and Its Performance for Partial Oxidation of Methane to Syngas

以乙酰丙酮铑(Rh(acac)_3)和乙酰丙酮钐(Sm(acac)_3)为前驱体,用浸渍法制备了Rh/SiO_2和Rh-Sm_2O_3/SiO_; 2催化剂。采用原位红外光谱、热重分析、低温N_2吸附、X射线粉末衍射、高分辨透射电子显微镜、H_2-程序升温还原和X射线光电子能谱等实验技术对催; 化剂的制备过程,比表面积和物相以及Rh与Sm_2O_3间的相互作用进行了表征,并以甲烷部分氧化制合成气为目标反应对催化剂的稳定性进行了考察。研究; 表明:以Rh(acac)_3和Sm(acac)_3为前驱体采用简单的浸渍法即可制备出Rh平均粒径为2.3; nm且具有良好抗烧结性能的Rh-Sm_2O_3/SiO_2催化剂。在浸渍过程中乙酰丙酮化合物通过与SiO_2表面羟基形成氢键而负载于载体表面。S; m(acac)_3在SiO_2表面的单层负载量(质量分数)约为31%,对应于Sm_2O_3的质量分数约为15%,只要Sm(acac)_3的质量分; 数低于这一阈值,均可保证分解后生成的Sm_2O_3以高分散形式负载于SiO_2上,且不会因高温(800; °C)焙烧而团聚。高分散于SiO_2表面的Sm_2O_3与Rh之间存在强的相互作用,可显著提高Rh的分散度,防止其在高温反应条件下烧结,进而使低; Rh负载量的催化剂表现出良好的甲烷部分氧化制合成气反应活性和稳定性。Rh/SiO2 and Rh-Sm2O3/SiO2 catalysts were synthesized by the conventional impregnation method using rhodium acetylacetonate (Rh(acac)(3)) and samarium acetylacetonate (Sm(acac)(3)) as precursors. The preparation and catalytic properties, as well as the interaction between Rh and Sm2O3, were characterized in detail by in situ infrared spectroscopy (IR), thermogravimetric analysis (TG), N-2 physisorption (Brunauer-Emmett-Teller (BET) method), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed reduction (H-2-TPR) and X-ray photoelectron spectroscopy (XPS). The performance of the catalysts for the partial oxidation of methane (POM) to syngas was also investigated. The results showed that a sinter-resistant Rh-Sm2O3/SiO2 catalyst with an average Rh particle size of similar to 2.3 nm could be synthesized using the conventional impregnation method with Rh(acac)(3) and Sm(acac)(3) as precursors. The surface silanol groups of SiO2 acted as the centers to interact with M(acac)(3) (M=Rh, Sm) molecules when SiO2 was impregnated in the M(acac)(3) solution, leading to the formation of a hydrogen-bonded M(acac)(3) layer on the SiO2 surface. In this experiment, the monolayer coverage of Sm(acac)(3) on the SiO2 surface was equal to a Sm(acac)(3) loading (mass fraction) of approximately 31%, which in turn corresponded to a Sm2O3 loading of approximately 15%. When a Sm(acac)(3)/SiO2 sample with Sm(acac)(3) loading below 31% was heated in air to approximately 360?, the monolayer Sm(acac)(3) species decomposed into highly dispersed Sm2O3 species on the SiO2 surface, which displayed superior stability against sintering at high temperature. No aggregation of the Sm2O3 species was observed even when the sample was heated to 800 degrees C in air. The strong interaction between the highly dispersed Sm2O3 and Rh plays a key role in increasing the dispersion of Rh species in the catalyst and preventing the Rh species from sintering under high temperature conditions. This factor should also be responsible for the superior activity and stability of the Rh-Sm2O3/SiO2 catalyst with extremely low Rh loading for the catalytic partial oxidation of methane to syngas.国家重点基础研究发展规划项目（2013CB933102）,国家自然科学基金（21473144,21373168）,国家基础科学人才培养基金项目（J1310024）及教育部创新研究团队项目（IRT_14R31）资

Expression of Fusion Protein of Parathyroid Hormone and Transferrin N-terminal Half-molecule in Pichia pastoris

利用重叠PCR技术将PTH(parathyroidhormone,甲状旁腺激素)基因与TFN(transferrinN_terminalhalf_molecule,转铁蛋白N端半分子)基因在体外融合,融合基因克隆至真核表达载体pPIC9中,转化毕赤酵母GS115。转化子经甲醇诱导后,融合蛋白得到了表达并分泌到发酵上清液中。经SPSepharoseFF阳离子交换层析、PhenylSepharoseFastFlow疏水层析纯化获得了纯度大于95%的PTH_TFN样品。Westernblot分析及腺苷酸环化酶实验证明融合蛋白中的PTH具有与抗PTH抗体结合能力及刺激腺苷酸环化酶的活性,铁饱和实验证明融合蛋白中的TFN和单独的TFN具有相同铁结合能力。因而TFN可望作为PTH的天然运输载体。The fused gene (PTH_TFN) of parathyroid hormone (PTH) gene and transferring N_terminal half_molecule (TFN) gene was amplified by multiple PCR and inserted into pPIC9 vector. The recombinant plasmid pPIC9_PTH_TFN was transformed into Pichia pastoris GS115 by PEG. After methanol induction, the target protein was expressed in fermentation supernatant at high level.The fused protein PTH_TFN with purity being higher than 95% was finally obtained after purification through two_step chromatography : SP Sepharose Fast Flow and Phenyl Sepharose Fast Flow.Western blot analysis and adenylate cyclase assay proved that the fused protein exhibited the bioactivity to stimulate cAMP synthesis and the ability to bind Fe ~3+ in the Fe ~3+ saturation study as the recombinant TFN did indicating that TFN could be used as the transcellar carrier of PTH.国家高技术研究与发展项目基金资助(No.2004AA215172)。~

A Novel Method for Preparation of Activated Alumina

[中文文摘]将结晶氯化铝与柠檬酸及淀粉等造孔剂混合,经直接干燥和焙烧制得了一种无定形活性氧化铝,并通过X射线粉末衍射、N2物理吸附及氨程序升温脱附等手段对活性氧化铝样品进行了表征,探讨了各组分对活性氧化铝样品性质所起的作用.与常规的活性氧化铝制备方法相比,这种制法省去了中和、老化、过滤和洗涤等步骤,缩短制备周期且过程容易控制.活性氧化铝具有适宜且可调节的比表面积和孔径分布,作为载体负载镍金属组分制成负载型催化剂后,对乙苯加氢饱和与加氢裂化表现出较高的催化活性.[英文文摘]A novel and simple method was developed to prepare alumina with suitable specific surface area and pore size distribution. First,AlCl3·6H2O and citric acid were heated without water in a water bath at 90 ℃ with stirring until a homogenous solution was obtained.Then starch was added into is solution.After the solution was dried at 110 ℃ and calcined at indicated temperature, activated alumina was obtained.The activated alumina was characterized by N2 adsorption,X-ray diffraction,and NH3 temperature-programmed desorption. Compared with the usual technology , this novel preparation did not include some steps such as aging , filtering , and washing. Moreover , the specific surface area and pore size distribution of the activated alumina could be controlled and modified by changing the preparation parameters. The supported Ni/ Al2O3 catalyst with the activated alumina as support showed higher activity for hydrogenation and hydrocracking of ethylbenzene.国家重点基础研究发展计划(973计,2004CB217805); 福建省“百千万人才工程”项目; 福建省自然科学基金(U0750016)

MoPO/SiO_2催化剂上丙烷选择氧化制丙烯醛反应机理

考察了丙烷以及丙烷选择氧化反应的有关中间体或其探针分子(如丙烯、烯丙醇、异丙醇和正丙醇)和产物(如丙烯醛、丙酮和丙醛)在MoPO/SiO2催化剂上的反应行为,用以探明该催化剂上丙烷选择氧化制丙烯醛反应的可能路径.结果表明,异丙氧基是MoPO/SiO2催化剂上丙烷选择氧化制丙烯醛反应的主要中间体,异丙氧基脱β-H生成丙烯或脱α-H生成丙酮,而丙烯则经σ-氧烯丙基转化为丙烯醛

Preparation and Characterization of Presulfidation-Free MoNiP/Al_2O_3 Catalyst for Thiophene Hydrodesulfurization

[中文文摘]在Mo-Ni-P-O浸渍液中添加一定量的极性有机物如柠檬酸等,采用共浸渍法制备了一种不需预硫化和焙烧也具有较高加氢脱硫活性的MoNiP/Al2O3催化剂,并用N2吸附、程序升温还原、X射线光电子能谱、红外光谱和元素分析对催化剂进行了表征.结果表明,柠檬酸的添加削弱了金属组分与载体间的相互作用,有利于金属组分在载体表面的分散,且改善了催化剂的还原性,使催化剂在与含硫反应物料接触过程中自发硫化,从而有利于催化剂加氢脱硫活性的提高.[英文文摘]A new type of MoNiP/Al2O3 catalyst for thiophene hydrodesulfurization was prepared by the co-impregnation method, wherein a suitable amount of citric acid was added in the Mo-Ni-P-O impregnation solution. The catalyst exhibits high activity for thiophene hydrodesulfurization under presulfidation- and calcination-free conditions. The catalyst was characterized by N2 adsorption, temperature-programmed reduction, X-ray photoelectron spectroscopy, infrared spectroscopy, and elemental analysis methods. The effect s of cit ric acid on the structure and activity of the MoNiP/ Al2O3 catalyst were studied. The result s show that the addition of cit ric acid weakens the interaction between the active metal components and support , improves dispersion of active metal component s on the support surface , and promotes the reduction and sulfidation of the catalyst by sulfur-containing feedstocks. Therefore, the hydrodesulfurization activity of the catalyst is improved.国家重点基础研究发展计划(973计划, 2004CB217805); 厦门大学科技创新项目(XDKJCX20051002)

Reactor model with cross-flow for aromatics catalytic hydrogenation

[中文文摘]提出了一种抗硫中毒的芳烃加氢催化反应器模型,称之为交叉流反应器模型,把反应物料分为两股,其中含有噻吩的乙苯物料采用轴向连续流动方式由反应器进口进入催化剂床层,而氢气由铅直导管直接进入催化剂床层中,然后与乙苯物料混合。在氢气导管出口处形成含硫乙苯浓度低而氢气浓度高的特殊区域,因而硫对催化剂的中毒效应大幅度降低,整体上提高了乙苯加氢饱和反应效率。与传统轴向混合流反应器进行比较,在相同条件下交叉流反应器具有更好的整体加氢反应性能。分别建立了交叉流反应器与传统轴向混合流反应器模型,提出了两种反应器的催化反应转化率方程;利用此转化率方程,对实验数据进行处理,得到动力学参数,模型的计算结果与实验数据相吻合,也验证了在交叉流反应器中,硫的中毒效应明显减弱。[英文摘要]A novel reactor model named cross-flow reactor for aromatics catalytic hydrogenation was proposed.The reactants were divided into two flows:ethylbenzene with thiophene was introduced to the catalyst bed along the axial direction of the columnar reactor,while hydrogen was introduced into catalyst bed through a vertical pipe with openings.Because special areas with high H2 pressure and low H2S pressure were formed near these openings,the poisoning of catalyst by thiophene was substantially decreased,and consequently the reaction of et hylbenzene hydrogenation was improved as compared with the traditional reactor with mixed co-flow. Finally , kinetic models were established for this cross-flow reactor and the traditional reactor1And the conversion equations of these two reactors were given.By using these equations , the experiments data were fitted to obtain kinetics parameters. The calculation results agreed well with the experimental data. It was also demonst rated that sulfur poisoning in cross-flow reactor was weakened.国家重点基础研究发展计划项目(2004CB217805); 福建省“百千万人才工程”支持项目; 福建省自然科学基金项目(U0750016)

厦门市某医院体检人群中有机氯农药暴露与胆石症发病的关联性研究

目的探讨厦门市第二医院体检人群中有机氯农药暴露与胆结石发生的关联及其发病危险因素。方法收集2015年2月-8月在医院健康体检人群中经B超确诊的新发胆囊结石患者100例,以同期参加体检的非胆囊结石者为对照,进行1∶2配比的病例对照研究。进行流行病学调查,采用气相色谱联用电子捕获器检测研究对象外周血中有机氯农药水平。应用多因素条件Logistic回归模型分析有机氯农药与胆囊结石发病的关系。结果病例组血清中α-HCH残留水平高于对照组,差异有统计学意义;Logistic回归分析非酒精性脂肪肝、2型糖尿病、血清α-HCH含量增高可能增加胆结石的患病危险,OR值及95%CI分别为5.134(1.952~13.502)、4.754(1.849~12.220)和1.357(1.094~1.854)。结论环境有机氯农药暴露可能是胆囊结石病发生的危险因素。厦门市科技计划项目(3502Z20163006)；厦门市集美区科技计划项目(20142C01)；厦门大学校长基金(20720152012)

Studies on VPO/SiO2 catalyst for selective oxidation of propane

VPO catalyst is one of promising catalysts for selective oxidation of C4H10 and C3H8. The catalysts VPO and VPO/SiO2 with different VPO loading were prepared. Using BET, XRD, LRS, XPS, H-2-TPR and C3H8-TPD techniques, the physicochemical properties of the catalysts, such as structure, reducibility, vanadium oxidation states and V-O bond, as well as the interaction between C3H8 and the catalysts, were comparatively investigated. The catalytic performance of the catalysts in selective oxidation of C3H8 was also tested. VPO/SiO2 had higher specific surface area and reducibility than VPO. In addition, the binding energy of V 2p(3/2) on VPO/SiO2 was higher than that on VPO, which indicated that the coordination environment of V changed and Vdelta+ (4 < delta < 5) might exist on VPO/SiO2. Compared with VPO, the stronger interaction between C3H8 and VPO/SiO2 was observed. The interaction between Si and V occurred on VPO/SiO2, which modified its physicochemical properties and in return changed its catalytic performance. In the case of VPO/SiO2, (VO)(2)P2O7 was the main phase (oxidation state) and highly dispersed on SiO2. With the increase of VPO loading, the reduction temperature of the catalyst and binding energy of V 2p(3/2) changed slightly, and the intensity of V-O bond and the H-2 consumption in TPR increased, indicating that the amount of V-O species increased on the surface. On the other hand, with the increase of VPO loading, the C3H8 conversion increased while the CA Selectivity reduced, and the acrolein selectivity appeared the maximum value on 5% VPO/SiO2 catalyst