Study on Preparation and Application of Ti／Si Complex Zeolite

A Ti/Si complex zeolite has been prepared. X-ray diffraction and infrared spectrometry study has shown that two structures, namely the ZSM-5 and MCM-41, exist in the sample. BET tests have revealed that the complex zeolite contains regular mesopores of 2.6 nm. Ultraviolet spectrometry analysis has shown that the Ti species exist in the zeolite skeleton in the form of tetra-coordinate valence. The Ti/Si complex zeolite (TS-1/Ti-MCM-41) has apparently improved catalytic activity with respect to the macromolecular organic compound oxidation as compared to individual components of either Ti or Si containing zeolites (TS-1 and Ti-MCM-41).     

催化热裂解工艺机遇及影响因素

分析了催化热裂解过程的反应机理及乙烯和丙烯形成的反应，乙烯和丙均可通过热裂解和催化裂解生成，讨论了影响乙烯，丙烯产率的因素：与USY和REY相比，使用ZSM－5催化剂能够提高乙烯，丙烯产率，磷改性ZRP－1经碱土金属改性后，可进一步提高乙烯和丙烯的产率，提高反应温度和降低剂油比，能够提高热裂解和催化裂解的比例，有利于乙烯产率的提高；增强蒸汽量能够减少焦炭产率，提高乙烯和丙烯产率。     

磷改性ZSM-5分子筛物化性质和裂解制乙烯性能的研究

The physicochemical features of phosphorus-modified ZSM-5 zeolites (SiO2/Al2O3 molar ratio is 25) were characterized by XRD(X-ray diffraction), BET(Brunauer, Emmett and Teller spcific surface area measurement), NH3-TPD(ammonia temperature-programmed desorption) and MASNMR(magic angle spinning nuclear magnetic resonance), and the performance on catalytic pyrolysis to produce ethylene was investigated with a light hydrocarbon fixed bed micro-reactor with n-octane as feed. The results show that the acid site density, acid intensity and hydrothermal stability of ZSM-5 zeolite were improved by phosphorus modification. When P205 content in ZSM-5 zeolite is higher than 2.5%, phosphorus modification can prevent ZSM-5 zeolite crystal structure transformation from orthorhombic to monoclinic. In addition, the dealumination of ZSM-5 zeolite framework was moderated by phosphorus modification under high temperature hydrothermal treatment. The results of n-octane pyrolysis on phosphorus-modified ZSM-5 zeolites show that ethylene yields of zeolites with different phosphorus content are almost the same under the same n-octane conversion. However, the modified zeolites with higher pyrolysis activity give lower yield of propene, butene and total olefin than lower pyrolysis activity under the same n-octane conversion.     

煤焦油沥青质与减压渣油沥青质结构组成的对比

基于核磁共振氢谱(¹H-NMR)、核磁共振碳谱(¹³C-NMR)和傅里叶变换离子回旋共振质谱(FT-ICR MS),分析了煤焦油和减压渣油中正庚烷沥青质的结构和分子组成的差异。在大气压光致电离源(APPI)和电喷雾电离源(ESI)下,质谱测得的煤焦油沥青质相对分子质量分布范围均小于减压渣油沥青质,但其中含氧类化合物或其他含氧多杂原子相对丰度高于减压渣油沥青质。各类化合物中,煤焦油沥青质均含有更小等效双键数(DBE)的化合物;在相同DBE下,减压渣油沥青质的碳数分布范围更大,意味着减压渣油沥青质的烷基侧链分布范围宽。计算了煤焦油沥青质和减压渣油沥青质结构单元平均分子式分别为C_30.54H_26.57S_0.04N_0.54O _2.80和 C_42.41H_41.54S_0.85N_0.63O_0.48。煤焦油沥青质结构单元的芳香度较高,而芳环数和芳环缩合度均小于减压渣油沥青质。煤焦油沥青质中的低缩合度化合物能够对沥青质聚集体中芳环的堆积作用产生直接的影响,但影响程度仍需进一步研究。     

TiSiW12O40/TiO2催化合成丁醛乙二醇缩醛

以固载杂多酸盐TiSiW₁₂O₄₀/TiO₂为多相催化剂,对以丁醛和乙二醇为原料合成丁醛乙二醇缩醛的反应条件进行了研究。实验表明TiSiW₁₂O₄₀)/TiO₂是合成丁醛乙二醇缩醛的良好催化剂。较系统地研究了醛醇的物质的量的比、催化剂用量、反应时间诸因素对收率的影响,得到最佳反应条件为:n(丁醛):n(乙二醇)=1:1.5,催化剂用量为反应物料总质量的0.5%,环己烷为带水剂,反应时间1.0 h。上述条件下,丁醛乙二醇缩醛的收率可达81.9%。

     

THEORETICAL PREDICTION OF SOUND RADIATION FROM A HEAVY FLUID-LOADED CYLINDRICAL COATED SHELL

０ＩＮＴＲＯＤＵＣＴＩＯＮＡｈｅａｖｙｆｌｕｉｄ－ｌｏａｄｃｙｌｉｎｄｒｉｃａｌｓｈｅｌｉｓｔｈｅｂａｓｉｃｓｔｒｕｃｔｕｒａｌｅｌｅｍｅｎｔｗｉｄｅｌｙｕｓｅｄｉｎｍａｎｙｉｎｄｕｓｔｒｉａｌｆｉｅｌｄｓ．Ｔｈｅｖｉｂｒｏａｃｏｕｓｔｉｃａｎａｌ...     

TiSiW12O40/TiO2 催化合成氯乙酸异戊酯

以固载杂多酸盐TiSiW12 O40 /TiO2 为多相催化剂 ,通过氯乙酸和异戊醇反应合成了氯乙酸异戊酯 ,并探讨了TiSiW12 O40 /TiO2 对酯化反应的催化活性 ,较系统地研究了醇酸物质的量比、催化剂用量、反应时间诸因素对产率的影响。实验表明 :TiSiW12 O40 /TiO2 具有良好的催化活性 ,醇酸物质的量比为 1.4∶1,催化剂用量为反应物料总量的 1.5 % ,反应时间 1.5h ,反应温度 98～ 12 6℃时 ,酯收率可达 92 .78%。     

粘性阻尼滞迟振子简谐激励响应的等效线性化计算方法研究

研究了单自由度、两自由度含有粘性阻尼双性滞迟振动简谐激励下的响应计算问题，将效线性化计算方法推广至含有迟滞环节的单自由度、两自由度非线笥振动系统，并证明了在首次近似意义上，等效线性化方法与Krylov-Bogoliubov慢变参数法、Fourier级数展开法是等价的，三者具有相同的计算精度。     

Molecular Simulation of Naphthenic Acid Removal on Acidic Catalyst II. Experimental results of catalytic decarboxylation over acidic catalysts

The energy barriers of thermal decarboxylation reactions of petroleum acids and catalytic decar-boxylation reactions of Brnsted acid and Lewis acid were analyzed using molecular simulation technology. Compared with thermal decarboxylation reactions of petroleum acids, the decarboxylation reactions by acid catalysts were easier to occur. The decarboxylaton effect by Lewis acid was better than Brnsted acid. The mechanisms of catalytic decarboxylation over acid catalyst were also verified by experiments on a...     

MIP Technology for Pruduction of Euro IV Clean Gasoline II. Correlation Model of Sulfur Content of MIP Naphtha and Its Application

On the basis of the reaction rules and its influencing factors of sulfur compounds in MIP naphtha, a correlation model for describing the correlation between mass fraction of sulfur in MIP naphtha, mass fraction of sulfur in feedstock and volume fraction of olefin in naphtha was developed and the model's parameters were estimated. The residual error distribution and statistical study showed that the developed model was reasonable and reliable and able to predict the mass fraction of sulfur compounds in naphtha. The correlation model can provide theoretical guidance and operation base for adjusting process parameters to produce EURO IV gasoline by the MIP units. The model was validated by its application on the MIP unit of Qingdao Refining & Chemical Company. On this unit, the tail oil with low sulfur content obtained via hydrotreating gas oil was used as the feedstock and the olefin content of naphtha was reduced by promoting hydrogen transfer reaction through adjustment of process parameters. Thus, EURO IV clean gasoline was manufactured by this MIP unit.