丁烯氢甲酰化制备低正异比混合戊醛新型催化剂开发及反应动力学的研究

将自主开发的低正异比（N/I）氢甲酰化催化（HY-IH）体系用于丁烯氢甲酰化合成制戊醛.通过小试工艺优化,2-甲基丁醛选择性大于50%（即N/I约为1∶1）,远高于国内现有工业装置3%~10%的水平.同时,得到反应速率与丁烯浓度、反应温度和催化剂铑（Rh）浓度的相关动力学方程.通过连续模试反应对小试动力学进行了修正,为工业化装置设计提供了依据.     

8 MPa下C307催化剂上甲醇合成反应的本征动力学

在等温积分反应器中研究了操作条件对甲醇合成反应的影响以及C307催化剂上甲醇合成反应的本征动力学.实验采用粒度为0.154～0.198 mm的细颗粒催化剂.实验压力为8MPa,空速5 500～11 000 h-1,反应温度200~260℃.实验结果表明:总碳转化率在实验温度范围内随温度的升高先增加后降低,245℃左右达到最大值,随压力的升高而增加.选取以各组分逸度表示的CO、CO2加氢合成甲醇的Langmuir-Hinshelwood双速率本征动力学模型,用全局通用算法结合马夸特算法确定动力学模型参数.残差分析和统计检验表明,动力学模型是适宜的.     

新型Al-Ti／C催化剂制备及催化EA合成研究

制备了新型AlCl3·6H2O-TiCl3/C（Al-Ti/C）复合催化剂,分别以AlCl3·6H2O/C、TiCl3/C、AlCl·6H2O-TiCl3/C为催化剂,乙酸和乙醇为原料,一步酯化法合成乙酸乙酯（EA）。讨论了醇酸物质的量比、反应温度、回流时间以及催化剂用量、种类与配比等因素对酯化反应的影响,并得出最佳反应条件。结果表明,AlCl3·6H2O-TiCl3/C复合型催化剂的催化活性优于AlCl3·6H2O／C和TiCl3/C,进一步提高了反应产率。     

烷基多苷合成的反应动力学研究

介绍了十二烷基多苷合成的动力学，建立了化学反应为控制阶段时合成十二烷基苷的动力学模型及其参数，利用模型可算出液态组份的浓度和葡萄糖的转化率。     

(Z)-3-水杨酰肼羰基丙烯酸乙酯的合成

为进一步探讨双酰肼羧酸酯的合成方法,以水杨酸甲酯和水合肼为原料,首先合成了水杨酰肼,再与顺丁烯二酸酐反应,合成了(Z)-3-水杨酰肼羰基丙烯酸((Z)-H4shcpa).然后由(Z)-H4shcpa和FeCl3·6H2O进一步构造了金属冠醚体系.通过内部自催化反应,(Z)-H4shcpa发生酯化,经过SnCl2/HCl溶液还原体系处理,最终得到了乙酯化的产物(Z)-3-水杨酰肼羰基丙烯酸乙酯((Z)-H3eshcp).对目标化合物进行了IR、1H-NMR、13C-NMR和元素分析等表征,结果表明:通过内部自催化反应,经由金属冠醚体系,可以解决双酰肼羧酸乙酯的合成难题.     

NC306铜基催化剂上甲醇合成的本征动力学研究

采用微型等温积分反应器,在5 MPa、225~271℃,原料气中CO、CO2和H2的摩尔分数分别为5.13%~14.23%、0.56~9.20%和61.96%~77.48%的条件下,对国产NC306型低压铜基甲醇合成催化剂的本征动力学特性进行了实验研究.基于CO和CO2竞争加氢双路线合成甲醇反应模式,以Simplex-Powell复合优化法和Merson迭代法对动力学实验数据进行搜索、选优,建立了NC306型低压铜基甲醇合成催化剂的L-H-H-W型动力学模型.统计检验结果表明,所建模型良好地吻合了实验数据,是适宜和可信的.     

四水合乙酸钴脱水反应的动力学

用等温热重法和非等温热重法研究了Co(CH3COO)2.4H2O的脱水反应.在51.4℃、55.9℃、59.6℃、61.4℃下的等温热重数据由等转化率下的lnt=E/RT+ln[g(α)/A]进行拟合确定了活化能的大小;升温速率为10℃/min的非等温热重曲线显示Co(CH3COO)2.4H2O的脱水反应发生在55.1~100.2℃,其数据通过Doyle-Zsako法进行拟合,以线性相关系数为判据并结合等温热分析拟合结果,得到该脱水反应的非等温积分动力学模式函数g()α=1-(1-α)1/2,相应的动力学方程是dα/dt=Aexp(-E/RT).2.(1-α)1/2,活化能E=74.16 kJ.mol-1,指前因子lg[A/s-1]=11.48.     

四水合乙酸鈷脱水反应的动力学

用等温热重法和非等温热重法研究了Co(CH3COO)2.4H2O的脱水反应.在51.4℃、55.9℃、59.6℃、61.4℃下的等温热重数据由等转化率下的lnt=E/RT ln[g(α)/A]进行拟合确定了活化能的大小;升温速率为10℃/min的非等温热重曲线显示Co(CH3COO)2.4H2O的脱水反应发生在55.1~100.2℃,其数据通过Doyle-Zsako法进行拟合,以线性相关系数为判据并结合等温热分析拟合结果,得到该脱水反应的非等温积分动力学模式函数g()α=1-(1-α)1/2,相应的动力学方程是dα/dt=Aexp(-E/RT).2.(1-α)1/2,活化能E=74.16 kJ.mol-1,指前因子lg[A/s-1]=11.48.     

相转移催化合成栀子醚的反应动力学研究

分别研究了以二氯甲烷、苯作为溶剂,四丙基溴化铵为相转移催化剂合成栀子醚的反应动力学特征,并探讨了不同结构催化剂对反应的影响.     

AlCl3*6H20催化合成醋酸异戊酯

以异戊醇和冰乙酸为原料,采用六水合三氯化铝作催化剂合成醋酸异戊酯.考察了催化剂用量、原料配比和反应时间等因素对反应的影响.确定了三氯化铝作为催化剂的最佳反应条件n冰乙酸∶n异戊醇＝1∶0.7(摩尔比),六水合三氯化铝用量为0.6 g,反应时间为3.0 h,转化率(以0.2 mol冰乙酸计)达94.2%.     

基于Pt-Au-MoS2-ITO传感器对于H2O2的还原检测

实验探究了二硫化钼（MoS₂）作为一种新型材料与贵金属纳米粒子金（Au）、铂（Pt）的复合基底对于过氧化氢（H₂O₂）的还原性检测,采用氧化铟锡导电玻璃（ITO）作为电极,制备出了基于Pt-Au-MoS₂-ITO的生物传感器,为H₂O₂还原性检测的便携性操作打下了基础.实验采用电化学沉积的方法制备材料,同时使用循环伏安（CV）法、计时电流法等传统电化学手段表征了传感器电化学性能,采用场发射扫描电子显微镜（FE-SEM）来表征传感器表面形貌.建立了用于H₂O₂还原检测的、具有高检测限、高灵敏度和宽检测范围的传感器.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

Distribution of C4 plants along the Northeast China transect and its correlation to the environmental factors

The distribution of C₄ plants and the C₄/C₃ ratio along Northeast China transect (NECT) have been studied. A model to quantify their relation with environmental factors has been set up. The ratio of the number of C₄ plants to that of C₃ plants along NECT shows two low and two high trends from east to west, and their distribution is mainly decided by annual average temperature and precipitation.     

Vegetation evolution on the central Chinese Loess Plateau since late Quaternary evidenced by elemental carbon isotopic composition

There are many controversial issues in loess studies such as natural vegetation types on the Chinese Loess Plateau during the historical periods and the spatial and temporal evolution of C3/C4 plants. Elemental carbon isotopic composition （δ^13Cec） in the loess section may offer new evidence for these problems. Elemental carbon （EC） is produced by incomplete combustion of vegetation, and its carbon isotopic composition has a very small difference from that of the formal vegetation, then δ^13Cec can be used as a record to recover the changes of vegetation. Elemental carbon was extracted by applying the oxidation method from the Ioess-paleosol sequence in the central Chinese Loess Plateau, and its car- bon isotope composition was analyzed by the isotope mass spectrometer. The results showed that the vegetation in this region was a mixed type of C3 and C4 plants, dominated with C3 plants in most of the time. Since late Quaternary, C3/C4 plants may not follow a simple glacial-interglacial cycle mode on the Chinese Loess Plateau, but showing fluctuations. C3 plants increased gradually in L4 period, and more C3 plants occurred during $3 period, and C4 plants increased again during L3-- L2 periods, after that, Cs plants dominated again during S1 --S0 periods. During periods of paleosol development, C3 plants were abundant in S3 and S1, and there were more Ca plants in S2 and SO. During periods of loess sedimen- tation, there were more C3 plants in L4 and L1, and there were more C4 plants in L3 and L2. On the orbital timescale, the vegetation variations revealed by δ^13Cec record are consistent with the results of pollen data and also similar to the results obtained by organic carbon isotopic composition since the last glacial period.     

VUV threshold photoelectron spectroscopy of the C2H3Cl molecule

The threshold photoelectron spectrum of the C₂H₃Cl molecule is studied by using synchrotron radiation light source and supersonic molecular beam. The vertical ionization potentials of different orbital electrons and some vibrational structures are obtained. The observed Rydberg autoionization peaks are assigned by A²A¹ state of C₂H₃Cl₊.     

钯催化剂丙烯腈气相加氢动力学研究

通过在固定床积分反应器上的动力学实验,得到了在钯催化剂上丙烯腈气相加氢制丙腈反应的本征动力学表达式为:rA=6.89×104exp(-41840/RT)cA0.71cH1.12。     

Theoretical study on the lithium bond interaction of furan homologues C4H4Y （Y=O,S） with LiCH3 via DFT and MP2

The optimizations geometries and interaction energy corrected by BSSE of the complexes between C4H4Y （Y=O, S） and CHiLi have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three complexes were obtained. Abnormally, the calculations showed that all the C10--Li14 bond lengths increased obviously but the blue-shift of C10-Li14 stretching frequency occurred after formed complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy corrections of complexes I-III is -45.757, -35.700 and -39.107 kJ·mol^-1, respectively. The analyses on the combining interaction with the atom-in-molecules theory （AIM） also showed that a relatively strong lithium bond interaction presented in furan homologues C4H4Y-LiCH3 systems. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the complex I is formed with n-σ type lithium bond interaction between C4H40 and LiCH3, complex II is formed with TT-s type lithium bond interaction between C4H4O and LiCH3, and complex III is formed with TT-s and n-s type lithium bond interactions between C4H4S and LiCH3, respectively.     

Spontaneous transformation of C60Br24 to C60 in solvents

It was found that C₆₀Br₂₄ transforms to C₆₀ spontaneously in some solvents. The intermediate, C₆₀Br₈, can be separated in some cases. When the bromine trap, phenol, was added,p-bromophenol and other brominated product were obtained and identified. The influences of time, the kind of solvent, etc were investigated. Possible mechanism was suggested. Supported by the National Natural Science Foundation of China Liu Ying: born in 1969, Ph. D     

Simulation experiments on the reaction system of CH4-MgSO4-H2O

H2S-rich gas in carbonate reservoirs is usually attributed to thermochemical sulfate reduction （TSR）. In this paper, thermal simulation experiments on the reaction system of CH4-MgSO4-H2O were carried out using autoclave at 425℃--525℃. The threshold temperature for initiating TSR is much lower than our previous studies （550℃）. Properties of the reaction products were analyzed by microcoulometry, gas-chromatography （GC）, Fourier transform-infrared spectrometry （FT-IR） and X-ray diffraction （XRD） methods. Thermodynamics and reaction kinetics of TSR processes were investigated on the basis of the experimental data. The results show that thermochemical reduction of magnesium sulfate with methane can proceed spontaneously to produce magnesium oxide, hydrogen sulfur, and carbon dioxide as the main products, and high temperature is thermodynamically favorable to the reaction. Ac- cording to the reaction model, the calculated activation energy of TSR is 101.894 kJ/mol, which is lower than that by most previous studies. Mg^2＋ may have played a role of catalytic action in the process of TSR. The elementary steps of TSR and reaction mechanism were discussed tentatively. The study can provide important information on the explanation of geochemical depth limit for natural gas and on the generation of high H2S gas in deep carbonates reservoirs.     

Rh/Ti3C2Tx MXene催化剂用于氨硼烷催化产氢

二维过渡金属碳/氮化合物基（MXene）催化剂对于水解产氢反应具有优异的催化活性.以二维过渡金属碳化钛（Ti₃C₂T_x MXene）材料为载体,采用原位还原法,制备了超高分散度的二维Ti₃C₂T_x MXene材料担载的金属铑（Rh）催化剂（Rh/Ti₃C₂T_x MXene）.利用单层二维Ti₃C₂T_x MXene材料高度暴露的表面,实现了Rh亚纳米团簇的高度分散.在常压的温和条件下,将制得的Rh/Ti₃C₂T_x MXene催化剂用于氨硼烷的常温分解.在35℃,0.1 MPa的条件下,氨硼烷可以在3 min内完全实现氢气（H₂）的释放.催化剂的结构表征证明：Rh亚纳米团簇的平均尺寸约为0.66 nm.构效关系研究表明：二维Ti₃C₂T_x MXene载体表面高度暴露的碳钛键（C-Ti）结构可以起到锚定和高度分散Rh亚纳米团簇的作用.