蒙旦树脂烃化学组成及结构特征

本文对中国三种蒙旦树脂烃潦浒树脂烃（ＬＨＴ）,寻甸树脂烃（ＸＤＴ）,舒兰树脂烃（ＳＬＴ）进行了ＧＣＭＳ分析,获取了树脂烃中单元化合物的组成和结构。结果表明,在这三种树脂烃中,主要是五环三萜烃类五环三萜烷,五环三萜烯,单环、二环、三环、四环芳构化五环三萜烷以及三环二萜烃类降松脂烷,降松香烷,降海松烷,松香烷,山达松脂烷,单环、二环芳构化三环萜烷。比较三种树脂的总离子色谱图,发现在寻甸蒙旦树脂烃和舒兰树脂烃中,五环二萜的各种化合物是该组分主要化学组成,尤其在舒兰蒙旦树脂烃中,具有四环芳构化的萜烷其含量占绝对优势。潦浒蒙旦树脂烃中,三环二萜的各种物质是其重要的化学组成。与此同时,阐述了中国蒙旦蜡精制漂白脱色不完全的原因。     

蒙旦树脂化学组成的研究

采用阴离子交换色谱和硅胶－氧化铝柱色谱对云南寻甸蒙旦树脂（ＸＤＳＺ）、潦浒蒙旦树脂（ＬＨＳＺ）、昭通蒙旦树脂（ＺＴＳＺ）和吉林舒兰蒙旦树脂（ＳＬＳＺ）进行了族组分的分离。树脂游离酸，树脂结合酸，树脂烃和树脂醇在各树脂中的百分含量分别为ＸＤＳＺ１１．８６，８．７６，１２．３０，４５．９９；ＬＨＳＺ１５．８９，１３．９１，４．９０，４５．９９；ＳＬＳＺ２５．４６，８．０７，１７．４０，３６．２２；ＺＴ     

褐煤树脂中游离酸的化学组成与结构特征

对云南潦浒、寻甸、吉林舒兰褐煤树脂中游离酸的化学组成及结构特征进行了对比研究。结果显示,潦浒和寻甸游离树脂酸主要是由云 氢松香酸组成,其它三环二萜酸,如松脂酸、三达松脂酸、氢化松香酸、松香酸以及五环三萜酸均有分布,但含量低。正构烷酸Ｃ１２￣Ｃ２８也存在着分布,且集中在Ｃ１６、Ｃ１８和Ｃ２０上,低碳数支链烷酸也被检出。因此,去氢松香酸是潦浒寻甸游离树脂酸的特征代表物,与此相反,舒半游离树脂酸则主要     

光催化-膜分离集成反应器及其应用

 设计了一种新型光催化-陶瓷膜分离集成反应器,在反冲条件下利用此集成反应器进行了甲基橙光催化氧化反应,分别考察了陶瓷膜对光催化剂TiO2微粉的截留率、膜的渗透通量、光催化氧化脱色率以及不同膜分离压力下的光催化反应速率常数. 结果表明,TiO2-甲基橙悬浆液体系中TiO2微粉的截留率可达到99.9%, 经集成反应器完成一个反应周期后甲基橙氧化脱色率达到10%, 光催化氧化脱色效果高于圆柱式反应器.     

褐煤蜡树脂中多环芳烃组织的研究

采用气相色谱法对云南寻甸褐煤炭树脂和吉林舒兰褐煤蜡树脂,进行了多环芳烃分布特征的研究,从树脂中鉴定出６８个化合物的同系物。两个树脂样均以菲系化合物占有优势,舒兰树脂中菲系列量约三倍于寻甸树脂的相应量。     

费托蜡热裂解制线性α-烯烃工艺研究

以煤制油工艺费托精制蜡为原料,在固定床反应器上进行了热裂解制线性α-烯烃（LAO）的实验,考察了原料组成、裂解温度、停留时间、水蜡比及循环工艺对转化率及裂解产物分布的影响,优化了工艺条件。结果表明,裂解温度及停留时间对原料转化率及LAO收率有显著影响,循环工艺可进一步提高LAO收率。过高的裂解温度或过长的停留时间均会导致生成的LAO的二次反应,对反应不利。在适合的工艺条件下可获得53%的LAO收率。     

阴离子交换色谱和硅胶柱色谱法用于褐煤蜡族组成的分离

叙述了用阴离子交换色谱和硅胶柱色谱分离褐煤蜡纯蜡中的游离酸、酯中酸、醇以及烷烃的方法。通过红外光谱鉴定,表明阴离子交换色谱对蜡中酸的分离效果相当好。实验表明,寻甸粗蜡主要是由长链酯的混合物组成,它是一种天然的酯型蜡。舒兰粗蜡中含有丰富的游离酸,其量达43%。HNO_3氧化后,蜡中游离酸的增加则是由于酯的水解和醇的进一步氧化所致。     

高效利用稻壳联产木糖、多孔炭和二氧化硅

用稀酸水解半纤维素制得木糖母液,并通过正交实验得到最佳水解条件,即在130℃、稀酸质量分数2%、反应6 h的条件下,水解率可达到96.8%(以稻壳中的半纤维素为基准),去除杂质精制后木糖产率为62.8%.水解后的稻壳残渣用来制备稻壳基多孔炭和二氧化硅,其中多孔炭孔隙发达、孔径均一,可用来对木糖母液进行脱色处理,在脱色过程中对木糖的吸附损失小,达到精制木糖的目的.同时,在制备稻壳基多孔炭的过程中可同步制取高纯度二氧化硅.     

臭氧氧化优尼素红B-B染料废水及脱色动力学研究

研究了在鼓泡反应器中,臭氧氧化优尼素红B-B模拟染料废水在10~70℃范围内的脱色反应动力学.发现并解释了不同温度下出现的反应速率交叉现象,利用紫外可见分光光度法定量分析染料特征颜色(浓度)变化情况.结果表明,在不同温度下,表观脱色反应动力学都符合一级动力学规律,相关系数都达到了0.95以上.40℃下,反应速率常数为0.011 83 s~(-1),臭氧氧化脱色过程符合y=exp(0.521-0.014x+5.02×10~(-6)x~2)方程.随着温度的升高,臭氧在高温下氧化染料的反应速率小于臭氧的分解速率,低温时臭氧氧化的速率高于臭氧的分解速率,导致高温下氧化速率变慢.在40~50℃时,臭氧氧化优尼素红B-B染料废水脱色率最高,利用紫外可见分光光度法对氧化后废水进行分析,结果表明脱色率达到了99.5%.     

非水介质中脂肪酶催化亚麻酸油醇酯合成的研究

已知脂肪酶（ＥＣ３．１．１．３）在非水体系中能够催化合成脂肪族、芳香族和其它多种多样的酯类．这些反应中的大多数都是以链较长的脂肪酸为底物．其中一类反应是高级脂肪酸和脂肪醇合成酯蜡的酯化反应．合成的酯蜡用途广泛,可以用在化工、纺织、医药、日化、食品等工业中．利用传统的化学法合成酯蜡,需要在高温高压及强酸条件下进行反应,副反应多,产物的分离纯化困难,生产成本高,且对于长链脂肪酸和醇的反应难度增大．利用脂肪酶水解反应的逆反应酯化反应合成酯蜡的方法,具有反应条件温和,产物的分离纯化容易等优点,能够弥补化…     

Products of the gas-phase reactions of OH radicals with (C2H5O)2P(S)CH3 and (C2H5O)3PS

Products of the gas-phase reactions of OH radicals with O,O-diethyl methylphosphonothioate [(C2H5O)2P(S)CH3, DEMPT] and O,O,O-triethyl phosphorothioate [(C2H5O)3PS, TEPT] have been investigated at room temperature and atmospheric pressure of air using in situ atmospheric pressure ionization mass spectrometry (API-MS) and, for the TEPT reaction, gas chromatography and in situ Fourier transform infrared (FT-IR) spectroscopy. Combined with products quantified previously by gas chromatography, the products observed were: from the DEMPT reaction, (C2H5O)2P(O)CH3 (21+/-4% yield) and C2H5OP(S)(CH3)OH or C2H5OP(O)(CH3)SH (presumed to be C2H5OP(O)(CH3)SH by analogy with the TEPT reaction); and from the TEPT reaction, (C2H5O)3PO (54-62% yield), SO2 (67+/-10% yield), CH3CHO (22-40% yield) and, tentatively, (C2H5O)2P(O)SH. The FT-IR analyses showed that the formation yields of HCHO, CO, CO2, peroxyacetyl nitrate [CH3C(O)OONO2], organic nitrates, and acetates from the TEPT reaction were <5%, 3+/-1%, <7%, <2%, 5+/-3%, and 3+/-2%, respectively. Possible reaction mechanisms are discussed.     

Synthesis and Characterizaion of a New Inorganic-organic Sulfate Compound--Crystal Structure of [Ni(H2O)6][H2N(C2H4)2NH2](SO4)2

[Ni(H2O)6][H2N(C2H4)2NH2](SO4)2 is an inorganic-organic compound with a new open framework synthesized by hydrothermal method, and characterized by means of single-crystal diffraction and spectroscopic data. The compound crystallized in a monoclinic space group P21/n with a=1.29089(2) nm, b=1.06301(3) nm, c=1.33202(4) nm, β=114.0870(10)°, V=1.67127(8) nm3, Z=4, and was solved by using the direct method and the least-squares refinement converged at R=0.0214[I>2σ(I)]. The structure consists of isolated Ni(H2O)6 octahedra and SO4 tetrahedra, with both of them hydrogen-bonded to piperazine cations.     

Improved quasi-unary nucleation model for binary H2SO4-H2O homogeneous nucleation

Aerosol nucleation events have been observed at a variety of locations worldwide, and may have significant climatic and health implications. Binary homogeneous nucleation (BHN) of H2SO4 and H2O is the foundation of recently proposed nucleation mechanisms involving additional species such as ammonia, ions, and organic compounds, and it may dominate atmospheric nucleation under certain conditions. We have shown in previous work that H2SO4-H2O BHN can be treated as a quasi-unary nucleation (QUN) process involving H2SO4 in equilibrium with H2O vapor, and we have developed a self-consistent kinetic model for H2SO4-H2O nucleation. Here, the QUN approach is improved, and an analytical expression yielding H2SO4-H2O QUN rates is derived. Two independent measurements related to monomer hydration are used to constrain the equilibrium constants for this process, which reduces a major source of uncertainty. It is also shown that the capillarity approximation may lead to a large error in the calculated Gibbs free energy change for the evaporation of H2SO4 molecules from small H2SO4-H2O clusters, which affects the accuracy of predicted BHN nucleation rates. The improved QUN model-taking into account the recently measured energetics of small clusters-is thermodynamically more robust. Moreover, predicted QUN nucleation rates are in better agreement with available experimental data than rates calculated using classical H2SO4-H2O BHN theory.     

Quasi-unary homogeneous nucleation of H2SO4-H2O

We show that the binary homogeneous nucleation (BHN) of H2SO4-H2O can be treated as quasi-unary nucleation of H2SO4 in equilibrium with H2O vapor. A scheme to calculate the evaporation coefficient of H2SO4 molecules from H2SO4-H2O clusters is presented and a kinetic model to simulate the quasi-unary nucleation of H2SO4-H2O is developed. In the kinetic model, the growth and evaporation of sulfuric acid clusters of various sizes are explicitly simulated. The kinetic quasi-unary nucleation model does not have two well-recognized problems associated with the classical BHN theory (violation of the mass action law and mismatch of the cluster distribution for monomers) and is appropriate for the situations where the assumption of equilibrium cluster distribution is invalid. The nucleation rates predicted with our quasi-unary kinetic model are consistent with recent experimental nucleation experiments in all the cases studied, while the most recent version of the classical BHN model systematically overpredicts the nucleation rates. The hydration of sulfuric acid clusters, which is not considered in the classical model but is accounted for implicitly in our kinetic quasi-unary model, is likely to be one of physical mechanisms that lead to lower nucleation rates. Further investigation is needed to understand exactly what cause the difference between the kinetic quasi-unary model and the classical BHN model.     

Dynamics of vibrational overtone excitations of H2SO4, H2SO4-H2O: hydrogen-hopping and photodissociation processes

Photochemical processes of sulfuric acid (H2SO4) and sulfuric acid monohydrate (H2SO4-H2O) following overtone excitation of the OH stretching mode are studied by classical trajectory simulations using the semiempirical PM3 potential suface in "on the fly" calculations. The main results are the following: (1) In the excitation of H2SO4 to the fifth OH-stretch overtone, hopping of the H atom between oxygen atoms is found to take place in 22% of the trajectories, only once during simulations of 400 ps. (2) All the trajectories for H2SO4 show a rapid cis-trans isomerization. (3) The photolysis of H2SO4 into SO3 + H2O takes place in 5% of the trajectories on a time scale of approximately 9 ps. (4) Only low overtone levels of H2SO4-H2O have sufficiently long lifetimes to be spectroscopically relevant. Excitation to these OH stretching overtones is found to result in the dissociation of the cluster. H hopping or dissociation of H2SO4 does not take place.     

Hydrogen-bonded Three-Dimensional Networks Encapsulating One-dimensional Covalent Chains: [Cu(3-ampy)(H2O)4](SO4)·(H2O) (3-ampy = 3-Aminopyridine)

A three-dimensional complex [Cu(3-ampy)(H2O)4](SO4)·(H2O) (3-ampy = 3-aminopyridine) has been synthesized. Crystallographic data: C5H16CuN2O9S, Mr = 343.80, triclinic, space group P, a = 7.675(2), b = 8.225(3), c = 10.845(3) (A), α= 86.996(4), β = 76.292(4),γ = 68.890(4)°, V = 620.0(3) (A)3, Z = 2, Dc = 1.841 g/cm3, F(000) = 354 and μ = 1.971 mm-1. The structure was refined to R = 0.0269 and wR = 0.0659 for 1838 observed reflections (I ＞ 2σ(Ⅰ)). The structure consists of [Cu(3-ampy)(H2O)4]2 cations, SO42- anions and lattice water molecules. 3-Ampy acting as a bidentate bridging ligand generates a 1D covalent chain. A supramolecular 2D framework is formed through π-π stacking of pyridine rings. The lattice water molecules and SO42- anions are located between the adjacent 2D frameworks. The hydrogen bonding interactions from lattice water molecules and SO42- anions to coordinate water extend the 2D framework into a 3D network.     

Cr_2O_7~(2-)/Cr~(3+)间接氧化环己醇合成己二酸

以Cr2O72-/Cr3+作为间接氧化剂电氧化环己醇制备己二酸.应用正交实验优化工艺条件,得出在原料比n(环己醇)∶n(Cr2O72-)=0.4∶1,t=35℃和CH2SO4=5mol.L-1条件下己二酸的收率可达70.29%.同时研究了Ag2SO4、(NH4)2SO4、H2SO4浓度、电流密度对Cr3+电氧化为Cr2O72-的影响,Cr3+的转化率可达82.52%.     

二维层状水合酸式硫酸铈H3O[Ce(SO4)2·(H2O)3]·H2O的水热合成与结构表征

镧系金属硫酸盐由于在稀土分离等方面具有重要的应用而受到广泛关注。但是，因其适于结构测定的单晶相对难以得到，迄今，关于稀土硫酸盐的结构报道仍然较少，且主要局限于水合硫酸盐和三元硫酸盐．近几年中，基于硫酸根与磷酸根在结构上的相似性，借鉴在水热／溶剂热体系中采用有机胺作模板剂大量合成具有空旷骨架结构的微孔磷酸盐的成功经验，以有机胺为模板剂合成具有空旷骨架结构的镧系金属硫酸盐的工作也已见诸报道．在这些化合物中，由于硫酸根配位方式的多样性和稀土元素配位数和配位构型的可调变性，展现出了一些有趣的结构特征．