活性白土上松节油直接制备对伞花烃的反应过程

以自制活性白土为催化剂,松节油为原料液相法直接制备对伞花烃,采用傅里叶红外光谱(FT-IR)和气相色谱-质谱联用技术(GC-MS)对反应产物进行了分析鉴定,研究其反应过程并探讨了反应机理。GC-MS分析共分离出44个峰,鉴定出41种化合物,其中主要产物为对伞花烃和3-对孟烯,相对质量分数分别为56.57%和10.46%;松节油主要成分蒎烯的转化率为100%,对伞花烃收率为62.78%;首次鉴定出松节油歧化产物中非挥发性物质和聚合物如西松烯的存在。FT-IR分析显示,产物中蒎烯环内双键的3022、1655 cm^-1特征峰及＝CH₂的3067 cm^-1特征峰基本消失,1611、1498、1458 cm^-1处的苯环骨架振动及815 cm^-1苯环对位双取代单峰的强度增大,也表明蒎烯已完全反应,主要生成对伞花烃。对活性白土催化松节油的反应过程进行了探讨,双环单萜蒎烯的异构及分子间氢转移歧化反应为主反应,并伴随深度开环异构、水合重排、聚合等副反应,倍半萜发生异构、脱氢及水合重排等反应。     

松节油催化异构-分子间氢转移反应的研究

以马尾松松节油为原料进行直接催化异构-分子间氢转移反应的研究,探讨了Pd/C-H2SO4协同催化反应的机理.采用500 r·min-1的搅拌转速与10～20 μm的催化剂粒径,以气相色谱-质谱联用(GC-MS)和气相色谱(GC)定性、定量分析了反应产物,考察了催化剂种类、酸种类、温度、催化剂含量、酸浓度及时间等条件对反应的影响,测定不同搅拌转速下的液-液-固非均相反应效果,结果表明,在Pd/C-H2SO4复合催化剂上,反应温度为120℃、催化剂用量为占松节油质量的 0.2 %,20 % H2SO4溶液及反应时间为8 h的最优反应条件下,蒎烯的转化率为99.13 %,对伞花烃的收率为61.56 %,并认为在Pd/C-H2SO4复合催化剂上松节油异构-分子间氢转移反应机理是酸性中心作用的正碳离子历程与金属中心作用的氢转移历程共同组成,其主要成分双环单萜蒎烯的异构及分子间氢转移歧化反应为主反应,实现异构-分子间氢转移平行连串反应的耦合,使反应时间从原来两步法的14 h降低为8 h.     

松节油催化异构-分子间氢转移反应集总动力学

以H2SO4-Pd/C为复合催化剂、N2为保护气研究了松节油直接异构-分子间氢转移反应的集总动力学。在消除内、外扩散影响的条件下,在线跟踪反应产物并用气相色谱法测定反应体系组成随时间的变化关系,借鉴集总思想和方法,建立了单萜烯、对孟烯结构的单环单萜烯、异构单萜烯、对伞花烃和氢化单萜烷复杂反应体系的集总动力学模型;采用Levenberg-Marquart法,以Matlab编程和SPSS软件对实验数据进行回归估算了模型参数,得到该复杂反应体系的活化能分别为77.86,80.18,71.33 kJ/mol,所建动力学模型与实验数据吻合良好。     

GC-MS法分析松节油及其氢化产物的化学成分

采用 DB- 5毛细管柱和 GC- MS- DS技术对松节油及其氢化产物的化学成分进行全分析。从原料松节油中分离出 36个组分 ,鉴定了其中的 32个组分 ,主要成分为 α-蒎烯、β-蒎烯、烯、长叶烯、对 -伞花烃、莰烯、α-香叶烯及石竹烯等。从相应的氢化松节油中分离出 32个组分 ,鉴定了其中的 2 4个组分 ,主要成分为顺 -蒎烷、反 -蒎烷、长叶烯、对 -烷、2 ,6 -二甲基辛烷及对 -伞花烃等。还对松节油各组分的加氢反应作了归类。     

用分子筛催化异构化α-蒎烯和β-蒎烯及其混合体系的研究

以HY型分子筛为催化剂,开展了α-蒎烯、β-蒎烯及其混合体系的异构化反应研究,考察了α-蒎烯和β-蒎烯含量、催化剂用量、反应温度对异构化反应的影响。结果表明,催化剂在350℃下焙烧2h,当其用量为2.5g/100mL原料,反应在140℃下保持4h时,松节油有更好的异构化效果,转化率达96.13%,异构化产物中莰烯的含量为40.80%,苧烯为24.24%;并且发现了原料中的氧化物对异构化反应产生不利影响。     

氯化锌直接催化α-蒎烯异构制备莰烯反应规律研究

研究了以无机氯化物为催化剂催化α-蒎烯异构制备莰烯的反应规律,考察了催化剂种类、催化剂用量、反应时间、反应温度对异构反应的影响,确定了最佳的反应条件。在最佳反应条件下,即以氯化锌(ZnCl2)为催化剂,用量占α-蒎烯质量的3%,α-蒎烯用量2.86g,温度140℃,反应时间10h,α-蒎烯异构化反应转化率为94.64%,莰烯选择性为50.42%。     

Pd/C催化剂上烯酮的选择性加氢反应

采用釜式反应器,在无溶剂条件下考察了金属Pd的负载量、催化剂粒度、载体预处理方式和反应温度等因素对Pd/C催化剂6,10,14-三甲基-13-烯-2-十五烷酮(FA-4H)选择性加氢性能的影响规律。实验结果表明:随着Pd负载量的增加,Pd/C催化剂FA-4H加氢的活性逐渐增加;当Pd负载量在0.5%~3.0%(wt),FA-4H完全转化时目标产物六氢法呢基丙酮(PA)的选择性为99.3%~99.5%。较小的催化剂粒度对应较短的催化剂孔道,有利于减少产物PA在催化剂孔道内停留的时间,从而在一定程度上防止了C=O双键的过度加氢。此外,活性炭载体的硝酸或氨水预处理、较低的反应温度等也有利于减少Pd/C催化剂上FA-4H完全转化时加氢副产物6,10,14-三甲基-13-烯-2-十五烷醇(FA-alcohol)和6,10,14-三甲基-2-十五烷醇(PA-alcohol)的生成量,从而使目标产物PA的选择性接近100%。     

响应面法优化Ni-P/APO-11非晶态催化剂催化松节油加氢反应

以二异丙胺、氢氧化铝为原料,采用水热合成法制得APO-11磷酸铝分子筛。采用化学还原法制备非晶态Ni-P/APO-11催化剂用于α-蒎烯加氢反应,考察了α-蒎烯加氢反应条件,通过响应面法实现进一步优化,而后采用XRD、BET、SEM、XPS、ICP等对该催化剂进行了表征。结果显示,在反应温度124.8℃,反应压力4.9 MPa,催化剂用量6.3%,反应时间90 min时,α-蒎烯转化率为99.45%,顺式蒎烷选择性97.35%。为进一步拓宽该催化剂使用范围及提高松节油体系的深加工利用水平,将该催化剂用于松节油其他组分的加氢反应中,展现出良好的催化活性,原料转化率均可达到99%以上,选择性65%以上。     

响应面法优化Ni-P/APO-11非晶态催化剂催化松节油加氢反应

以二异丙胺、氢氧化铝为原料,采用水热合成法制得APO-11磷酸铝分子筛。采用化学还原法制备非晶态Ni-P/APO-11催化剂用于α-蒎烯加氢反应,考察了α-蒎烯加氢反应条件,通过响应面法实现进一步优化,而后采用XRD、BET、SEM、XPS、ICP等对该催化剂进行了表征。结果显示,在反应温度124.8℃,反应压力4.9 MPa,催化剂用量6.3%,反应时间90 min时,α-蒎烯转化率为99.45%,顺式蒎烷选择性97.35%。为进一步拓宽该催化剂使用范围及提高松节油体系的深加工利用水平,将该催化剂用于松节油其他组分的加氢反应中,展现出良好的催化活性,原料转化率均可达到99%以上,选择性65%以上。     

Pd／Al2O3催化剂上裂解C5馏分选择性加氢反应研究

研究了负载在Al2O3载体上的贵金属钯（Pd）基催化剂在裂解C5馏分中选择性加氢反应中的性能。结果表明,Pd／Al2O3催化剂上可进行选择性加氢的反应条件区域为压力0．5～1．0MPa、体积空速2—4h^-1、氢油体积比100：1～300：1和反应温度为55—65℃,在此反应条件下,炔烃能被完全加氢去除,同时二烯烃发生部分转化,转化产物主要为单烯烃,其中二烯烃转化的产物主要是热力学相对稳定的单烯烃;在选定的反应条件中,随温度升高、压力增加、氢油比增加,炔烃、二烯烃转化率提高;而随液时空速增加,二烯烃转化率有所下降;在各反应条件中,温度和压力对催化剂加氢性能影响较为显著;制备的Pd／Al2O3催化剂对于炔烃和二烯烃具有好的选择性加氢能力,可能原因一方面是由于反应条件选择较缓和,另一方面是原料中硫的存在。     

Isomerization of Alpha-pinene Over Acid Treated Natural Zeolite

In this study, isomerization of α-pinene was studied over several acid-treated natural zeolite catalysts rich in clinoptilolite. Zeolite samples were contacted with HCl at different concentrations at 30°C or at 60°C for 3 and 24 hours and tested in isomerization reaction of alpha-pinene. The catalysts prepared were characterized by XRD, nitrogen adsorption, and acidity studies. Acidity strength and the distribution of Lewis and Brönsted acid sites of the catalysts were determined, and their catalytic activities in α-pinene isomerization and selectivities to main reaction products, camphene and limonene, were investigated. Acid treatment improved the selectivity of catalyst samples to camphene, decreasing the selectivity to limonene, probably forcing limonene to secondary reactions at high conversions.

The kinetics of α-pinene consumption was described by first-order kinetics. Two kinetic models were tested for the reaction mechanism and one model was found to give a good correlation between the theoretical and experimental data. In the models, the key intermediate was the pinylcarbonium ion, which was formed irreversibly from α-pinene.

Number and distribution of Lewis and Brönsted acid sites affect the formation of bicyclic and monocyclic products.     

Generation and Quantification of Ultrafine Particles through Terpene/Ozone Reaction in a Chamber Setting

Terpene/ozone reactions produce gas- and condensed-phase products and thus contribute to both indoor and outdoor aerosol. These reactions may be important in indoor settings, where terpenes are generated from indoor sources and ambient ozone can reach significant levels. Moreover, airway irritation has been observed in mice exposed to terpene oxidation products (OPs). The aim of this study was to characterize a system for generating and quantifying ultrafine particles formed through terpene/ozone reactions in preparation for inhalation toxicology experiments. Two common monoterpenes, f -pinene and d -limonene, and a hemiterpene, isoprene, were investigated. Ozone and gas-phase terpene were introduced continuously into a reaction flow tube, from which reaction products entered a plexiglass chamber. Particle number, mass, and size distribution (～15-750 nm) were monitored in the chamber for various reactant concentrations and air exchange rates (AERs). In all experiments, ozone was the limiting reagent and the reaction rate was much more rapid than the AER. Particles formed rapidly and in high concentrations in the pinene and limonene systems. Particle formation was slower in the isoprene system and fewer particles were formed; moreover, particle diameters were smaller. In all 3 systems, progressive growth of particles was observed due to condensation and coagulation processes. The isoprene system displayed instability with respect to aerosol characteristics and did not reach steady-state conditions. In the pinene system, ozone concentration was a strong predictor of steady-state particle number and mass concentration and particle diameter. The particle number was greater at higher AERs, but particles were smaller. This study is the first to incorporate measurement of ultrafine particles formed from terpene/ozone reactions into a controlled exposure chamber setting. Following system characterization, we will conduct mouse exposures to further investigate the respiratory effects of gas- and particle-phase terpene OPs.     

茶用香花珠兰的香气成分分析

用水蒸气蒸馏法提取珠兰挥发油,并用气相色谱-质谱联用仪对珠兰挥发油的化学成分进行了分离和鉴定,分离并鉴定出27个组分,占峰面积的85.89%,并用峰面积归一化法测定了各成分的质量分数。其主要挥发性成分为:w(反-罗勒烯)=5.71%、w(3,6二-甲基-4,5二-乙基-3,5-辛二烯)=4.61%,w〔1-(1,4二-甲基-3环-己烯基)乙酮〕=3.53%、w(2,6二-甲基-2,4,6辛-三烯)=1.45%、w(大根香叶烯B)=1.44%、w(顺-罗勒烯)=1.43%、w(大根香叶烯D)=1.40%、w(3蒈-烯)=1.25%、w(杜松醇)=1.02%。     

合成类胡萝卜素关键中间体十碳烯醛的新方法

对类胡萝卜素关键中间体十碳烯醛的合成方法作出重要改进,新的合成路线包括以反式-1,4-二氯-2-丁烯为起始原料,经格氏反应、缩合反应与酸性水解反应合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛（十碳烯醛）。反应选择性好,副产物少,工艺较简单,操作方便。     

Synthesis of terpene alcohols from isoprene oligomers

Various terpene alcohols were prepared from isoprene oligomers via two steps: epoxidation with peracetic acid and isomerisation with aluminium triisopropoxide. For example, 2-methylene-6-methyl-7-octene-1-o1 was prepared from 2,6-dimethyl-1,7-octadiene. From 2,6-dimethyl-2,7-octadiene, 3,3,6-trimethyl-1,5-heptadiene, 2,7-dimethyl-2,6-octadiene, 2,6-dimethyl-1,3,6-octatriene, 1-methyl-4-isopropenyl-1-cyclohexene, and 1,5-dimethyl-1,5-cyclooctadiene, the corresponding alcohols were obtained, respectively.     

活性炭负载硅钨酸催化α-蒎烯的异构化研究

以活性炭负载硅钨酸为催化剂 ,研究了 α-蒎烯的异构化反应 ;考察了反应温度、反应时间、配料比和溶剂等因素对异构化反应的转化率和选择性的影响。实验结果表明 ,反应温度升高 ,反应时间增加 ,配料比减小 ,蒎烯的转化率增大。在乙醇介质中 ,α-蒎烯能发生异构化和乙氧基化反应。主要产物是莰烯、苎烯和 α-松油基乙醚 ,总醚选择性约 5 0 %     

Copolymerization of isobutene with 2,4,6-octatriene and other triconjugated trienes

Summary The cationic homogeneous Copolymerization at low temperature of 2,4,6-octatriene (OT), 1,3,5-heptatriene (HPT), 2,5-dimethyl-1,3,5-hexatriene (DMH) and alloocimene (AO) with isobutene (I) was performed and the structure of the resulting copolymers examined spectroscopically. OT reacted mainly by 2,7-opening of the triene system yielding soluble copolymers with block character and containing a low amount of cyclized units. Soluble I-HPT copolymers containing 2–4 mol % of conjugated double bonds were obtained. DMH alway gave insoluble copolymers and only traces of conjugated unsaturations were found in I-AO copolymer.     

刺梨和无籽刺梨挥发性香气成分分析

用固相微萃取技术和气相色谱-质谱联用技术,对刺梨和无籽刺梨的香气成分进行了分析测定,峰面积归一化法测定各成分相对质量分数。从刺梨中检测鉴定了33个化合物,无籽刺梨中共检测鉴定了30个化合物,在刺梨和无籽刺梨中都存在的化合物有14个。刺梨中的主要成分为:3,7-二甲基-1,3,7-辛三烯(20.469%),壬醛(5.029%)、1-石竹烯(6.101%)、γ-芹子烯(12.733%)、正二十八烷(6.507%);无籽刺梨中的主要成分为:乙酸顺式-3-己烯酯(10.649%)、(Z)-3,7-二甲基-1,3,6-十八烷三烯(5.672%)、1-石竹烯(10.643%)、α-石竹烯(5.911%)、γ-芹子烯(18.218%)、α-芹子烯(5.412%)、正十七烷(11.573%)。刺梨与无籽刺梨的主要成分有一定的差异,可能是造成二者气味及口感差异的原因。     

Study on the pinene isomerization catalyzed by TiM

The isomerization reaction of pinene is one of the most important chemical reactions in the deep processing of pinene. The purpose of this study is to improve the performance of the metatitanic acid by composite. The composite metatitanic acid catalyst TiM was prepared by adding Mn elements in the preparation process. The catalytic performance of TiM was evaluated. Comparison of TiM and metatitanic acid catalyst (Ti-FGP), the reaction rate of TiM catalyst was faster, and after the reaction, the yield of camphene and tricyclene increased about 1%. The catalysts were characterized by an SEM, FT-IR and laser particle size analyzer. The results show that the pinene isomerization reaction requires the synergistic action of the Brönsted acid and Lewis acid. Brönsted acid has great influence on the activity of catalyst, and Lewis acid has a great influence on the selectivity of the catalyst. The structure and morphology of the catalyst have a certain effect on the selectivity of pinene isomerization reaction.