生物质热解制备木醋液及其性质研究

对杉木屑、棉杆、竹屑三种生物质热解制得的木醋液产率、基本理化性质及其有机成分进行了分析研究。结果表明,三种生物质原料在350℃下热解制得的粗木醋液、精制木醋液产率相差不大,相同条件下氯化钾浸渍处理后的杉木屑热解所得的粗木醋液、精制木醋液的产率有所降低。三种原料制得的精制木醋液的理化性质不同,杉木屑木醋液的pH值最小,密度最大,竹屑和棉杆木醋液的有机酸含量相对较高。采用GC-MS对精制木醋液中的有机成分进行了分析,结果表明,杉木屑木醋液中的主要组分为酸类、酚类和酮类化合物,棉杆和竹屑木醋液中的主要组分除这三类有机物质外,还含有相对含量较高的醇类化合物。酸类和酚类化合物在三种木醋液中的相对含量依次是竹屑 >棉杆 >木屑;酮类的相对含量依次是木屑 >棉杆 >竹屑。氯化钾处理后的木屑热解所得的木醋液中主要组分酚类和酮类化合物的相对含量有所降低,酸类化合物的相对含量增加,主要表现为乙酸相对含量的增加。与杉木屑木醋液相比,KCl处理后的杉木屑木醋液中的醇类化合物相对含量增加了1倍左右。     

阔叶树皮木醋液与木焦油有机成分的气相色谱分析

运用气相色谱对阔叶树皮木醋液及木焦油水提取液的有机成分,如醇类、羧酸类、酮类、酚类等进行了定量分析.结果表明,木醋液随着蒸馏处理,甲醇、乙醇、丙酮等低沸点物质主要分布在前馏液中,2,6-二甲氧基苯酚、甲基环戊烯醇酮、2-甲基-3-羟基-4-吡喃酮等高沸点物质主要分布在残馏液中.通过阔叶树皮木醋液及木焦油水提取液的两种主馏分所含有机成分的定量分析比较,表明除甲醇、乙酸、丙酸、2-呋喃醛等成分以外,二者具有相似的化学成分组成.     

木醋液的成分分析

采用KarlFisher法测定了木醋液中的水分含量;在样品未经过处理的条件下和经乙醚萃取、浓缩后,分别采用气相色谱–质谱联机技术(GC/MS)分析,测得了其中的有机成分和它们的相对含量。实验结果表明,木醋液中除了主要成分乙酸外,另外还含有含量较少、种类繁多的酮类化合物、酚类化合物、酯类、醛类和醇类等化合物。     

镍基催化剂催化木醋液重整制氢实验研究

为了实现木醋液的高值化利用,在固定床反应器中,进行木醋液催化重整制氢实验,采用浸渍法制备一系列不同Co添加量的Ni基催化剂,以产氢率、碳转化率、H_2选择性和积炭量为主要评价指标,探究液时空速、反应温度、镍钴比等工况对木醋液催化重整制氢的影响,同时采用XRF、H_2-TPR、SEM及元素分析等方法对催化剂进行了表征。结果表明,液时空速增加,产气量增大,但液时空速过高会加速催化剂失活。高温有利于木醋液的催化重整制氢反应,温度到达900℃时,氢气产率最高。随着钴添加量的增加,反应产生的积炭降低,但氢气产率也会有所下降。因此,当液时空速为60 h~(-1),温度为800℃时,采用Ni-0.5Co/Al_2O_3催化剂,最适于木醋液的催化重整制氢实验。     

有机叔膦催化缺电子炔酯(炔酮)环加成反应研究进展

有机膦小分子催化剂是一类具有较强亲核性的路易斯碱,在有机合成研究领域具有广泛应用.缺电子炔酯或炔酮与叔膦发生亲核加成反应可以生成两性离子中间体,进而发生各种有机化学反应,包括异构化反应、α-、β-、γ-加成反应以及[2+2]、[3+2]、[4+2]环加成反应,其中环加成反应为构建各种药物分子、天然产物以及生物活性分子提供了有效的手段,因此研究有机膦催化缺电子炔酯(炔酮)的环加成反应具有重要的意义,综述了近年来有机膦催化缺电子炔酯(炔酮)环加成反应研究进展与应用.     

制备有机-无机杂化纳米材料的研究进展

有机-无机杂化纳米材料由于小尺寸和兼具有机、无机材料的各种优良性质,在许多领域都有巨大的应用潜质。本文介绍了模板法、嵌段聚合物自组装、含特殊官能团的乙烯基单体直接聚合法等制备纳米有机-无机杂化材料的方法,并对各自的特点进行了说明。     

现代分析技术在PM_(2.5)组份识别中的应用

以上海市闵行地区的大气细颗粒物PM_(2.5)为研究对象,综合多种分析测试手段对颗粒物的成份进行分析,以识别PM_(2.5)中主要污染物的来源。采用扫描电镜和透射电镜技术观察颗粒物的形貌特征,红外光谱技术识别颗粒物中的特征官能团,再结合碳分析仪,电感耦合等离子体质谱,离子色谱和气相色谱等技术对颗粒物中的元素碳和有机碳、无机金属元素、无机水溶性离子及有机化合物PAHs进行定量分析。结果表明PM_(2.5)是由大量的微米颗粒物及部分超细颗粒物组成,颗粒物主要以烟尘聚集体的形式存在;PM_(2.5)中有无机盐类和有机化合物的官能团共存在,有机官能团主要为羧基和芳烃化合物,无机化合物主要为硫酸盐和氨类化合物;各化学组份的质量分数表明了二次离子(SO_4~(2-),NO_3~-,NH_4~+)和有机碳是PM_(2.5)中的主要污染物,并明确解析了PM_(2.5)中各种污染来源的分担率。     

油田水中烷基酚的胶束电动色谱分离

采用硼酸盐-十二烷基硫酸钠胶束电动色谱对油田水中存在的烷基酚进行了分离分析。考察了影响分离的各种不同因素：缓冲液浓度、体系的pH值、胶束溶液浓度、分离电流、管住温度及有机添加剂β-环糊精等。在恒流100μA下,38min内可分离20种烷基酚。采用Cl－TBP萃淋树脂对油田水样进行了浓缩富集预处理。     

当归化学成份分析研究——根部非挥发性成份分析

本文报导了甘肃岷县当归根部非挥发性成份的分析结果。共鉴定出37个有机成份,其中15种未见报导。用等离子体发射光谱检出当归中13种微量元素。     

分析科学中的综合分析—剖析技术进展

本文从分析方法和应用两方面，对分析科学中的一个重要分叉－剖析技术予以综合介绍。从方法论看剖析，它充分体现了分析科学综合性的特点、集分离分析、结构分析和成份分析于一体，全面表征物质的结构和成份信息；从应用方面看，它囊括无机，有机，物化和生化等领域中的分析课题，以材料科学、生命科学和环境科学中的各种复杂样品的分析，因此剖析又是把分析科学与合成，加工和应用技术紧密联系的一种系统工程。它的学科地位和广泛的     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。