农作物秸秆解聚研究

农作物秸秆是重要的生物质资源.本文从我国建立资源节约和环境友好社会目标的角度,论述了农作物秸秆高效利用的重要性和研究农作物秸秆解聚对开发农作物秸秆高效利用的新工艺的重要意义.介绍了农作物秸秆解聚的典型工艺及解聚产物组成分析和利用研究的进展,预测了农作物秸秆解聚研究的发展方向.     

农作物秸秆解聚研究

农作物秸秆是重要的生物质资源。本文从我国建立资源节约和环境友好社会目标的角度,论述了农作物秸秆高效利用的重要性和研究农作物秸秆解聚对开发农作物秸秆高效利用的新工艺的重要意义。介绍了农作物秸秆解聚的典型工艺及解聚产物组成分析和利用研究的进展,预测了农作物秸秆解聚研究的发展方向。     

酸碱解聚玉米秸秆分子结构的实验研究

以玉米秸秆为研究对象,分别采用5%H2SO4和5%NaOH溶液对秸秆进行解聚处理,并对解聚前后秸秆结构、化学组成、热稳定性等进行分析和表征。结果表明,与未处理前相比,经酸或碱解聚处理后,秸秆纤维结晶度由51.8%分别提高到63.5%和67.0%,秸秆中大部分半纤维素和部分木质素组分被脱除,半纤维素由29.10%分别降至7.02%和6.86%,木质素由38.12%分别降至32.21%和16.52%,而纤维素则由31.54%分别升至60.54%和76.15%。经酸碱处理后,秸秆表面形态结构变得疏松,出现小孔和裂缝,降解温度达到350℃,热稳定性能增加。上述结果说明,稀酸或稀碱均对玉米秸秆分子结构有一定程度的解聚作用,但就解聚溶出木质素而言,稀碱的解聚溶出效果要优于稀酸的。     

碱解聚对玉米秸秆的影响

以玉米秸秆为研究对象,氢氧化钠为解聚剂,研究了碱解聚前后玉米秸秆组份、表面形态、化学官能团和纤维结晶度的变化。结果表明:玉米秸秆中木质素的主要组成单体是H-木质素,解聚液中的酚类物质有4-羟基苯甲醛、香草醛、紫丁香醛、对香豆酸和阿魏酸。玉米秸秆经碱解聚,表面形态变得疏松而多孔,红外光谱下木质素的特征吸收峰消失,85%的木质素和52%的半纤维素被脱除,而纤维素的相对含量增加,结晶度增大。说明碱解聚有利于后续酶解和(或)其它生化方法的实施,以实现秸秆纤维的高值转化。     

秸秆材料的改性及其在水处理中的应用研究

当前水体污染问题日趋严重,寻求高效、环保,且成本低廉的水处理剂一直以来是水处理技术研究中的重要方向之一.秸秆是一类农作物废弃物,材料中富含纤维素和木质素等天然高分子,来源十分广泛,且是一类可再生资源.然而目前过剩的秸秆材料大多仍是通过焚烧处理,这不仅给大气环境带来危害.还造成资源的极大浪费.将秸秆材料通过适当的处理和改性,作为水处理剂,应用于污水处理中,无疑具有重要的现实意义和经济价值.本文详细综述了近年来国内外就秸秆材料的改性处理方法及其在水处理中的应用研究情况.     

亚/超临界乙醇液化秸秆纤维素解聚反应研究与机理初探

利用间歇式高压反应釜,在反应温度200～330 ℃、乙醇用量0～150 mL条件下,考察了亚/超临界乙醇直接液化秸秆纤维素的解聚行为,并初步探讨了其液化机理。结果表明,反应温度、乙醇用量和反应停留时间对秸秆纤维素的液化均有显著影响,反应温度由200 ℃升高至330 ℃,重油和气体收率分别增加了12.55%、28.83%;乙醇用量增加,反应压力随之升高,乙醇进入超临界状态,残渣和气体收率相比单纯热裂解分别降低11.10%和8.44%。通过GC/MS、FT-IR分析生物油组分和残渣特性,表明秸秆纤维素在亚/超临界乙醇中断键裂解,且酮类和乙酯类化合物是生物油的主要成分。     

农作物秸秆红外指纹图谱双指标序列分析

采用傅立叶红外光谱技术研究了不同地区、不同种类农作物秸秆的红外指纹图谱,对其谱带归属进行了判别分析;并利用共有峰率和变异峰率双指标序列法对农作物秸秆样品进行分析鉴别。结果表明:同种农作物秸秆化学成分相似,不同农作物秸秆化学成分差异较大,其中花生秆与其他农作物秸秆化学成分差异最大。     

电催化氧化木质素解聚:温和高效的生物质增值策略（英文）

木质素是一种天然可再生芳香族聚合物,通过催化反应过程可实现其解聚制备芳香族化学品,其高附加值转化对实现生物燃料、精细化学品和大宗化学品的绿色生产具有重要意义.其中,电催化氧化解聚为木质素的高值化利用提供了一种高效节能途径.凭借电催化过程中电位或电流易于调节的特性,可实现产物的选择性和反应物转化率的有效调控.但实现木质素的可控降解,首先需对其解聚机理充分了解掌握.其中,由催化剂、电解质和催化反应池等组成的电催化系统均需合理设计.本文以木质素解聚过程中C—C键和C—O键的断裂机理为基础,综合评述了近年来木质素及其模型化合物在电催化氧化制备芳香族单体过程中不同的断键机制,总结了自由基中间体在C—O和C—C键的高选择性断裂中发挥的决定作用.最后,展望了电催化木质素解聚的发展前景以及面临的挑战.     

废旧聚酯（PET）的化学循环利用

废旧PET 聚酯可通过化学解聚来实现其循环利用。本文总结了废旧PET 聚酯化学循环利用领域的研究现状, 介绍了目前国内外开发的主要化学解聚工艺方法, 包括水解法、甲醇解聚法、乙二醇解聚法等, 同时对各种工艺过程的优缺点进行了综合比较。     

废轮胎和天然橡胶在超临界甲苯中的解聚研究

在300 ℃～360 ℃、3.7 Mpa～7.0 Mpa、反应20 min～90 min、投料比(甲苯与废轮胎或天然橡胶的质量比)5.0～10.0下,分别研究了废轮胎和天然橡胶在超临界甲苯中的解聚,着重考察了解聚率与反应条件的关系、以及解聚产物分布.在临界点附近,解聚率随温度、压力升高而增加;高于临界压力后,压力对解聚率的影响减弱.解聚产物主要为液相物和固相物,液相产物用色质联谱(GC/MS)分析表明,以芳香烃和烯烃类为主,且分子量大多小于300;固相产物经分析以碳黑为主.废轮胎和天然橡胶的解聚产物大部分是相似的,天然橡胶可以完全解聚,在同样条件下废轮胎解聚率低于天然橡胶.超临界甲苯在反应中对实验样品不仅起到溶胀和溶解作用,同时也参与了解聚反应.研究结果为选择解聚介质和操作参数提供了依据.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.