煤热解过程中含氮气相产物转化规律的实验研究

为了研究煤在热解过程中含氮气相产物的生成规律,在滴管炉反应系统中对四种原煤以及两种脱除矿物质煤样分别在500℃、700℃、900℃和1100℃进行了实验研究。结果表明,随着温度的升高,作为NO前驱物的HCN和NH3的收率随之增加,N2的收率也增加。煤种对含氮气相产物的生成规律也有着较大的影响,煤化程度比较低的煤在热解过程中,燃料氮向气相含氮产物的转化率较高;煤化程度比较高的煤转化率则偏低,大部分的氮缩聚在多环芳香结构中,成为焦炭氮。煤中的矿物质对燃料氮向N2的转化起到了促进作用,而对燃料氮向HCN和NH3的转化起到了抑制作用。     

过滤介质对低阶煤热解焦油气反应行为的影响研究

低阶煤热解焦油气通过颗粒床过滤器除尘时,过滤介质在一定程度上会影响热解焦油气的反应行为。本研究采用下行床热解反应器考察了陶瓷球(CB)、膨胀珍珠岩(EP)、活性炭(AC)和γ-Al_2O_3四种颗粒床过滤介质对淖毛湖长焰煤热解焦油气反应性的影响,结果表明,热解产物的分布、组成及其积炭行为受过滤介质种类的影响显著。CB、EP相对惰性,因延长了焦油气的停留时间,加剧了裂解和缩聚反应,焦油产率减小、沥青含量升高,热解气、热解水及积炭产率增加,但焦油积炭量和化学组成没有明显变化;AC、γ-Al_2O_3具有较强的催化裂解活性,可明显降低焦油沥青含量和积炭量,但会使焦油向热解气、热解水及积炭转化,导致焦油产率显著下降。同时,AC、γ-Al_2O_3可裂解焦油气中部分含氧化合物和含氮、硫杂环化合物,使其转化为芳香烃。     

典型烟煤热解机理的反应动力学模拟

建立合理有效的烟煤大分子模型,采用基于反应力场(Reactive Force Field,ReaxFF)的分子动力学方法模拟1400-2600 K典型烟煤的热解过程,得出产物分布和中间自由基的演变历程。研究表明,随着热解温度的升高,焦炭产量先增加后降低,焦油产量的变化趋势与焦炭相反,热解气产量单调增加。煤在低温下热解主要发生一次反应,生成焦油自由基碎片和小分子气体;高温下焦油碎片的二次反应显著,生成含量较多但数量较少的焦炭及含量与数量较多的小分子气体。2000 K是一次反应向二次反应的温度转折点。在高温热解时,煤中的C与H逐渐迁移到焦炭和焦油中,而含氧官能团较为活跃,O逐渐迁移到热解气中。二次反应阶段,O最活泼,H次之,C最稳定。热解过程中最先产生的气体是H2O; NH3主要来源于二次反应; H2S在二次反应阶段被消耗转化为其他产物; H2产量最多,且随热解温度升高而增加,尤其在二次反应中大量生成,主要源于裂解产生的氢自由基碰撞和芳香结构的缩合。基于ReaxFF模拟结果得到煤热解失重活化能为39. 45 k J/mol。     

典型烟煤热解机理的反应动力学模拟

建立合理有效的烟煤大分子模型，采用基于反应力场（Reactive Force Field，ReaxFF）的分子动力学方法模拟1400-2600 K典型烟煤的热解过程，得出产物分布和中间自由基的演变历程。研究表明，随着热解温度的升高，焦炭产量先增加后降低，焦油产量的变化趋势与焦炭相反，热解气产量单调增加。煤在低温下热解主要发生一次反应，生成焦油自由基碎片和小分子气体；高温下焦油碎片的二次反应显著，生成含量较多但数量较少的焦炭及含量与数量较多的小分子气体。2000 K是一次反应向二次反应的温度转折点。在高温热解时，煤中的C与H逐渐迁移到焦炭和焦油中，而含氧官能团较为活跃，O逐渐迁移到热解气中。二次反应阶段，O最活泼，H次之，C最稳定。热解过程中最先产生的气体是H₂O；NH₃主要来源于二次反应；H₂S在二次反应阶段被消耗转化为其他产物；H₂产量最多，且随热解温度升高而增加，尤其在二次反应中大量生成，主要源于裂解产生的氢自由基碰撞和芳香结构的缩合。基于ReaxFF模拟结果得到煤热解失重活化能为39.45 kJ/mol。     

金催化分子间炔烃的氮烯转移反应合成含氮杂环化合物

含氮杂环是很多天然产物、生物医药活性物种、光电新材料等的重要结构单元,也是有机合成中非常重要的合成子.主要介绍金催化分子间炔烃与氮烯前体的反应,合成多取代氮杂环化合物.在该类反应中,炔烃经金催化剂活化后,与各种不同的氮烯前体反应,以一种高效、快捷的转化模式构建多官能团化的含氮杂环化合物.     

焦粉对低阶煤热解焦油气反应行为的影响研究

热解焦油气在输送管路或除尘设备中会发生一定程度的反应,进而影响热解产物的分布和组成,而其中夹带的焦粉粉尘会对焦油气反应产生影响。本研究利用两段流化床热解反应器,考察了不同反应温度下(400-500℃),焦粉对淖毛湖长焰煤热解焦油气反应的影响。结果表明,添加焦粉后,焦油气不仅发生热裂解和热缩聚反应,还会被焦粉作用发生催化裂解反应,焦油产率和沥青含量减小,热解气和积炭产率增加;随着反应温度的升高,焦油气热裂解和热缩聚反应加剧,反应后焦油气较为稳定,不易被焦粉催化,因此,焦粉对焦油产率、沥青含量及热解气产率的影响随温度升高逐渐减弱;而反应温度升高,焦油气催化裂解生成的自由基更容易发生缩聚反应,焦粉对积炭产率的影响变强。此外,焦粉的催化裂解作用使不同反应温度下焦油中杂环化合物含量下降;同时焦粉促进了热解水与焦油气反应,导致不同反应温度下焦油中脂肪烃、芳香烃含量下降,酚类和含氧化合物含量上升。     

离线热解-热脱附-气相色谱-质谱法用于研究烟草中主要糖类对挥发性成分的影响

提出了离线热解-热脱附-气相色谱-质谱法测定烟草中挥发性成分的方法,并将此方法用于研究烟草中主要糖类化合物(果糖、葡萄糖和蔗糖)对烟草挥发性组分的影响。结果表明:①糖类在高温下裂解,主要生成呋喃类、羧酸类及酯类化合物,不同糖类的裂解产物有较明显差异;②加入蔗糖后,烟草的挥发性成分中醛、酮类和含氮、硫杂环类化合物增加显著;③加入葡萄糖后,醇、酚类和含氧杂环类化合物增加明显;④而加入果糖后,各类化合物增加均较少,其中含氧杂环类化合物含量几乎没有变化。可见糖类物质在热解过程中不仅自身发生氧化还原反应,还与烟草中的成分发生了一系列化学反应,从而显著影响烟气的化学组成。     

吡啶型氮快速热解中HCN和NH3生成机理研究

考虑煤中吡啶六元环与其他杂环的结合形式,对四种典型的吡啶型氮杂环结构及其热解中间产物中各键的Mayer键级进行了计算。通过对比Mayer键级的大小判断热解时最易发生断裂的键,进而对吡啶型氮热解时氮的逸出机理进行了分析。计算结果表明,吡啶型氮热解产生的含氮污染物主要是HCN;由于吡啶环与其他环结合方式的不同,氮的逸出过程也有差异。利用高频炉快速热解装置对吡啶和吖啶两种模型化合物进行了快速热解实验以验证计算结果。结果表明,吡啶和吖啶热解时虽有少量NH₃生成,但含氮污染物仍以HCN为主,实验结果可为计算所得的结论提供一定支持。
     

从氮气直接合成含氮有机化合物

作为与人类文明和生存密切相关的重大研究方向,温和条件下氮气的活化与转化（固氮）研究在1970~1990年代曾经是国际上备受关注的研究领域.但是,由于该领域极具挑战性,研究进展缓慢以及世界学术文化的变化,进入21世纪以来从事相关基础研究工作的化学研究者急剧减少.然而,毋庸置疑,实现温和条件下氮气的活化与转化是人类需要解决的重大科学问题,是人类社会可持续发展的要求,是科学家尤其是化学家最重要的使命之一.将氮气直接转化为含氮有机化合物是氮气的直接应用之一,本综述总结和归纳了文献报道的金属促进的以氮气为原料直接生成含氮有机化合物的转化方法和反应机理,产物主要包括胺类,酰胺类,酰亚胺类,腈类,二氮烯类,连氮类,碳二亚胺类,异氰酸酯类及杂环类有机化合物.本综述不包括将氮气转化成氨气和部分还原及质子化产物的文献.     

吡咯型氮快速热解中NH3和HCN生成机理研究

根据煤中吡咯五元环与其他杂环结合形式的不同,选择五种典型的吡咯型氮杂环结构作为考察对象,利用量子化学计算方法对吡咯型氮杂环及其热解中间产物中各键的Mayer键级进行了计算。通过对比Mayer键级的相对大小对分子结构中最易发生断裂的键进行判断,进而分析了吡咯型氮热解时NH₃和HCN的生成机理。通过计算结果表明,热解时吡咯型氮以-NH和-NH₂自由基的形式逸出,并主要转化为NH₃;氮的逸出过程因吡咯环与芳环结合方式的不同而存在差异。为验证计算结果,利用滴落式高频炉热解装置对吡咯和咔唑两种模型化合物进行了快速热解实验。结果表明,吡咯和咔唑热解时NH₃和HCN均有生成,NH₃是主要的含氮气体污染物。计算所得的结论在一定程度上得到了实验结果的支持。     

Acceptorless dehydrogenative synthesis of primary amides from alcohols and ammonia

The highly desirable synthesis of the widely-used primary amides directly from alcohols and ammonia via acceptorless dehydrogenative coupling represents a clean, atom-economical, sustainable process. Nevertheless, such a reaction has not been previously reported, and the existing catalytic systems instead generate other N-containing products, e.g., amines, imines and nitriles. Herein, we demonstrate an efficient and selective ruthenium-catalyzed synthesis of primary amides from alcohols and ammonia gas, accompanied by H₂ liberation. Various aliphatic and aromatic primary amides were synthesized in high yields, with no observable N-containing byproducts. The selectivity of this system toward primary amide formation is rationalized through density functional theory (DFT) calculations, which show that dehydrogenation of the hemiaminal intermediate into primary amide is energetically favored over its dehydration into imine.

An efficient and selective synthesis of primary amides from alcohols and ammonia, with H₂ evolution, has been achieved by an unprecedented acceptorless dehydrogenative process catalyzed by a pyridine-based PNN–ruthenium pincer complex.     

LiClO4 Accelerated Michael addition of amines to α,β-unsaturated olefins under solvent-free conditions

Several primary and secondary amines were added to α,β-unsaturated esters, nitriles, amides, and ketones to give the corresponding saturated amines mediated by solid lithium perchlorate under solvent-free and environmentally friendly conditions at room temperature.     

Polymer‐anchored Ru(II) complex as an efficient catalyst for the synthesis of primary amides from nitriles and of secondary amides from alcohols and amines

A polymer‐anchored ruthenium(II) catalyst was synthesized and characterized. Its catalytic activity was evaluated for the preparation of primary amides from aqueous hydration of nitriles in neutral condition. A range of nitriles were successfully converted to their corresponding amides in good to excellent yields. The catalyst was also effective in the preparation of secondary amides from the coupling of alcohols and amines. The catalyst can be facilely recovered and reused six times without a significant decrease in its activity. Copyright © 2014 John Wiley & Sons, Ltd.     

Fragmentation and rearrangement processes in the mass spectra of perhalogeno-aromatic compounds—VII. Pentafluorophenyl derivatives of nitrogen

The mass spectra of several perfluoroaromatic nitrogen compounds, including primary and secondary amines, diamines, nitriles, hydrazines, azines and azo compounds, are presented. Fragmentation patterns of these compounds are described and the data are discussed in terms of comparisons amongst perfluoroaromatic nitrogen compounds, and with reference to the hydrogen substituted analogs, or to oxygen and sulfur analogs of a particular compound.     

基于流化床热解的中药渣两段气化基础研究

以中药渣为原料,研究了流化床热解和固定床半焦催化/重整焦油及半焦气化的特性,特别是对固定床重整前后焦油中组分的变化进行了分析。结果表明,随着热解气体在固定床半焦中停留时间从0 s延长到0.95 s,焦油中-OH、C-H、C-O、C=O和C=C官能团的含量显著减少,芳香类物质含量明显增加;向固定床中加入水蒸气后,焦油中芳香类、C-O和羟基-OH官能团的含量增加;而加入氧气后,焦油中羟基-OH、C-H、羰基C=O、C=C和C-O官能团物质含量变化不大,但芳烃类物质明显增多。虽然向固定床中加入水蒸气或氧气均能降低焦油含量,但水蒸气的作用稍弱,两者联合对焦油脱除和半焦气化效果更好,生成的燃气中基本不含焦油。     

Synthetic Aspects of Metal-Catalyzed Oxidations of Amines and Related Reactions

The metabolism of amines is governed by a variety of enzymes such as amine oxidase, flavoenzyme, and cytochrome P-450. A wide variety of compounds are produced such as ammonia and alkaloids in selective and clean oxidation reactions that proceed under mild reaction conditions. Simulation of the functions of these enzymes with simple transition metal complex catalysts may lead to the discovery of biomimetic, catalytic oxidations of amines and related compounds. Indeed, metal complex catalyzed oxidations have been found to proceed with high efficiency. The first section of this review discusses the dehydrogenative oxidations of amines with transition metal catalysts by transition metal catalysts that simulate amine oxidase. The second section highlights the catalytic oxidation of secondary amines to nitrones by simulation of flavoenzymes. The third section describes the simulation of the function of cytochrome P-450 with lowvalent ruthenium complexes and peroxides. Biomimetic ruthenium-catalyzed oxidations of tertiary amines, secondary amines, and other substrates such as amides, β-lactams, nitriles, alcohols, alkenes, ketones, and even nonactivated hydrocarbons can be performed selectively under mild conditions. These three general approaches provide highly useful strategies for synthesis of fine chemicals and biologically active compounds such as alkaloids, amino acids, and β-lactams.     

Titanium(IV) isopropoxide mediated solution phase reductive amination on an automated platform: application in the generation of urea and amide libraries

Amine libraries and their derivatives are important targets for high throughput synthesis because of their versatility as medicinal agents and agrochemicals. As a part of our efforts towards automated chemical library synthesis, a titanium(IV) isopropoxide mediated solution phase reductive amination protocol was successfully translated to automation on the Trident(TM) library synthesizer of Argonaut Technologies. An array of 24 secondary amines was prepared in high yield and purity from 4 primary amines and 6 carbonyl compounds. These secondary amines were further utilized in a split synthesis to generate libraries of ureas, amides and sulfonamides in solution phase on the Trident(TM). The automated runs included 192 reactions to synthesize 96 ureas in duplicate and 96 reactions to synthesize 48 amides and 48 sulfonamides. A number of polymer-assisted solution phase protocols were employed for parallel work-up and purification of the products in each step.     

The selective reaction of primary amines with carbonyl imidazole containing compounds: selective amide and carbamate synthesis

A new highly selective synthesis of amides and carbamates is described. In both cases the syntheses involve the formation of carbonyl imidazole intermediates which subsequently undergo previously unreported selective reactions with primary amines. Acid imidazolides with sufficient chain length will exclusively react with primary amines even in the presence of secondary and tertiary functionality. The imidazole carboxylic esters of secondary or tertiary alcohols also react selectively with primary amines, forming controlled carbamate structures.     

ZrOCl2·8H2O on montmorillonite K10 accelerated conjugate addition of amines to α,β-unsaturated alkenes under solvent-free conditions

At room temperature, ZrOCl₂·8H₂O on montmorillonite K10 efficiently catalyzes conjugate addition of amines to a variety of conjugated alkenes such as α,β-unsaturated carbonyl compounds, carboxylic esters, nitriles and amides under solvent-free conditions. The catalyst can be recycled for subsequent reactions without any appreciable loss of efficiency.     

固定床中纤维素热解及其焦油裂解机理研究

研究了500~900℃条件下微晶纤维素在固定床中的热解过程;分别采用气质联用(GC-MS)和气相色谱分析了热解过程中生成的焦油和不可凝气体。结果表明,随热解温度升高,焦油产率减少、气体产率升高、焦产率略微下降,同时CO、CH4和H2的产率明显升高,而CO2的产率变化不明显。焦油主要由二次反应产生,不可凝气体则由一次热解产物和二次热解产物共同产生。使用Gaussian 09软件对热解过程进行了模拟,发现纤维素分子在热解过程中首先分解为纤维素单体,然后纤维素单体上的羟基官能团优先脱除,生成的中间产物重组生成焦油。随热解温度升高,焦油中醚、醇、酸等化合物分解成自由基,自由基间发生重组、结合,导致烯烃和炔烃增多以及不可凝气体含量的升高。