基于TG-FTIR的生物质催化热解试验研究

运用热重－傅里叶红外光谱联用技术(TG-FTIR)，以麦秸为研究对象，探讨催化与非催化条件下生物质的热解挥发分析出特性，分析研究热解温度、催化剂种类对生物质热解主要析出产物的影响。通过热重TG和DTG曲线，获得了相关热解特性参数及动力学参数。结果表明，添加NiO和CaO存在两个失重峰，并促进麦秸热解反应进行，降低表观活化能，其中NiO对提高热解析出产率作用更显著。通过红外光谱对热解产物实时测量的分析表明，CO与CO2的析出与失重峰基本一致，而CH4的析出滞后于前两者。添加NiO和CaO有利于减少热解产物中的CO2的浓度，促进挥发分产物CO、CH4的生成。其中CaO更有利于生物质在温度800℃以下的热解性能改善，而NiO在800℃以上具有更好的催化作用。     

Monitoring of N-doped organic xerogels pyrolysis by TG–MS

Pyrolysis of N-doped organic xerogels prepared from different N-containing precursors has been studied by TG–MS. The pyrolytic process has been ascertained to consist of three steps. The first step (up to cca. 250 °C) has been interpreted as water loss (humidity, fixed water from pores) and in some cases as formaldehyde loss. The second step has been connected with volatile substances evolution (cca. 250–450 °C) with predominant release of NH₃, CO₂ and products of melamine (M) or urea decomposition. Reaction/pore water and formaldehyde have also been detected in this step. The third step of pyrolysis (450–1,000 °C) has been ascribed to carbonization reaction when the other releases of NH₃, CO₂, reaction/pore water and M decomposition products have continued. This was accompanied with evolution of H₂ and 3-hydroxypyridine. On the basis of TG measurements, it was found that increasing time of condensation of organic xerogels and amount of used catalyst lead to higher yield of carbonaceous products. In addition, adsorption experiments of Pb(II) on N-doped carbon xerogels proved that relationship between adsorption properties of xerogels and nitrogen loss during pyrolysis exists. When the sample contains only amino groups, they are lost during pyrolysis as ammonia and the adsorption ability is low, while nitrogen comprised in the aromatic rings of N-precursors stays in the structure and causes enlarging of adsorption capacity.     

煤与混合废塑料共热解固体产物中氯的赋存形态及在燃烧时的释放特性

通过红外光谱、热重 质谱及燃烧 水解实验，研究了煤与废塑料共热解固体产物中氯的赋存形态及在燃烧过程中氯的释放特性。结果表明，温度低于600℃热解的半焦中存在有机氯化合物；600℃以上热解的半焦（或焦炭）中氯主要以无机盐类存在。燃烧过程中氯的释放率与燃烧温度，煤与废塑料共热解的温度以及共热解时废塑料的加入量有关。燃烧温度越高，氯的释放率越大，900℃燃烧时，氯的释放率都在94%以上；在同一温度燃烧时，热解温度越高，氯的释放率越低。400℃热解的半焦最高释放率达99.86%，而1000℃热解的焦炭的最高释放率为94.35%。     

Application of different thermal analysis techniques for the evaluation of petroleum source rocks

In the paper, various laboratory pyrolytic methods were used to evaluate selected petroleum source rocks. The methods used are: Rock–Eval pyrolysis, Py–GC pyrolytic technique and TG/DTG/DSC. The experiments of the last method were performed according to three different procedures. Each of them provided different, specific data. The selected rock sample material was diversified in terms of stratigraphical position, structural unit and place of collection (outcrop or borehole). Based on the Rock–Eval analysis results, kerogen in samples can be classified as type II. Additional information on the quality of pyrolysis products was obtained from the Py–GC analysis. Thanks to the combination of the all three implemented pyrolytic techniques, the quality of the generation potential of the source rocks can be evaluated in details. In some samples, the oxidation and pyrolysis of organic matter occur in two stages, what is the evidence of the complex nature of the organic substance. The maximum of pyrolysis reaction is detected by TG/DTG measurement in the range of temperature from 450 to 580 °C, depending on the maturity of organic matter. The maturity level increases with the rock stratigraphic position. The proportions of loss in mass observed in respective stages of pyrolysis in course of TG/DTG experiment are in correspondence with the observations of the released fractions in the Py–GC analysis. The Carpathian Menilite shales could be classified as source rocks with high oil generation potential. Also, the Lower Silurian and Ordovician shales are characterized by high oil-producing potential with a lower content of mineral matter. Cambrian rocks show a different character and gas-prone generation potential.

     

Thermal degradation behaviour of some metal chelate polymer compounds with bis(bidentate) ligand by TG/DTG/DTA

Seven novel divalent transitional metal chelate polymers compounds (commonly known as chelate compounds or metal coordination complexes or polymer complexes) have been characterized by thermogravimetry (TG), differential thermal gravimetry (DTG) and differential thermal analysis (DTA) methods. Thermal decomposition behaviour of Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II) polymers with terphthaoyl-bis(p-methoxyphenylcarbamide) has been investigated by thermogravimetric analysis (TGA) at heating rate 10 °C min^?1 under nitrogen atmosphere. TG/DTA of chelate compounds were shown to be a stable compound against thermal decomposition which was measured on the basis of final decomposing temperature, but it is observed in some curves that decomposition takes place at low temperature due to the lattice water, which is always placed at outer coordination sphere of the central metal ion. The presence of both lattice and coordinated water were noteworthy investigated in Co(II), Ni(II) and Cu(II) chelate polymer compounds, whereas lattice water found in Zn(II), Cd(II) and Hg(II). However, Mn(II) showed only coordinated water. Thermal stabilities for release of lattice water, coordinated water and organic moiety that occur in sequential decomposition of chelate compounds are explained on the basis of ionic size effect and electronegativity. The processes of thermal degradation taking place in seven chelate polymers were studied comparatively by TG/DTG/DTA curves which indicating the difference in the thermal decomposition. Coats–Redfern integral method is used to determine the kinetic parameters for the successive steps in the decomposition sequence of TG curves. Scanning electron microscope images of some chelate polymers were shown in previous publication revealed that particle sizes of chelate polymers were found to be of nanomaterial level therefore, resulting chelate compounds might be called as nanomaterial.     

油棕废弃物热解的TG-FTIR分析

利用热重分析(TGA)和傅里叶红外光谱(FTIR)联用技术对油棕废弃物的热解特性及其气体产物的释放特性进行了研究，采用一级反应计算了油棕废弃物的热解动力学参数。研究表明，油棕废弃物较易于热解，失重集中在220℃～400℃，其热解活化能较小，约为60kJ/mol；气体产物的析出与生物质的热解失重有着相似的特性，气体产物主要在200℃～400℃析出，主要成分为H2O、CO2、CO、CH4和有机碳水化合物的混合物, 其中CO2和有机混合物的析出温度较低，而CO和CH4的析出温度相对较高。随着温度的进一步升高(>400℃)，除少量的CO2和CO外，无其他气体产物析出。气体产物的析出量与生物质样品的化学组成和结构有关，CO2和有机混合物的析出与生物质的热解失重曲线(DTG)有着相似的特性，是引起油棕废弃物热解失重的主要原因。     

Synthesis,structure, spectra and redox activities of model compounds for methanogenic bacteria

Synthetically accessible benzimidazoles have been synthesized and the benzimidazole ligands were complexed with nickel(II) nitrate. A nickel(II) complex of N,N'-bis(benzimidazole-2-ylethyl)ethylenediamine was crystallized in single-crystal form and the structure was investigated by X-ray crystallography. The structure of the complex is bicapped axial coordinated octahedral. Ni(bbes)(2+)(2)[bbes=bis(benzimidazole-2-ylethyl)sulfide] exhibits broad low energy bands in electronic spectra and high redox potential in cyclic voltammetry (CV) rather than Ni(enbzim)(2+) [enbzim =N,N'-bis(benzimidazol-2-ylethyl)ethylenediamine], where high energy well separated bands were observed in the visible region and a more negative redox potential was detected in CV. Experimental studies show that an increasing amount of pi-orbital interaction with the Ni(2+)ion, irrespective of chelate ring may favour the higher redox potential. The higher redox potential of methanogenic bacterial [Ni(II)/Ni(I)] than nickel compounds is one of the main factors for the degradation of organic biodegradable compounds and the further transformation to methane.     

A Piezoelectric crystal detector for continuous monitoring of water evolved during thermal decomposition reactions

A method for the continuous monitoring of water vapour evolved during thermal decomposition reactions is developed based on the reversible adsorption of water on a bare piezoelectric crystal with nickel electrodes. Gaseous decomposition products formed in the furnace chamber of the thermoanalytical equipment are collected and transported to the detector cell by the carrier gas. A linear relationship exists between the decrease in vibrational frequency of the crystal and the concentration of water in the carrier gas up to 900 mug/l. H(2)O [1200 ppm (v/v)]. The signal curve of the piezoelectric water monitor can be recorded simultaneously along with the TG, DTG and DTA curves and used to identify the decomposition step(s) in which water was formed. CO, CO(2) and low molecular weight hydrocarbons do not interfere. Condensable organic crack products can be removed by a suitable pretrap.     

The S2 emission characteristics of several organic sulfur compounds obtained by molecular emission cavity analysis and pyrolysis

Emission profiles of several organic sulfur compounds are investigated by modified molecular emission cavity analysis (MECA). Thiourea, 1,3-diethylthiourea, S-methyl- cysteine and taurine are pyrolyzed in a hydrogen stream and the pyrolytic products are determined by gas chromatography. The S₂ emission mechanism is discussed on the basis of emission profiles and the composition of the pyrolytic products. Although some compounds give multipeaked responses, the splitting disappears when a worn surface cavity is used or oxalic acid is added to the sulfur compound in the cavity. When the emission profile from thiourea is compared with that from 1,3-diethylthiourea, it is clear that the multipeaked response is due to quenching by degradation products of the latter compound. The main product of pyrolysis is hydrogen sulfide. The emission intensity is related to the yield of hydrogen sulfide in pyrolysis. As methylmercaptan was not detected in the pyrolysis products, it is suggested that the quenching by the organic fragments results from their hydrogen consumption rather than their reaction with sulfur species. The S₂ emission from sulfur-containing compounds is rapidly complete in the presence of oxalic acid, and it is suggested that such compounds are subject to reductive breakdown in the cavity.     

Studies on coordination compounds VI. Thermogravimetric,differential thermogravimetric,differential thermal analysis and mass spectrometric studies of some cobalt(II), nickel(II) and copper(II) salicylaldoximates, 2-indolecarboxylates and 2-thiophenecarboxylates

Some cobalt(II), nickel(II) and copper(II) complexes of salicylaldoxime, 2-indolecarboxylic and 2-thiophenecarboxylic acids were prepared and their thermal behaviour studied by TG, DTG, DTA and mass spectrometric methods. Kinetic parameters were calculated for the decomposition reactions if possible. The decomposition processes are discussed     

城市污水污泥燃烧特性和动力学特性分析

采用热重分析仪对城市污水污泥进行热重实验,通过TG(热重)、DTG(微分热重)和DSC(差示扫描量热)曲线的分析对比,获得污水污泥热解和燃烧不同阶段的特性。低于250℃,燃烧与热解的热重曲线基本吻合,说明在此之前,失重速率主要受控于有机物的分解以及析出,燃烧过程对失重影响不明显。燃烧DTG曲线呈现“W”峰型,第一个失重速率峰与热解DTG曲线基本对应,高于410℃,燃烧DTG曲线出现显著的加速。采用Coats-Redfern 积分法,假设不同的反应模型进行拟合,推断出污泥燃烧过程中两个DTG峰体现出不同的反应机理。借鉴煤燃烧机理分析认为,污泥燃烧反应初期挥发分的燃烧受控于化学反应速率,随着温度的不断提高,剩余挥发分的燃尽和固定碳的燃烧总反应速率逐渐受扩散因素控制。基于分析所得污泥燃烧机理,采用四个独立的平行反应模型模拟污泥的燃烧过程,拟合曲线与实验数据吻合良好。     

Pyrolysis of N-doped organic aerogels with relation to sorption properties

Resorcinol–formaldehyde aerogels (five samples, three of them with addition of nitrogen containing precursors—3-hydroxypyridine, 3-aminophenol and melamine) have been prepared by sol–gel polycondensation, subcritical drying and pyrolysis. The pyrolysis of prepared organic aerogels has been studied by non-isothermal TG at constant heating rate. The process of pyrolysis has been found to consist of three steps with the total mass loss 40.2–61.7% (room temperature—1,000 °C). The resulted carbon aerogels have been tested as sorbents of Ni(II), Pb(II) and Cu(II) ions from aqueous solutions. Various relations have been found among the results obtained from the pyrolysis experiments and properties affecting adsorption. Besides the expected correlation between the mass loss gained from TG (isothermal step at 500 °C was applied) and from heating in the laboratory oven, the relationship between the mass loss during pyrolysis and sorption capacities for all three metal ions has been found. Other relations among pyrolysis behaviour, surface area and content of nitrogen have been also examined. Batch adsorption experiments show (with an exception of one sample) that N-doped samples have higher adsorption capacity for metal ions. In addition, changing of nitrogen functionalities during the pyrolysis has been considered and pyridinic-N (N-6) functionality has been contemplated as a suitable structure for the adsorption process.     

Zinc organic compounds of some oximes coordinated with nickel(II), palladium(II) and copper(II) ions

Coordinated oximes with nickel(II), palladium(II) and copper(II) ions proved capable of giving substitution reactions with a series of zinc organic compounds. Studies have revealed that, in the cases of dimethylglyoxime and salicylaldoxime, the reaction products result from substitution of the O? H···O hydrogen bridges existing in such compounds by O? Zn? O bridges. All compounds reported in this paper were separated as colored powders and characterized by elemental analyses, IR spectroscopy, X‐ray diffraction and magnetic measurements. The new zinc organic compounds form amine adducts. Among the amine adducts, only those with pyridine were isolated and characterized. Copyright © 2001 John Wiley & Sons, Ltd.     

Physicochemical Studies and Thermal Decomposition Kinetics of Co(II), Ni(II), Cu(II) and Zn(II) Complexes of Citronellal Anthranilic Acid

Cobalt(II), nickel(II), copper(II) and zinc(II) complexes of two new Schiff-bases, citronellal anthranilic acid and citronellal-5-bromoanthranilic acid have been synthesized. On the basis of spectral, magnetic and thermal data, octahedral structure was assigned to all complexes [ML₂(H₂O)₂]. Thermal decomposition of these complexes was studied by TG. Kinetic parameters, viz activation energy, E, pre-exponential factor, A, and order of reaction, n, were calculated from the TG curves using mechanistic and non-mechanistic integral equations. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation of the main degradation compounds from arabinose,xylose, mannose and arabinitol during pyrolysis

The thermochemical behaviour of sugars (D- and DL-arabinose, D- and DL-xylose and D-mannose) and sugar alcohol (D- and DL-arabinitol) was investigated by TG and pyrolysis-gas chromatography with mass-selective detection (Py-GC/MSD). The temperature of pyrolysis was 500 and 550°C. The TG-curves were measured both in air and nitrogen atmospheres, from 25 to 700°C with the heating rate of 2°C min^-1. In each case, the main pyrolysis products were classified into the following compound groups: (i) furanes, (ii) pyranes, (iii) cyclopentanes, (iv) cyclohexanes, (v) anhydroglucopyranoses, (vi) dianhydroglucopyranoses and (vii) saturated fatty acids. For example, the main peaks of the chromatograms of pentoses (arabinose, xylose), hexose (mannose) and sugar alcohols (arabinitols) were different. The greatest peak of pentoses in gas-chromatogram was 2-furancarboxaldehyde and that of hexose was (2H)-furan-3-one. The greatest peak of arabinitols at pyrolysis temperature of 500°C was furan methanol and at 550°C a-angeligalactone. 5-hydroxymethyl-2-furan carboxaldehyde was found only in the pyrolysis of D-mannose (hexose). The former study showed that it was not found in pyrolysis of pentoses. The amount of CO₂ and H₂O was not determined. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal decomposition of metal methanesulfonates in air

The thermal decompositions of dehydrated or anhydrous bivalent transition metal (Mn, Fe, Co, Ni, Cu, Zn, Cd) and alkali rare metal (Mg, Ca, Sr, Ba) methanesulfonates were studied by TG/DTG, IR and XRD techniques in dynamic Air at 250–850 °C. The initial decomposition temperatures were calculated from TG curves for each compound, which show the onsets of mass loss of methanesulfonates were above 400 °C. For transition metal methanesulfonates, the pyrolysis products at 850 °C were metal oxides. For alkali rare metal methanesulfonates, the pyrolysis products at 850 °C of Sr and Ba methanesulfonates were sulphates, while those of Mg and Ca methanesulfonate were mixtures of sulphate and oxide.     

Thermal studies on 2,6-xylyliminodiacetato compounds of some transition metal ions

Some new 2,6-xylyliminodiacetato compounds of Mn(II), Fe(III), Ni(III), Zn(II) and Cd(II) have been prepared in aqueous media. The thermal behaviour of these compounds has been studied by TG, DTG, and DSC techniques. Heats of dehydration have been calculated from the DSC curves.     

The thermal properties of inorganic compounds: I. Some mercury(I) and (II) compounds

The TG and DTA (DSC) curves of the yellow and red forms of mercury(II) oxide, mercury(II) chloride, bromide and iodide, and mercury(I) iodide are reported. A lower initial procedural dissociation temperature, 400°C, was observed for the yellow form of HgO versus 460°C for the red form. This lower value is consistent with the postulate of a smaller particle size for the yellow form. Although only sublimation behavior was indicated in the DSC curves of the mercury(II) halides, by the use of sealed-tube DTA, fusion transitions were also observed. These data may be of unusual importance in ecological and environmental problems.     

Aluminiumorganic compounds of some metaldioximates

Coordinated dioximes with nickel(II), palla‐dium(II) and copper(II) ions proved capable of giving substitution reactions with a series of aluminiumorganic compounds. Studies made on the reaction products have revealed that in the case of both dimethylglyoxime and diphenylglyoxime. The reaction products result from substitution of the O? H…O hydrogen bridges existing in such compounds by O? Al? O bridges. All compounds reported in this paper were separated from the reaction mixture as coloured powders and were characterized by chemical analyses, IR spectroscopy, X‐ray diffraction spectra, proton NMR spectra and magnetic properties. Copyright © 2001 John Wiley & Sons, Ltd.     

Controllable synthesis of VSB-5 microspheres and microrods: growth mechanism and selective hydrogenation catalysis

Nanoporous VSB-5 nickel phosphate molecular sieves with relatively well controllable sizes and morphology of microspheres assembled from nanorods were synthesized at 140 degrees C over a short time in the presence of hexamethylenetetramine (HMT) by a facile hydrothermal method. The pH value, reaction time, and ratio of HMT to NaHPO2.H2O crucially influence the morphology and quality of the final products. By adjusting the pH value of the initial reaction solution, the morphology changes from disperse rods to microspheres assembled from rods and finally to a large quantity of fibers, and the diameters of the VSB-5 rods can be varied. The catalytic activity of VSB-5 in selective hydrogenation of several unsaturated organic compounds was tested. Nickel(II) in VSB-5 can selectively catalyze hydrogenation of C=C in trans-cinnamaldehyde and 3-methylcrotonaldehyde. In addition, since nitrobenzene (NB) and 2-chloronitrobenzene could be reduced to aniline (AN) and 2-chloroaniline with high selectivity, VSB-5 could have potential applications in synthesizing dyes, agrochemicals, and pharmaceuticals.