Identification of straight-chain fatty acids in coal extracts and their geochemical relation with straight-chain alkanes

Mono-carboxylic, straight-chain fatty acids are present in extracts of lignite and subbituminous coal (0.4–1.0 wt%, daf basis), but not in those of a bituminous coal. They are removed with nearly equal ease by both solvent and supercritical gas (SCG) extraction. Octacosanoic acid is the major constituent, and values of the carbon preference index (even over odd) lie between 2 and 6. Solvent extraction of the coals also removes small quantities (< 0.08 wt%) of straight-chain alkanes which are closely related in composition to the straight-chain fatty acids and are probably derived from them during maturation. However, previous SCG extraction of the coals yielded much larger quantities of straight-chain alkanes (0.3–0.7 wt%). Pyrolysis experiments with a lignite fatty acid fraction and with tetracosanoic acid show that these acids largely survive SCG extraction and, therefore, are not the main source of the relatively large quantity of straight-chain alkanes in these extracts.     

The chemical nature of asphaltenes from some coal liquefaction processes

Average chemical structures of asphaltenes from three coal liquefaction processes, namely hydroliquefaction (SRC-II), hydrogen-donor solvent extraction (HDS) and supercritical gas extraction (SCG), have been deduced using a structural analysis scheme in which data from ¹H and ¹³C NMR are combined with those from elemental, molecular weight and functional group analyses. Compared with SRC-II and HDS asphaltenes, SCG asphaltenes contain less-condensed aromatic nuclei which can be largely represented by 1- and 2-ring structures. They also contain more oxygen groups and slightly larger aliphatic substituents. CH₃ accounts for between 30 and 40% of the aliphatic carbon in all the asphaltenes investigated. Small amounts of long alkyl chains are present in the SCG asphaltenes but not in the SRC-II and HDS asphaltenes. SCG extraction is chemically less severe than the SRC process and HDS extraction since neither hydrogen nor HDS are employed and, as a result, SCG extracts are considered to be much more representative of the organic matter in the parent coals.     

Estimation of aliphatic H/C ratios for coal liquefaction products by spin-echo 13C n.m.r.

The direct estimation of aliphatic H/C ratios for coal liquefaction products using a part-coupled spinecho (PCSE) ¹³C n.m.r. method is described. The method, which enables proportions of aliphatic C, CH, CH₂ and CH₃ groups to be deduced, has been applied to a low molecular weight (<200) aromatic fraction of hydrogenated anthracene oil (HAO) and to higher molecular weight (?280) aromatic and asphaltene fractions of supercritical gas (SCG) extracts and a hydrogenation residue (pitch). Aliphatic H/C ratios for these occur in the range 1.9-2.3, the SCG extract fractions having the highest values because they contain significantly more CH₃ and less CH than the HAO and pitch fractions.     

Characteristics and carbonization behaviors of coal extracts

N-methyl pyrrolidone (NMP) raw coal extract (EXT), hydrogenated coal extract (HEXT) and the blend of EXT and HEXT in NMP (BLD), from two bituminous coals, were studied. The extracts were carbonized in both tube-bomb and a temperature programmable furnace. Elemental analysis, FTIR spectroscopy and optical microscopy techniques were employed to characterize the extracts and the carbonization residues. It was found that the extracts resembled petroleum-derived pitches in the hydrogen content and (C/H)_atomic ratio. Higher oxygen and nitrogen contents differentiated the coal extracts from commercial petroleum pitch. More carbon and hydrogen, and lesser oxygen and sulfur differentiated HEXT from EXT. The ratios of integrated IR band intensity for aromatic and aliphatic CH stretching indicate that the relative content of aliphatic hydrogen in EXT is higher than in HEXT. HEXT contains comparatively more aromatic hydrogen, a feature necessary for thermal stability and fluidity during carbonization. BLD materials are at a place somewhere in between. Kinetic modeling of the aliphatic hydrogen change during carbonization reveals that EXT has high carbonization rate and low apparent activation energy. This can be related to the optical texture size of carbonization residues. The residues made from EXTs exhibited fine mosaic optical texture and limited mesophase development. HEXTs were readily converted into highly anisotropic coke. BLDs produced carbonization residues with intermediate properties. Extracts with similar activation energies produced similar residues in the same coal series. The degree or extent of anisotropy displayed by the carbonization residues was found to be dependent on the relative distribution of aromatic and aliphatic hydrogen.     

Variation of coal extract structure with molecular mass

Asphaltenes and benzene-insolubles, and their methylated counterparts, of high-yield supercritical gas (SCG) and hydrogen donor solvent (HDS) extracts have been separated by size exclusíon chromatography (SEC) on cross-linked polystyrene microspheres so as to investigate the variation in coal extract structure with molecular mass (MM). Narrow SEC fractions have been obtained which have been subjected to elemental, molecular mass (MM), functional group, n.m.r. and voltammetric analyses. The analytical results revealed that the M M range of the solvent fractions was 300 to ≈3000. With increasing MM the following trends were observed: aromaticity decreased, but the degree of condensation of aromatic nuclei did not vary significantly; the size of aliphatic substituents increased; and phenolic hydroxyl content decreased for SCG extract fractions but, in contrast, increased for HDS extract fractions. These variations about averages are considerable and demonstrate that caution is necessary in making use of analytical results for gross fractions. Solubility in benzene of coal extracts results from low MM or from low polarity for higher MM materials.     

Extraction of phenolic fraction from guava seeds (Psidium guajava L.) using supercritical carbon dioxide and co-solvents

In this work the supercritical fluid extraction (SFE) with carbon dioxide (CO₂) and with ethyl acetate (EtAc) and ethanol (EtOH) as co-solvents was applied to obtain the phenolic fraction from guava seeds (Psidium guajava L.). The extraction was explored at various operating conditions, using 10, 20 and 30 MPa and 40, 50 and 60 °C. The use of EtAc and EtOH as co-solvents in SFE was also studied. The supercritical process was compared with traditional techniques such as Soxhlet extraction using EtAc and EtOH as solvents. The quality of the different extracts, obtained using SFE and Soxhlet methods and different solvents, was evaluated through the antioxidant activity, obtained by the collection methods of scavenging DPPH and bleaching of β-carotene, and also through the total phenolic content (TPC) of the samples, by the Folin-Ciocalteu method. The antioxidant potential indicates the use of ethanol as co-solvent as the best modifier in SFE, used in concentration of 10% (w/w) at 50 °C and 30 MPa. The quality of the extracts obtained by SFE with EtOH varied with the operating conditions of temperature and pressure, with higher values obtained at 10 and 20 MPa for TPC results and also antioxidant methods. The process yield of the phenolic fraction was also evaluated for all the extraction procedures studied (SFE and Soxhlet), with results varying from 0.380 to 1.738% (w/w).     

Evolution mechanism of active groups and thermal effects of Chinese lignite in low-temperature oxidation

Abstract

The evolution of active groups at low temperature was examined using Chinese lignite by infrared technology and X-ray photoelectron spectroscopy (XPS). The results showed that the hydroxyl, aliphatic ether, methylene, and methyl groups played important roles in the low-temperature oxidation of lignite below 200?°C. Carbonyl and carboxyl groups were important intermediates. Thus, a multi-step evolution mechanism involving the hydroxyl, aliphatic ether groups, and alkane was reasoned to describe the low-temperature oxidation of lignite. In addition, according to the oxidation kinetics experiment and the evolution laws of the active groups, the ratios of the reaction lines were determined considering the accuracy of thermal effects. The thermal effects and the heat release intensities of each temperature interval were obtained based on the evolution mechanism and the reaction ratios. The shortest spontaneous combustion period of lignite was calculated and compared with the experimental value, which proved that the reasoned evolution mechanism of the active groups and the calculations of the thermal effects were reliable.     

Action of aerobic microorganisms on the macromolecular fraction of lignite

Microorganisms able to utilize untreated Morwell lignite and the fraction insoluble in tetrahydrofuran (THF) as their sole carbon and energy source were isolated by enrichment from coal exposures in Victoria. Most isolates can use a variety of long-chain aliphatic and single-ring aromatic compounds but not more complex aromatic substrates, indicating that their growth on whole lignite is due to use of the low-molecular-weight compounds constituting the mobile phase and bound aliphatic moieties which can be cleaved from the macromolecular coal matrix. Organisms able to utilize THF-insoluble lignite are less abundant than those able to use whole coal. Amongst these are isolates able to utilize diaryl compounds and anthraquinones, compounds with structures analogous to components of the macromolecular matrix of lignite. Two fungal isolates, CJ2 and CJ4, were found to alter the elution profile of alkali-solubilized Morwell lignite in size-exclusion chromatography. When incubated with these fungi in growth medium, the apparent molecular weight of the lignite increased by 10000. However, when polyvalent metal ions were removed, the apparent molecular weight was lower than that of uninoculated coal, indicating attack on the macromolecular matrix of the lignite.     

Quantitative study on cross-linking reactions of oxygen groups during liquefaction of lignite by a new model system

Cross-linking reactions (CLR) of oxygen groups during liquefaction of lignite were quantitatively studied by a new model system. Chinese Yitai lignite (YT) was first oxidized by nitric acid at 70 °C and about 98% of the oxidized sample could be dissolved in tetrahydrofuran (THF) at room temperature. Then benzyl alcohol, PhCH₂OH (BA), as a model compound was added into the oxidized coal, also acted as solvent in the subsequent liquefaction. Temperature-programmed reactions (TPR) at liquefaction conditions under hydrogen atmosphere were performed to evaluate the CLR by quantitative analysis of THF-insoluble solid products (THFI) after reaction. Extensive CLR were observed even under high pressure of H₂ at 200-400 °C, and more than 51.7% and 81.2% of the THFS fraction was converted into the THFI at 300 °C with tetralin (TET) and BA as solvent, respectively. The THFI fraction was almost solely caused by the CLR, which makes it possible to quantitatively study the CLR by analyzing the amount of the cross-linked solid products (CSP). The pyrolysis behaviours of CSP and oxidized coal were examined by TG. Other model compounds containing oxygen-functional groups (alcohol, phenol, carboxyl, carbonyl and ether groups) can also be used in this model system to study CLR of oxygen groups in low-rank coals.     

Production of low ash coal by thermal extraction with <Emphasis Type="Italic">N</Emphasis>-methyl-2-pyrrolidinone

Present study was conducted for the purpose of producing low ash coal from LRC (low rank coals) such as lignite and sub-bituminous coal through thermal extraction using polar solvent. Extraction from bituminous coal was also investigated for comparison. NMP as a polar solvent was used. The ratio of coal to solvent was adjusted as 1: 10. Experimental conditions were established which include the extraction temperature of 200–430 °C, initial applied pressure of 1–20 bar and extraction time of 0.5–2 hr were used. Extraction yield and ash content of extracted and residual coal were measured. The extraction yield increased with the increase of extraction temperature, and the ash content of extracted coal decreased below 0.4% at 400 °C from the raw coal samples that have the ash contents of 4–6%. According to the analysis of experiments results, fixed carbon and calorific value increased, and H/C and O/C decreased.     

Optimization of the supercritical fluid coextraction of oil and diterpenes from spent coffee grounds using experimental design and response surface methodology

The reported work aimed at the optimization of operating conditions of the supercritical fluid extraction (SFE) of spent coffee grounds (SCG) using pure or modified CO₂, with particular emphasis on oil enrichment with diterpenes like kahweol, cafestol and 16-O-methylcafestol. The analysis comprised the application of Box–Behnken design of experiments and response surface methodology, and involved three operating variables: pressure (140–190 bar), temperature (40–70 °C) and cosolvent (ethanol) addition (0–5 wt.%). The best conditions to maximize total extraction yield are 190 bar/55 °C/5 wt.% EtOH, leading to 11.97% (g_oil/100 g_SCG). In terms of the concentration of diterpenic compounds in the supercritical extracts, the best operating conditions are 140 bar/40 °C/0 wt.% EtOH, providing 102.90 mg g⁻¹_oil. The measurement of extraction curves near optimized conditions (140 bar/55 °C/0 wt.% EtOH and 190 bar/55 °C/0 wt.% EtOH) confirmed the trends of the statistical analysis and revealed that SFE enhances diterpenes concentration by 212–410% at the expenses of reducing the extraction yield between 39% and 79% in comparison to n-hexane extraction.     

Carbon foams from coals. A preliminary study

Carbon foams were obtained from a bituminous coal with good plasticity properties by a two-stage thermal process under different pressure and temperature conditions. The first stage was a controlled carbonisation treatment under pressure at 450 and 500 °C. In the second stage the carbonisation product was baked at 1100 °C. The foams produced display a macroporous texture with pressure and temperature determining the mean pore size and the amount of pores. The pressure increase reduces the pore size, while the increasing temperature increases the pore volume.     

胜利褐煤超临界乙醇脱氧实验研究

为有效脱除褐煤中含氧官能团,采用超临界乙醇工艺处理胜利褐煤,研究温度、停留时间和醇煤质量比对胜利褐煤脱氧效果的影响,并利用FT-IR和GC/MS对固液相产物进行表征。结果表明,胜利褐煤超临界乙醇脱氧的最佳工艺条件为:温度270℃,停留时间90 min,醇煤质量比5∶1,此时煤样总氧含量为9.29%,脱氧率为61.40%,固相产率为89.62%。在220℃得到的液相产物中,80%左右为芳香族类化合物,酚类和酯类含氧化合物体积分数低于5%,其他含氧类化合物11.29%。270℃得到的液相产率中芳香族类化合物体积分数降低31.69%,含氧类化合物体积分数增加2.81%,酚类和酯类含氧化合物增至35%左右。褐煤经超临界醇解后,乙醇与煤分子作用发生了醚氧桥键的断裂反应,煤分子发生了脱羧反应,液相产物中含有大量酚类(主要为苯酚及其取代物)和酯类(主要为乙酯类)。     

胜利褐煤超临界醇解反应行为研究

对胜利褐煤在甲醇、碱体系中的超临界反应行为进行了研究,考察了反应温度、反应时间和碱的种类分别对胜利褐煤转化率、产物收率和分布规律的影响.结果表明,反应温度显著影响褐煤的转化率和产物收率,产物主要为四氢呋喃可溶组分(占67%～85%)和甲苯可溶组分(占8%～22%);300℃时,胜利褐煤在甲醇-NaOH体系中转化率和收率最高(99%左右);反应时间显著影响褐煤的转化率和产物收率,80 min后褐煤的转化率和产物收率分别为99%和100%;反应过程中四氢呋喃可溶组分可转化为甲苯可溶组分、正己烷可溶组分和水溶性组分;碱的种类对褐煤超临界醇解转化率和产物收率有显著影响.     

水热处理过程中伊敏褐煤微观结构的演变规律

褐煤水热处理可以脱除有害元素,降低n(O)/n(C)比,提高煤阶,有利于煤的洁净利用。利用高压反应釜对褐煤进行水热处理,采用拉曼光谱(Raman)和傅立叶红外光谱(FTIR)对处理后的煤样的化学结构进行分析,探索了不同温度水热处理后煤样微观结构的演变规律。结果表明:150℃水热处理时部分含氧官能团脱除,同时,部分脂肪族侧链断裂及不稳定大分子芳环结构分解形成小分子芳环结构,部分CO分解形成各类醚和羟基;当水热温度升至200℃,处理后褐煤的芳香度指数(R)和芳香结构稠合指数(DOC)上升,表明煤内缩合结构增加,同时,缺陷结构和杂环被去除,大分子芳环结构相对增加,CO大量分解;水热温度继续升高至250℃,褐煤发生氢转移反应导致脂肪族侧链增加;当水热温度达到300℃时,褐煤的芳环结构被破坏,交联结构和无定形碳增加。     

A comparison of spontaneous combustion susceptibility of coal according to its rank

This study investigated spontaneous combustion susceptibility of coal according to the rank. To estimate the spontaneous combustion susceptibility of coal, both crossing-point temperature (CPT) measurement and gas analysis by using gas chromatography (GC) were performed. For the experiment, Eco coal and Kideco coal, Indonesian lignite, and Shenhua coal that is Chinese bituminous coal were used. The lignite such as Eco coal and Kideco coal contains more functional groups that easily react to oxygen more so than Shenhua coal. For this reason, the lignite is more easily oxidized than bituminous coal at low temperature, which results in high O₂ consumption, increase in CO and CO₂ generation, and low CPT. Although the CPT of Eco coal and Kideco coal is identical to each other as they are the lignite, Kideco coal has a lower initial oxidation temperature (IOT) and maximum oxidation temperature (MOT) than those of Eco coal. This means that although each coal has the same rank and CPT, spontaneous combustion susceptibility of coal may vary because the initial temperature of the coal at which oxidation begins may be different due to the substances that participate in oxidation.     

Controlling the excess heat from oxy-combustion of coal by blending with biomass

Two different biomass species such as sunflower seed shell and hazelnut shell were blended with Soma-Denis lignite to determine the effects of co-combustion on the thermal reactivity and the burnout of the lignite sample. For this purpose, Thermogravimetric Analysis and Differential Scanning Calorimetry techniques were applied from ambient to 900 °C with a heating rate of 40 °C/min under dry air and pure oxygen conditions. It was found that the thermal reactivities of the biomass materials and the lignite are highly different from each other under each oxidizing medium. On the other hand, the presence of biomass in the burning medium led to important influences not only on the burnout levels but also on the heat flows. The heat flow from the burning of lignite increased fivefold when the oxidizing medium was altered from dry air to pure oxygen. But, in case of co-combustion under oxygen, the excess heat arising from combustion of lignite could be reduced and this may be helpful to control the temperature of the combustion chamber. Based on this, co-combustion of coal/biomass blends under oxygen may be suggested as an alternative method to the “Carbon Dioxide Recycle Method” encountered in the oxyfuel combustion systems.     

呼伦贝尔褐煤溶剂萃取及萃余煤的双氧水氧化产物分析

以CS2、乙醇和丙酮作为溶剂,对呼伦贝尔褐煤进行连续萃取,并利用气相色谱/质谱联用(GC/MS)技术对萃取物进行分析。结果表明:CS2萃取物主要由长链脂肪烃和芳烃组成,而这些脂肪烃存在于3种溶剂萃取物中。在40℃条件下,用H2O2溶液采用恒温水浴和超声两种方式氧化萃余煤,超声条件下氧化剧烈,并用FTIR分析了原煤、萃余煤、氧化煤的化学结构的变化。氧化后的水溶物用乙酸乙酯萃取后,用GC/MS检测萃取物,恒温水浴氧化可以检测到30种化合物,而超声氧化只检测到14种,且都是以酯类为主。     

烟煤和褐煤分级萃取物的GC/MS分析

采用乙醇、丙酮、离子液体/N-甲基吡咯烷酮(ILs/NMP)和在微波辅助下ILs/NMP分别对宁夏双马烟煤(SM)、宁夏鸳鸯湖烟煤(YYH)、云南莲花塘褐煤(LHT)、内蒙古通辽褐煤(TL)进行分级萃取,依次得到了萃取物(E 1~E 4)和萃余煤(R 1~R 4)。利用气相色谱质谱联用(GC/MS)对E 1~E 4进行分析,傅立叶变换红外光谱(FT-IR)对R 1~R 4进行分析。结果表明:经乙醇、丙酮分级萃取之后,不同种类的亲水型离子液体对同一种煤的萃取率不同,亲水型离子液体与疏水型离子液体对同一种煤的萃取效果也不同,疏水型离子液体的萃取率更高。[Bmim]NTf 2/NMP的可检测化合物中发现酰胺类化合物,[Bmim]Cl/NMP的可检测化合物没有发现酰胺类化合物。分级萃取的萃余煤(R 1~R 4)中脂肪族化合物,芳香族化合物及含氮化合物的含量逐级减少,相应地,它们在萃取液中含量增大。微波辅助下,离子液体的加入可使煤中强键断裂,使萃取液中含氮化合物的种类明显增加。     

Solubilization of Neyveli lignite by oxidative degradation: A potential source of carbochemicals

The recent and possible future shortages of petroleum-derived hydrocarbons for use as starting materials for the synthesis of organic chemicals/products have stimulated renewed interest in the use of coal as raw material for chemical production. Oxidatively solubilized coal and or lignite (OSC) in alcohol is a potential substitute for value added carbo-chemicals of the future. Phenomenal increase in the solubility of lignite in organic solvent consequent on treatment with dilute nitric acid under mild conditions was considered to be an expedient pathway for its direct utilization. The primary requirements for the solubilization are generation of functional groups like free carboxyl groups and size degradation. For the desired product the reaction should also be guided in such a manner, so that the aromatic/hydroaromatic moieties of the coal/lignite are preserved. The present study aims at the selection of the required reaction parameters for the conversion of lignite to such a product. Characterization of the original lignite and the products have been done chemically and spectroscopically. FT-IR, ¹³C (solid state) and ¹H NMR spectra have shown that substances posses both aromatic and aliphatic characteristics. The dominant functional groups which contribute to the reactivity of the substances are phenolic and carboxylic acids.