低阶煤有机溶剂萃取的研究进展

鉴于煤有机溶剂萃取的迅速发展,以低温和高温热萃取作对比,对相应的萃取机理、影响因素及萃取物的应用等进行分析。结果表明:萃取温度在200℃以下的多为低温物理萃取,萃取率一般较低,所得萃取物多用于研究煤的分子结构;而温度在300~400℃的萃取多为高温溶剂萃取,所得萃取率较高,萃取过程中会伴随化学键的断裂及相应化学反应的发生,所得萃取物多用在研究配煤炼焦、劣质煤的气化液化、新型煤基材料等领域。     

煤的溶剂萃取研究进展

综述了近年来溶剂萃取煤的研究进展 ,讨论了影响萃取率的主要因素 ,包括溶剂、煤阶、煤岩组分及辅助手段等以及单一及混合溶剂的萃取机理。指出从分子水平上对煤进行分离进而分析是确定煤的化学结构的关键 ,而可溶化是从分子水平上分离煤的必要条件。溶剂分级萃取是一种行之有效的萃取方法 ,并提出了煤的溶剂萃取技术的若干研究方向     

The occurrence of trace elements in coal

The standard comparison of relationships of trace element concentrations in coal is based on a comparison of mean values of elemental concentrations. This method is extended by including some functions of covariances among trace element concentrations. In the proposed method, the comparison is based on: the pattern of the mass spectrum of mean values of concentrations; the spectrum of the covariance matrix; the eigenvectors of the covariance matrix; and the order of eigenvectors. The method has been applied to the coal of the Istrian coal basin and the same genesis of the elements calcium, sulphur, iron, titanium and vanadium throughout the considered coal seam has been established.     

利用有机溶剂提取微藻油脂的方法探究

在传统化石能源日益枯竭的趋势下,微藻生物柴油作为第三代绿色可再生的替代型能源越来越受到人们的重视.在微藻生物柴油的产业链上,油脂的提取是影响其推广应用的一个关键环节.本文实验利用有机溶剂提取微藻油脂,探究在不同的条件下微藻油脂的提取效果,并特别研究了先后使用甲醇和石油醚两种有机溶剂对微藻油脂提取率的影响.研究结果表明:温度、液料比、浸提时间对提取效率都有一定的影响,并且使用甲醇和石油醚两种溶剂分步提取时会使微藻油脂提取率明显提高;在液料比为15mL/g、提取温度为45℃、提取时间为5h时,使用石油醚作为提取剂的提取率为58.71%;使用甲醇溶剂提取后再使用石油醚提取时,在液料比和提取时间相同的条件下,温度为35℃时提取率即可达87.90%     

煤中微量元素测定研究进展

对煤中微量元素测定常用的前处理方法和测定技术进行了总结,综述了湿法消解、燃烧法和碱熔法的原理、操作步骤和优缺点。介绍了固体测定技术和溶液测定技术的仪器原理和发展历程。旨在为测试煤中微量元素时选择合适的前处理方法和测试仪器来获得准确的数据。最后对煤中微量元素的应用方向和测试方法的发展方向进行了展望。     

煤的CS2/NMP溶剂抽提

综述了溶剂抽提的发展和现状,介绍了V(CS2)∶V(NMP)=1∶1的混合溶剂,对影响该混合溶剂抽提率的因素、抽提机理和相关理论计算研究进行了讨论,展望了该领域的研究方向。     

中国煤中微量元素的研究

论述了中国煤中微量元素地球化学研究的现状、分析方法、发展趋势和存在的不足,提出了相应的建议。认为应加强微量元素的富集机理、赋存状态、环境影响、富集元素的综合利用等方面的工作。     

Effect of pretreatment conditions on the determination of major and trace elements in coal fly ash using ICP-AES

Microwave-assisted acid digestion (MW-AD) followed by atomic spectrometries such as inductively coupled plasma-atomic emission spectrometry (ICP-AES) was examined for the determination of major and trace elements in coal fly ash (CFA). Effective digestion conditions were studied using four certified reference materials of CFA, with particular focus on the composition of acid mixture and the removal of HF after MW-AD. When MW-AD was conducted without using HF (HNO₃+H₂O₂), the tested elements yielded fairly poor recoveries. When MW-AD with HF (HNO₃+HF+H₂O₂) was carried out, two methods for HF removal were attempted, H₃BO₃ addition and evaporation of acids. In the former method, while the recoveries of major elements (Al, Ca, Fe, and Mg) were satisfactory, those of trace elements were not satisfactory; in particular, the recovery of Pb was fairly low. In the latter method, the recoveries of Al, Ca, and Mg were extremely poor; however, those of other elements including the trace elements (Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) were satisfactory. In this paper, the optimization of the digestion method for ICP-AES is discussed. Further, the advantages and limitations of ICP-AES in the determination of elements in CFA are assessed.     

Fractionation of brown coal by sequential high temperature solvent extraction

Separation of brown coal into fractions having rather uniform structure is believed to be one of the promising pretreatment methods for effective utilization of brown coal. The authors have recently presented a new coal fractionation method that can separate a bituminous coal into several fractions having different molecular weight compounds without decomposing the coal. The method extracts coal using a flowing stream of non-polar solvent such as tetralin or 1-methylnaphthalene by increasing the extraction temperature stepwise up to 350 °C. In this study the fractionation method was applied to fractionate a brown coal. Water was used as an extracting solvent in addition to tetralin and 1-methylnaphthalene by intending to utilize inherent water of brown coal as the extraction solvent. An Australian brown coal was successfully fractionated into six fractions by any solvents, but the properties of the fractions were significantly different depending on the extraction solvent. This is because tetralin, 1-methylnaphthalene, and water interacted significantly with the brown coal in different ways even at less than 350 °C. The difference in chemical structure and thermal properties of the fractions were examined in detail through ultimate analysis, ¹³C NMR, molecular weight distribution, and thermogravimetric and thermomechanical analyses.     

Reactivity of cycloalkanes during the solvent extraction of coal

The reactivity of cycloalkanes, either alone or as part of a solvent mixture, during the solvent extraction of coal at 430 °C has been studied. When used with polyaromatic compounds (? 3 rings) as solvents, cycloalkanes participate in hydrogen donation reactions giving rise to high extraction yields of the coal.     

超声波作用下溶剂萃取法分离镧铈元素

针对溶剂萃取法分离稀土元素的工艺中采用氨水为皂化剂造成排放的废水中氨氮含量超标,采用氢氧化钠为皂化剂使得排放废水中钠盐含量超标而造成环境污染的问题,研究了以未皂化的P204为萃取剂,超声波作用下镧铈元素萃取分离的方法。考察了料液酸度、超声波强度、超声波频率分别对镧铈分配比、分离系数及饱和萃取容量的影响。结果表明：当超声波强度为20 W/cm2、超声波频率为30 kHz、料液酸度为5时,镧铈元素的分配比、饱和萃取容量和元素间的分离系数达到最大,其中饱和萃取容量分别为35 g/L和19 g/L,镧铈间的分离系数最大为4.63。通过红外光谱检测可知溶剂萃取法分离镧铈元素时,由于超声波的作用使得萃取剂P204二聚体中的氢键部分断裂,因此有更多的单体P204能够与稀土离子发生萃取反应,所以超声波作用下镧铈的饱和萃取容量和分配比均大于无超声波作用。     

Volatility and chemistry of trace elements in a coal combustor

The volatility of 16 trace elements (TEs) (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sb, Se, Sn, Te, Tl, V, Zn) during coal combustion has been studied depending on the combustion conditions (reducing or oxidizing) and type of coal (high- or low-ash coal), together with their affinities for several active gaseous atoms: Cl, F, H, O, and S.

The elements can be divided into three groups according to their tendencies to appear either in the flue gases or in the fly ashes from a coal combustor:

Group 1: Hg and Tl, which are volatile and emitted almost totally in the vapor phase.

Group 2: As, Cd, Cu, Pb and Zn, which are vaporized at intermediate temperature and are emitted mostly in fly ashes.

Group 3: Co, Cr, Mn and V, which are hardly vaporized and so are equally distributed between bottom ashes and fly ashes. In addition, Sb, Sn, Se and Te may be located between Groups 1 and 2, and Ni between 2 and 3.

At 400 and 1200 K, the 16 TEs behave differently in competitive reactions with Cl, F, H, O and S in a coal combustor.     

用P_(204)萃取脱除硫酸钴溶液中的微量元素

研究了用P_(204)萃取脱除硫酸钴溶液中微量金属元素萃取工艺,试验结果表明,在P_(204)有机相组成为25%P_(204)+75%航空煤油,4级逆流萃取,30%NaOH皂化,皂化率75%,萃前液pH值3.5,萃取温度25~35℃,萃取相比O/A=1.5~2/1,混合萃取5min的条件下,P_(204)萃取除杂后硫酸钴溶液中Co/Zn、Co/Mg、Co/Cd、Co/Mn、Co/Fe、Co/Ca的浓度比分别为87516/1、31918/1、79794/1、82212/1、64595/1、67825/1萃取除杂效果均比较好,均可满足生产精制CoSO_4·7H_2O和电钴的要求,且钴直收率可达96.17%。     

有机溶剂提取萃取法生产茶多酚工业试验

介绍了以质量分数75%的酒精为提取溶剂、氯仿为去杂萃取剂、乙酸乙酯为纯化萃取剂生产茶多酚的工艺流程、相关装置和生产过程。对不同浓度的酒精提取、杂质去除萃取、纯化萃取等过程和干燥条件进行了工业生产研究,制得的产品茶多酚质量分数大于94.5%,其中活性成分儿茶素总量达80.0%。     

Distributions of trace elements in Western Canadian coal ashes

Concentrations of 52 minor elements in coal ash were determined using spark source mass spectroscopy. Hg levels in raw coal were investigated by cold vapour atomic absorption spectrophotometry. The concentration of elements are compared to other available data and to levels in the Earth's crust. F levels in coal ash exceed 500 μ g^?1 and may be greater than 1 wt% in raw coal. Approximately half the elements (B, S, Ni, Zn, Ga, Ge, Se, Sr, Y, Mo, Sn, Sb, I, Ba, Pr, Nd, Sm, Eu, Ho, Hf, Pt, Hg, Pb, Tl, Bi, U) investigated are enriched in the coal ash with respect to the Earth's crust. The ranges in minor element concentrations in coal ash and coal from different global regions are very similar.     

Biodesulphurization of coal: behaviour of trace elements

The purpose of this study is to show how the different size fractions of coal are affected during a process of biodesulphurization in a packed column and to examine the repercussions of the process on the elimination of certain heavy and trace elements. The total desulphurization obtained in 51 days is about 25 wt%, as only pyritic sulphur is attacked. The greatest reduction in sulphur content was for the 1-0.5 mm fraction although the lowest actual sulphur content was found in particles of under 0.125 mm, where it dropped from 1.76 to 1.17 wt%. The most important changes in the metal content were decreases in Ni, Cu, Zn, As, Cr, Co and Sr, mainly in the smaller sizes.     

煤的溶剂热萃取研究进展

综述了近年来在煤的溶剂热萃取（不小于300℃）的研究进展。讨论了主要影响因素包括极性溶剂、酸处理、萃取时间等对热萃取率的影响。结论表明：酸处理、使用强极性溶剂有利于提高煤的热萃取产率;时间和温度是热萃取的两个重要参数,在不同程度上影响着煤的热萃取率;萃取物活性很高,并且基本无灰,是煤直接液化的极好的原料也可以作为内燃机燃料。     

Certification of the contents of some trace elements in a coal

The preparation of a coal reference material to be used in trace element analysis is described, as well as the tests to ascertain the homogeneity and stability of the material. Several analytical methods were applied by several laboratories to certify the contents of As, Cd, Cr, Co, F, Mn, Hg, Ni, Pb and Zn. The procedure followed for certification is explained.     

Bituminous coal extraction in terms of electron-donor and -acceptor interactions in the solvent/coal system

Experiments on high volatile bituminous coal extraction at ambient temperature have been carried out by means of 18 solvents having their electron-donor and -acceptor properties quantitatively determined (DN and AN numbers) by Gutmann's method. A model for coal extraction, based on the assumption that donor-acceptor bonds occur in coal and are responsible for binding together macromolecular network and extractable substances filling the pores of a network, has been worked out and verified on the basis of experimental data.The results lead to the conclusion that extraction is in principle, a substitution reaction: pore substances are replaced by a solvent molecule in their Donor_network → Acceptor_{pore substance} or Donor_{pore substance} → Acceptor_network bonds. Solvents capable of substitution are characterized by specific DN and AN values.     

Activated extraction of coal using a hydrogen-donor solvent

The kinetics of the extraction of a high-volatile bituminous coal with 1,2,3,4-tetrahydronaphthalene (tetralin) under the influence of ultrasonic energy has been studied at five temperatures: from 47 to 87°C. The effects of intensity of ultrasonic energy, particle size, and hydrogen content of the coal were also recorded. Analysis of the results showed that a second-order reaction followed by a first-order reaction best describes the kinetics of the extraction process. The enthalpies of the second-order and first-order regions were respectively 8.7 and 2.5 kcal/mol, suggesting essentially physical control. The entropies were respectively ?44 and ?70 e.u. Auxiliary experiments and the kinetic data obtained suggest a model for the extraction process. The mechanism of the overall reaction is undoubtedly complex, but the data indicate that van der Waals and hydrogen-bonding forces are most affected by the ultrasonic energy, although stronger bonding is also affected giving much higher yields than would be expected. From the yields obtained in this study it is concluded that ultrasonic energy acts by rupturing bonds that are not affected by the solvent alone; the bonds affected are either strong hydrogen bonds or aliphatic covalent bonds, but not aromatic bonds.