顺、反异构钼硫簇合物〔(C_2H_5)_4N〕_2〔Mo_2S_4(SCH_2CH_2S)_2〕的合成、结构和性质研究

用（ＮＨ４）２ＭｏＳ４，ＣｏＣｌ２，ＮｉＣｌ２，ＨＳＣＨ２ＣＨ２ＳＨ和Ｅｔ４ＮＢｒ在ＣＨ３ＯＨＣＨ３ＯＮａ溶液中反应，得到了顺（Ａ），反（Ｂ）异构体的原子簇化合物［（Ｃ２Ｈ５）４Ｎ］２［Ｍｏ２Ｓ４（ＳＣＨ２ＣＨ２Ｓ）２］的晶体。用Ｘ—射线单晶衍射法测定了顺、反异构体簇合物Ａ和Ｂ晶体结构，其晶胞参数Ａ为ａ＝２．６０４４（２）ｎｍ，ｂ＝１．９８８６（２）ｎｍ，Ｃ＝２．６３０２（Ｉ）ｎｍ，Ｖ＝１３．５８６ｎｍ３，β＝９３．３３°（２）；Ｂ为ａ＝１．０４４（２）ｎｍ，ｂ＝１．４１５８（２）ｎｍ，Ｃ＝１．１４１７（２）ｎｍ，Ｖ＝１．６３８ｎｍ３，β＝１００．４７°，经块距阵最小二乘法修正最终得偏离因子Ｒ＝０．０８８（Ａ），Ｒ＝０．０８９（Ｂ）。同时还对簇合物的红外光谱和紫外可见光谱也进行了研究。     

煤中致粘组分与不粘组分

用二硫化碳－Ｎ－甲基－２－吡啶烷酮（ＣＳ２－ＮＭＰ）混合溶剂对五种不同阶煤进行了萃取,考察了煤的可溶性与粘结性的关系,结果表明,煤的可溶性与粘结性密切相关,由此提出了煤中主要存在的“致粘组会”和“不粘组分“的概念,即煤在ＣＳ２－ＮＭＰ中的萃取物为致粘组分,萃余物为不粘结分。     

N,N′-双(2-氨乙基)草酰胺合铜的Cu(Ⅱ)-Mn(Ⅱ)双核配合物的合成及其性质的研究

以Ｎ，Ｎ′－双（２－氨乙基）草酰胺合铜［Ｃｕ（ｏｘｅｎ）］作为螯合剂，合成和表征了４个草酰胺桥联的异双核配合物［Ｃｕ（ｏｘｅｎ）Ｍｎ（Ｌ）２］（ＣｌＯ４）２。ｏｘｅｎ表示Ｎ，Ｎ′－双（２－氨乙基）草酰胺根阴离子；Ｌ分别为Ｎ，Ｎ，Ｎ′，Ｎ′－四甲基乙二胺（ｔｍｅｎ）、１，３－丙二胺（ｔｍｄ）、１，２－丙二胺（ｔｍｅ）和乙二胺（ｅｎ）。测定了配合物［Ｃｕ（ｏｘｅｎ）Ｍｎ（ｔｍｅｎ）２］（ＣｌＯ４）２的变温磁化率（４～３００Ｋ）；其数值用最小二乘法和从自旋Ｈａｍｉｌｔｏｎｉａｎ算符（Ｈ＝－２ＪＳ１·Ｓ２－ＤＳ２Ｚ１）导出的磁方程拟合，求得交换积分Ｊ＝－２６．８ｃｍ－１，表明双核配合物中金属离子间存在反铁磁性超交换作用。实验还发现双核配合物的抑菌活性优于配体的抑菌活性。     

μ—草酰二胺铜（Ⅱ）—锰（Ⅱ）双核配合物的合成与磁性研究

合成和表征了两种新的异双核配合物「Ｃｕ（ｏｘｅｎ）Ｍｎ（Ｌ）２」（ＣｌＯ４）２，ｏｘｅｎ表示Ｎ，Ｎ‘－双（２－氨乙基）草酰胺根阴离子；Ｌ为Ｎ，Ｎ，Ｎ’，Ｎ‘０四甲基乙二胺和１，３－丙二胺；测定了配合物「Ｃｕ（ｏｘｅｎ）Ｍｎ（ｔｍｅｎ）２」（ＣｌＯ４）２的变温磁化率（４－３００Ｋ）；其数值用最小二乘法和从自旋Ｈａｍｉｌｔｏｎｉａｎ算符Ｈ＝－２ＪＳ１Ｓ２－ＤＳ２１导出的磁方程拟合，求得交换积分Ｊ＝－６     

影响中间相沥青电解加氢反应因素的研究

在隔离式电解槽中,用泡沫铅（ＳＰｂ）作阴极,铂（Ｐｔ）作阳极,饮和甘汞电极（ＳＣＥ）作参考电极,以ＣＨ３ＣＮ＋Ｃ２Ｈ５ＯＨ＋Ｈ２Ｏ＿Ｂｕ４ＮＢｒ为电解体系,对由煤沥青为原料制得的中国相沥青（ＭＰ）进行电解加氢研究,当ｃ（ＣＨ３ＣＮ）：ｃ（Ｃ２ＨＯＨ）：ｃ（Ｈ２Ｏ）＝０．４：０．１：１（浓度比）,ｃ（Ｂｕ４ＮＢ４）＝０．３１ｍｏｌ／Ｌ,ｔ＝３０Ｃ,ｐ（ＭＰ）＝５０ｇ／Ｌ,阴极电解电位为－２．４Ｖ时,     

聚乙烯醇存在下耐尔蓝－铈钼、钪钼杂多酸体系连续光度测定铈和钪

在聚乙烯醇（ＰＶＡ）存在下，耐尔蓝（ＮＢ）与铈钼、钪钼杂多酸络阴离子形成离子缔合物，其最大吸收均位于５８５ｎｍ，表观摩尔吸光度分别为εｃｗ＝３．５２×１０６和εＳｃ＝３．５９×１０＿５Ｌ·ｍｏｌˉ１·ｃｍˉ１，铈和钪服从比耳定律的浓度范围分别为０～０．８μｇ／２５ｍｌ和０～２．０μｇ／２５ｍｌ，测定极限分别为１．３ｎｇＣｅ／ｍｌ（ｎ＝１０）和３．０ｎｇＳｃ／ｍｌ（ｎ＝７），对于０．０２μｇＣｅ／ｍｌ或０．０４μｇＳｃ／ｍｌ测定的相对标准偏差分别为２．７％（ｎ＝９）和２．８％（ｎ＝１０），离子缔合物的摩尔比分别为Ｃｅ：Ｍｏ：ＮＢ＝１：６：４和Ｓｃ：Ｍｏ：ＮＢ＝１：１２：３。本法用于地质标样分析，结果满意。     

MNA-TBP从盐酸介质中萃取Ir(Ⅳ)

对ＭＮＡ－ＴＢＰ从盐酸介质中萃取Ｉｒ（Ⅳ）作了研究．结果表明：ＭＮＡ－ＴＢＰ对Ｉｒ（Ⅳ）萃取有协同效应．当ＭＮＡ和ＴＢＰ在正辛烷中的浓度各为０．４５ｍｏｌ／Ｌ，待萃液中ＨＣｌ总浓度为４ｍｏｌ／Ｌ，铱浓度为１７３．１３μｇ／ｍｌ，相比为１时，协萃系数Ｒ为２．３３，协萃合物的组成为（ＭＮＡＨ）＋．ＩｒＣｌ＄２－６．（ＨＴＢＰ）＋．     

含草酰胺桥的新型铜（Ⅱ）─镍（Ⅱ）双核配合物的合成和磁性研究

本文合成和表征了两种新的杂双核配合物：［Ｃｕ（ｏｘｄｎ）Ｎｉ（ｔｍｎ）＿２（ＣｌＯ＿４）＿２（１）和［Ｃｕ（ｏｘｄｎ）Ｎｉ（ｔｍｄ）＿２］（ＣｌＯ＿４）２（２），ｏｘｄｎ代表Ｎ，Ｎ＇－双（３－氨丙基）草酰胺根阴离子；ｔｍｎ为Ｎ．Ｎ．Ｎ＇－四甲基乙二胺；ｔｍｄ表示１．３－丙二胺。测定了配合物（１）的变温磁化率（４～３００Ｋ），其数值用最小二乘法和从自旋哈密顿算符Ｈ＝－２ＪＳ＿１·Ｓ＿２导出的磁方程拟合，求得交换积分Ｊ＝－１１８．８ｃｍ￣（－１）。文中还用Ｋａｈｎ理论解释了这种反铁磁自旋交换作用。     

Mo（Ⅵ）与Tiron的显色反应及应用研究

研究了Ｍｏ（Ⅵ）与Ｔｉｒｏｎ的反应，发现在ｐＨ４．０的ＨＡｃ－ＮａＡｃ介质中形成１：１配合物，该配合物在２５２ｎｍ、３１５ｎｍ有两个吸收峰，而在可见光区无吸收峰。测得ε２５２＝６．９×１０￣３Ｌ·ｍｏｌ－１·Ｃｍ－１，ε３１５＝３．５×１０３Ｌ·ｍｏｌ－１·Ｃｍ－１。据此建立了测定Ｍｏ（Ⅵ）的方法，在２５２ｎｍ和３１５ｎｍ处的线性范围分别为１．６×１０－６ｍｏｌ·Ｌ－１～２．Ｏ×１０－４ｍｏｌ·Ｌ－１和３．２×１０－４ｍｏｌ·Ｌ－１～２．０×１０－４ｍｏｌ·Ｌ－１。检出限分别为８．Ｏ×１０－７ｍｏｌ·Ｌ－１和１．６×１０－６ｍｏｌ·Ｌ－１．ＰＯ＿４￣３＋、ＳｉＯ＿３￣２－对测定无干扰，而Ｗ（Ⅵ）、Ｖ（Ⅴ）、Ｆｅ（Ⅲ）等有干扰。该法试用于有机磷合钼聚多酸盐样品的测定，结果满意，方法回收率９６％～１０２％，变异系数≤１．ｌ％（ｎ＝１２）。     

金—钼酸盐—丁基罗丹明B体系显色反应研究

研究了在高氯酸和聚乙烯醇（ＰＶＡ）存在下，金与钼酸盐和丁基罗丹明Ｂ（ＢＲＢ）的显色反应。其适宜条件ＣＨＣｌＯ４＝１．５ｍｏｌ／Ｌ，ＣＭｏＯ２－４＝９．１×１０－４ｍｏｌ／Ｌ，ＣＢＲＢ＝３．８×１０－５ｍｏｌ／Ｌ及０．０８％ＰＶＡ。金钼杂多酸—丁基罗丹明Ｂ离子缔合物的最大吸收位于５７０ｎｍ，表观摩尔吸光系数为３．３６×１０６Ｌ·ｍｏｌ－１·ｃｍ－１，金量在０～４０μｇ／Ｌ范围内服从比尔定律，测定极限（Ｓ／Ｎ＝３）０．９０μｇ／Ｌ（ｎ＝１０），对于２８μｇＡｕ（Ⅲ）／Ｌ测定的相对标准偏差２．１％（ｎ＝７）。缔合物至少可稳定５ｈ，摩尔比Ａｕ∶ＢＲＢ＝１∶３。考察了４４种共存离子的影响，大多数常见离子不干扰，用活性炭分离富集金，对砂矿和炭粉中金的测定，结果满意。     

Electrochemical oxidation of coals: Voltammetry and mass spectrometry

The anodic oxidation of sulphuric acid slurries of lignite, bituminous, and anthracite coals; a high-yield extract of coal; and carbon black, has been investigated voltammetrically and with simultaneous m.s. monitoring of evolved gases. The previously reported evolution of carbon dioxide at very low voltages was shown to be chemically released from minerals. The low rank coals and the asphaltite did show considerable electrochemical activity near to 1.0–1.2 V, mainly from the conversion of leached ferrous ion to the ferric form. Further activity near 1.4–1.5 V arose from the oxidation to CO₂ of leached organic matter. For well-washed low rank coals, the coal extract and the anthracite, CO₂ release was only observed at high (>2.8V) anode voltages, with simultaneous release of oxygen. Electrochemical gasification of coal via anodic oxidation of macromolecules at low voltages did not occur.     

煤与天然气气流床共气化制合成气试验研究

为提高煤、天然气资源综合利用效率,优化合成气成分,进行了煤与天然气气流床共气化技术研究。介绍了煤与天然气气流床共气化的试验装置及工艺流程,考察了气化温度、压力、水煤浆浓度、CH4与煤比对共气化反应的影响。结果表明,气化温度和CH4与煤比是共气化反应的主要影响因素,较高的气化温度对共气化反应有利,气化温度为1 350℃时,共气化指标较好,有效气体积分数大于90%;随着CH4与煤比的增大,合成气n(H2)/n(CO)增高。CH4与煤比为0.9 m3/kg时,合成气中n(H2)/n(CO)约1.2。根据后续合成工艺要求,通过调节气化温度和CH4与煤比,可获得n(H2)/n(CO)在0.8~2.0的合成气。     

The macromolecular nature of bituminous coal

Considerable insight into the macromolecular state of coal has been obtained by examining the optical anisotropy of untreated solvent-swollen, and chemically derivatized thin sections of coal. From the effect of pressure on the optical anisotropy, and from the rate and degree of recovery after release of pressure, it was found possible to determine whether the coal is in a plastic or rubbery state, whether a rubbery state is cross-linked and how mobile the macromolecular chain segments are. The experimental technique utilized for this work was transmission optical microscopy in polarized light of uncontaminated thin sections of vitrinite from a bituminous coal. The study included in-situ microscopic examination of swollen coal immersed in pyridine, THF, toluene and several other solvents. Some samples were O-methylated to assess the impact of hydrogen bonding. New results and conclusions derived from this study include: (1) the vitrinite of raw bituminous coal is a plastic macromolecular substance; (2) coal swollen in pyridine (and some other ‘specific’ solvents) is a cross-linked rubber and its macromolecular chain segments have substantial mobility; (3) when pyridine-extracted coal dries, it reverts to a plastic; (4) the large discrepancies previously found between values of M_c (molecular weight between crosslinks) measured by solvent-swelling and by stress-strain techniques is caused by differences in secondary interactions; (5) various solvents can, by their effect on secondary interactions, create appreciably different macromolecular structures in the coal; (6) different solvents, depending on their effect on secondary interactions in the coal, can be expected to extract chemically different molecules from a coal - rates of extraction and the ability of solvents to extract larger molecules should also differ; (7) O-methylated coal is a plastic, and thus, in addition to hydrogen bonding, other secondary interactions are of great importance; (8) it is likely that in their dry condition, solvent-treated coal and O-alkylated coal, as well as untreated coal, are in glassy states; (9) pyridine by itself appears to relax substantially all secondary interactions which are weakened by O-methylation, only permanent bonds are not relaxed; (10) previous measurements of M_c can now be reassessed in view of these results.     

Influence of cultural conditions on coal solubilization by Penicillium simplicissimum

Sub-bituminous coal, preoxidized with nitric acid and treated with sodium hydroxide solutions to obtain a water-soluble extract, was used for the study of coal degradation by Penicillium simplicissimum. The influence of different carbon and nitrogen sources was examined in connection with growth and production of acid-precipitable coal polymers. The yield was increased after the addition of maltose, lactose and cellobiose while glucose, fructose and xylose had little effect. An organic nitrogen source, yeast extract, was an improved source of nitrogen compared with ammonium chloride. The coal-degrading system appeared before the depletion of the carbon or nitrogen source. In addition, the effects of initial pH of the culture medium demonstrated an increase in the yield of coal polymers up to a pH of 7.5. Above this pH, non-biological catalysis increased gradually. However Ca²⁺ and Mn²⁺ increased the yield of coal polymers over a 14-day period, but yield was unaffected by Cu²⁺, Al³⁺ and Fe²⁺.     

Evidence for mineral matter forms in coal liquefaction extracts

High- and low-temperature ashes from feed coal, coal extract solution and filter cake from a two-stage coal liquefaction process have been studied by X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive X-ray fluorescence (SEM/EDX). Hydrocracking experiments using alumina support only, in place of the active Ni/Mo catalyst on alumina, were also carried out, with trace metal analysis of the coal extract solution feed and hydrocracked extracts using atomic absorption and emission spectroscopy. The major mineral transformations occurring were of pyrite to pyrrhotite and the fixation of organic sulphur by calcium carbonate. Mineral particles were not observed in the coal extract solution ashes, even under high magnification, and the study indicated that size alone was not a determining factor as to whether a coal mineral was to be found in a coal-derived liquid. None of the trace metals was deposited on the alumina support under hydrocracking conditions, in marked contrast to the results obtained with the normal Ni/Mo catalyst. These results lead to the conclusion that for the deposition of trace elements to occur a reaction must take place and hence the trace elements must be chemically bound in some form.     

Liquefaction of subbituminous coals with a basic nitrogenous model process solvent

Liquefaction reactions in a tubing-bomb reactor have been carried out as a function of coal, coal sampling source, reaction time, atmosphere, temperature, coal pre-treatment, SRC post-treatment and process solvent. Pyridine as well as toluene conversions ranging from 70 to > 90 wt% involving both eastern bituminous and western subbituminous coals are obtained. 1,2,3,4-Tetrahydroquinoline (THQ) has been extensively used as a process solvent under optimized liquefaction conditions of 2:1 solvent: coal, 7.5 MPa H₂, 691 K and 30 min reaction time. Comparisons of THQ with other model process solvents such as methylnaphthalene and tetralin are described. Liquefaction product yield for conversion of subbituminous coal is markedly decreased when surface water is removed from the coal by drying in vacuo at room temperature prior to liquefaction. The effect of mixing THQ with Wilsonville hydrogenated process solvent in the liquefaction of Wyodak and Indiana V coals is described.     

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。     

Comparative reactivities of coal asphaltenes during hydropyrolysis

Comparisons have been drawn in the relative reactivities of three coal asphaltenes during hydropyrolysis. All were derived from hydrogen donor-solvent extracts of bituminous coal, but had different hydrotreatment histories and different carbon contents (87.1, 91.9 and 90.8 wt% for asphaltenes 1, 2 and 3, respectively). The hydropyrolyses were carried out in the presence of CoO–MoO₃ catalyst and gaseous hydrogen at 8.7 MPa. For two of the asphaltenes (1 and 2) systematic comparisons were made for different reaction times at 425°C; for all three asphaltenes comparisons were made for l h of hydropyrolysis at 425°C. The general pattern of asphaltenes conversion indicated that more pentane-soluble product was produced from asphaltene isolated from straight coal extract (asphaltene 1). For the asphaltenes isolated from hydrotreated extracts, the extent of conversion to liquids was limited when the carbon content was high (asphaltene 2) although the pattern of conversion was similar in the other hydrotreated asphaltene (asphaltene 3). The aliphatic content of the liquid products formed was low, and the distribution of hydrogenated species in the highly aromatic liquid products indicated that complete hydrogenation of the polyaromatics produced in pyrolysis is difficult. Altogether the aliphatics made up ≈ 10 wt% of the asphaltene 1 hydropyrolysate. Aromatic hydrocarbons made up 90% of the liquid product. Phenanthrene, pyrene and anthracene were prominent, and the largest component in the mixture was phenanthrene which, together with other polyaromatics such as fluoroanthene, dominated the liquid product.     

Investigation of the remaining major and trace elements in clean coal generated by organic solvent extraction

A sub-bituminous Wyodak coal (WD coal) and a bituminous Illinois No. 6 coal (IL coal) were thermally extracted with 1-methylnaphthalene (1-MN) and N-methyl-2-pyrrolidone (NMP) to produce clean extract. A mild pretreatment with acetic acid was also carried out. Major and trace inorganic elements in the raw coals and resultant extracts were determined by means of inductively coupled plasma optical emission spectrometry (ICP-OES), flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS), and cold vapor atomic adsorption spectrometry (CV-AAS). It was found that the extraction with 1-MN resulted in 73–100% reductions in the concentration of Li, Be, V, Ga, As, Se, Sr, Cd, Ba, Hg, and Pb. The extraction with NMP yielded more extract than that with 1-MN, but it retained more organically associated major and trace metals in the extracts. In the extraction of WD coal with NMP, the acid pretreatment not only significantly enhanced the extraction yield but also significantly reduced the concentrations of alkaline earth elements such as Be, Ca, Mg, Sr, and Ba in the extract. In addition, the modes of occurrence of trace elements in the coals were discussed according to their extraction behaviors.     

Growth and coalescence of mesophase in pitches with carbon black additives and in coal

The techniques of polatized light optical microscopy and of washing the surfaces of solid pyrolysis products with chloroform prior to SEM examination are used to monitor the growth and coalescence of growth units of mesophase in a petroleum pitch, a coal extract and a caking coal. Additions of 1 wt% of carbon black retard growth and coalescence and promote clustering of these units because of adhesion of carbon black particles. This has the effect ultimately of reducing the size of the optical texture in coke from the coal extract, but not with coke from the petroleum pitch which has lower viscosity. With the coal, mesophase growth units tend to form clusters and do not coalesce. Mesophase can form an anisotropic skin on the inside of developing pores (bubbles) in the fluid phase and this may limit their growth.