Investigation of nitrogen compounds in coal tar products. 2. Basic fractions

Gas chromatography (g.c.), in conjunction with nitrogen-selective alkali flame detection (AFD) and mass spectrometry (m.s.), has been used for the detailed examination of nitrogen compounds in basic fractions from an anthracene oil and a low-temperature coal tar. The compounds identified were mainly aza species, but some di-nitrogen and mixed heteroatomic compounds were detected in the anthracene oil bases. Nitrogen-selective g.c.—AFD chromatograms of the extraction residues showed complex mixtures of non-basic nitrogen compounds; the major peaks were identified, but further g.c.-m.s. investigation of these compounds will require the preparation of hydrocarbon-free fractions.     

Cyclic alkanes as geochemical markers in coal liquefaction products

Branched-chain/cyclic alkanes have been obtained, by solvent extraction and molecular-sieve adsorption, from a UK low-temperature (Rexco) coal tar, a USA fluidized-bed pyrolysis (FMC COED) coal tar, and a novel supercritical-gas-extract of a Turkish (Elbistan) lignite. Mass spectrometry (with gas chromatography and field-desorption) established the presence of mono-, di (including sesquiterpanes), tri-, tetra- (steranes only), and pentacyclic (triterpanes only) alkanes, including several steranes and triterpanes not previously reported as coal-tar constituents. The potential of cyclic alkanes as geochemical markers, even for commercial coal products subjected to appreciable heat treatment, is demonstrated by the identification of C₁₂, C₁₃, C₁₅ and C₁₆ dicyclics (including isoprenoid alkanes), C₁₇-C₂₆ tricyclics, and C₂₇ and C₂₉ hopane-type pentacyclics (triterpanes) in FMC, and of C₁₆-C₃₈ monocyclics, C₃₄-C₃₆ dicyclics, C₂₂-C₃₆ tricyclics, C₂₇-C₃₀ tetracyclics (steranes), and C₂₇, C₂₉, C₃₀, C₃₁, C₃₂, and C₃₃ hopane-type pentacyclics (triterpanes) in Rexco tar. Tetra- and pentacyclic alkanes were also preserved in the lignite extract.     

Determination of aromatic and aliphatic CH groups in coal by FT-i.r.: 1. Studies of coal extracts

A set of coal extracts have been characterized by FT-i.r. and proton n.m.r. spectroscopy. The n.m.r. measurements of aliphatic and aromatic hydrogen allow a direct calibration of the absorption coefficients of appropriate i.r. bands. This allows methods for calculating these coefficients based on relating i.r.-band intensities to elemental hydrogen to be tested directly. Reasonable agreement was obtained.     

FTIR analaysis of coal. 1. techniques and determination of hydroxyl concentrations

The preparation of coal samples for the determination of hydroxyl content by FTIR is described. It is concluded that the FTIR method provides good quality infrared spectra on opaque materials such as coal and char. If sample preparation procedures are followed carefully, quantitative spectra of coals can be reproduced within ±5%. Beer's law is followed in the range 0.3–1.3 mg of coal/cm². The broad absorbance in the range 2000–3600 cm^?1 appears when using several different preparation techniques and is caused by hydrogen-bonded OH. The use of quantitative FTIR specta offers a simple method of estimating the hydroxyl content of a coal. Reasonable results have been obtained despite the problem of interference by water. The KBr pellets were dried for 48 h at 105 °C and the absorbance was reduced at 3200 cm^?1 and the problem of scattering was minimized by using a rectilinear baseline. With these procedures the hydroxyl oxygen concentrations in the coal were determined to an accuracy of ±10%.     

Coal tar nitrogen bases

A method involving acid extraction, fractionation, derivatization and g.c.-m.s. analysis was used to characterize the basic nitrogen compounds in coal tar. It was found that these compounds fall into ten compound types belonging to eighteen homologous series. Separation of aza-arenes from amines by derivatization is recommended as a better procedure.     

Assignment of aliphatic carbon peaks in the 13C n.m.r. spectra of coal liquefaction products

Aliphatic carbon peaks in the complex ¹³C n.m.r. spectra of coal-derived liquids can be unambiguously assigned to C, CH, CH₂ and CH₃ groups using a spin-echo technique.     

E.p.r. study of molecular phases in coal

E.p.r. spectra from coals of various carbon content are reported. The e.p.r. signal from coals in a vacuum consists of two lines with different widths. The results are interpreted using the Larsen-Kovac structural model (Am. Chem. Soc. Div. Fuel Chem. Preprints 1977, 22, 181). The paramagnetic centres, disposed in the macromolecular phase, give a narrow line whereas the spins of the molecular phase are responsible for the broad line. These results provide a good interpretation of the changes in e.p.r. signal-shape under the influence of various organic solvents observed by Yokokawa (Fuel 1968, 47, 273; Fuel 1969, 48, 29).     

Characterization of extracts of coals and coal-derived products by liquid chromatography using optical activity detection

Extracts from various coals and coal-derived products were studied using liquid chromatography with optical activity detection. The chromatograms show that there are substantial numbers of optically active components in these samples. Since both dextrorotatory and laevorotatory components are present, some mutual cancellation would result if only the bulk optical rotation were measured. The chromatograms are generally rich in structure and contain distinct features which may be good fingerprints for establishing the origins of the coals and monitoring coal processing.     

Solid state magnetic resonance spectra of Illinois No. 6 coal and some reductive alkylation products

Illinois No. 6 coal and its reductive methylation and butylation products have been studied by magnetic resonance techniques. Conventional CP-MAS¹³Cn.m.r. spectroscopy indicates that 62% of the carbon atoms in the coal are aromatic and that about 6% of the carbon atoms are carbonyl. Esters are more abundant than carboxylic acids. The resonances of methoxy groups and other novel etheric carbon atoms are apparent in the high field region. Dipolar dephasing experiments suggest that methyl carbon atoms constitute no more than 16% of the carbon, methylene and methine carbon atoms about 14% and quaternary aliphatic carbon atoms about 2%. The dipolar dephasing experiments in conjunction with previous work also permit estimates of the hydrogen atom distribution. The THF-insoluble products obtained in the reductive alkylation reactions with¹³C-enriched alkylating agents contain paramagnetic and ferromagnetic substances that adversely influence the solid state n.m.r. spectra. However, good ¹³C n.m.r. spectra were obtained after these substances were extracted with aqueous hydrochloric acid. The O:C alkylation ratios are 1.2 and 1.0 for methylation and butylation, respectively. Dipolar dephasing experiments establish that the decay constants of functional groups in the whole coal and of C- and O-methyl-¹³C and C- and O-butyl-1 -¹³C nuclei in the labelled coal molecules are very similar to those of reference compounds. These findings suggest that the decay constants measured for the ¹³C nuclei in coals and coal-derived solids provide reliable information about their degree of substitution.     

Reductive alkylation of illinois No. 6 coal. 1H and 13C n.m.r. spectra of the 13C-enriched alkylation products

The reductive alkylation of Illinois No. 6 coal has been carried out using potassium and naphthalene in tetrahydrofuran and methyl-¹³C and butyl-1 -¹³C iodides to alkylate the resultant polyanion. The soluble products of the reductive alkylation reaction were isolated by extraction and chromatography. Proton and carbon n.m.r. spectra were recorded. The intense resonance signal at δ3.95 which appears in the proton n.m.r. spectra of Illinois No. 6 coal butylated with unenriched butyl iodide is split into a doublet by the ¹³C nuclei. Similar results were obtained for the methylation products. The chemical shift and coupling interaction establish that aryl ethers are a very important constituent of the alkylated coal. The carbon n.m.r. spectra of the coal alkylated with ¹³C-enriched alkyl iodides are intense. The resonances of the C-alkylation products appear in a single broad band with a maximum intensity in spectral regions compatible with the formation of the reductive alkylation products of certain polynuclear aromatic hydrocarbons or the base-catalysed alkylation of certain benzylic carbon atoms. The resonances of the N -alkylation products appear in two distinct bands. These resonances are tentatively assigned to amines produced as a result of reductive alkylation of heterocyclic compounds. The resonances of the 0-alkylation products appear in three distinct bands which can be assigned to alkyl aryl ethers, alkyl aryl ethers with substituents at the adjacent positions, and to alkyl carboxylates. The ratio of ethers to carboxylates in the soluble alkylation products was determined to be 7.8 for butylation and 8.0 for methylation. The Chromatographic fractions contain different amounts of C-, N-, and 0-alkylation products. This finding suggests that the coal structure is not highly uniform.     

Compositions of distillate recycle solvents derived from direct coal liquefaction in the SRC-I process: 1. Hydrocarbons

The qualitative and quantitative compositions of 260–427 °C distillate recycle solvents derived from direct liquefaction of subbituminous Wyodak coal and bituminous Kentucky $\text{9}\text{14}$ coal in the SRC-I process are discussed. A liquid chromatography method which involves a column switching technique was used to provide solubility characteristics and compound-class compositions. The hydrocarbon compounds, which accountfor> 60 wt% of the distillate recycle solvents, were further analysed using a unique combination of high-performance liquid chromatography (h.p.l.c.) and field ionization mass spectrometry (f.i.m.s.). Thirty homologous series were identified. Carbon number and distribution and concentration of the homologous series were determined. The h.p.l.c./f.i.m.s. method unravelled various hydroaromatic types which otherwise would be very difficult or impossible to determine.     

Estimation of the concentration of donatable hydrogen in a coal solvent by n.m.r.

¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectroscopies have been used to study the changes in composition of a hydrogenated anthracene oil solvent that occur during extraction of a UK bituminous coal. It has been shown that the principal hydrogen donor groups in the solvent are hydroaromatic and naphthenic rings in hydroaromatic species. Good agreement was achieved between the concentration of donatable hydrogen estimated from n.m.r., and the amount of hydrogen transferred from the solvent during exhaustive extraction.     

E.s.r. study of pyrolysis vapour of coal

Wyodak and Heatburg subbituminous coals were pyrolysed in-situ in an e.s.r. microwave cavity at ≈510 °C in an evacuated sealed tube. At least two kinds of radicals are detected; first, phenalenyl-like radicals and then, polymerized radicals from the initial ones.     

Mössbauer studies of iron-bearing minerals in coal and coal ash

⁵⁷Fe Mössbauer spectroscopy has been used to characterize the iron-bearing minerals present in some British Columbia coals. The minerals observed in a range of samples include pyrite/marcasite, siderite, jarosite, rozenite or melanterite, and Fe²⁺ -bearing clay minerals such as illite. The presence of jarosite is confirmed through the magnetic hyperfine interaction observed at 4.2 K. The absence of magnetic ordering at 4.2 K for the ferrous sulphate component indicates the presence of rozenite, FeS0₄ · 4H₂0, or melanterite, FeS0₄ · 7H₂0, rather than szomolnokite, FeS0₄ · H₂0 or FeS0₄. The effects of ashing on two of the coals is also studied.     

低温煤热解焦油产率和品质影响因素研究

煤焦油是低温煤热解技术的主要产物,是重要的化工原料,其产率和品质是评价煤热解工艺的重要指标。从原煤性质(煤种和煤粒径)、热解反应器结构形式及热解工艺条件(原煤预处理、热解温度、压力、升温速率、停留时间、热解气氛及催化剂)等方面综合分析了煤热解焦油产率和品质的影响因素,认为通过优选煤种和热解反应器,对煤样进行适当预处理,选择合适的工艺操作条件和引入加氢催化热解等有助于提高焦油产率和品质。     

国内煤焦油市场分析

分析了国内煤焦油产量、消费情况及地区的分布状况,论述了深加工和炭黑行业是煤焦油的主要消费方向。近2年来,受宏观调控、经济增长放缓等因素的影响,深加工和炭黑行业呈现弱势运行。     

Pyrolysis—gas chromatography of Australian coals. 1. Victorian brown coal lithotypes

Pyrolysis—gas chromatography (Py—g.c.) has been shown to be a useful technique for characterizing Victorian brown coal lithotypes. The pyrograms show marked changes in the predominance and distribution of specific molecular classes as a function of lithotype. Hydrogen-rich triterpenoid components are predominantly associated with the lighter lithotypes, whereas hydrogen-deficient phenolic components are more abundant in pyrolysates from the darker lithotypes. Carbon preference indices (CPIs) are >1 for the alkanes but <1 for the alkenes released by pyrolysis. All CPI values generally increase with darkening lithotype. Correlations of the components released with the maceral composition of the lithotypes have also been established. This information is used to establish some details of the mechanism of pyrolysis and the probable relative liquefaction behaviour of these lithotype samples.     

Structural analysis of tars from fluidized-bed pyrolysis of coal. 1. Gas-liquid chromatography of aliphatic and aromatic subfractions

The effect of pyrolysing gas composition on the low-molecular-weight aliphatic and aromatic components of fluidized-bed tars has been investigated. Two tars from the rapid pyrolysis of coal in a fluidized-bed were solvent-fractionated into oils, asphaltenes and benzene-insoluble materials. The aliphatic and low-molecular-weight aromatic subfractions of the oils were then analysed by glass-capillary column gas-liquid chromatography. The results show that pyrolysis in a more active atmosphere of char gasification gases is ‘deeper’, and, to some extent, similar to hydrogen-assisted pyrolysis; the yield of tar is higher, and the product has higher aromaticity and average molecular weight compared with pyrolysis in nitrogen-rich flue gases.     

高温煤焦油过滤分离的研究

煤焦油是煤在干馏和气化过程中获得的液体产品。由于煤焦油中的煤粉、焦粉和热解碳等物质的存在,对煤焦油催化加氢制取汽油、柴油存在不利影响,所以在煤焦油加工之前,必须控制其含固质量分数。本实验室以陕西某化工厂的煤焦油为原料,在小型过滤分离装置上采用固液过滤分离法对煤焦油进行了过滤分离实验,目的是降低煤焦油中的含固质量分数。通过过滤分离实验,煤焦油中的含固质量分数大大降低,过滤效果达到90%以上,过滤后的煤焦油可以达到催化加氢制取汽油、柴油的要求。     

煤焦油制炭黑发展前景

介绍了世界炭黑生产技术以及国内炭黑生产的主要工艺,对煤焦油制炭黑的前景进行了分析。