Effect of process distillation on mutagenicity and cell-transformation activity of solvent-refined,coal-derived liquids

Blended SRC-II process streams, representing a full boiling range distillate material, were fractionally distilled into non-overlapping 50 °F cuts with boiling points between 300 and 850 °F. Another set of 18 distillate cuts were obtained with boiling points ranging between 138 and 1055 °F. Distillate cuts were assayed for mutagenic activity using the histidine reversion assay with Salmonella typhimurium strains TA98, TA100, TA1535 and TA1537, as well as for mammalian-cell transformation activity in the Syrian hamster embryo test, and DNA damage in the prophage induction assay. Samples were also separated into chemical class fractions by alumina column chromatography and analysed by high resolution gas chromatography so that the chemical composition of the cuts could be related to their relative activity in the different assays. In the mammalian cell transformation and microbial mutagenicity assays, significant activity was found almost exclusively in distillate cuts with components boiling > 700 °F, with the highest activity in the transformation assay observed for cuts > 800 °F. All of the distillate cuts showed increased levels of DNA damage as expressed by lambda prophage induction in Escherichia coli 8177. However, the greatest activity was associated with distillate cuts with boiling points in the 800 °F + range. Chemical analysis of the 50 °F distillate cuts showed a variety of polycyclic aromatic hydrocarbons (PAH) and amino-PAH compounds to be present in the distillate cuts boiling > 700 °F and essentially absent from cuts boiling < 700 °F. The sample set of non-overlapping (50 °F) cuts were reblended according to the proportions of each cut found in the original blend material. These reblended composites were then assayed to compare their activity with that predicted from the activities of the component distillate cuts. The reblending experiments indicated the microbial mutagenicity response was essentially additive. Mammalian cell transformation activities were non-additive, indicating a compositional effect on the expression of transforming agents in the complex mixture.     

Short contact time dissolution of vitrinite and inertinite concentrates

The short contact time dissolution of vitrinite and inertinite concentrates of an Australian bituminous coal was studied under isothermal conditions with tetralin as solvent. The reactivity of the two maceral types and the yields and nature of the products were determined for a range of reaction temperatures (400, 420 and 440 °C) and reaction times (2–20 min). The dissolution of vitrinite proceeded at a significantly greater rate than for inertinite and was associated with greater selectivity to soluble non-gaseous products. At very short reaction times (2 min), the vitrinite underwent solubilizing reactions to yield products of higher molecular weight and greater oxygen functionality than was the case for inertinite, for which changes in the chemical nature of the products were negligible over the range of conditions studied. At longer reaction times (5 min), the composition of the vitrinite-derived products was similar to that of the inertinite-derived products.     

Steric requirements for coal swelling by amine bases

A set of six coals ranging in rank from lignite to hvA bituminous was swollen with a series of alkyl-substituted pyridines and a smaller set of 4-alkylanilines. The size and branching of the alkyl groups was varied and the effect of this variation on the dissolution of the amines in the coal and the resulting coal swelling was measured volumetrically. In a few cases, substituents which hindered the amine nitrogen were studied. The lignite and subbituminous coal have a much higher tolerance to branched, bulky groups than do the bituminous coals. The presence of tertiary groups in a solute strongly inhibits their dissolution in bituminous coals. Bituminous coals behave as if extensive parallel packing of structures occurs. Often, they can accept very large planar groups but have a low capacity for branched groups.     

Kinetics of hydantoin formation

The reaction of lignite in a slagging gasifier produces reactants which in turn form 5,5-dimethylhydantoin (DMH) as a major constituent in the condensate water. Variations in plant operating conditions made it impossible to accurately study the kinetics of formation of DMH in the actual gasifier water, and thus a model system was chosen. The reaction of acetone cyanohydrin in the presence of excess ammonium carbonate at concentrations approaching those obtained in the condensate water were studied at 50,70, and 90 °C. Secondorder kinetics were obeyed, and the pseudo second-order rate constants at the respective temperatures were 1.86, 3.6, and 4.62 dm³ mol^{? 1} h^{? 1}. Independent variation of the concentration of either acetone, cyanide, ammonia or carbonate gave results consistent with the interpretation that the formation of DMH is first order in all reactants: rate of formation of DMH = k[acetone][HCN][NH₃][CO₂]. The pseudo second-order rate constant is a complex rate constant including several rapid equilibria. A mechanism consistent with the kinetic data is presented.     

Hydrogenation of brown coal: 6. Reactions of coal-derived products with hydrogen in the presence of metal-based catalysts

The product from the hydrogenation of an iron-tin treated Morwell, Victorian coal was separated into a number of fractions by solvent separation. Each of these fractions (tetrahydrofuran-insoluble materials, asphaltols, asphaltenes and oils) was reacted separately with hydrogen in tetralin both with and without added catalysts. The effect of added catalyst and of temperature, pressure, time and solvent on the hydrocracking and repolymerization reactions is discussed. The interconvertibility of the brown coal-derived products is clearly established, reinforcing the importance of incorporating reversibility of reactions in mechanistic models developed to describe coal hydroliquefaction.     

Coal-oil mixture from a synthetic oil obtained by hydroliquefaction of a South African coal

A coal-oil mixture (COM) was prepared from a South African coal and a synthetic oil derived from the same coal by hydroliquefaction. The settling and rheological properties of this mixture were compared with those of a mixture of the same coal with fuel oil. The synthetic oil mixture showed greater settling stability, comparable with that of a commercial COM containing additives. The increased stability may be related to polar compounds present in the oil and on the coal surface.     

Carbonization of coals into anisotropic cokes: 7. Copreheat-treatment under short contact-time conditions at high temperature

The copreheat-treatment of non-fusible and slightly fusible coals with A240 and hydrogenated A240 under high temperature-short contact-time conditions around 500 °C has been examined in an attempt to produce a formed coke with better anisotropic development. These conditions shortened the copreheat-treatment time and provided better anisotropic development in the resultant coke after carbonization. Effectiveness of short contact-time has been discussed in terms of the extent of depolymerization of coal molecules suitable for anisotropic development, this being related to coal liquefaction under similar conditions.     

H2S optimization for lignite liquefaction

Two lignite samples, Beulah No. 3 and Big Brown No. 1, were liquefied at 420 °C using H₂ and synthesis gas to determine the optimum beneficial amount of H₂S in the batch autoclave reactor. Under the conditions employed, 50–100 psi partial pressure of H₂S, nominally 4–10 wt% of daf lignite, was optimum for both samples. Synthesis gas outperformed H₂ with and without H₂S for the liquefaction of the two coals.     

Coal liquefaction using a hydrogenated creosote oil solvent: H-atom transfer from hydrogen donor components in the solvent

The presence of hydroaromatic, hydrogen donor components in a coal-derived solvent is one of the more important factors in the successful operation of a non-catalytic coal liquefaction process. Various hydrogen donor species present in a hydrogenated creosote oil have been identified. Their rate of disappearance under conditions that are consistent with a short residence time coal liquefaction process has been used to rank the reactivities of the various hydrogen donors. 1,2,3,10b-Tetrahydrofluoranthene was found to be an exceptional donor while 4,5-dihydropyrene, the hexahydropyrenes and 9,10-dihydrophenanthrene were found to be quite active. Sym.-octahydrophenanthrene and 2a,3,4,5-tetrahydroacenaphthene exhibited moderate activity. Tetralin and the four methyltetralin isomers were found to be unreactive under the coal liquefaction conditions employed.     

Analysis of polar compound classes in SRC-II liquids: Comparison of non-aqueous titrametric,i.r. spectrometric and h.p.l.c. methods

Results for various types of polar compounds in SRC-11 coal-derived liquids and other fuels were obtained by one or more of the three analytical methods: non-aqueous titration, i.r. spectroscopy and h.p.l.c. Practical aspects as well as precision, accuracy and assumptions necessary for effective application of each of the methods are discussed. H.p.l.c. is applicable to the widest variety of compound types, is the most rapid, most sensitive and shows the best promise for increased development and improvement. Application and development of these techniques is a logical step toward improving process monitoring, catalyst development, toxicological screening and general fuel analysis.