Benzene Soluble Matter Research Articles

Short Contact Time Liquefaction of Coal by Binary System Vehicle

Short contact time liquefaction of subbituminous Taiheiyo coal by using binary system vehicles at 400°C for 10 minutes under autogenous condition was studied. These vehicles were mainly quinoline + 1, 2, 3, 4-tetrahydroquinoline (THQ), anthrathene oil THQ, petroleum vacuum residue pitch (VR-Pitch) + THQ, tetralin + THQ.On the coal liquefaction, THQ has a noticeable effect as a hydrogen donor vehicle for coals under d. a. f. C % 80. And petroleum vacuum residue is also very important hydrogen donor source for Solvolysis liquefaction of coal.In the case of mixtures of hydrogen non-donor and THQ, the conversion to benzene soluble matter (BS) increased with increase of THQ content and approached to that (84.5%) by THQ only.In the case of mixtures of hydrogen donor and THQ, especially VR-Pitch and THQ, the large conversion to BS more than 84.5% (THQ only) was obtained in the range of 10 to 40 wt% content of VR-Pitch. The conversion to BS was nearly 100% with a mixture of 30 wt% VR-Pitch and 70 wt% THQ.However, in the mixtures of hydrogen donor vehicles such as tetralin, hydrogenated anthrathene oil and THQ respectively, the conversion to BS was not enhanced among various mixing ratios.

Catalytic hydrogen transfer due to FeSO 4 and Co&z.sbnd;Mo in coal liquefaction

The liquefaction behaviour of a Kentucky coal was studied in batch autoclave experiments at 410 °C under either a H 2 or a N 2 atmosphere (≈ 13.8 MPa) for reaction times of up to 2 h. To understand the catalytic roles of FeSO 4 and a Co&z.sbnd;Mo catalyst in coal liquefaction and to assess the feasibility of using FeSO 4 as a model for coal pyrites, effects of impregnation of the coal with FeSO 4 and direct charges of a Co&z.sbnd;Mo catalyst on coal liquefaction and tetralin dehydrogenation were examined. Both catalysts increase the conversion to benzene-soluble material by 7–10%, and improve the selectivity values for conversion to oil and gas. In addition they are also active in the dehydrogenation of tetralin. The dehydrogenation activities of these catalysts correlate with their catalytic activities during coal liquefaction. Analyses of the mean chemical structures and the product distributions of the coal-derived liquid from liquefaction in H 2 and in N 2 atmospheres indicate that: 1. (1) H-transfer from tetralin is the only major mechanism of coal liquefaction; and 2. (2) both pyrrhotite, generated in-situ from FeSO 4, and Co&z.sbnd; Mo catalyst can provide a major liquefaction mechanism by catalysing the H-transfer from the donor solvent to the coal or the coal-derived liquid.

Depolymerization of Turkish lignites. 2. Effect of phenol concentration in a closed system

A lignite (C, 66.9 wt%) was depolymerized, using sulphuric acid as a catalyst, in a closed system in which the phenol/coal ratio was varied from 1.5 to 10. The products were separated by solvent extraction and silica gel chromatography. The i.r. and n.m.r. spectra, and the molecular weight of the products were measured. In the experiments with a phenol/coal ration of 10, complete depolymerization of the coal was seen provided the temperature of depolymerization was at least 210 °C. The products generally contained disubstituted aromatic structures connected by methylene bridges, it was found that as the phenol/coal ratio was increased there was a decrease in the number of methylene bridges connecting the aromatic structures. The molecular weights of the straight-chain pentane and benzene-soluble material were lower than the molecular weights of similar fractions in depolymerization experiments carried out in open systems. A method for the structural analysis of straight-chain pentane and benzene-soluble material based on i.r., 1H n.m.r. and molecular weight measurements is suggested.

Depolymerization of Turkish lignites. I. Effect of substituted phenols

A lignite (C, 67.4 wt%) was depolymerized with phenol, p-nitrophenol and o-chlorophenol using sulphuric acid as catalyst. The solubility of the lignite was enhanced by these treatments, with phenol being the most reactive reagent whereas p-nitrophenol was the least reactive. The distribution of nitro- and chloro-groups in the solubilized products was investigated by infrared spectrometry and it was found that these groups were redistributed among the pyridine- and methanol-soluble materials. It is suggested that benzene-soluble material is produced by self-depolymerization of coal or by degradation of pyridine- and methanol-soluble material.

Conversion of halophilic algae into extractable oils

A salt water slurry of Dunaliella Parva, an halophilic alga, was treated in order to convert it into benzene-soluble material, as rich as possible in carbon and hydrogen. Several features have been brought to light during the course of this work: 1. (1) 25% of the combined carbon can be extracted under mild conditions of pressure (atmospheric) and temperature; 2. (2) the presence of CO as well as transition metals salts, had only minor effect on the conversion and the composition of the product; 3. (3) up to 75% of the combined carbon is converted by in-situ presence of benzene during the pyrolysis of the alga-salt water slurry.

Formation and stability of mesophase during coal hydrogenation 2. Destruction of mesophase

Results from Part 1 suggest that mesophase formation during coal hydrogenation is controlled, not only by temperature and time, but also by hydrogen availability. Further work was done to test whether mesophase, once formed from asphaltene, could be re-liquefied if sufficient hydrogen were made available. Several mesophase samples were hydrogenated in an autoclave without vehicle solvent. After hydrogenation, the samples produced up to 33% of benzene-soluble material and the microscopic features of the remaining solid material changed. Mesophase formation is temperature- and time-dependent, and this process cannot be reversed by simply lowering the temperature. However, if the chemical changes occurring have been introduced by hydrogenation, mesophase can be reliquefied.

Mutagenicity in Salmonella typhimurium mutants of the benzene-soluble organic matter derived from air-borne particulate matter and its five fractions

Air-borne particulate matter was collected on a filter, then extracted with benzene. The benzene-soluble material was separated into 5 fractions, namely acidic, basic, alipathic, polyaromatic and oxygenated fractions. The mutagenic activities of these fractions were examined with a set of Salmonella typhimurium mutants. The 6 mutants were from the TA1535 series, deep rough strains without excision repair, namely TA100 and TA98 (having a resistance-transfer factor) and the standard strain TA1535, TA1536, TA1537 and TA1538. Linear dose—response curves were obtained for the benzene-soluble organic matter, and its acidic, polyaromatic and oxygenated fractions with strain TA98 and a 9000 × g liver supernatant from both phenobarbital(PB)- and dibenz( a,h)anthracene(DBA)-treated rats. Among the 5 fractions tested, 3 fractions, namely the acidic, polyaromatic and oxygenated, played an important role in the mutagenicity of the benzene-soluble organic matter derived from air-borne particulate matter. The 9000 × g rat-liver supernatant was not required to make the acidic fraction mutagenic.

Liquefaction of coal in hydrogen-donor and non-donor vehicles

Coal, slurried with tetralin, and heated rapidly to 400 °C, was converted to benzene-soluble, liquid products through a reaction path which appears to involve thermal cleavage of chemical bonds in the coal (so-called depolymerization). Free radicals formed pyrolytically were stabilized in the early stages by autogenous hydrogen transfer, and in later stages by abstraction of hydrogen from the hydrogen-donating tetralin (which was converted to dihydronaphthalene and then to naphthalene). Vitrinite of the coal particles became almost completely soluble in pyridine after 5 min reaction, and dispersed in the vehicle (tetralin) within about 10 min. Reaction in non-donor vehicles (naphthalene, dodecane) resulted in dispersion, but ‘repolymerization’ formed a benzene-insoluble material. Hydrogen transfer from tetralin increased exponentially with increased conversion of the coal to benzene-soluble material. Negligible influence of particle size (below 2–3 mm) implies that mass transfer is not a rate-limiting factor. High-volatile c bituminous coal and coals of lower rank converted at about the same rate and to the same extent (given equivalent petrographic compositions); approximately two-thirds of the ultimately achievable conversion occurs within 20 min. Higher-rank coals converted at a lower rate. Oxidation of the coal was deleterious to ultimate conversion.

Aromatic Ring Structure in Solvent Extracts of Binder Pitches

In order to investigate ring structure of polycondensed aromatic hydrocarbons in binder pitches, solvent extracts of the pitches were analyzed by using a square wave polarography. Pitches used were five kinds, that is, straight coal-tar pitch, reformed coal-tar pitches and naphtha-tar pitch. Their pitches were fractionated by benzene and N, N-dimethylformamide (N, N-DMF). The reduction wave of the fractions (bezene soluble matter, and N, N-DMF soluble but benzene insoluble matter) were gained in N, N-DMF solution at the potential between 0 V and -2.35V vs Hg pool. Qualitative identification of reduction wave was carried out refering to the reduction potential of standard aromatic hydrocarbons.Results obtained were as follows, 1) All of polarograms for the benzene soluble matter showed the peak pattern having several reduction waves. Components in the straight and the reformed coal-tarpitches had aromatic ring structures such as shown in Table 3. But the reduction wave for the ring structure of anthracene, which may be included in coal-tra pitches, could not be detected. Naphtha-tar pitch consisted of aromatic ring structure such as tetracene, fluoranthene, pyrene and acenaphthene. The content of these components, however, was smaller than those in coal-tar pitches.2) For the N, N-DMF soluble but benzene insoluble matter, the polarograms showed the pattern having two reduction waves at about 0.5V and about-1.5V, and a broad line from about-0.5V to-1.5V. For this fraction, therefor, it is consi-dered that the identification of aromatic ring structure by using a square wave polaro-graphy is rather difficult.

METABOLISM OF THE STEROID HORMONES. ADRENAL CORTICAL-LIKE MATERIAL IN HUMAN URINE1

IT HAS BEEN established from recent studies in this laboratory that an extract may be obtained from the urine of normal men which has physiological properties identical with those of adrenal cortical compounds. The extract shows the following activities when tested on the adrenalectomized rat: it protects against exposure to cold (Dorfman, Horwitt and Fish, 1942); it elevates liver glycogen (Horwitt and Dorfman, 1943); it maintains life (Dorfman and Horwitt, 1943); it prolongs muscle work performance (Shipley, Dorfman and Horwitt,1943); and it prevents water intoxication (Schiller and Dorfman, 1943). Evidence that-urine contains adrenal cortical-like material was brought forward by the finding of Perla and Marmorsten-Gottesman (1931) that a benzene extract of human urine would increase the resistance of adrenalectomized rats to histamine. Shortly afterward, Grollman and Firor (1932–33) reported that benzene soluble material obtained from urine wouldprolong life when administered to adrenalectomized rats.