Further developments in crude oil processing

The processing conditions for obtaining high oil quality and yield in continuous caustic refining of the following crude oils are given: tallow, palm, fish, rapeseed, and sunflower. pH Monitoring of reaction mixture assures proper caustic dosage. pH Set point range for various crudes is noted.     

A kinetic investigation of coal liquefaction at short reaction times

Coal liquefaction kinetics have been studied at very short reaction times (less than 250 seconds) in order to emphasize the initial underlying physical and chemical processes involved. These studies were made possible by the use of a continuous flow stirred tank reactor (CSTR) which avoids the problems of slow heat up and cool down associated with the massive equipment required for running high-temperature and high-pressure liquefaction reactions. Preliminary physical (NMR and ESR) and chemical analytical results are presented on the coal liquids and reaction residues from Illinois No. 6 hv bituminous and Wyodak Black Thunder subbituminous coals.

ESR results showed that radical concentration in the solid residue changed during coal liquefaction. These changes were accompanied by changes in the NMR-derived aromaticity. The rate of decrease of organic-based radicals was different for Wyodak Black Thunder and Illinois No. 6 coals, perhaps indicating a different mechanism for the quenching of radicals in these bituminous and subbituminous coals. NMR spectra of the liquid products indicated that the initially produced material was relatively aromatic, and that subsequent products had lower aromatic content. This is consistent with secondary hydrogenation of the primary liquefaction products. Finally, the total oxygen contents of the coal residues decreased gradually during the first three minutes of coal liquefaction at 390°C. A corresponding decrease in the hydroxyl content of these residues was also noted.     

Zur optimierung der Polymerfraktionierung auf der Grundlage von Lösungsgleichgewichten in Lösungsmittel-Fällungsmittel-Systemen

The phase separation behavior of dilute polydisperse polymer solutions primarily depends on the partial concentration of each polymer component. So the equilibrium data obtained by turbidimetric titration with “calibration” fractions and their mixtures can be used for the construction of a solubility diagram (Claesson-diagram) which generally allows to describe fractionation processes. It can be shown that the characteristic features of precipitation fractionations can well be derived from the solubility diagram. This diagram then offers the possibility for a complete discussion of parameter variation (concentration, step of γ-variation, process-scheme, temperature, solvent/nonsolvent-system) on the efficiency of a fractionation step. On one hand these results correspond – as for the concentration variation – to well known experimentell experiences. On the other hand it is possible for the first time to give definite predictions for the influence of temperature and the solvent/nonsolvent system. The temperature selection can be shown to be inconsiderable for the separation effect. The usual characterization of solvents and nonsolvents as “good” or “poor” is absolutely insufficient, if not misleading, for there is no connection between these properties and the shape of the solubility diagram. Based on the analysis of the single parameters the optimum conditions for the preparation of narrow preparation of narrow precipitation fractions can be derived.     

Bile acid sulfates: II. Synthesis of 3-monosulfates of bile acids and their conjugates

Bile acid 3-monosulfates were synthesized by the sulfation of 3-hydroxy formyloxy bile acids with sulfur trioxide-triethylamine in dimethylformamide at 25 C for 0.5 hr. The protecting formyl groups were then hydrolyzed under mild alkaline conditions, and the deformylated products were isolated as p-toluidinium salts. These p-toluidinium salts were converted easily to the corresponding disodium salts by methanolic sodium hydroxide. Disodium salts were then isolated by precipitation from methanolether. The corresponding glycine conjugates were similarly synthesized by the sulfation of ethyl esters of 3-hydroxy formyloxy bile acid glycine conjugates. However, the taurine-conjugated bile acid sulfates were obtained by conjugating bile acid 3-monosulfates, either as triethylammonium salt or as disodium salt, with taurine in dimethylformamide in the presence of N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline. These procedures produced the desired bile acid sulfates in high yield (typically above 90%) with minimum manipulation. No time-consuming and capacity-limited chromatographic purification was needed to isolate the pure sulfates. The thin layer chromatographic mobilities, the infrared spectra, and some of the preliminary studies of the properties of these synthesized 3-monosulfates are also discussed. Part I of this series, see reference 18.     

Crystallization of calcium sulphate hemihydrate in concentrated phosphoric acid solutions

We aim to show the existence of agglomeration by measuring and modelling secondary nucleation and crystal growth rates of calcium sulphate hemihydrate, CaSO₄-0.5 H₂O, in concentrated phosphoric acid solutions. Using a batch crystallizer we measured the evolution of the population density as a function of supersaturation, H₂SO₄ excess and stirring rates. All experiments were carried out at 90 °C in solutions at 40 wt.% of P₂O₅, simulating the usual conditions for crystallizing hemihydrate in the industrial processes of phosphoric acid production. Nucleation and growth rates were calculated from the population number densities, using the moments analysis method. A model is presented for describing the crystallization process of hemihydrate. It is shown that secondary nucleation and growth rates are quadratic functions of supersaturation. H₂SO₄ concentrations affect supersaturation but at the same supersaturation the growth rates are not significantly different. Nucleation is independent of the stirring rate, whereas growth rates are slightly affected for stirring rates up to 500 rpm. Taking agglomeration into account, the moments method fits very well the experimental data.     

合成二氧化氯的催化剂和方法及该催化剂的制备

使用一种失活速率降低的催化剂用亚氯酸钠的水溶液合成二氧化氮。催化剂最好为钯,钯与其它钯系金属的混合物（如Ｐｂ＋Ｐｔ）或者是钯与第１副族金属的混合物（Ｐｂ＋Ａｕ）,所用的载体为可用第１主族金属的硕酸盐如（Ｋ２ＣＯ３）、第２主族金属的碳酸盐（如ＣａＣＯ３）或者是可转化成ＭｇＯ的镁盐改性的物质,载体还可以是第１主族金属的碳酸盐（如Ｋ２ＣＯ３）或者是可转化成ＭｇＯ的镁盐改性的物质,载体还可以是第１主族金属