Rotating autoclave

The reactor was a 1 liter stainless steel rotating autoclave. In these experiments the ratio of anthracene oil to coal was 3 1. Coal (50 g) impregnated with catalyst (1% Sn as SnC ) was mixed with sand (200 g). The autoclave was pressurized with hydrogen to 10 MPa at room temperature and heated (ca 7°C/minute) to the final reaction temperature (450°C). The pressure at reaction temperature was approximately 25 MPa. 

Figure 4. Percentage conversion against volatile matter yield (rotating autoclave...

The slopes of the regression lines for conversion yield against reactive macerals for the hot-rod and for the rotating autoclave modes of hydrogenation are shown by statistical analysis to be similar (compare Figures 9 and 10). This suggests that the relationship between total reactive macerals and coal reactivity as measured by conversion is not dependent on the conversion technique. 

Figure 10. Percentage conversion against vitrinite + exinite (+) and total reactive macerals (X) (rotating autoclave mode)...

The changes that occur with solid residence time in the hot-rod reactor were not very pronounced because only the nonvolatile portion of the oil remaining on the coal bed would be expected to undergo secondary reactions such as aromatization and loss of heteroatoms. However, the oils from the hot-rod reactor were also compared with those obtained in a rotating autoclave with much longer solid and vapour residence times and the changes with residence time were more noticeable in this case as can be seen in Table II. 

Using Rotating Autoclave Determined by vapour pressure osmometry... 

Ethyl, n-propyl and isopropyl fluoroacetates were also readily prepared by heating the corresponding esters of chloroacetic acid with potassium fluoride in the rotating autoclave. Their toxicities were similar to that of methyl fluoroacetate. (It... 

As previously stated (p. 53) di-(2-chloroethyl) phosphoro-fluoridate can be prepared by the action of phosphorus oxydi-chlorofluoride on ethylene chlorohydrin. The compound can also be prepared by the fluorination of di (2-chloroethyl) phos-phorochloridate, prepared from di-(2-chloroethyl) hydrogen phosphite (XVIII), obtained by the action of phosphorus trichloride on ethylene chlorohydrin. This partial fluorination was effected by means of sodium fluoride, although the yield was not high. The chlorine atoms of the 2-chloroethyl groups were not affected by this procedure, a fact which falls into line with the observations of Saunders and Stacey (p. 12) that ethylene chlorohydrin is not readily fluorinated by sodium fluoride, but only by potassium fluoride under pressure in a rotating autoclave.1... 

It was obviously of interest to determine whether other esters of fluoroacetic acid would prove to be more or less toxic than the methyl ester. In the phosphorofluoridate series, for example, we found that esters of secondary alcohols were far more potent than those of primary alcohols for instance, di-isopropyl fluorophosphonate (I) was a compound of considerable activity. Accordingly ethyl, ra-propyl and isopropyl fluoroacetates were prepared by heating the corresponding esters of chloroacetic acid in the rotating autoclave with potassium fluoride. The toxicity figures of these esters were very similar to those of methyl fluoroacetate. 

Methyl fluoroacetate.1 Methyl chloroacetate (108-5 g., 1 mol.) and neutral anhydrous potassium fluoride (70 g., 1-2 mol.) are mixed and heated (with glass marbles) in an inclined rotating autoclave at a... 

In Report no. 3 on fluoroacetates and allied compounds to the Ministry of Supply2 we described a very simple and efficient preparation of fluoroethanol (F.E.A.) by heating together ethylene chlorohydrin and potassium fluoride in a rotating autoclave at 135° for 4 hr.3... 

Reaction ofvinylacetylene with Te-KOH-DMSO triad A mixtnre of Te (25.9.), KOH (20 g), H2O (10.9 mL) and DMSO (100 mL) was heated (110°C) with vinylacetylene (31.7 g) in 1 L steel-rotating autoclave for 3 h. The reaction mixtnre was ponred into water, and extracted with Et20. The extracts were washed with H2O. The solvent was stripped off and the residne was distilled in vacuum to collect the rnn with b.p. 80-86°C (2.2 g) consisting of bis(l,3-butadienyl) telluride (1.1 g). 

Preparation of alkylvinyl tellurides by reaction of Te/KOH/alkyl iodides, SnCf in HMPA/H2O with pressurized acetylene. Methylvinyl telluride. 12.8 g of Te, 1.42 g of methyl iodide, 48.7 g KOH, 24.7 g SnCl2, 80 mL HMPA and 70 mL HjO were heated (105-115°C) in a rotating autoclave 1 L under acetylenic pressure (initial pressure 14 atm, residual pressure 7 atm, absorbed acetylene 0.8 mol) tor 5 h. The reaction mixture is evacuated at 1 mmHg. The fraction (10.5 g) collected into a cooled trap (-70°C) contains, according to GLC data, methylvinyl telluride (0.34 g, yield 20%), divinyl telluride (10 g, yield 55%) and dimethyl telluride (0.12 g, yield 8%) b.p. 115-116°C. 

Alkyl ethynyltellurides from dialkylditellurides and pressurized acetylene in the presence of electrophilic reagents (typical procedure) To a mixture of di-isopropyl ditellurides (4.5 g, 13 mmol), powdered KOH (20 g, 303 mmol), methyl iodide (2 g, 14 mmol), dibenzo-18-crown-6 (0.2 g) and benzene (50 mL) was heated (40-50°C) in a 1 L rotating autoclave under acetylene pressure (14 atm) for 5 h. After addition of water the mixture was extracted with benzene, the organic layer was separated and dried over KjCOj. After evaporation of benzene the residue was diluted with ether and precipitated dibenzo-18-crown-6 was fdtered off. After evaporation of ether the residue was distilled in vacuo giving the product (2.3 g, 96% yield). 

The completed emulsion is then filled into large-volume glass containers and sealed with oil-resistant composition stoppers. These containers are then autoclaved, in some cases using shaking or rotating autoclaves to minimize any thermal damage to the product as a whole. 

The incorporation of TiIV into a zeolite having the structure of ZSM-48 has resulted from the use of fumed silica (Cabosil), TBOT, H202, and diamino-octane. The titanium alkoxide is transformed into a titanium peroxo compound and added to a suspension of Si02 in diaminooctane. Crystallization for 10 days at 448 K in rotated autoclaves produced Ti-ZSM-48 (Serrano et al., 1992). The synthesis of Ti-ZSM-48 has also been obtained by using the base hexamethon-ium hydroxide [(CH3)3NCH2(CH2)4CH2N(CH3)3(OH)2] (Section III.C). 

The reaction was carried out at 200-220°C in a rotating autoclave for 8 hr. Maximum pressure developed in the course of synthesis is 27 atm. Under these conditions, when acetylene instead of CaC2 is used, the yield of pyridines grows to 20-30% (80KGS1299 84MI1). Thus, from cyclohexanone oxime 6-methyl-l,2,3,4,6,8,9,10-octahydrophenanthridine (106) can be prepared. 

As an example, data of a somewhat qualitative nature for coronene (C24H12) will be used (19). The experiments were made in a rotating autoclave containing 300 ml. (800 g.) of pelleted tungsten sulfide catalyst. The coronene was treated in decahydronaphthalene solution. 

Ethyl Vinyl Tellurium2 A mixture of 2.8 g (22 mmol) tellurium, 1.1 g (10 mmol) ethyl bromide, 48.7 g (868 mmol) potassium hydroxide, 24.7 g (130 mmol) tin(II) chloride, and 150 ml water are heated in a 1 -l rotating autoclave under an acetylene pressure of 15 atm for 5 h at 105-115c. The lower organic layer is separated from the reaction mixture, dried with potassium hydroxide, and fractionated at 1 torr. According to GLC data, the material collected in a trap cooled at — 70° contains 1.27 g (7%) ethyl vinyl tellurium, 10 g (55%) divinyl tellurium, and 0.11 g (6%) diethyl tellurium. Ethyl vinyl tellurium boiled at 138 7720 torr. 

Table 1. Sulfuring piperylene fraction with element sulfur in constantly rotating autoclave (V=17 ml), t=130°C, x= 3 h...

To achieve good results in this preparation, it is absolutely essential 1 to maintain as rapid stirring as possible in the autoclave, with the sthrer reaching to the bottom (the rotating autoclave described on page 359 is not suitable for this preparation), (2) to maintain the prescribed temperature exactly, and (3) to use sodium hydroxide that is no more concentrated than described. It the alkali is too concentrated or the temperature too high, resinification occurs and the yield is appreciabty lowered. 

The resulting dye is of no value in itself and is carried directly into the next step. The broken-up press cake is placed in a rotating autoclave with 50 cc. 30 per cent sodium hydroxide, 200 grams of water, and 1 gram of copper sulfate. The mixture is heated, with continuous agitation, for 10 hours at 140°C (pressure, 4 atmospheres), during which time the chlorine is replaced by a hydroxyl group. 

The rotating autoclave is especially suitable for handling pasty mix-... 

Fig. 51. Detail of the rotating autoclave (A) support frame (B) connecting bearing (C) bronze bushing (D) axle (E) positioning ring (F) oil hole (G) (five pulley...

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