Separation of nuclear reaction products in the gas phase—II

1975 ◽  
Vol 37 (5) ◽  
pp. 1115-1119 ◽  
Author(s):  
W. Bögl ◽  
K. Bächmann
Author(s):  
V.P. Bondarenko ◽  
O.O. Matviichuk

Detail investigation of equilibrium chemical reactions in WO3–H2O system using computer program FacktSage with the aim to establish influence of temperature and quantity of water on formation of compounds of H2WO4 and WO2(OH)2 as well as concomitant them compounds, evaporation products, decomposition and dissociation, that are contained in the program data base were carried out. Calculations in the temperature range from 100 to 3000 °С were carried out. The amount moles of water added to 1 mole of WO3 was varied from 0 to 27. It is found that the obtained data by the melting and evaporation temperatures of single-phase WO3 are in good agreement with the reference data and provide additionally detailed information on the composition of the gas phase. It was shown that under heating of 1 mole single-phase WO3 up to 3000 °С the predominant oxide that exist in gaseous phase is (WO3)2. Reactions of it formation from other oxides ((WO3)3 and (WO3)4) were proposed. It was established that compound H2WO4 is stable and it is decomposed on WO3 and H2O under 121 °C. Tungsten Oxide Hydrate WO2(OH)2 first appears under 400 °С and exists up to 3000 °С. Increasing quantity of Н2О in system leads to decreasing transition temperature of WO3 into both liquid and gaseous phases. It was established that adding to 1 mole WO3 26 mole H2O maximum amount (0,9044–0,9171 mole) WO2(OH)2 under temperatures 1400–1600 °С can be obtained, wherein the melting stage of WO3 is omitted. Obtained data also allowed to state that that from 121 till 400 °С WO3–Н2O the section in the О–W–H ternary system is partially quasi-binary because under these temperatures in the system only WO3 and Н2O are present. Under higher temperatures WO3–Н2O section becomes not quasi-binary since in the reaction products WO3 with Н2O except WO3 and Н2O, there are significant amounts of WO2(OH)2, (WO3)2, (WO3)3, (WO3)4 and a small amount of atoms and other compounds. Bibl. 12, Fig. 6, Tab. 5.


The gas-phase thermal oxidation of butene-2 has been examined over the temperature range 289 to 395°C. No difference in behaviour of the cis and trans forms could be detected. At the higher temperatures the reaction resembled that of the oxidation of propylene in the shape of the pressure-time curve and in the identity of many of the reaction products. At the lower temperatures a decrease in pressure partly due to peroxide formation followed the induction period, and by the end of this time much of the initial oxygen had been consumed. At all temperatures excess olefin produced an apparent inhibiting effect manifested by a decreased yield of carbon monoxide and a fall-off in the maximum rate of pressure change and total pressure change. Reaction processes are discussed, and it is suggested that a peroxide precedes the formation of acetaldehyde. Branching occurs largely through reaction of acetyl radicals produced from the acetaldehyde. The inhibiting effects produced by excess olefin are attributed to the replacement of reactive radicals by the less reactive allylic-type radicals, and the addition reactions of olefin at higher olefin concentrations lead to polymerization and a low or negative overall pressure change.


2015 ◽  
Vol 122 ◽  
pp. 513-520 ◽  
Author(s):  
Jason E. Ham ◽  
Stephen R. Jackson ◽  
Joel C. Harrison ◽  
J.R. Wells

1999 ◽  
Author(s):  
D.C. Bomberger ◽  
J.L. Bomben ◽  
A. Amirbahman ◽  
M. Asaro

2019 ◽  
Vol 58 (4) ◽  
pp. 40-47
Author(s):  
Ratmir R. Dashkin ◽  
◽  
Dmitry A. Gordeev ◽  
Khusrav Kh. Gafurov ◽  
Sergey N. Mantrov ◽  
...  

Butyl isocyanate is widely distributed as a precursor for the production of a number of biologically active substances: fungicides, preservatives, insecticides, personal care products, etc. Nowadays, there are a number of methods for the preparation of isocyanates, which can be divided into liquid phase and gas phase. One of the perspective methods for the production of isocyanates is the thermolysis of carbamate and/or the actions of various reaction activating agents, accompanied by the elimination of alcohol, but this process is reversible, which greatly complicates its use in industry. The paper presents the results of studies of non-catalytic thermal decomposition of N-alkylcarbamates with the formation of alkylisocyanates on the example of butylisocyanate in the gas phase, flow reactor in a wide temperature range (200 to 450 °C). In addition, a series of experiments was carried out using a catalyst, dibutyltin dilaurate, in order to reduce the thermolysis temperature and increase the yield of the final product. To implement the isocyanate production process, an experimental laboratory setup, consisting of a gas flow meter (argon) regulator, a packed column (for heating) and a sorption solution tank, was developed and tested. The thermolysis of N-n-butylcarbamate was carried out in two variations: the preparation of an individual n-butylisocyanate and the passage of reaction products through a sorption solution linking the n-butyl isocyanate to N-n-butyl-N '-(1-phenylethyl)urea, which allows to estimate the yield of the target n-butylisocyanate without additional losses. The analysis of the obtained substances was carried out by high performance liquid chromatography with a UV detector (target product) and a mass detector (analysis of by-products). According to the results of research, a modification of the laboratory facility was proposed, as well as n-butylisocyanate was obtained with a yield of 49% on the basis of a new technique.


Sign in / Sign up

Export Citation Format

Share Document