Research of nitric acid aqueous solution neutralization process with ammonia gas were performed on model of a periodic action apparatus. This model is implemented on a fundamentally new laboratory unit for analyzing the process of absorption in a gas-liquid system and includes a measuring tank containing selected gas, which is installed vertically and a measuring container with selected liquid, which is connected to the measuring gas container from below. During the process, the numerical values of the piston position are fixed according to the measured time scale and the kinetic curves of the process are constructed, these curves are processed using known algorithms and a conclusion is made about the physicochemical (kinetic and diffusion) process parameters. Investigations have shown that the process of nitric acid aqueous solutions neutralization with ammonia practically does not depend on the concentration of nitric acid in the liquid phase and is directly proportional to the concentration of ammonia in the gas phase. Analysis of the kinetic curves, taking into account the fact that the chemical reaction between ammonia and nitric acid proceeds almost instantly, allows us to make an assumption about the mechanism of ammonia absorption by aqueous solutions of nitric acid - as a diffusion process, the limiting stage of which is the diffusion of ammonia in a thin film of gas at the phase contact surface. At the same time, growth of the phases contact surface area and the rate increase of surface renewal are the main tasks for intensifying the process. A method is proposed to intensify the process of ammonia absorption by nitric acid solutions based on using vortex apparatus with a high degree of gas turbulization and a rapid renewal of the phases contact surface.
An experimental study of the effect of stepwise dosing of sulfuric acid in the process of decomposition of apatite with sulfuric acid has been performed. The process of decomposition of apatite in the apatite-H3PO4-H2SO4-H2O system was carried out with stepwise dosing of sulfuric acid. At the beginning of the process, the calculated amount of phosphoric acid and half of the stoichiometric amount of sulfuric acid required for the decomposition of the loaded amount of apatite was loaded into the batch reactor. It was experimentally shown that the pH of the reaction mixture at the beginning of the process increases to a pH value of 6.13, at the same time there is a decrease in the concentration of sulfuric acid and the formation of phosphoric acid, this is due to the decomposition of apatite in the reaction mixture. Already in the seventh minute, the concentration of sulfuric acid is zero, and the concentration of phosphoric acid has the first peak value, after which it begins to decrease. Thus, at the beginning of the process, the formation of phosphoric acid occurs due to the decomposition of apatite with sulfuric acid. Since sulfuric acid was added at the beginning of the process with a deficiency (0.5 mol) of sulfuric acid is not enough to decompose the charged apatite, a decrease in the concentration of phosphoric acid and the formation of monocalcium phosphate are observed after the peak. This is due to the consumption of phosphoric acid on the decomposition of the remaining apatite with the formation of monocalcium phosphate. At the 140th minute, the remaining stoichiometric amount of sulfuric acid was added to the reactor (0.5 mol), a sharp drop in pH to 5.48 and a simultaneous increase in the concentration of phosphoric acid were observed. Consequently, sulfuric acid is consumed for the decomposition of monocalcium phosphate. Thus, it was shown that with an insufficient amount of sulfuric acid, the resulting phosphoric acid is spent on the decomposition of apatite with the formation of monocalcium phosphate. Adding sulfuric acid makes it possible to extract production phosphoric acid from monocalcium phosphate.
Experimental research of the kinetics of the decomposition process of Kovdorsky apatite with a size = 0.16 mm with sulfuric acid in a 1 dm3 batch reactor. Phosphoric acid with the concentration of 68.6 % wt and the sulfuric acid with the concentration of 12.3% wt in stoichiometric amount was introduces at the beginning of the process. The process was carried out at a ratio of liquid and solid phases 2.5:1 respectively at the boiling point of the mixture equal to 136 °C. The observing the progress was carried out according to the method of joint designation of sulfuric and phosphoric acids by titrimetric analysis. With methyl orange and then phenolphthalein 2 titration jumps were recorded, the first of which corresponded to the neutralization of sulfuric acid to Na2SO4 and phosphoric acid to NaH2PO4, the second to the neutralization of NaH2PO4 to Na2HPO4. The change in temperature of the reaction mixture was fixed during the process using a mercury thermometer. In the analysis of the derived experimental values of specified parameters that the boiling point decreases from 136 to 133.1 оС within 50 minutes during the process. A comparison of the reported values with the concentration values of sulfuric and phosphoric acids measured during the process shows that the change in boiling point of the reaction mixture is proportional to the change in the concentrations of sulfuric and phosphoric acids. This model is a closed system that provides thermal insulation and no loss of material balance. Thus, the kinetics of the decomposition of apatite with sulfuric acid at the boiling point can be monitored by the temperature change under specified conditions.
An experimental study of the decomposition process of Kovdorsky apatite with certain particle sizes, in a 1 dm3 batch reactor with stirring of the reaction mixture, initial phosphoric acid concentration 17% by weight, in the system: Apatite-H3PO4 – H2SO4-H2O. Sulfuric acid was introduced in stoichiometric amount at the beginning of the process. The process was carried out at a ratio L:S 2.5:1, at a temperature of 78– 82 °C. The process was monitored by the method of joint determination of sulfuric and phosphoric acids by titrimetric analysis of the composition of the reaction mixture in the presence of methyl orange, and then phenolphthalein. Determined the concentration of phosphoric acid, the concentration of excess or deficiency of sulfuric acid and the concentration of monocalcium phosphate gel were determined. The acidity of the reaction mixture was recorded according to the indications of a Ph-meter (pH-105 MA with a combined glass electrode – ESK-10603). In the system: Apatite-H3PO4-H2SO4-H2O, when analyzing the obtained experimental values of these parameters, it was shown that during the process the pH of the reaction mixture rises to pH 6.3 for about 30 minutes, and then decreases to pH 4.5–5. Comparison of the dependence of pH values on the concentration of sulfuric acid in an aqueous solution of phosphoric acid and the pH values of the reaction mixture with the corresponding concentrations of sulfuric and phosphoric acids shows that the pH value of the reaction mixture is determined by the presence in the mixture between weft product - monocalcium phosphate gel. The process of decomposition of apatite in the system Apatite-H3PO4-H2SO4-H2O proceeds in several stages. At the beginning, a rapid decomposition of phosphate raw materials with phosphoric acid and a corresponding change in the pH of the reaction mixture, associated with the accumulation of monocalcium phosphate in solution, takes place. Then there is a slow decomposition of monocalcium phosphate with sulfuric acid and a corresponding decrease in pH to 4.5–5. The pH value at the end of the process is determined by the physicochemical properties of phosphoric acid present in the reaction mixture. At all stages of the process there is a constant increase in the concentration of phosphoric acid associated with the decomposition of monocalcium phosphate gel.
Experimental studies of the kinetics and mechanism of the process, decomposition of apatite by phosphoric acid, in the Apatite-H3PO4-H2O system without the addition of sulfuric acid have been performed. The study of the decomposition process of Kovdorsky apatite with certain particle sizes was carried out in a batch reactor with a volume of 1 dm3 with stirring of the reaction mixture, and an initial concentration of phosphoric acid of 17% by weight, at a temperature of 78–82 °C. Observation of the process was carried out by determining the concentration of phosphoric acid and the concentration of monocalcium phosphate. The acidity of the reaction mixture was determined by the pH meter readings (pH-105 MA with a glass combined-ESC-10603 electrode). It was shown that during the whole process a constant smooth increase in the pH value of the reaction mixture to pH 6 occurs. Comparison of the pH values of the reaction mixture during the actual at the time of determining the concentration of phosphoric acid and pH of phosphoric acid of the corresponding concentration in the aqueous solution shows that the pH value of the reaction mixture is significantly affected by the presence of monocalcium phosphate gel. During the process, during the first thirty minutes, the concentration of phosphoric acid decreases from 17 to 10% by weight, the corresponding quantitative formation of monocalcium phosphate gel and a proportional increase in the pH of the reaction mixture. Then, as the concentration of phosphoric acid decreases, the process slows down and does not proceed to the end under the experimental conditions. The dependence of the concentration of hydrogen ions in the reaction mixture on the time of the process of decomposition of apatite in phosphoric acid, which is presented in logarithmic coordinates, shows that the mechanism of formation of hydrogen ions during the whole process does not change. Thus, it is shown that the process of decomposition of apatite by phosphoric acid in the Apatite-H3PO4-H2O system proceeds with the formation of an intermediate product - monocalcium phosphate gel. When this occurs, a corresponding significant change in the pH values of the reaction mixture occurs. During the whole process there is a constant decrease in the concentration of phosphoric acid.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.