A Study on Byproducts in the High-Pressure Melamine Production Process.

The industrial production of melamine is carried out by the thermal decomposition of urea in two technological processes, using high or low pressure. The reaction may be accompanied by the formation of undesirable byproducts, oxoaminotriazines, and so-called polycondensates, mainly melam, melem, and melon, as well as their hydrates and adducts. Their presence leads to the deterioration of the quality of the final product and may lead to the release of troublesome deposits inside the apparatus of the product's separation node. With the limited possibility of controlling the crystallization of the byproducts of the process, improving the technological process requires the precise determination of the composition of the separated insoluble reaction byproducts, which is the main objective of this work. This work presents the results of qualitative and quantitative analyses of the composition of deposits sampled in the technological process of melamine production. The full characterization of the deposits was performed using inductively coupled plasma optical emission spectroscopy (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) techniques. The elemental analysis (EA) of carbon, hydrogen, and nitrogen allowed us to obtain characteristic C/H, C/N, and H/N ratios. X-ray diffraction (XRD) and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy were also performed to confirm the obtained data. In addition, the morphology of the solid byproducts of the reaction was investigated, and the characteristics of the structures were determined using a scanning electron microscope. The elemental composition was investigated using scanning electron microscopy and the energy-dispersive X-ray spectroscopy (SEM-EDS) technique. The key finding of this research is that about 95% of the deposits are a mixture of melem and melem hydrate. The soluble part of the deposits contains melamine, urea, and oxyaminotriazines, as well as trace inorganic impurities.

Investigations of the Density and Solubility of Ammonium Perrhenate and Potassium Perrhenate Aqueous Solutions.

Rhenium is largely used as an additive to nickel- and cobalt-based superalloys. Their resistance to temperature and corrosion makes them suitable for the production of turbines in civil and military aviation, safety valves in drilling platforms, and tools working at temperatures exceeding 1000 °C. The purity of commercial rhenium salts is highly important. Potassium, which is a particularly undesirable element, can be removed by recrystallization. Therefore, it is crucial to possess detailed knowledge concerning process parameters including the dissolved solid concentration and the resulting saturation temperature. This can be achieved using simple densimetric methods. Due to the fact that data concerning the physicochemical properties of ammonium perrhenate (APR) NH4ReO4 and potassium perrhenate (PPR) KReO4 are imprecise or unavailable in the scientific literature, the goal of this study is to present experimental data including the solubility and density of water solutions of both salts. In the experiments, a densimeter with a vibrating cell was used to precisely determine the densities. Although the investigated solutions did not fit into the earlier proposed mathematical model, some crucial conclusions could still be made based on the results.

Cenospheres-Reinforced PA-12 Composite: Preparation, Physicochemical Properties, and Soaking Tests.

The main aim of this research was the preparation of a polymer-ceramic composite with PA-12 as the polymer matrix and modified aluminosilicate cenospheres (CSs) as the ceramic filler. The CSs were subjected to an early purification and cleaning process, which was also taken as a second objective. The CSs were surface modified by a two-step process: (1) etching in Piranha solution and (2) silanization in 3-aminopropyltriethoxysilane. The composite was made for 3D printing by FDM. Raw and modified CSs and a composite with PA-12 were subjected to the following tests: surface development including pores (BET), real density (HP), chemical composition and morphology (SEM/EDS, FTIR), grain analysis (PSD), phase composition (XRD), hardness (HV), and static tensile tests. The composites were subjected to soaking under simulated body fluid (SBF) conditions in artificial saliva for 14, 21, and 29 days. Compared to pure PA-12, PA-12_CS had generally better mechanical properties and was more resistant to SBF at elevated temperatures and soaking times. These results showed this material has potential for use in biomedical applications. These results also showed the necessity of developing a kinetic aging model for aging in different liquids to verify the true value of this material.

Stimuli-Responsive Star Polymer as an Admixture for Crystallization of Hollow Crystals.

Polymers are becoming a very popular tool in the crystallization of different compounds. In this work, a new method of crystallization is proposed using stimuli-responsive star polymer in order to obtain hollow structure crystals. In these experiments, amphiphilic copolymer of acrylic acid (AA) and methyl acrylate (MA) were used for isohydric crystallization via they cooling of KCl in deionized water solution. The experiments were realized in quartz cuvette with a magnetic stirrer using a specialized spectrometer with precise temperature control. The crystallization course was monitored by the absorbance readings and analysis of the nucleation energetic effect. It was proved that the moment of the polymer's phase transition occurrence had an important role in the crystal growth process. On the other hand, the occurrence of phase transition did not trigger the nucleation. The supercoolings achieved in the presence of the polymer were significantly higher compared to pure salt crystallization. On the basis of analysis of Particle Size Distribution (PSD) and Critical Aggregation Concentration (CAC) of the polymer, it was proposed that the hydrophobic particles of macromolecules created from polymeric aggregates served as templates for the formation of hollow crystals. Their purity was verified using thermogravimetric analysis (TGA), 1H NMR, and XRD. Only trace amounts of polymer were found in the crystalline product.

Application of Polymers as a Tool in Crystallization-A Review.

The application of polymers as a tool in the crystallization process is gaining more and more interest among the scientific community. According to Web of Science statistics the number of papers dealing with "Polymer induced crystallization" increased from 2 in 1990 to 436 in 2020, and for "Polymer controlled crystallization"-from 4 in 1990 to 344 in 2020. This is clear evidence that both topics are vivid, attractive and intensively investigated nowadays. Efficient control of crystallization and crystal properties still represents a bottleneck in the manufacturing of crystalline materials ranging from pigments, antiscalants, nanoporous materials and pharmaceuticals to semiconductor particles. However, a rapid development in precise and reliable measuring methods and techniques would enable one to better describe phenomena involved, to formulate theoretical models, and probably most importantly, to develop practical indications for how to appropriately lead many important processes in the industry. It is clearly visible at the first glance through a number of representative papers in the area, that many of them are preoccupied with the testing and production of pharmaceuticals, while the rest are addressed to new crystalline materials, renewable energy, water and wastewater technology and other branches of industry where the crystallization process takes place. In this work, authors gathered and briefly discuss over 100 papers, published in leading scientific periodicals, devoted to the influence of polymers on crystallizing solutions.

Upper Critical Solution Temperature Polymer Phase Transition as a Tool for the Control of Inorganic Salt Crystallization Process.

In this paper, the experimental research concerning the impact of the hydrophilic-hydrophobic transition of a polymer exhibiting the Upper Critical Solution Temperature (UCST) onto the crystallization process of inorganic salt is presented. A hypothesis was postulated that under favorable process conditions the sudden change of macromolecules properties and the resulting appearance of insoluble particles will induce the nucleation process of the salt. Since the transition point parameters may be precisely designed, the described mechanism would eliminate the stochastic nature of the crystallization process. Although performed experiments proved that the postulated process mechanism was incorrect, the presence of macromolecules had a significant impact on the crystallization course. The stochastic nature of the process was not eliminated; nevertheless, it seems that a specific point of nucleation was created which was independent of the cloud point temperature (TCP) of the polymer. Moreover, the surface morphology of crystals was changed.

Temperature and pH-Dependent Response of Poly(Acrylic Acid) and Poly(Acrylic Acid-co-Methyl Acrylate) in Highly Concentrated Potassium Chloride Aqueous Solutions.

In this study, the phase transition phenomena of linear poly(acrylic acid) (PAA) and linear or star-shaped poly(acrylic acid-co-methyl acrylate) (P(AA-co-MA)) in highly concentrated KCl solutions were investigated. The effects of polymer molecular weight, topology, and composition on their phase transition behavior in solution were investigated. The cloud point temperature (TCP) of polymers drastically increased as the KCl concentration (CKCl) and solution pH increased. CKCl strongly influenced the temperature range at which the phase transition of PAA occurred: CKCl of 1.0-2.2 M allowed the phase transition to occur between 30 and 75 °C. Unfortunately, at CKCl above 2.6 M, the TCP of PAA was too high to theoretically trigger the crystallization of KCl. The addition of hydrophobic methyl acrylate moieties decreased the TCP into a temperature region where KCl crystallization could occur. Additionally, the hydrodynamic diameters (Dh) and zeta potentials of commercial PAA samples were examined at room temperature and at their TCP using dynamic light scattering. The salt concentration (from 1 to 3 M) did not impact the hydrodynamic diameter of the molecules. Dh values were 1500 and 15 nm at room temperature and at TCP, respectively.

A Simple Densimetric Method to Determine Saturation Temperature of Aqueous Potassium Chloride Solution.

The precise control of crystallization is a key issue in providing a high quality crystalline product. It has to be achieved by, among other means, a proper choice of the solution processing temperature, which is determined on the basis of the metastable zone width and type of solubility curve. In this article experimental data for potassium chloride solution density, as a function of temperature and its correlation in the range from under- to supersaturation, are reported for solution concentrations between 24.62 % w/w and 31.84 % w/w. As could be expected in the case of undersaturated solutions and low supersaturation, the temperature dependence of density for solutions of different saturation may be described by a linear equation within the investigated range of concentrations. It was also proved that for the undersaturation range there exists a pole point, which allows calculation of the saturation temperature, based on the density measured at any temperature.

Impact of heating method on the flocculation process using thermosensitive polymer.

The impact of suspension heating method on the flocculation process using thermosensitive polymer is reported in this paper. In experiments a model suspension of chalk in RO water (purified by Reverse Osmosis) was destabilized using a copolymer of N-isopropylacrylamide (NIPAM) and cationic diallyldimethyl ammonium chloride (DADMAC). The measurements were made using a laboratory setup consisting of a mixing tank with four baffles, Rushton turbine, laser particle sizer Analysette 22 by Fritsch and a system of pump and thermostating devices. Two different modes of heating were used. In the first case the temperature of the system was gently raised above the Lower Critical Solution Temperature (LCST) using an electrical heater placed inside the tank, while in the second case the system temperature was rapidly raised by an injection of hot water directly into the tank. It was proven that heating method as well as the polymer concentration was crucial to the shape and size of created flocs.