Development of a Thermodynamic Database for Copper Smelting and Converting

L'introduction de la modélisation thermodynamique dans la pratique de la production pyrométallurgique du cuivre pourrait augmenter significativement l'efficacité économique et le respect de l'environnement par l'industrie. Une base de données thermodynamiques fiable, en combinaison avec le logiciel de minimisation de l'énergie de Gibbs, est capable de prédire le bilan énergétique, la distribution des éléments, les transformations de phases au cours du procédé chimique. Mis en œuvre dans le couplage contrôle/simulation, la base de données thermodynamiques et le logiciel pourront réhausser l'automatisation du procédé à un nouveau niveau. L'objectif de cette thèse est le développement de la base de données capable de prédire les propriétés thermodynamiques et les équilibres de phases dans le système chimique de base pour la production pyrométallurgique du cuivre, à savoir le système Al–Ca–Cu–Fe–Mg–O–S–Si. Cela implique l'évaluation critique et l'optimisation thermodynamique des données expérimentales disponibles pour toutes les phases. La base de données est auto-cohérente, c'est-à-dire que les phases solides, liquides et gazeuses sont évaluées simultanément. 4 systèmes binaires, 5 systèmes ternaires, 7 systèmes quaternaires, 2 systèmes quinaires et 1 système à six composants ont été évalués ou réévalués. Le projet est réalisé en étroite collaboration avec le groupe Pyrosearch (Université de Queensland, Australie), qui a effectué des expériences cruciales. Certains des systèmes mentionnés ci-dessus ont été optimisés avec T. Hidayat. En outre, 4 systèmes ternaires et 5 systèmes quaternaires ont été optimisés par T. Hidayat en collaboration avec le présent auteur et ont été rapportés dans une autre thèse de doctorat [1]. En particulier, les phases du métal liquide et de la matte ont été décrites comme une solution unique en utilisant le Formalisme Quasichimique Modifié dans l’approximation des paires. La solution a été construite en utilisant un sous-réseau et les espèces non chargées: (CuI, CuII, FeII, FeIII, O, S). De cette façon, le modèle est capable de décrire un large écart à la stoechiométrie de la phase sulfurée en direction de l'excès de métal ou de l'excès de soufre et d'oxygène. La solubilité de l'oxygène dans la phase sulfurée est correctement décrite. Le modèle prend en compte l'existence de compositions d’ordonnancement maximal à courte distance entre premiers voisins au voisinage de Cu2O, CuO, FeO, Fe2O3, Cu2S et FeS et il prédit les changements drastiques de P(O2) et P(S2) à ces compositions. Il évalue précisément les solubilités du soufre et de l'oxygène dans la zone métallique de la solution. Il peut être utilisé pour prédire les équilibres solides-liquides dans les systèmes chimiques contenant les phases d'oxyde et de sulfure à des pressions partielles d'oxygène faibles et élevées. La solution de laitier est modélisée à l’aide du Formalisme Quasichimique Modifié dans l’approximation des quadruplets. Les cations sont chargés et placés sur un sous-réseau séparé de celui des anions : (Al3+; Ca2+, Cu1+, Fe2+, Fe3+, Mg2+, Si+4)(O2-, S2-). Ce modèle tient compte de l'ordre à courte distance entre les cations seconds voisins {cations basiques (Ca2+, Fe2+, etc.) et acides (Si4+)}, tandis que l'ordre à courte distance entre les premiers voisins est supposé être complet. Les bases de données pour les sous-systèmes d'oxydes optimisées auparavant, ré-optimisées et récemment obtenues ont été combinées et complétées avec les composants à base de soufre. La base de données de laitier résultante est capable de décrire les relations de phases dans les systèmes d'oxydes, ainsi que les capacités du soufre. L'effet du soufre sur la solubilité du cuivre dans les scories est démontré et modélisé. Ceci est d'une importance primordiale pour l'industrie qui s’efforce d’éviter les pertes de cuivre dans les scories. L'effet du calcium sur la solubilité du cuivre et du soufre dans le laitier de fayalite est modélisé quantitativement pour la première fois. Le cuivre et le calcium sont ajoutés dans la base de données de la spinelle d'une manière thermodynamiquement compatible. La base de données de la spinelle peut être utilisée pour estimer l'usure des matériaux réfractaires et pour surveiller les conditions permettant d’éviter la précipitation de spinelle ; cette dernière pouvant provoquer l'occlusion des réacteurs. Cette base de données est capable de prédire la distribution des cations entre les sous-réseaux ; ce qui est important pour les applications électroniques. La capacité prédictive de la base de données est testée au cours de la simulation d'un four de fusion. Les résultats des calculs sont comparés aux données d’usine. Un très bon accord est démontré lors de l'estimation des bilans d’énergie et de matière et lors de la prédiction des distributions d'éléments entre les sorties du four. Ainsi, la base de données thermodynamiques pour les applications dans la production pyrométallurgique du cuivre que nous avons développée dans le cadre de ce projet est la plus précise et la plus complète au monde. Elle est destinée à être utilisée avec le logiciel FactSageTM. En utilisant les méthodes affinées dans cette étude, d'autres éléments peuvent être facilement ajoutés à la base de données. Les travaux se poursuivent actuellement par l'ajout de Co, Pb, Ni et Zn. ---------- Introduction of thermodynamic modeling into the practice of the pyrometallurgical copper production may significantly increase the economic efficiency and environmental friendliness of the industry. A reliable thermodynamic database in combination with the Gibbs energy minimizing software is able to predict the energy balance, distribution of elements, phase transformations during the chemical process. Implemented in the control/simulation package, such thermodynamic database and software will be able to raise the process automation to a new level. The goal of this thesis is the development of the database able to predict the thermodynamic properties and phase equilibria in the basic chemical system for the pyrometallurgical copper production, which is the Al–Ca–Cu–Fe–Mg–O–S–Si system. This involves the critical evaluation and thermodynamic optimization of available experimental data for all phases. The database is self-consistent, i.e. solid, liquid and gas phases are assessed simultaneously. 4 binary, 5 ternary, 7 quaternary, 2 quinary and 1 six-component system were evaluated or re-evaluated. The project is performed in close collaboration with the Pyrosearch group (University of Queensland, Australia), who performed some crucial experiments. Some of the above-mentioned systems were optimized together with T. Hidayat. In addition, 4 ternary and 5 quaternary systems were optimized by T. Hidayat in co-operation with the present author and reported in another Ph.D. thesis [1]. In particular, liquid metal and matte phases were described as one solution using the Modified Quasichemical Formalism in the pair approximation. The solution was built using one sublattice and uncharged species: (CuI, CuII, FeII, FeIII, O, S). In this way, the model is able to describe wide deviations from stoichiometry in the sulfide phase towards excess metal or excess sulfur and oxygen. The oxygen solubility in the sulfide phase is correctly described. The model takes into account the existence of compositions of maximum first nearest neighbor short-range ordering near Cu2O, CuO, FeO, Fe2O3, Cu2S and FeS and predicts the drastic changes in P(O2) and P(S2) at these compositions. It accurately estimates the solubilities of sulfur and oxygen in metal region of the solution. It can be used to predict solid-liquid equilibria in chemical systems containing sulfide and oxide phases at low and high oxygen partial pressures. The slag solution was modeled within the Quasichemical Formalism in quadruplet approximation. Cations are charged and placed in a separate sublattice from anions: (Al3+, Ca2+, Cu1+, Fe2+, Fe3+, Mg2+, Si+4)(O2-, S2-). The model of this type takes into account the second nearest neighbor short-range ordering between basic (Ca2+, Fe2+, etc.) and acidic (Si4+) cations, while the first nearest neighbor short range ordering between metals and non-metals is assumed to be complete. Previously optimized, re-optimized and newly obtained databases for oxide subsystems were combined together and complemented with sulfide components. The resulting slag database is able to describe phase relations in oxide systems, as well as sulfide capacities. The effect of sulfur on the solubility of copper in slag is demonstrated and modeled. This is of primary importance for the industry which is trying to avoid copper losses into slag. The effect of calcium on the solubility of copper and sulfur in fayalite slag is modeled quantitatively for the first time. Copper and calcium were added into the spinel database in a thermodynamically consistent way. The spinel database may be used to estimate the wearing of refractory materials and to monitor the conditions to prevent the spinel precipitation, which might cause occlusions of reactors. It is able to predict cation distribution between sublattices, which is important for electronic applications. The predictive ability of the database was tested during the simulation of a smelting furnace. The calculation results are compared with the plant data. Very good agreement is demonstrated in the estimation of energy and mass balance and in the prediction of element distributions between outputs of the furnace. Thus, the thermodynamic database for the applications in the pyrometallurgical production of copper, developed during the course of this project, is the most accurate and complete in the world. It is intended to be used with the FactSageTM software. Using the methods, refined in this study, more elements can be easily added to the database. The work currently continues on the addition of Co, Pb, Ni and Zn to the database. [1] T. Hidayat, "Equilibria Study of Complex Silicate-based Slag in the Copper Production," Ph.D. thesis, The University of Queensland, 2013

The System of Teaching at the Department of Art History at the Ural University named after A. M. Gorky

В статье рассматривается работа кафедры истории искусств Уральского государственного университета им. А. М. Горького. Представляется научная и педагогическая деятельность Б. В. Павловского и его коллег. Рассказывается о некоторых образовательных методах и подходах, сложившихся на кафедре. Дается описание наиболее характерных черт уральской школы искусствознания. Предпринимается попытка связать деятельность кафедры в научном плане с направлением в искусствознании, получившем название знаточества.The article examines the work of the Department of Art History of the Ural University named after A. M. Gorky. The scientific and pedagogical activity of B. V. Pavlovsky and his colleagues is presented. It tells about some of the educational methods and approaches that have developed at the department. The description of the most characteristic features of the Ural school of art studies is given. An attempt is being made to link the activities of the departmentin scientific terms with the direction in art studies, which has received the name of cognition.Исследование выполнено при финансовой поддержке РФФИ и Алтайского края в рамках научного проекта № 19-412-220003ра «Экспликация потенциала художественной культуры Алтайского края и определения механизмов его использования в региональных и международных туристических проектах»

Endoscopic tunnel dissection and its role in the treatment of gastrointestinal stromal tumors of the stomach

A. S. Loginov Moscow Clinical Scientific and Practical Centre, Moscow, Russia, Al XIII-lea Congres al Asociației Chirurgilor „Nicolae Anestiadi” și al III-lea Congres al Societății de Endoscopie, Chirurgie miniminvazivă și Ultrasonografie ”V.M.Guțu” din Republica MoldovaBackground: To determine the effectiveness of submucosal tunnel dissection in patients with gastrointestinal stromal tumors. Methods and materials: Since March 2014 24 patients were operated with gastrointestinal stromal tumors with a tunneling method. 27 tumors were removed. Among patients there were 3 men and 21 women. The average age of patients was 62,8 years old. Among operated there were as patients with first identified tumors, as patients who were under a doctor’s care for a long time about submucosal tumors. Surgical indication for these patients was a negative dynamics according to endosonographies in the form of increasing the size of the tumor and the change of structure. The average size of tumor was 19 mm. The nature of operation is in the formation of tunnel in submucosa through mucous membrane’s incision and enucleation of tumor with protecting the integrity of capsule. Results: All surgeries were carried out endotracheal anesthesia. Intraoperative carboxyperitoneum occurred in 4 patients, it was contained by abdominal decompression with the help of verres needle. No other intraoperative complications were observed. Based on IHC test, nine removals of neoplasms of the stomach were low-grade gastrointestinal stromal tumors, seven tumors were related to intermediate group. Seх tumors, including small tumors of multiple lesions, were leiomyomas. Two patients refused from spending IHC test. Conclusion: Endoscopic tunnel operations are technically feasible and can be used in the surgical treatment of small submucous tumors of myogenic origin. The introduction of minimally invasive methods is based on the observation that small gastrointestinal stromal tumors are limited to fibrous capsule and through this don’t metastasize in lymph nodes. Oncological evidence is based on the absence of recurrence and progression of the disease over the observation period. Besides, a minimal access significantly reduces the number of complications and a period of patients’ rehabilitation after operation

New methodology endoscopic treatment of diverticule of the Zenker

A. S. Loginov Moscow Clinical Scientific and Practical Centre, Moscow, Russia, Al XIII-lea Congres al Asociației Chirurgilor „Nicolae Anestiadi” și al III-lea Congres al Societății de Endoscopie, Chirurgie miniminvazivă și Ultrasonografie ”V.M.Guțu” din Republica MoldovaBackground: To evaluate the effectiveness of endoscopic cryo-pharingo-esophago-myotomy using a combination technique in the treatment of patients with Zenker's diverticulum. Methods and materials: The initial incision of the mucous membrane and the subsequent dissection of the muscles takes place in the middle of the cricopharyngeal fold. After the complete intersection of the cricopharyngeal muscle, the actual tunneling stage of the operation is performed, the purpose of which is to perform an upper esophageal myotomy. After performing the myotomy of the required length, the apparatus is removed from the tunnel and the mucous membrane is subsequently dissected. First, the mucosa from the diverticulum to its bottom is cut in the longitudinal direction. The second stage on the same length dissects the mucosa of the esophagus. You should strive to dissect the mucous strictly in one direction without bias. Subsequently, this is the key to successful application of clips and hermetic information of the mucous membranes. In the period from June to November 2018 in the MKNC A.S. Loginov on the Zenker's diverticulum 18 surgical interventions were performed using a new combined technique. The average age of patients was 62 (from 35 to 80 years). The time of surgical intervention averaged 40 minutes. Results: The peculiarity of the patients who underwent surgery using the new combined method was the almost complete absence of the residual cavity of the diverticulum during the X-ray control examination. Conclusions: Combined endoscopic surgery for Zenker's diverticulum allows to successfully expand the scope of surgical intervention by performing an extended myotomy and dissection of the mucous membrane of the septum. This allows you to create conditions for the prevention of recurrence of the disease, thereby providing the best result of treatment

Peroral endoscopic myotomy in the treatment of achalasia of the esophagus

A. S. Loginov Moscow Clinical Scientific and Practical Centre, Moscow, Russia, Al XIII-lea Congres al Asociației Chirurgilor „Nicolae Anestiadi” și al III-lea Congres al Societății de Endoscopie, Chirurgie miniminvazivă și Ultrasonografie ”V.M.Guțu” din Republica MoldovaBackground: Peroral endoscopic myotomy (POEM) is a promising new method of radical treatment of neuromuscular diseases of the esophagus, estimated effectiveness of which is comparable to traditional surgery. Aim: To compare the efficacy of peroral endoscopic myotomy and laparoscopic cardiomyotomy in the treatment of neuromuscular diseases of the esophagus. Methods and materials: The study included two groups of patients with neuromuscular diseases of the esophagus. The first group included patients who underwent peroral endoscopic myotomy. The second group included patients who underwent laparoscopic cardiomyotomy. In the period from July 2014 to may 2016 made 39 peroral endoscopic myotomy and 42 laparoscopiс cardiomyotomy. During this period we analyzed the results of 16 patients of the first group and 15 patients of the second group. The average age of patients is 47 years (from 20 to 71 years). The perioperative protocol of examination included endoscopy, X-ray examination of the esophagus, the manometry of the esophagus, evaluation of the severity of dysphagia on a scale Eckardt before and after 3 and 12 months after surgery. Statistical differences were not observed. The average score on a scale Eckardt before surgery was 6.6. Results: Protocol postoperative examination was performed in 31 patients. According to manometry of the esophagus normal values in both groups were registered. The average score on a scale Eckardt – of 0.9 (0-2). In the first group in five observations endoscopic signs of insufficiency of the cardia were detected at endoscopy, clinically pronounced in three patients. In the second group – in two cases, in one – with clinical manifestations. Symptoms relieved by taking inhibitor of proton pump. Conclusions: When comparing the results of laparoscopic and POEM of cardiomyotomy statistically significant differences were revealed. Thus, peroral endoscopic myotomy may be an analogue of laparoscopic cardiomyotomy

Peroral endoscopic myotomy after operative interventions on the gastroesophageal junction

A.S. Loginov Moscow Clinical Scientific Center, Moscow, Russia, Al XIII-lea Congres al Asociației Chirurgilor „Nicolae Anestiadi” și al III-lea Congres al Societății de Endoscopie, Chirurgie miniminvazivă și Ultrasonografie ”V.M.Guțu” din Republica MoldovaIntroduction: Per oral endoscopic myotomy (POEM) may be a challenge in patients with previous interventions on the esophagealgastric junction. The degree of fibrosis in submucosal space plays a key role in the feasibility and safety of tunnel technique. Aim: To evaluate the safety of per oral endoscopic myotomy in patients previously operated on the esophageal-gastric junction. Material and methods: Between July 2014 and May 2018, 123 patients underwent POEM in the Moscow Clinical Scientific Center, including 46 (37%) patients previously operated on the esophageal-gastric junction. The group of operated patients involved 41 (89%) patients after pneumatic balloon dilation, 3 (6.5%) patients after Heller myotomy, 1 (2%) patient after previous esophagogastroplication, 1 (2%) after POEM. Results: The POEM procedure was successfully completed all patients. The mean operative was comparable in both groups: 106 min (55-195 min) in previously operated patients and 103 min (45-180 min) in naïve patients. F0 degree was detected in 14 (30%) cases, F1 in 29 (63%), maximal fibrosis (F2) in 3 (6.5%) patients who had previously undergone pneumatic balloon dilation. In patients after Heller's myotomy and esophagogastroplication, the degree of fibrosis reached F1, despite the expected more pronounced fibrosis. In the group of primary patients F0, the degree was detected in 27 (35%) observations, F1 - 46 (60%), severe fibrosis (F2) was detected in 4 (5%). There were no intraoperative complications affecting the tactics of surgical intervention in one observation. There were no major bleeding episodes requiring blood transfusion in either group. In one case in the group of previously operated patients, a mucosal defect was detected after the formation of the tunnel. The lesion was clipped. The technical success of the surgical intervention was up to 100%. There were no intraoperative complications. X-ray examination on the 1st day after intervention with a water-soluble contrast showed appropriate evacuation and no leakage. Patients were discharged the 2nd day after surgery. Conclusions: The history of failed previous surgical interventions is not a contraindication to the POEM procedure and does not significantly affect the course of surgical intervention

High-temperature experimental and thermodynamic modelling research on the pyrometallurgical processing of copper

Uncertainty in the metal price and competition between producers mean that the daily operation of a smelter needs to target high recovery of valuable elements at low operating cost. Options for the improvement of the plant operation can be examined and decision making can be informed based on accurate information from laboratory experimentation coupled with predictions using advanced thermodynamic models. Integrated high-temperature experimental and thermodynamic modelling research on phase equilibria and thermodynamics of copper-containing systems have been undertaken at the Pyrometallurgy Innovation Centre (PYROSEARCH). The experimental phase equilibria studies involve high-temperature equilibration, rapid quenching and direct measurement of phase compositions using electron probe X-ray microanalysis (EPMA). The thermodynamic modelling deals with the development of accurate thermodynamic database built through critical evaluation of experimental data, selection of solution models, and optimization of models parameters. The database covers the Al-Ca-Cu-Fe-Mg-O-S-Si chemical system. The gas, slag, matte, liquid and solid metal phases, spinel solid solution as well as numerous solid oxide and sulphide phases are included. The database works within the FactSage software environment. Examples of phase equilibria data and thermodynamic models of selected systems, as well as possible implementation of the research outcomes to selected copper making processes are presented

Гипербарическая оксигенация при рецидивирующих ректальных кровотечениях на фоне лучевого проктита

Radiation proctitis is a complication of radiation therapy used in the treatment of pelvic malignant tumors. The leading clinical symptom of this kind of late radiation complications is recurrent rectal bleeding, leading to the development of anemia. Despite the availability of modern drugs, conservative treatment methods remain ineffective, and minimally invasive endoscopic technologies are not applicable in all cases and can lead to the development of complications in the form of ulcers and fi stulas. About 20 years ago, the world scientifi c community recommended hyperbaric oxygenation (HBO) as a method of treating late radiation damage to the rectum. However, this technique has not been widely used.  We have presented the experience of treating the successful use of HBO in the treatment of a 50-year-old patient with chronic radiation proctitis complicated by recurrent rectal bleeding. Conservative and endoscopic methods of treatment in this patient were ineffective. This clinical observation demonstrates that HBO is an effective method of treating rectal bleeding associated with radiation proctitis.Лучевой проктит — это осложнение лучевой терапии, применяемой в лечении злокачественных опухолей тазовой локализации. Ведущим клиническим симптомом данного рода поздних лучевых осложнений являются рецидивирующие прямокишечные кровотечения, приводящие к развитию анемии. Несмотря на наличие современных лекарственных препаратов, консервативные методы лечения остаются неэффективными, а малоинвазивные эндоскопические технологии применимы не во всех случаях и могут приводить к развитию осложнений в виде язв и свищей. Около 20 лет назад мировым научным сообществом гипербарическая оксигенация (ГБО) была рекомендована как способ лечения поздних лучевых повреждений прямой кишки. Однако данная методика не получила широкого применения.Нами представлен опыт успешного применения ГБО в лечении пациентки 50 лет с хроническим лучевым проктитом, осложненным рецидивирующими прямокишечными кровотечениями. Консервативные и эндоскопические методы лечения у данной пациентки были неэффективны. Данное клиническое наблюдение демонстрирует, что ГБО является эффективным методом лечения прямокишечного кровотечения на фоне лучевого проктита

ПРИМЕНЕНИЕ РОПИВАКАИНА У ВЗРОСЛЫХ ПРИ ВЫПОЛНЕНИИ ПЕРОРАЛЬНОЙ ЭНДОСКОПИЧЕСКОЙ МИОТОМИИ

Currently, peroral endoscopic myotomy (POEM) gains increasingly frequent use for management of esophageal achalasia. Despite POEM being minimally invasive, the problem of the post-operative pain syndrome is still crucial for this type of surgery.The objective of the study: to compare the degree of pain syndrome in the early post-operative period in different POEM methods.Methods: 79 patients were divided into 2 groups depending on the solution injected into submucosal tissue in order to provide the safe performance of myotomy. 0.15% solution of ropivacaine was used in Group 1, and 0.9% solution of NaCl in Group 2. The severity of the pain syndrome was compared in all patients using a visual analog scale, as well as consumption of analgesics during first three days after surgery.Results. On the first post-operative day, the clinically significant pain syndrome was more frequent in Group 2 (p < 0.05). The need in non-steroidal anti-inflammatory drugs did not differ between the groups. On the 2nd day it was observed that the need in NSIAD went down in Group 1 (p < 0.01).Conclusion. The use of 0.15% solution of ropivacaine as an injection into submucosal tissue during surgery reduces the severity of the pain syndrome and the number of analgesics used in the early post-operative period.В настоящее время все большее распространение получает методика пероральной эндоскопической миотомии (ПОЭМ) при ахалазии кардии. Несмотря на малоинвазивность ПОЭМ, проблема послеоперационного болевого синдрома при этом вмешательстве остается актуальной.Цель исследования: сравнение степени болевого синдрома в раннем послеоперационном периоде при различных методиках выполнения ПОЭМ.Методы: 79 пациентов были разделены на две группы в зависимости от раствора, инъецируемого в подслизистое пространство с целью безопасного выполнения миотомии. В 1-й группе использовали 0,15%-ный раствор ропивакаина, а во 2-й – 0,9%-ный раствор NaCl. У всех пациентов оценивали степень болевого синдрома по визуальной аналоговой шкале, а также потребление анальгетиков в первые три дня после операции.Результаты. В первый послеоперационный день клинически значимый болевой синдром чаще встречался во 2-й группе (p < 0,05). Потребность в НПВС в первый послеоперационный день не отличалась между группами. На 2-е сут наблюдали снижение потребности в нестероидных противовоспалительных средствах в 1-й группе (p < 0,01).Заключение. Использование 0,15%-ного раствора ропивакаина для инъекции в подслизистый слой во время операции уменьшает болевой синдром и снижает количество использованных анальгетиков в раннем послеоперационном периоде