The first year

Within the framework of the project, a number of works were completed in 2022. An analytical review of modern scientific, technical, regulatory, methodological literature was conducted, affecting the scientific and technical problem of recycling large-tonnage waste from fuel energy and obtaining marketable products with a minimum carbon footprint on their basis." A search and analysis of modern scientific, technical, regulatory and methodological literature was carried out. Most of the scientific literature is represented by 50 scientific articles in journals included in the Scopus scientometric database and the Russian RSCI database, of which 16 were published by Russian scientists and 34 by foreign ones. The largest number of articles have been published by scientists from China, Russia, India and England.

The analysis of regulatory documentation in the field of waste recycling has revealed a number of GOST standards (GOST R 56618-2015 on the topic "Resource conservation. Waste management. Technical requirements for the characteristics of coal ash and fly ash intended for secondary use" - M.: Standartinform, 2016. – 11 p., GOST R 57789-2017 "Ashes, slags and ash–slag mixtures of thermal power plants for the production of artificial porous aggregates" – M.: Standartinform, 2017. – 8 p., GOST 25592-2019 "Interstate standard. Ash and slag mixtures of thermal power plants for concrete" – Moscow: Standartinform, 2019. – 16 p.), the requirements of which should be guided when using these types of waste in various industries.

Within the framework of patent research, such parameters as the technical level and trends in the development of the object of economic activity, the use of industrial (intellectual) property and their legal protection, the study of the patent purity of the object of technology, the analysis of the activities of an economic entity and the prospects for its development were determined. The search for patent information was carried out in the patent database of the Russian Federation (www.fips.ru ), the EPO patent database (http://ru.espacenet.com ) and the PATENTSCOPE search engine. The articles were searched using the Scopus database (https://www.scopus.com ) and the RSCI (https://www.elibrary.ru ). The depth of search for patent information and articles was 30 years (1992-2022).

Within the framework of the section "Substantiation of the direction of research based on the analysis of the state of the problem under study, the results of patent research and the choice of the most promising direction of recycling", an analysis and generalization of the data obtained during the review of modern scientific, technical, regulatory and methodological literature was carried out. The main ways to minimize the carbon footprint have been identified. The international standards used to determine the carbon footprint are considered: the international greenhouse gas accounting standards GHG (Greenhouse Gas) protocol and the ISO 14064 standard. The main features of "green" technology and "green" products are identified, the methodology for assessing their impact on reducing greenhouse gas emissions at the stage of production and application of products is studied. It is shown that information on the mode and volume of production, production technology and equipment used, advantages over traditional products, emissions of pollutants and methods of their purification are used to assess the carbon footprint of the production of "green" products.

Two ways of solving the problems caused by the existence of waste are proposed: reducing the harmful effects of waste on humans and the environment and reuse of waste as an alternative source of energy and raw materials. The possibilities of involving ash and slag waste (ASH) from thermal power plants, as well as overburden and host rock formed as a result of coal mining, in the processes of manufacturing building materials are considered. The most promising area of application is their use in construction work or in the production of building materials as a raw material. The cost of production of building materials using ash and slag is reduced by 12-25%.

Physico-chemical studies of large-tonnage energy waste (waste from mining, enrichment and combustion of coal fuels) were carried out on the example of selected facilities in the Southern Federal District to establish the possibility of using coal combustion waste from Novocherkassk GRES and clastic (host) rock formed during underground coal mining in the Rostov region for the production of geopolymer materials, it is necessary to establish their chemical composition the composition. As the studied samples, 7 types of man-made materials were used such as: ash, ash-slag mixture, slag (Novocherkasskaya GRES), clastic rock (Novoshakhtinsk, landfill No. 1), clastic rock (Novoshakhtinsk, landfill No. 2), clastic rock (Krasnosulinsky district, Gukovo, Almazny settlement, landfill No.1), detrital rock (Krasnosulinsky district, Gukovo, dump No. 2). The choice of the Novocherkassk GRES as the main source of coal burning waste is justified by the fact that this power plant is the only one in the South of the Russian Federation operating on coal. The analysis of the chemical composition showed that the content of SiO 2 in the studied waste is 45.09 – 56.12 %, Al 2 O 3 – 11,35 – 23,59 %. This makes it possible to classify the waste under study as aluminosilicate materials suitable for the production of geopolymers, since the latter are materials consisting of Si–O–Si and Al–O–Si chains.

The microstructure of combustion waste (fly ash, fuel slag, ash and slag mixture) and coal mining (host rock during underground coal mining) was studied. It was found that the microstructure of fuel slag is represented by glazed particles of irregular acute-angled shape, while their size varies in the range of 10-100 microns. The microstructure of fly ash is characterized by the presence of hollow aluminosilicate microspheres, the size of which is 1-30 microns, while in the fly ash, unalloyed particles consisting of the smallest mineral and coke grains with a spongy surface are visible, which The inner parts may contain a large amount of crystalline substances. The microstructure of the ash and slag mixture is characterized by the presence of hollow aluminosilicate microspheres in it, which confirm the presence of the ash part, as well as irregular glazed particles of fuel slag. It was found that the structure of the selected characteristic rocks of the dumps is characterized by the presence of microcrystalline phases and partially amorphized zones, whereas the sample of burnt rock is distinguished by a vitrified structure containing mullite, quartz and spinel, and having signs of melting and sintering.

Mineralogical studies of selected energy waste were carried out. The mineralogical composition of the feedstock has been studied, since the presence of various basic or accessory phases in it can affect the final properties of the synthesized product. It was not possible to subject the briquette with fly ash to petrographic analysis, since it is a fine powder with a particle diameter of up to 30 microns, which is a small value for optical-petrographic methods. Based on this, it was decided to conduct a study of fly ash using only X-ray phase analysis.

The study of a 0.3 mm thick slag plume by the optical-petrographic method showed that the slag is represented by a glassy translucent mass with a striped texture with brownish-brown and yellowish-brown shades of individual homogeneous zones with a thickness of 50 microns to 10 mm. The structure of the sample is vitreous, fluid with obvious traces of plastic flow. When studying the strip in passing polarized light, it was found that the bulk, by more than 99%, consists of an isotropic vitreous material. With the gradual rotation of the polarizer, the anisotropic mineral fades, represented by rounded-oval, less often angular with rounded edges, quartz grains (SiO 2) with sizes from 40 to 80 microns. Opaque black tetragonal manganese dioxide dendrites in the form of pyrolusite (MnO 2 ) were also found in the most densely colored slag zones with sporadic or linearly concentrated distribution in the plane of the slot.

When using reflected light in an ash-slag mixture, microinclusions of pyrite (FeS2) were diagnosed, both in the form of xenomorphic grains and in the form of cubic habit crystals. Pyrite is most often completely oxidized, much less often partially oxidized pyrite can be observed. Pseudomorphoses of hematite (Fe2O3 ) were also diagnosed in the main matrix, represented by separate fragment-like separations with a reddish tinge. Often, pyrite relics are preserved in the core of such separations. In addition to the minerals presented in the ash and slag mixture, it is possible to observe spherical and oval metal inclusions of various sizes ranging from 10 to 30 microns, which are characterized by traces of malleability under mechanical action. Probably, the presence of these metal inclusions is associated with the long-term storage of the ash and slag mixture in ash dumps.

The conducted qualitative X-ray phase analysis showed that in all the studied mineral wastes of coal generation such as ash-slag mixture, fly ash and slag there are identical crystalline phases in the form of α-quartz (PDF card: 46-1045) and hematite (PDF card: 33-0664), which is identified at the sensitivity limit of the measurement device.Their presence is confirmed by the conducted optical and petrographic studies.

The quantitative X-ray phase analysis using the MAUD software showed that ash and slag waste is represented by 72.86±0.72% amorphous structure and 27.14% crystalline (20.39±0.84% α-quartz and 6.75±0.00% hematite); fly ash is represented by 81.61±0.47% amorphous structure and 18.39% crystalline(14.44±0.23% α-quartz and 3.95±0.03% hematite); fuel slag, in turn, is represented by 98.89 ±0.03% amorphous structure and 1.12% crystalline (0.49±0.01% α-quartz and 0.62±0.01% hematite).

Qualitative X-ray phase analysis of clastic (host) rocks showed that the N.-1.1 rock (landfill No. 1, Novoshakhtinsk, Rostov region) is formed by quartz, albite (Na[AlSi 3 O 8 ]), muscovite(KAl 2 (AlSi 3 O 10 )(OH) 2 ), clinochlor ((Mg,Al) 6 [Si 3 , 1-2 , Al) 0.9–1.2 O 10 ](OH) 8 ); rock N.-1.3 (Nesvetaevsky settlement, Novoshakhtinsk, Rostov region) is characterized by a similar composition except for the presence of ankerite(Ca(Fe,Mg,Mn)(CO 3 ) in it 2 ); burnt rock G.-2.1 (landfill No. 1, Almazny settlement, G. Gukovo, Krasnosulinsky district, Rostov region) mainly consists of hematite, mullite (3Al 2 O 3 ·2SiO 2), opal(SiO 2 ·nH 2 O), cordierite ((Mg,Fe) 2 Al 4 Si 5 O 18 ·nH 2 O); whereas the rock of G.Sh.-1 (dump No. 2, Sherlovskaya-Oblique mine, Gukovo, Krasnosulinsky district, Rostov region) made of quartz, muscovite (KAl 2 [AlSi 3 O 10 ](OH) 2 ) and microcline (K[AlSi 3 O 8 ]).

Radiological studies of selected energy waste were conducted, which should show the possibility of using it as a raw material for building materials and their safety. The analysis of the results of radiological studies showed that the waste of Novocherkassk GRES meets the unified sanitary, epidemiological and hygienic requirements in terms of value the effective specific activity of natural radionuclides Ra-226, Th-232, K-40 and are characterized by the following values of Aeff, Bk/kg: ash –(282±28); ash–slag mixture – (267±26); slag - (287±29); clastic rock (Novoshakhtinsk, landfill No. 1) – (165±18); detrital rock (Novoshakhtinsk, terrikon №2) – (220±24); detrital rock (Krasnosulinsky district, Gukovo, Almazny settlement, terricon №1) – (205±22); detrital rock (Krasnosulinsky district, Gukovo, dump No. 2) –(244±24).

Thus, the fuel waste of the Novocherkassk GRES and the clastic (host) rock during underground coal mining in the Rostov region is characterized by an Aeff of less than 370 Bq / kg, which allows them to be classified as the 1st class of materials and used for all types of construction.

During the reporting period, laboratory staff participated in the following conferences and forums:

1. 1. International Scientific and Technical Conference "Construction, Architecture and Technosphere Safety"; (ICCATS), Sochi, from 04.09.2022 to 11.09.2022.;
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3. 2. International Conference "Modern trends and prospects for the development of processing technologies and equipment in mechanical engineering 2022" (ICMTMTE 2022), Sevastopol, from 09/05/2022;
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5. 3. XII International Kurnakov Meeting on physico-chemical analysis "KURNAKOV 2022", St. Petersburg, from 09/25/2022 to 10/01/2022.;
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7. 4. Scientific School-conference with international participation for young scientists "Functional glasses and glassy materials: Synthesis. Structure. Properties", St. Petersburg, from 02.10.2022 to 08.10.2022.
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Equipment, materials and components for scientific research equipment were purchased in order to implement the project, including:

1. 1. Electric furnace tubular rotating TC.3.1100.3F is designed for heat treatment of bulk materials and is equipped with an adjustment of the material supply to the furnace chamber;
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3. 2. The TL – 020 granulator mixer is designed to study and refine the processes of mixing and granulating powders in a periodic mode. Bulk materials and liquid binder are used as recyclable materials;
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5. 3. Drying cabinet is designed for heating, drying and heat treatment of various materials in an air environment at temperatures up to +350 ° C.
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7. 4. Water bath - designed to maintain a constant temperature, gradual evaporation and extraction;
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9. 5. Analytical scales are designed for weighing solids, bulk materials or liquids, using the required capacity, in such modes as simple weighing, counting the number of objects and percentage weighing.
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11. 6. The Polar digital metallographic microscope is designed to study opaque objects in reflected polarized and ordinary light, as well as transparent objects in transmitted light at low magnifications: lenses available in 5×, 10×, 20× and 50×.
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13. 7. The PULVERISETTE 7 classic line planetary mill is designed for fine and ultrafine grinding of various materials.

The laboratory staff has published the following articles in scientific publications indexed in the Web of Science Core Collection database:

1. 1. The article "Influence of various coal energy wastes and foaming agents on foamed geopolymer materials synthesis" by Yatsenko E.A., Goltsman B.M., Trofimov S.V., Novikov Yu.V., Smoliy V.A., Ryabova A.V., Klimova L.V. published in the journal "Materials" Q1, 2022, December, Vol. 16, 264.
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Within the framework of section 1.10 "Development of 2 intellectual property objects" in the reporting period, the laboratory staff developed three intellectual property objects:

1. 1. Certificate of state registration of the computer program No. 2022683046 "Generator of hierarchical geopolymer structures". Copyright holder: Federal State Budgetary Educational Institution of Higher Education "South Russian State Polytechnic University (NPI) named after M.I. Platov". Authors Lazarenko G.I., Kasprzhitsky A.S., Kruglikov A.A., Yatsenko E.A., Goltsman B.M. Application No. 2022681927. The date of receipt is November 18, 2022. The date of state registration in the Register of computer programs is November 30, 2022. The program is registered in the USISU of R&D. The validity period is 120 months.
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3. 2. The secret of production (know-how) "The composition of the charge for functional foamed material" by the authors Yatsenko E.A., Goltsman B.M., Lazorenko G.I., Smoliy V.A., Ryabova A.V., Kasprzhitsky A.S., Kruglikov A.A., Klimova L.V., Trofimov S.V., Izvarin A.I.

Kurdashov V.M., Novikov Yu.V. Order of the YURSPU (NPI) No. 2-68 dated 10/31/2022 "On the introduction of a trade secret regime". Trade secret No.16-06 CT-22. The know-how is registered in the USISU of R&D. The validity period is until the cancellation of the protection of the trade secret regime.

1. 3. The secret of production (know-how) "The composition of the charge for geopolymer material based on ash and slag waste" by the authors

Yatsenko E.A., Goltsman B.M., Smoliy V.A., Ryabova A.V., Klimova L.V., Trofimov S.V., Romanyuk V.S., Izvarin A.I., Kurdashov V.M., Novikov Yu.V. Order of the YURSPU (NPI) No. 2-72 dated 11/28/2022 "On the introduction of a trade secret regime". Trade secret No.16-07 KT-22. The know-how is registered in the USISU of R&D. The validity period is until the cancellation of the protection of the trade secret regime.

An analytical review of the market of functional foamed materials, including geopolymer ones, was conducted. The purpose of the analytical review is to study the foamed materials market, identify major leading manufacturers of the products under study, further determine the prospects for the development and application in the construction industry, the creation of new foamed thermal insulation materials based on the use of large-tonnage waste fuel energy.

The total volume of the global foamed materials market reaches 1009 billion US dollars and 11.56 billion cubic meters in physical terms. The leading positions are occupied by the countries of the Asia-Pacific region: China, Japan, India, as well as a number of European countries and the United States. The total volume of the Russian foamed materials market is 439 billion rubles and 110.57 million cubic meters in physical terms.

The geopolymer materials market belongs to young, actively developing markets with high growth rates. The volume of the global market in 2021 amounted to 5 billion US dollars, in physical terms 920 million cubic meters. The volume of the Russian market does not exceed 70 thousand cubic meters and 250 million rubles in value terms. Of the Russian manufacturers of geopolymer materials, the largest are: Geobeton LLC (Russia); Distributors of geopolymer concrete in the Russian Federation (IP Kozinov, Beton Vsem Company, Beton Company, RSK Company). Foreign manufacturers of geopolymer materials include: Geopolymer Solutons LLC (USA); International Group of Companies Imerys Group; PCI Augsburg (Germany); Rocla (Australia); Universal Enterprise (India); Schlumberger Ltd (Netherlands); Murray & Roberts (South Africa); Zeobond Pty Ltd (Australia); Uretek (Lithuania); Corning Inc. (USA); Nu-Core (Australia); Pyromeral Systems (France); Orbix (Belgium).

Foamed polymers and concrete are the most popular among consumers – up to 90%, both on the global and Russian market. The remaining 10% are foamed silicate, glass and geopolymer materials. Based on the results of an analytical review of the foamed materials market, it can be argued that technologies for producing foamed materials based on the use of large-tonnage waste from fuel energy make it possible to expand the raw material base of the construction industry and introduce environmentally friendly, energy-saving, waste-free production technologies.