The article deals with the research of component composition and catalitic reactivity of metallurgical waste products. The slags component composition was investigated by X-ray fluorescence analysis. The slag stuff has been modified with alkali (NaOH) and mineral acids (HNO3, H2SO4, HCI and H3PO4), and their catalytic reactivity in the catalytic decomposition of ethyl alcohol and hydrogen peroxide has been determined for the first time. The revealed catalytic reactivity of the slag staff for the decomposition of ethyl alcohol and hydrogen peroxide indicates the need for a more detailed research and development of an industrial non-ferrous waste treatment technology

Ivashchenko, Y. N.

Kabdrakhmanova, S. K.

Ramazanova, R. A.

Saurbayeva, B. S.

Tantybayeva, B. S.

English

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29METALURGIJA 62 (2023) 1, 29-32B.S. SAURBAYEVA, Y.N. IVASHCHENKO, R.A. RAMAZANOVA,  B.S. TANTYBAYEVA, S.K. KABDRAKHMANOVARESEARCH OF COMPONENT COMPOSITION AND CATALITIC REACTIVITY OF METALLURGICAL INDUSTRY SLAGReceived – Primljeno: 2022-03-29Accepted – Prihvaćeno: 2022-06-30Original Scientific Paper – Izvorni znanstveni radThe article deals with the research of component composition and catalitic reactivity of metallurgical waste prod-ucts. The slags component composition was investigated by X-ray fluorescence analysis. The slag stuff has been modified with alkali (NaOH) and mineral acids (HNO3, H2SO4, НCI and H3PO4), and their catalytic reactivity in the catalytic decomposition of ethyl alcohol and hydrogen peroxide has been determined for the first time. The re-vealed catalytic reactivity of the slag staff for the decomposition of ethyl alcohol and hydrogen peroxide indicates the need for a more detailed research and development of an industrial non-ferrous waste treatment technology.Key words: slag, modification, component composition, catalitic reactivity, X-ray research.ISSN 0543-5846METABK 62(1) 29-32 (2023)UDC – UDK 666.88.002.23:66.014:66.097:539.26=111INTRODUCTIONCurrently nonutilizable waste from various indus-tries ar routinely stored on slurry sites with unfavoura-ble environmental effect. Such wastes often contain valuable components and can be considered as techno-genic deposits.Slags are important by-products of pyrometallurgi-cal steel and non-ferrous metal production, and annual-ly hundreds of millions of tons of them are produced worldwide. Depending on the chemical and mineralogi-cal composition of the slags, they can be recycled as waste, which can then be weathered and released into the environment. Their utilization is not only promising in terms of saving raw materials, but also improves the environmental situation [1].So far, a number of scientists have studied slag ma-terials. For example, the article [2] discusses the types, application and metal recovery from slag. The article considers gravimetric, magnetic, flotation, pyrometallic and hydrometallurgical slags processing for extraction of ions of various metals. The authors [3] describe detailed various experimental tests used to determine the charac-teristics of the slag. Moreover, thermo–chemical prop-erties of slags, thermophysical properties and correla-tions between them are measured and modeled. The work [4] focuses on improving the catalytic perfor-mance of the modified steel slag to increase efficiency, purity and low cost.B.S. Saurbayeva, Y.N. Ivashchenko, R.A. Ramazanova (raigul_77_33@mail.ru), D. Serikbayev East Kazakhstan Technical university, Ust-Ka-menogorsk, KazakhstanS.K. Kabdrakhmanova, K. Satpaev Kazakh National Research Techni-cal University, Almaty, KazakhstanB.S. Tantybayeva, S. Amanzholov East Kazakhstan University, Ust-Kamenogorsk, KazakhstanAccording to [5], there are two ways of recycling of slags from metallurgical industries. The first is the use of precipitation as a component of raw materials for produc-tion of building materials. The second is the use of modi-fied precipitation in production making the most of the specific properties of compounds including iron, nickel, zinc, copper, chromium, as the most common compo-nents in slag. According to the metallurgical slags analy-sis many of them have compositon with the ratio of iron oxides to non-ferrous metals approximates the composi-tion of mineral pigments for ceramic paints and colored glazes [5]. At the same time, metallurgical waste is rich in metal content and can be used as a promising techno-genic raw materials. Taking into account the crisis phe-nomena in the economy, issues of development and early introduction of advanced waste disposal technologies and the use of secondary material resources in the metal-lurgical industry have become urgent.Our research needed to study the catalitic reactivity of non-ferrous metallurgy slags to obtain certain benefi-cial effect, which could contribute to solving the prob-lems of accumulation and growh of industrial wastes and their impact on the environment.EXPERIMENTAL PARTThe slag materials are fine black crystals. Slag sam-pling was carried out by the point technique. Spot sam-ples of slags were taken by the “diagonal envelope”. Samples of slag up to 0,5 kg were taken from the points of the controlled “elementary” section, layer by layer from a depth of 20 cm using a tubular sampler. Pooled samples were formed from spot samples.The samples were ground in a Puluerisette 6 ball mill (Gemany), sifted through a sieve (400 mesh) and 30  METALURGIJA 62 (2023) 1, 29-32B.S. SAURBAYEVA et al.: RESEARCH OF COMPONENT COMPOSITION AND CATALITIC REACTIVITY…homogenized. The composition of the samples was de-termined by X-ray fluorescence analysis.Photomicrographies of slag and slag granules were obtained with a Leica DM 6000M optical microscope (Figures 1 and 2).Slag granules are of various shapes and sizes, char-acterized by a purple hue. With an increase in the reso-lution of the microscope, inclusions of glassy transpar-ent substances, apparently silicon compounds, are ob-served in the slag granules.Further the component composition of unmodified slags and slag materials treated with distilled water is presented.Table 1 presents the results of the fractional analysis of unmodified and slag materials treated with distilled water.The research results proved that slag materials con-tain large quantities of iron - 43,901 %, zinc - 20,163 % and silicon - 16,064 %. There is also small amount of calcium - 9,071 and aluminum - 2,343 %, and trace amount of lead, copper, indium, arsenic and some other substances.After treatment of slags with distilled water, no fun-damental change in the component composition was observed (Table 1).In the following studies, the slag has been modified in distilled water, with the following mineral acids (concen-tration of 0,1 n): sodium hydroxide, nitric, sulfuric, hydro-chloric and phosphoric acids without pre-cleaning.Crushed slag material with a mass of 5g was added separately into HNO3, H2SO4, НCI and H3PO4 dissolved in distilled water by alkali (NaOH) and acids, and heat-ed with intensive agitation to a temperature of 50 0С for 3 - 5 hours. The resulting mixture was filtered by the Büchner funnel and repeatedly washed with water to remove the acid residues (when using hydrochloric acid). Then the filtered slag material was dried in the drying chamber at a temperature of 100 - 110 0С for 2 - 3 hours.The modified slag samples were studied by X-ray fluorescence analysis and atomic emission spectrosco-py to determine its composition after modification.The component composition of slag materials is given in Table 2. The component composition of slag materials undergoes certain changes after modification with mineral acids and alkali. There is a decrease in light metals, which is associated with their interaction with acids. An increase of silicon and a slight decrease in the amounts of iron and zinc are found. This is appar-ently due to the fact that the hydrochloric acid treatment of slag is accompanied by the release of monomeric si-licic acid. These results were proved by the analysis of atomic emission spectroscopy of acid solutions after modification of slag materials (Table 2).Table 2 (column 1) show the study results of the slag chemical compound after alkali modification, where changes in amphoteric metal content, i.e. lead and zinc, are observed. Solutions obtained after modifica-tion with mineral acids and alkali have been subjected to atomic emission spectroscopy (Table 3).The results of the analysis to determine the concen-tration of metal ions by atomic emission spectroscopy (Table 3) show that solutions obtained after the slags Figure 1 Slag photomicrographyFigure 2 Photomicrography of a slag granuleTable 1  Component composition of unmodified slags  and treated with distilled water slag materials  Slag materialsunmodied,mslag = 1,6720 gdistilled water treated,mslag = 1,083 gcomponents quantity/% components quantity/%Mg 0,509 Mg 0,508AI 2,343 AI 2,259Si 16,064 Si 15,874P 0,705 P 0,463K 0,964 K 0,927Ca 9,071 Ca 8,876Zn 20,163 Zn 19,487Mn 0,268 Mn 0,276Fe 43,901 Fe 43,050Cu 0,987 Cu 0,939In 0,022 In 0,152Pb 0,986 Pb 0,905As 0,176 As 0,17431B.S. SAURBAYEVA et al.: RESEARCH OF COMPONENT COMPOSITION AND CATALITIC REACTIVITY…METALURGIJA 62 (2023) 1, 29-32modification with mineral acids have a high content of light metals, in particular calcium, magnesium, respec-tively, solutions obtained after slag treatment with al-kali have a high content of ions such as zinc and lead. This once again proves that modification with acids de-creases metal ions content of the first and second groups, the main subgroups of the periodic table.Modified and unmodified slag materials were stud-ied for the catalytic decomposition of ethanol and hy-drogen peroxide by the volumetric method. During the research, we measured the decomposition rate of hydro-gen peroxide of a given concentration in modified and unmodified slag materials at various temperatures.Next, the kinetics of ethyl alcohol decomposition by slag material washed with distilled water and hydro-chloric acid was studied (Figures 3 and 4). It should be noted that prior to this, the kinetics of zinc leaching from calamine and smithsonite with sulfuric acid [6–7] was investigated.Table 2  The component composition of slag materials modified with various mineral acids and alkalisSlag materialsNaOH modied,mslag = 1,0080 gHNO3 modied,mslag = 1,0885 gH2SO4 modoed,mslag = 1,1637 gHCl modied,mslag = 1,0816 gH3PO4 modied,mslag = 1,0774 gmetals % metals % metals % metals % metals %Mg 1,009 Mg 0,021 Mg 0,011 Mg 0,011 Mg 0,002Al 3,680 Al 4,086 Al 3,759 Al 4,042 AI 3,728Si 12,873 Si 13,611 Si 15,075 Si 13,350 Si 17,521P 0,529 P 0,566 P 1,585 P 0,495 P 1,342K 2,018 K 0,025 K 0,012 K 0,013 K 0,016Mn 0,837 Mn 0,818 Mn 0,821 Mn 0,800 Mn 0,819Fe 42,662 Fe 42,790 Fe 42,010 Fe 42,467 Fe 40,161Cu 1,017 Cu 1,372 Cu 1,847 Cu 2,522 Cu 1,414Zn 0,024 Zn 3,205 Zn 3,136 Zn 3,036 Zn 3,280Mo 0,053 Mo 0,057 Mo 0,056 Mo 0,057 Mo 0,053Table 3  Metal ion concentration of the solution obtained after the slag modification by different mineral acids and alkaliMetalsNaOH HNO3 H2SO4 HCl H3PO4Concentration/ mg/mlFe3+ 0,165 7,260 0,366 4,530 0,022Ca2+ 26,641 493,800 434,720 1350,900 430,020Cu2+ 0,307 12,393 0,017 20,523 0,084Mg2+ 0,138 54,871 29,904 50,238 26,287AI3+ 3,178 8,447 0,143 24,059 0,266Mn2+ 0,007 41,718 6,275 37,972 7,701Zn2+ 10,497 75,284 0,407 63,773 2,463Pb2+ 14,619 0,442 0,231 0,425 0,181Figure 3  Ethyl alcohol decomposition kinetics with slag material washed with distilled water (mkt = 0,03 g, V(С2Н5OН 90 %) = 1 ml, t = 50 0С)Figure 4  Ethyl alcohol decomposition kinetics with a hydrochloric acid-washed slag (mkt = 0,03 g, V(С2Н5OН 90 %) = 1 ml, t=50 0С)Figure 5  Comparative hydrogen peroxide decomposition kinetics with slag material, washed with distilled water, and modified with mineral acids and hydrochloric acid alkali (mkt = 0,05 g, V(H2O2 30 %) = 1 ml, t = 45 0С)32  METALURGIJA 62 (2023) 1, 29-32B.S. SAURBAYEVA et al.: RESEARCH OF COMPONENT COMPOSITION AND CATALITIC REACTIVITY…Higher catalytic activity is observed for slag materi-als washed with hydrochloric acid (Figure 4). At the same time, an increase in the hydrochloric acid concen-tration to 1n contributes to a decrease in the hydrogen output, which is associated with a change in the slag chemical composition towards the silicon compounds formation.Figure 5 presents the comparative decomposition ki-netics of hydrogen peroxide with a slag material washed with distilled water, also modified with mineral acids and hydrochloric acid alcali.Non-ferrous metallurgy slag materials have been es-tablished to have catalytic activity for ethyl alcohol de-composition. The hydrogen output in the decomposition of ethyl alcohol with washed water-distilled slag ma-terialAccording to the data obtained, except for slags modified with sulfuric and hydrochloric acids, all have much the same activity in the decomposition of hydro-gen peroxide. The non-modified slag material for cata-lytic activity is not inferior to the modified material. This is apparently due to the fact that the content of transition metals, which are active components, de-creases insignificantly during modification. The de-composition process is completed ten minutes after the start of the hydrogen peroxide decomposition reaction. In the case of sulphuric acid, equilibrium is established after sixty minutes.RESULTS AND DISCUSSIONSThe component composition of slag materials after modification with mineral acids and alkali undergoes certain changes. There is a decrease in light metals asso-ciated with their interaction with acids. Also an increase in the silicon content and a slight decrease in the amounts of iron and zinc are observed. This is apparently due to the fact that the hydrochloric acid slag treatment is fol-lowed by the release of monomeric silicic acid.It was determined that the solutions obtained after the modification of slags with mineral acids have a high content of light metals, in particular calcium and mag-nesium, respectively, solutions obtained after the alkalia slags treatment contain high content of such ions as zinc and lead. This proves that modification with acids leads to a decrease in metal ions of the first and second groups, the main subgroups of the periodic table.It has been established that non-ferrous metallurgy slag materials have catalytic activity for the decomposi-tion of ethyl alcohol and hydrogen peroxide.CONCLUSIONThe chemical composition and catalytic reactivity of non-ferrous metallurgy slag wastes have been in-vestigated. The research has determined that slag mate-rials contain iron in large quantities - 43,901 %, zinc - 20,163 % and silicon - 16,064 %; a small amount of calcium - 8,876 and aluminum - 2,343 %.The component composition of slag materials was studied. The slag composition was modified with slag mineral acids and their catalytic reactivity was deter-mined for the first time during the catalytic decomposi-tion of ethyl alcohol and hydrogen peroxide.The slag catalytic reactivity for the decomposition of ethyl alcohol and hydrogen peroxide has been identi-fied, which indicates the need for more detailed research and development of an industrial non-ferrous waste treatment technology.REFERENCES[1] N. M. Piatak, V. Ettler, Metallurgical slags: Environmental geochemistry and resource potential [E-Book]. Cambrid-ge: Royal Society of Chemistry, 2021.[2] A. Habib, H.N. Bhatti, M. Iqbal, Metallurgical Processing Strategies for Metals Recovery from Industrial Slags. Zeitschrift für Physikalische Chemie. 234 (2019) 2, 1–31. https://doi.org/10.1515/zpch-2019-0001.[3] E. Brandaleze, E.R. Benavidez, L.Santini, Treatments and Recycling of Metallurgical Slags, Chapters, in: Y. Zhang (ed.), Recovery and Utilization of Metallurgical Solid Wa-ste, 2019, https://doi. 10.5772/intechopen.80595.[4] F.P. Wang, T.J. Liu, S. Cai, D. Gao, Q. Yu, X.M. Wang, Y.T. Wang, Y.N. Zeng, J.G. Li, A Review of Modified Steel Slag Application in Catalytic Pyrolysis, Organic Degrada-tion, Electrocatalysis, Photocatalysis, Transesterification and Carbon Capture and Storage. Applied Sciences. 11 (2021), 4539. https://doi.org/10.3390/app11104539.[5] G.P. Tischenko, N.Yu. Moisenko, V.S. Juravlev, Utiliza-ciya promishlennih othodov galvanicheskih proizvodstv. NIItehim, (1991) 3, 1-84.[6] R.A. Ramazanova, V.I. Samoilov, N.V. Seraya, G.K. Dau-mova, E.M. Azbanbayev, R.A. Aubakirova, Investigation of the kinetics of sulphuric acid leaching of zinc from cala-mine. Metalurgija. 60 (2021) 1-2, 113-116. URI https://hrcak.srce.hr/246104.[7] R.A. Ramazanova, S.V. Mamyachenkov, N.V. Seraya, G.K. Daumova, R.A. Aubakirova, Zh.T. Bagasharova, Re-search of kinetics of zinc leaching with sulfuric acid from smithsonite. Metalurgija, 60 (2021) 3-4, 407–410. URI https://hrcak.srce.hr/256122.Note:  The responsible translator for English language is E.V.Popkova, Ust-Kamenogorsk, Kazakhstan

Research of component composition and catalitic reactivity of metallurgical industry slag

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