Prof. Dr. Krasimir Ivanov

University: Agricultural University
Department: Department of Chemistry
Research Fields: Catalysis, Chemical engineering,Ecology


1 Deactivation of Cu - Cr/γ-alumina Catalysts for Combustion of Exhaust Gases

Authors: Krasimir Ivanov, Boyan Boyanov, Dimitar Dimitrov


The paper relates to a catalyst, comprising copperchromium spinel, coated on carrier γ-Al2O3. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. It was found that the activity of carbon monoxide, DME, formaldehyde and methanol oxidation reaches a maximum at an active component content of 20 – 30 wt. %. Temperature calcination at 500oC seems to be optimal for the γ– alumina supported CuO-Cr2O3 catalysts for CO, DME, formaldehyde and methanol oxidation. A three months industrial experiment was carried out to elucidate the changes in the catalyst composition during industrial exploitation of the catalyst and the main reasons for catalyst deactivation. It was concluded that the CuO–Cr2O3/γ–alumina supported catalysts have enhanced activity toward CO, DME, formaldehyde and methanol oxidation and that these catalysts are suitable for industrial application. The main reason for catalyst deactivation seems to be the deposition of iron and molybdenum, coming from the main reactor, on the active component surface.

Keywords: Catalyst Deactivation, CuO-Cr2O3 catalysts, deep oxidation

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9 Research and Innovation Centre

Authors: Krasimir Ivanov, Nguyen Nguyen, Alexander Peltekov, Tonyo Tonev, Anyo Mitkov


Maize is among the most economically important crops and at the same time one of the most sensitive to soil deficiency in zinc. In this paper, the impact of the foliar zinc application in the form of zinc hydroxy nitrate suspension on the micro and macro elements partitioning in maize leaves and grain was studied during spring maize season, 2017. The impact of the foliar zinc fertilization on the grain yield and quality was estimated too. The experiment was performed by the randomized block design with 8 variants in 3 replications. Seven suspension solutions whit different Zn concentration were used, including ZnO suspension and zinc hydroxyl nitrate alone or nixed with other nutrients. Fertilization and irrigation were the same for all variants. The Zn content and the content of selected micro (Cu, Fe) and macro (Ca, Mg, P and K) elements in maize leaves were determined two weeks after the first spraying (5-6 sheets), two weeks after the second spraying (9-10 sheets) and after harvesting. It was concluded that the synthesized zinc hydroxy nitrate demonstrates potential as the long-term foliar fertilizer. A significant (p < 0.05) effect of zinc accumulation in maize leaves by foliar zinc application during the first growth stage was found, followed by its reutilization to other plants organs during the second growth stage. Significant export of Cu, P, and K from lower and middle leaves was observed. The content of Ca and Mg remains constant in the whole longevity period, while the content of Fe decreases sharply.

Keywords: foliar fertilization, maize, zinc, zinc hydroxy nitrate

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8 Supported Gold Nanocatalysts for CO Oxidation in Mainstream Cigarette Smoke

Authors: Krasimir Ivanov, Dimitar Dimitrov, Tatyana Tabakova, Violina Angelova, Stefka Kirkova, Anna Stoilova


It has been suggested that nicotine, CO and tar in mainstream smoke are the most important substances and have been judged as the most harmful compounds, responsible for the health hazards of smoking. As nicotine is extremely important for smoking qualities of cigarettes and the tar yield in the tobacco smoke is significantly reduced due to the use of filters with various content and design, the main efforts of cigarettes researchers and manufacturers are related to the search of opportunities for CO content reduction. Highly active ceria supported gold catalyst was prepared by the deposition-precipitation method, and the possibilities for CO oxidation in the synthetic gaseous mixture were evaluated using continuous flow equipment with fixed bed glass reactor at atmospheric pressure. The efficiently of the catalyst in CO oxidation in the real cigarette smoke was examined by a single port, puf-by-puff smoking machine. Quality assessment of smoking using cigarette holder containing catalyst was carried out. It was established that the catalytic activity toward CO oxidation in cigarette smoke rapidly decreases from 70% for the first cigarette to nearly zero for the twentieth cigarette. The present study shows that there are two critical factors which do not permit the successful use of catalysts to reduce the CO content in the mainstream cigarette smoke: (i) significant influence of the processes of adsorption and oxidation on the main characteristics of tobacco products and (ii) rapid deactivation of the catalyst due to the covering of the catalyst’s grains with condensate.

Keywords: CO oxidation, cigarette smoke, gold catalyst, mainstream

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7 Evaluating of Chemical Extractants for Assessment of Bioavailable Heavy Metals in Polluted Soils

Authors: Krasimir Ivanov, Dimitar Dimitrov, Violina Angelova, Stefan Krustev


Availability of a metal is characterised by its quantity transgressing from soil into different extractants or by its content in plants. In literature, the terms 'available forms of compounds' and 'mobile' are often considered as equivalents of the term 'accessible' to plants. Rapid and a sufficiently reliable method for defining the accessible for plants forms turns out to be their extraction through different extractants, imitating the functioning of the root system. As a criterion for the pertinence of the extractant to this purpose usually serves the significant statistic correlation between the extracted quantities of the element from soil and its content in plants. The aim of this work was to evaluate the effectiveness of various extractions (DTPA-TEA, AB-DTPA, Mehlich 3, 0.01 M CaCl₂, 1M NH₄NO₃) for the determination of bioavailability of heavy metals in industrially polluted soils from the metallurgical activity near Plovdiv and Kardjali, Bulgaria. Quantity measurements for contents of heavy metals were performed with ICP-OES. The results showed that extraction capacity was as follows: Mehlich 3>ABDTPA>DTPA-TEA>CaCl₂>NaNO₃. The content of the mobile form of heavy metals depends on the nature of metal ion, the nature of extractant and pH. The obtained results show that CaCl₂ extracts a greater quantity of mobile forms of heavy metals than NH₄NO₃. DTPA-TEA and AB-DTPA are capable of extracting from the soil not only the heavy metals participating in the exchange processes but also the heavy metals bound in carbonates and organic complexes, as well as bound and occluded in oxide and secondary clay minerals. AB-DTPA extracts a bit more heavy metals than DTPA-TEA. The darker color of the solutions obtained with AB-DTPA indicates that considerable quantities organic matter are being destructed. A comparison of the mobile forms of heavy metals extracted from clean and highly polluted soils has revealed that in the polluted soils the greater portion of heavy metals exists in a mobile form. High correlation coefficients are obtained between the metals extracted with different extractants and their total content in soil (r=0.9). A positive correlation between the pH, soil organic matter and the extracted quantities of heavy metals has been found. The results of correlation analysis revealed that the heavy metals extracted by DTPA-TEA, AB-DTPA, Mehlich 3, CaCl₂ and NaNO₃ correlated significantly with plant uptake. Significant correlation was found between DTPA-TEA, AB-DTPA, and CaCl₂ with heavy metals concentration in plants. Application of extracting methods contains chelating agents would be recommended in the future research onthe availabilityof heavy metals in polluted soils.

Keywords: Availability, Heavy Metals, chemical extractants, mobile forms

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6 Effect of the Nature of the Precursor on the Performance of Cu-Mn Catalysts for CO and VOCs Oxidation

Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov


The catalytic oxidation of methanol to formaldehyde is an important industrial process in which the waste gas in addition to CO contains methanol and dimethyl ether (DME). Evaluation of the possibility of removing the harmful components from the exhaust gasses needs a more complex investigation. Our previous work indicates that supported Cu-Mn oxide catalysts are promising for effective deep oxidation of these compounds. This work relates to the catalyst, comprising copper-manganese spinel, coated on carrier γ-Al₂O₃. The effect of preparation conditions on the active component composition and activity behavior of the catalysts is discussed. Different organometallic compounds on the base of four natural amino acids (Glycine, Alanine, Valine, Leucine) as precursors were used for the preparation of catalysts with Cu/Mn molar ratio 1:5. X-Ray and TEM analysis were performed on the catalyst’s bulk, and surface composition and the specific surface area was determined by BET method. The results obtained show that the activity of the catalysts increase up to 40% although there are some specific features, depending on the nature of the amino acid and the oxidized compound.

Keywords: Amino Acids, heterogeneous catalysis, Cu-Mn/γ-Al₂O₃, CO and VOCs oxidation

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5 Alumina Supported Copper-Manganese-Cobalt Catalysts for CO and VOCs Oxidation

Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov, Tatyana Tabakova, Vasko Idakiev


Formaldehyde production by selective oxidation of methanol is an important industrial process. The main by-products in the waste gas are CO and dimethyl ether (DME). The idea of this study is to combine the advantages of both Cu-Mn and Cu-Co catalytic systems by obtaining a new mixed Cu-Mn-Co catalyst with high activity and selectivity at the simultaneous oxidation of CO, methanol, and DME. Two basic Cu-Mn samples with high activity were selected for further investigation: (i) manganese-rich Cu-Mn/γ–Al2O3 catalyst with Cu/Mn molar ratio 1:5 and (ii) copper-rich Cu-Mn/γ-Al2O3 catalyst with Cu/Mn molar ratio 2:1. Manganese in these samples was replaced by cobalt in the whole concentration region, and catalytic properties were determined. The results show a general trend of decreasing the activity toward DME oxidation and increasing the activity toward CO and methanol oxidation with the increase of cobalt up to 60% for both groups of catalyst. This general trend, however, contains specific features, depending on the composition of the catalyst and the nature of the oxidized gas. The catalytic activity of the sample with Cu/(Mn+Co) molar ratio of 2:1 is gradually changed with increasing the cobalt content. The activity of the sample with Cu/(Mn+Co) molar ratio of 1: 5 passes through a maximum at 60% manganese replacement by cobalt, probably due to the formation of highly dispersed Co-based spinel structures (Co3O4 and/or MnCo2O4). In conclusion, the present study demonstrates that the Cu-Mn-Co/γ–alumina supported catalysts have enhanced activity toward CO, methanol and DME oxidation. Cu/(Mn+Co) molar ratio 1:5 and Co/Mn molar ratio 1.5 in the active component can ensure successful oxidation of CO, CH3OH and DME. The active component of the mixed Cu-Mn-Co/γ–alumina catalysts consists of at least six compounds - CuO, Co3O4, MnO2, Cu1.5Mn1.5O4, MnCo2O4 and CuCo2O4, depending on the Cu/Mn/Co molar ratio. Chemical composition strongly influences catalytic properties, this effect being quite variable with regards to the different processes.

Keywords: Oxidation, VOCs, carbon oxide, Cu-Mn-Co catalysts

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4 Some Observations on the Preparation of Zinc Hydroxide Nitrate Nanoparticles

Authors: Krasimir Ivanov, Elitsa Kolentsova, Violina Angelova, Nguyen Nguyen, Alexander Peltekov


The nanosized zinc hydroxide nitrate has been recently estimated as perspective foliar fertilizer, which has improved zinc solubility, but low phytotoxicity, in comparison with ZnO and other Zn containing compounds. The main problem is obtaining of stable particles with dimensions less than 100 nm. This work studies the effect of preparation conditions on the chemical compositions and particle size of the zinc hydroxide nitrates, prepared by precipitation. Zn(NO3)2.6H2O and NaOH with concentrations, ranged from 0.2 to 3.2M and the initial OH/Zn ratio from 0.5 to 1.6 were used at temperatures from 20 to 60 °C. All samples were characterized in detail by X-ray diffraction, scanning electron microscopy, differential thermal analysis and ICP. Stability and distribution of the zinc hydroxide nitrate particles were estimated too.

Keywords: Nanoparticles, Preparation, zinc hydroxide nitrate, foliar fertilizer

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3 Potential of Castor Bean (Ricinus Communis L.) for Phytoremediation of Soils Contaminated with Heavy Metals

Authors: Krasimir Ivanov, Violina Angelova, Mariana Perifanova-Nemska


The aim of this research was to investigate the potential for the use of Ricinus communis L. (castor oil plant) to remediate metal-polluted sites. This study was performed in industrially polluted soils containing high concentrations of Zn, Pb and Cd, situated at different distances (0.3, 2.0 and 15.0 km) from the source of pollution - the Non-Ferrous Metal Works near Plovdiv, Bulgaria. On reaching commercial ripeness, the castor oil plants were gathered and the contents of heavy metals in their different parts – roots, stems, leaves and seeds, were determined after dry ashing. Physico-chemical characterization, total, DTPA extractable and water-soluble metals in rhizospheric soil samples were carried. Translocation factors (TFs) were also determined. The quantitative measurements were carried out with ICP. A soxhlet extraction was used for the extraction of the oil, using hexane as solvent. The oil was recovered by simple distillation of the solvent. The residual oil obtained was investigated for physicochemical parameters and fatty acid composition. Bioaccumulation factor and translocation factor values (BAF and TF > 1) were greater than one suggesting efficient accumulation in the shoot. The castor oil plant may be preferred as a good candidate for phytoremediation (phytoextraction). These results indicate that R. communis has good potential for removing Pb from contaminated soils attributed to its fast growth, high biomass, strong absorption and accumulation for Pb. The concentrations of heavy metals in the oil were low as seed coats accumulated the highest concentrations of Cd and Pb. In addition, the result of the fatty acid composition analysis confirms the oil to be of good quality and can be used for industrial purposes such as cosmetics, soaps and paint.

Keywords: Heavy Metals, Phytoremediation, castor bean, polluted soils

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2 Alumina Supported Cu-Mn-Cr Catalysts for CO and VOCs oxidation

Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov, Petya Petrova, Tatyana Tabakova


This work studies the effect of chemical composition on the activity and selectivity of γ–alumina supported CuO/ MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether (DME) and methanol. The catalysts were prepared by impregnation of the support with an aqueous solution of copper nitrate, manganese nitrate and CrO3 under different conditions. Thermal, XRD and TPR analysis were performed. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor. Flow-line equipment with an adiabatic reactor for simultaneous oxidation of all compounds under the conditions that mimic closely the industrial ones was used. The reactant and product gases were analyzed by means of on-line gas chromatographs. On the basis of XRD analysis it can be concluded that the active component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4, Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio. Chemical composition strongly influences catalytic properties, this influence being quite variable with regards to the different processes. The rate of CO oxidation rapidly decrease with increasing of chromium content in the active component while for the DME was observed the reverse trend. It was concluded that the best compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and Mn/Cr molar ratio from 1:3 to 1:4.

Keywords: Volatile Organic Compounds, Cu-Mn-Cr oxide catalysts, deep oxidation, dimethyl ether (DME)

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1 Alumina Supported Copper-Manganese Catalysts for Combustion of Exhaust Gases: Effect of Preparation Method

Authors: Krasimir Ivanov, Elitsa Kolentsova, Dimitar Dimitrov


The development of active and stable catalysts without noble metals for low temperature oxidation of exhaust gases remains a significant challenge. The purpose of this study is to determine the influence of the preparation method on the catalytic activity of the supported copper-manganese mixed oxides in terms of VOCs oxidation. The catalysts were prepared by impregnation of γ-Al2O3 with copper and manganese nitrates and acetates and the possibilities for CO, CH3OH and dimethyl ether (DME) oxidation were evaluated using continuous flow equipment with a four-channel isothermal stainless steel reactor. Effect of the support, Cu/Mn mole ratio, heat treatment of the precursor and active component loading were investigated. Highly active alumina supported Cu-Mn catalysts for CO and VOCs oxidation were synthesized. The effect of preparation conditions on the activity behavior of the catalysts was discussed. The synergetic interaction between copper and manganese species increases the activity for complete oxidation over mixed catalysts. Type of support, calcination temperature and active component loading along with catalyst composition are important factors, determining catalytic activity. Cu/Mn molar ratio of 1:5, heat treatment at 450oC and 20 % active component loading are the best compromise for production of active catalyst for simultaneous combustion of CO, CH3OH and DME.

Keywords: copper-manganese catalysts, VOCs oxidation, exhaust gases

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