Chemistry. Ecology. Biotechnology – 2015

ous forms of iodine, such as: gas-aerosol composed of elemental iodine (isotopes 131I (half-life 8.04 days), 129I (half-life 17 million years) and 133I (half-life 21 hours), different iodine ions entering into the aqueous phase and transported into the soil.

In this regard, a problem arises of acquiring sorbents that can effectively adsorb iodine of various forms from air-gas phase. The existing inorganic adsorbents for gaseous iodine have significant drawbacks, such as low rate sorption, low sorption capacity, deterioration of the sorption properties under high humidity conditions, complexity and high economic costs in the production process. The most acceptable alternative are sorbents based on biological objects.

The present work is devoted to obtaining biosorbents based on three types of algae – Zostera marina, Cystoseirabarbata and Cladophoraglomerata. These algae can accumulate iodine due to the high content of carbohydrate components. A presence on the surface of carboxyl groups of alginic, ascorbic, malonic and other carboxylic acids allows immobilizing on their surface the complex compounds, including organometallic complexes. Besides, the selected algae belong to different species, have different specific surface structures and surface layer structures.

From the works it is well known that iodine forms stable complexes with organic amines and their derivatives. Based on experimental data, hexamine (С6H12N4) has been selected as a ligand for the complex compound, while CaCl2 as a complexing compound. The choice of a complexing compound is conditioned by the fact that the pharmaceutical industry produces the “Calcex” medical drug, which is a complex compound of hexamine and CaCl2 (whose formula is (С6H12N4)2· CaCl2·10H2O)). Moreover, the sorbent based on a complex compound with hexamine showed high iodine sorption characteristics, and is not toxic, which is an important feature for biosorbents.

A dependence of deposition of the complex compound on the surface of algae on treatment temperature and concentrations of the initial solutions was investigated. It was established that the treatment temperature does not have a significant influence on deposition and subsequent complex compound sorption capacity. With increased concentration of

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the starting solutions a coprecipitation of the complex compound occurs as a separate phase. So, later each type of algae was treated sequentially with solutions of 0.1M CaCl2 and 0.2 M С6H12N4 at room temperature for four days. The sorbents produced have been studied for sorption properties. It was found that the air-gas phase adsorption maximum of iodine adsorbents under dynamic conditions is approximately 10 minutes. The highest adsorption capacity (E mg I2 / g. sorbent) was demonstrated by the sorbents based on Zostera marina (E = 883,5 mg I2 / g. sorbent), while the sorbents based on Cladophoraglomerata and Cystoseira barbata have much lower sorption performance (E mg I2 = 448 mg I2/ g. sorbent and 163 mg I2/ g. sorbent, respectively). So different sorption capacity values obviously depend on different structures of algae, in particular, the pore size of cell walls of the algae, as well as the surface area available for the complex. It is proved that there is a directly proportional dependence between the amount of iodine adsorbed from the air-gas phase and the mass concentration of the complex compound in the composition of the sorbent.

It is established that the received biosorbents are not toxic, and their inhibitory effects on the growth of culture E.coli were not revealed.

УДК 579

A.I. Semicheva, A.V. Portnova

CREATION OF BIOSORBENT BASED ON HUMIC ACIDS FOR PURIFICATION OF MINE WATERS FROM Fe3+ IONS

Perm National Research Polytechnic University

Water pollution with heavy metal ions is dangerous for the biosphere. Heavy metals are toxic for living organisms and tend to accumulate in food chains. The greatest danger for water bodies is acid mine waters of Kizelovsky coal basin, which contain a large amount of iron oxides. The river B. Kizel and N. Vilva are completely excluded from water

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supply as a result of mine water pollution. Due to the high levels of pollution of small rivers, the other rivers of Kizel coal basin, such as South Vilva, Usva are polluted, too. They ultimately influence Yayva and Chusovaya rivers. According to the 2011 data the iron content in mouth of r.Usva is equal to 0.1–2.3 mg/l under MPC of 0.3 mg/l. A discharge of iron in all surface waters of Kizelovsky basin is 17122.5 tons in 2010. Until now, the problem is pressing; the best solution has not been found yet.

This work is devoted to this issue. It is planned to receive an environmentally safe biosorbent based on humic acid with immobilized microorganisms. In future, a possibility of regeneration of the spent biosorbent is considered. Another possibility is using it as a fertilizer for soils poor in organic matter content.

Humic substances are natural compounds heterogeneous in terms of molecular weight, structure, and content of the different functional groups. Humic acids include about 15 different functional groups, among which the most important are carboxyl, phenolic, amino and thio groups. Humic acid of soils have a significant impact on the migration of ions and metals and radionuclides in the hydrosphere and lithosphere. Binding ions of heavy metals, humic acid decrease their bioavailability and toxicity.

To create a HA-based biosorbent with immobilized microorganisms it is expected to isolate a culture of microorganisms from the sample of mine water. The culture of microorganisms needs to be stable to the acidic environment with the high concentration of Fe3+ ions.

At present time the experiments of Fe3+ ions sorption by the humic acid are carried out. A humic acid was isolated from the peat by the standard method. The samples of humic acid (0.1 g) were placed in a metal salt solution (100 ml). In experiments the salt FeCl3×6H2O was used. The concentration of metal ions was from 0 to 40 mg/l. The solution samples with humic acids were exposed to constant stirring (at 150 rpm) and temperature of 28°C for 24 hours. The analysis was performed by atomic absorption spectrophotometer. The data obtained are presented in the table.

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Sorption experiment results

Based on the static experiment we can estimate the degree of saturation of humic acids by Fe3+ ions. In the experiment the value of maximum sorption of iron ions is equal to 27.5 mg/g was reached. The maximum percentage of absorption is 80 %. The sorption experiments will continue

to determine the maximum sorption capacity of humic acids in relation to Fe3+ ions.

УДК 665.3+665.58

E.A. Sukhoplecheva, I.A. Permyakova, D.A. Kazakov, V.V. Vol’khin

THE DEVELOPMENT OF METHODS

FOR INTENSIFICATION OF BIODIESEL PRODUCTION

FROM WASTE OIL AND ETHANOL

Perm National Research Polytechnic University

The process of biodiesel synthesis involves a series of problems caused by heterogeneity of the oil–ethanol system. These compounds form two phases that are insoluble in each other. For system homogenization a cosolvent could be added.

Waste vegetable oils contain free fatty acids that may act as homogenizers for oil-ethanol mixture. Previously, we have studied the effect of oleic, stearic, lauric and butyric acids on the phase equilibrium of oil-ethanol mixture and we proved that they can contribute to the sys-

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tem’s homogenization. In this part of our work we tested the ability of alcohols to act as cosolvents. Furthermore, it is known from the literature that alcohol additions could affect the properties and performance of the internal combustion engine and composition and properties of the exhaust gases.

The phase equilibrium of triglycerides of fatty acids (sunflower oil) (TAG) – ethanol (EtOH) – alcohol (Alcohol) systems were studied. As alcohols we took only primary ones in a range of C3-C6 to compare the effect of hydrocarbon radicals of alcohols on TAG + EtOH system homogenization. Ethanol and Methanol were not tested in the experiment because they are used as a feedstock for biodiesel production. After addition of alcohols the TAG-EtOH system’s homogenization occurs. We made ternary phase diagrams of the studied mixtures and from these diagrams we can see that with increasing hydrocarbon radical of alcohol its ability to work as a cosolvent increases as well. For example, to homogenize the TAG + EtOH mixture with 1:1 mass ratio at 70oC we need 44 mass % of propanol, 32 mass % of butanol, 26 % pentanol and 24.5 % of hexanol. It can be explained by the fact that a larger size of hydrocarbon radical increases the number the induced dipoles functioning in the interaction and dispersion strength of intermolecular interactions. The lower molecular weight of hydrocarbon radical, the weaker the affinity of TAG and its associates to the alcohol in EtOH phase. Therefore, to reach the desired affinity between the TAG and EtOH phases high concentration of Alcohol – EtOH associates in alcohol phase is required, that under the given conditions can be achieved only by increasing the proportion of Alcohol in the mixture.

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УДК 623.19.47

D.А. Rozhina, А.U. Druk, L.S. Pаn, V.V. Vol’khin

SYNTHESIS OF COMPOSITE BIOSORBENTS BASED ON IRON POTASSIUM HEXACYANOFERRATE AND SEAWEED, THEIR BIOTESTING AND USE FOR DRINKING WATER

Perm National Research Polytechnic University

Seaweed is able to absorb ions of metals mainly thanks to the structure of a cellular wall containing algnat (a heteropolymer formed by the residue of mannuron and guluron acids), fukoidan (a polysaccharide constructed mainly by the residue of sulfatised L-fukoze), cellulose (a polysaccharide formed by the residue of D-glucose). Due to the ability to connect heavy metals and radionuclides alga are used in medicine as enterosorbents.

In our work seaweed is suggested as a basis for caesium sorbents. To produce a selective caesium to ions sorbent, seaweed is originally processed by a solution of salt of transitive metal. The polymers forming a cellular wall of seaweed contain the various functional groups, capable of connecting ions of transitive metals which during the further processing of seaweed by a solution of potassium gexacianoferrate serve as the formation centers of ferrocianids of transitive metals. It is shown that increase of FOC-component having H0,6K0,2Fe1,07 [Fe(CN)6] in biosorbent composition does not significantly increase the sorption capacity and time required to establish equilibrium. At the same time the selectivity of the sorbents with respect to cesium ions slightly increases.

It has been established that the received sorbents possess good kinetics of sorption. A balance in the system "sorbent-solution" is established within several minutes.

The sorption properties were studied under dynamic conditions. It is shown that the modified seaweed have significantly higher sorption char-

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acteristics as compared to pure seaweed. It was found that the sorption of cesium implies two ion exchanges, H+↔Cs+ and K+↔Cs+. After the sorption a selection of H+ and K+ ions into solution was detected. The sorbents produced have a high adsorption capacity and selectivity for cesium ions. In the case of sodium and potassium ions Kd values begin to decrease at concentrations of potassium equal to 10–12 mM and sodium 18–20 mM, despite a 40-fold excess in the solution’s cesium concentration. However, the Kd value during the sorption of the modified algae in 30 mM potassium concentration is maintained at 560–590 ml/g of the sorbent, while Kd cesium sorption by clean algae under the same conditions is reduced to near zero.

Evaluation of biological safety by bioassay showed that the obtained sorbents are not toxic. This conclusion was also confirmed by testing the sorbent in rats.

During the research the sorbents possessing high sorption capacity on Сs+ and good kinetic characteristics have been produced which could be recommended for purifying milk and potable water.

УДК 579.26

O.I. Bakhireva, A.A. Ananko

STUDY OF THE POSSIBILITY OF EXTRACTING Sr2+ IONS FROM SOLUTIONS USING MICROORGANISMS

Perm National Research Polytechnic University

Salts and Strontium combinations are referred to as non-poisonous substances, although bones, liver and brain are damaged by excessive amounts of Strontium. Being close by chemical properties to Calcium, Strontium differs from it entirely by its biological reaction. Its overconcentration in soil, water and food products cause humans and animals to get sick with “Kashin-Bek disease” – lesion and deformation of joints, growth retardation and other disorders.

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Applying the selective non-organic sorbents, which are able to selectively absorb Strontium out of solutions seems to be promising, whereas natural waters contain calcium ions which are hardly separable from strontium ions. Nowadays numerous works in this direction are being held in our country and abroad. Sorbents based on sodium-potassium manganite and sodium momotitanate have the best characteristics of all the described and tested materials. Such materials have sorptive Strontium capacity of 50 mg/g of sorbent and can be used for purification of solutions which are highly mineralized (5.6 g/l sodium и 0.2 g/l calcium). A disadvantage of the treatment method based on such materials is a lack of purification efficiency.

The aim of this research is to create a multipurpose purification method to clean water poluted with strontium ions by using sorption materials and culture of microorganisms.

The research revealed that superfinevaterit – a metastable modification of CaCO3 – may appear as an effective sorbent of Sr2+ ions from the neutral water solutions. The sorption passes through two stages: the first relates to the adsorption of Strontium ions on the most active surface centres; while in the second stage, there is a massive irreversible takeover of Strontium ions during the vaterit transformation into calcite in a recrystallized mechanism.

However, as the research shows, Strontium sorption is low at the first stage. We may assume that at the first stage, not the whole surface of vaterit is sorptially active in relation to Sr2+, but only a small part of it.

Under the static and dynamic conditions the ISM–S oxyhydrate sorbent having a composition (Na,K)xMnO2 synthesized at the Chemistry and Biotechnology Department of PNRPU was explored: the maximum capacity in dynamic conditions for strontium is 0.32 mEg/g, and for calcium 0.64 mEg/g; in static conditions for strontium 0.244 mEg/g, for calcium 0.31 mEg/g.

The microorganism culture was acquired from the Tulva river water samples (the town of Osa, Perm krai). Earlier, there were nuclear explosions, and the culture’s main characteristics can be seen in the table below.

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The morphological characteristics of microorganisms

It was established by the disco-diffusional method that the distinguished culture of microorganisms is capable of active growth in the Sr2+ and Ca2+ ions in its wide concentration range, and it is able to accumulate ions by showing perfect tolerance to Strontium.

The research established that the culture of microorganisms may be used for absorption of Sr2+ ions from the solution, as well as for extermination of Sr2+ ions, previously absorbed by the sorption materials.

УДК 663.43

Y.V. Andreeva, O.V. Kolesova, S.Y. Solodnikov

MANUFACTURE OF FOOD ADDITIVES ON THE BASIS

OF THE JUICE OF WHEAT SPROUTS

WITH MICROBIOLOGICAL UTILIZATION

OF RESIDUAL OILCAKE

Perm National Research Polytechnic University

The problem of rational healthy diet is important for many countries, including the Russian Federation. The current nutrition requirements at global scale are not satisfied, both in quantitative and qualitative terms. A quantitative lack of food affects up to 15 % of the world population, mainly in developing countries.

Disposal of food industry waste is a rather acute problem as well. Such waste, given its full and rational use, turns into secondary material resources to expand the range of products for food, fodder and industrial purposes, to create additional sources of raw materials.

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The SOMA company implements technology of producing food additives using a juice of wheat sprouts. Young wheat sprouts are the best source of physiologically active chlorophyll – the basis of life of the plants.

Our concern was to determine a possibility and efficiency of producing dry feedstuff for animals by decomposing a polysaccharide component of the residual oilcake by a consortium of microorganisms.

Intentionally, a small volume of the one-time leaven was prepared, for which purpose associations of microorganisms with cellulolytic activity were put into the oilcake. The mixture was held at 00C during four hours to activate a biological product. The quality of the leaven was assessed by changes in the substrate structure. The ready leaven was put into a larger volume of oilcake and mixed for the following biofermentation during 5 to 10 hours with occasional stirring. Such a treatment reduces the fiber content by 7 to 10 % with a simultaneous RA increase by a factor of 4 to 8.

In addition, a method of biomass granulation allowing dosed animal feeding was developed. The studies have shown that lab rats, whose diet included a microbiologically processed meal, reach the optimum weight faster than animals eating only food.

Based on the preliminary data it may be concluded that preliminary biofermentation of meal increases the biological purity of the feedstuff due to a partial decomposition of cellulose and its enrichment with protein and vitamins of B group.

УДК 623

F. Khakimova, K. Sinyaev, A. Mukhtarov, Y. Sypacheva

ABOUT ECF-BLEACHING OF SULPHITE PULP

Perm National Research Polytechnic University

One of the most important requirements for bleaching technology is the introduction of efficient and environmentally more safe bleaching process. At present, ECF (Elemental Chlorine Free) – and TCF (Total

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