Polish Journal of Chemical Technology (v.9, #3)
Epoxidation of 2-buten-1-ol over Ti-MCM-41 and Ti-MCM-48 titanium silicalite catalysts
by Agnieszka Wróblewska; Ewelina Ławro; Eugeniusz Milchert; (pp. 1-4).
The results of the epoxidation of 2-buten-1-ol with 30 wt% hydrogen peroxide have been presented. As a solvent methanol was used. The process was carried out over the titanium silicalite catalysts: Ti-MCM-41 and Ti-MCM-48. The influence of temperature (20 - 120°C), the molar ratio of CRA/H2O2 (5:1 - 5:1), methanol concentration (5 - 90 wt%), catalyst concentration (0.1 - 5.0 wt%) and the reaction time (30 - 300 min) was investigated. The obtained results were used for the determination of optimum conditions of running the epoxidation process of 2-buten-1-ol.
Keywords: epoxidation; 2,3-epoxybutan-1-ol; Ti-MCM-41; Ti-MCM-48
The effect of Atpolan 80 EC on atrazine residues in the soil
by Maria Swarcewicz; Elżbieta Skórska; Waldemar Paździoch; (pp. 5-8).
The persistence of atrazine residues in soils may have an effect on the contamination of the ground water or surface water. Besides the active ingredients, pesticide formulations contain many other compounds called adjuvants. One of them is the Atpolan 80 EC which belongs to the group of oil mineral adjuvants used as tank-mix. The utilization of a fraction of paraffin oil 1113 is one of the examples of utilising waste as the component of Atpolan 80 EC in agriculture. When the Atpolan concentration comprised 1.25% (v/v), the atrazine degradation rate decreased in the sandy loam and muck soil. The half-life of atrazine increased over a period of 40 or 57 days, depending on the type of the soil. The least significant effect was caused by Atpolan concentration at 0.25 and 0.75%. This result points at the capability of limiting atrazine run-off and leaching down the soil profile. Each ingredient of the pesticide, besides having the overall ability to distribute between different phases, also demonstrates some single compound behaviour. This paper shows our current understanding of the factors that influence the adjuvant performance and their potentially complex interactions with the pesticide.
Keywords: atrazine; adjuvant; persistence; soil
Production of suspension fertilizers as a potential way of managing industrial waste
by Daniel Mikła; Krystyna Hoffmann; Józef Hoffmann; (pp. 9-11).
Research on the possibilities of utilizing several waste substances for the production of suspension fertilizers has been carried out. The substances were: sludge from the ALWERNIA S.A. Chemical Plant - a potential source of phosphorous (~20% by wt. P2O5) and waste sludge from the production of magnesium sulphates and nitrates in the Złotniki S.A. Chemical Plant - a substance aiding the stability of suspension and magnesite (a source of magnesium). The possibility of chemical activation of clayey minerals through ion exchange was investigated. Na2CO3 was used for this purpose. Fertilizer samples PK and NPK were found to be highly stable (syneresis < 25%). The NPK +3% MgO sample was found to have particularly good properties. The activation of the clayey materials by Na2CO3 resulted in an increase in the stability coefficient in the case of bentonite SN and clay TIK by 0.88964 and 0.516304, respectively.
Keywords: waste; bentonite; suspension fertilizers; activation
Utilization of poultry droppings in mineral-organic fertilizers
by Krystyna Hoffmann; Barbara Lewandowska; Magdalena Borowiec; Józef Hoffmann; (pp. 12-14).
The results of physicochemical analyses of raw and composted turkey droppings and those of germination tests carried out using the droppings are presented. On the basis of the results formulas for microelement mineral-organic fertilizers have been developed and fertilizer rates have been determined for winter wheat.
Keywords: composted turkey droppings; mineral-organic fertilizers
Assessment of the use of municipal and industrial wastes in agriculture
by Czesława Jasiewicz; Jacek Antonkiewicz; Agnieszka Baran; (pp. 15-19).
Agricultural usability of urban and industrial wastes was investigated in 2004 - 2006 in a pot experiment carried out in the vegetation hall. In the first year of the experiment maize was the test plant, oat grass in the second and oat in the third. The experimental design comprised 11 treatments differing with fertilizer and the kind of the supplied fertilizer components. The experiment used: mineral salts, farmyard manure, compost, municipal sewage sludge and industrial sewage sludge in two fertilizer doses. Metal concentrations in the test plants were diminishing in the following direction: oat grass < maize < oat. The lowest concentrations of the analyzed heavy metals were assessed in the plants fertilized with farmyard manure and compost (Zn, Cu). Among the tested plants the highest quantities of Zn, Cu, Ni, Pb and Cd were removed with the yield of the oat grass, then maize and oat. The highest uptake of Zn, Cu, Ni and Pb by plants was registered on a double dose of industrial sludge and Cd on a single dose of municipal sludge.
Keywords: heavy metals; farmyard manure compost; municipal and industrial sewage sludge
The effect of hard coal ashes on the amount and quality of maize yield
by Jacek Antonkiewicz; (pp. 20-25).
The research was conducted in 2003 - 2005 as a pot experiment on mineral soil to which ash doses of between 13.33 g and 800.0 g · pot-1 were supplied in proportions corresponding to the amounts of between 10 and 600 t · ha-1. The investigations aimed at learning the effect of diversified ash doses upon the content, ionic relations and the uptake of Mg, Ca, Na and P by maize. Macroelement concentrations in maize were diversified depending on the object and the plant part, fluctuating from 1.52 - 7.49 g Mg; 3.79 - 11.01 g Ca; 8.07 - 23.86 g K; 0.17 - 1.52 g Na; 1.23 - 3.16 g P · kg-1 d.m. It was found that with the growing ash dose the contents of Mg, Ca, K and Na in maize were increasing systematically, whereas P concentrations were decreasing. Magnesium and potassium content in maize aboveground parts met the requirements for a good quality fodder. The level of calcium, sodium and phosphorus in maize did not remain within the optimal range. A systematic increase in Mg uptake but a decline in P absorption by the aboveground parts were registered in maize in effect of growing ash doses.
Keywords: maize; Mg; Ca; K; Na; ratios; uptake; ash; mineral soil
Utilization of used contact masses from the oxidation state of sulfur(IV) oxide to sulfur(VI) oxide
by Mieczysław Trypuć; Krzysztof Mazurek; Urszula Kiełkowska; Sebastian Drużyński; (pp. 26-28).
The research was conducted to determine the influence of the urea concentration in the leaching solutions on the efficiency of recovery of vanadium and iron compounds from the used vanadium catalyst from the node of oxidation of sulfur dioxide to sulfur trioxide.
Keywords: sulfuric acid; sulfur oxide; urea solutions; used vanadium catalysts; leaching process
Catalysts for the utilization of methane from the coal mine ventilation air
by Beata Stasińska; Andrzej Machocki; (pp. 29-32).
The paper indicates coal mines as the source of permanent emission of low-concentrated gases, which have increased the greenhouse effect. This paper proposes the catalytic oxidation of methane as the solution to the problem of methane utilization when its concentration in the air is insufficient for flame combustion. The studies which have been conducted for many years enabled finding the active oxide and metallic catalytic systems for the reaction of methane oxidation. For the utilization of gases with low-concentrated methane, using the low-temperature catalysts, especially palladium catalysts, seems to be economically well-justified. Depending on technological solutions it can be considered as the method for methane utilization or as an environmentally friendly way for the generation of electric and thermal energy.
Keywords: coal mine ventilation air; utilization of methane; catalytic oxidation of methane; oxide catalysts; palladium catalysts
Optimization of an active phase composition in the low-temperature nitric oxide reduction catalyst
by Marek Kułażyński; Krystyna Bratek; Jerzy Walendziewski; (pp. 33-37).
In the first research studies series a selection of the quantitative composition of catalyst active phase composition (iron, copper and manganese) deposited on mineral-carbon support was carried out. It was found on the basis of the selection studies series that the best results were attained when copper and manganese were used as catalyst components. The quantitative composition of the denitrogention catalyst was estimated using a statistical method of experiment planning and metals content changed in the range 0.5 - 1.5wt % for both metals. Catalyst activity in nitric oxide reduction by ammonia was determined in the dependence on an active phase composition in the temperature range 100 - 200°C, at GHSV (Gas Hour Space Velocity) 6 000 and 10 000 Nm3/m3h, NO concentration 400 ppm, NH3/NO ratio 1:1. A graphic presentation of the obtained results was made using the UNIPLOT program. The highest activity in nitric oxide reduction by ammonia presented copper - manganese catalysts prepared by the impregnation of mineral-carbon support with active metals salts solutions and calcination after each metal impregnation with copper (up to 1.5 wt %) and manganese (up to 1.5 wt %).
Keywords: NOxSCR; catalyst; optimization; mineral-carbon carrier
Biodegradability of the compounds introduced with microelement fertilizers into the environment
by Magdalena Borowiec; Paulina Polańska; Józef Hoffmann; (pp. 38-41).
The results of laboratory studies into the oxygen biodegradation of chelating substances in aqueous medium under kinetic and static test conditions with added glucose as an additional source of carbon, are presented. It has been found that S,S-ethylenediaminedisuccinic acid (S,S-EDDS) and methylglycinediacetic acid (MGDA) are more readily degradable than ethylenediaminetetraacetic acid (EDTA), most commonly used in the production of microelement fertilizers. It has also been found that the presence of additional carbon sources accelerates biodegradation.
Keywords: biodegradation; microelement fertilizers; EDTA; S; S-EDDS; MGDA
Biorefineries - from biofuels to the chemicalization of agricultural products
by Jacek Kijeński; (pp. 42-45).
The recent research into the viable economy in sustainable energy from renewable sources has prompted a review into the potentials of Polish-oriented raw material sources as a catalyst for technological advance, product diversification and consumer satisfaction. The elongation of the process chain in vegetable (rape seed, potato), alcohol additives and glycerin processing has been found to drastically improve energy balances for the short processing methods adopted presently and can make Poland self sustainable in the future.
Keywords: biorefinery; rape seed; transesterification; glycerin economy; FAME
Fuel fractions obtained in the recycling of plastics
by J. Sokołowski; G. Rokicki; M. Marczewski; J. Krajewska; (pp. 46-50).
The decomposition of mixtures of polystyrene, polyethylene, and motor oil was studied at 470 - 510°C in a flow-through setup supplied with a fluidized bed reactor and a cascade of receivers. The aim of the work was to determine the role of the fluidized bed in the reactor, in the process of degradation of plastics in the cases where it was only a carrier of heat for the endothermal process of pyrolysis or it was both a carrier of heat and a catalytic bed for the process. The effect of the catalyst granulation and of the method of the organization of work in the reactor on the yield of the process and on the composition of the products obtained, was also studied.
In the cases where Al2 O3 of granulation 0.2 mm was used as a fluidized bed catalyst the liquid products of the decomposition of the polymers contained mainly alkyl-aromatic derivatives of styrene, benzene and alkane hydrocarbons. If nano-Al2 O3 was used as a catalyst and it was introduced into the reactor with a stream of raw materials, the obtained products were solids, composed mostly of styrene and alkene hydrocarbons.
Keywords: plastic recycling; catalytic cracking
Studies on solidification of wastes from metal coating
by Kamil P. Banaszkiewicz; Tadeusz Marcinkowski; (pp. 51-55).
There are over 1000 electroplating workshops functioning in Poland; they are agglomerated in automotive industry, agricultural and construction machines industry, precision instruments industry, electronics, electrotechnics, etc.2. The chemical composition of wastes from galvanizing plants strictly depends on the technological processes as well as the methods of neutralization of industrial wastewaters. The wastes mentioned can be neutralized, among other possibilities, using cement, fly ashes or lime. The material that gains the widest applicability for treating a wide spectrum of hazardous wastes is Portland cement. Using cement enables an improvement of the physical (solidifying) and chemical characteristics of various kinds of wastes, that ensures a decrease in the mobility of contaminants (stabilization). The process using Portland cement (CEM I 32,5 R) was used towards galvanic sludges. The results presented in this article allow for the assesment of the applicability of mixture of cement with mortar sand, as well as the mixture of cement and flotation tailings for the stabilizing and solidifying galvanic sludge, containing mainly Cr, Cu, Zn and Ni. The presented study was also concentrated on the limitation in the transport of leached contaminants to the environment, the reduction of the solubility of hazardous contaminants, as well as a change in the physical structure of the waste - in other words, derivation of the product that could be mechanically durable during transport and storage.
Keywords: stabilization/solidification; portland cement; sand; flotation tailings; galvanic sludges; heavy metals
Impact of sewage sludge and composts prepared from sewage sludge on the content and uptake of macronutrients by straw of miscanthus sacchariflorus
by Anna Iżewska; Edward Krzywy; Krzysztof Balcer; (pp. 56-59).
The pot experiment was set up under the conditions of the hall of vegetation in 2002. The municipal sewage sludge and composts produced with the GWDA method in 2001 based on municipal sewage sludge with the 30% addition of structuring materials, in conversion to the dry matter, were used in the experiment. The pot experiment was set up with the split-split-plot method in three repetitions. The objects of the first factor were the doses of sewage sludge and composts (1 dose = 13 g, 2 dose = 26 g, 3 dose = 39 g, 4 dose = 52 g of dry matter in relation to the soil weight in the pot), the objects of the second factor were the types of organic fertilization (sewage sludge, 0,5-year compost prepared from sewage sludge, 1,5-year compost prepared from sewage sludge), objects of the third factor were the variants with and without nitrogen and potassium fertilization in the rates of 0.27 g N and 0.26 g K per pot. The experiment was conducted in Kick-Brauckmann's pots of 9 dm3 capacity in which 8 kg of soil were placed. The test plant cultivated in the experiment was Miscanthus sachariflorus. Seedlings of Miscanthus were planted in the first year of the experiment. The obtained results show that the content of macronutrients: nitrogen, phosphorus, potassium in straw of Miscanthus sachariflorus was not dependent on the type of organic fertilizers used in the experiment. However, supplemental nitrogen-potassium fertilization significantly increases the content of potassium in the test plant in all three years of research and nitrogen in the second year.
The conducted research shows that the uptake of macronutrients depended on the dry matter yield quantity and the content of a given element in the yield. Within three years the straw of Miscanthus sacchariflorus took up the most of potassium - 11.63 g from the pot and the least of magnesium 1.20 g from the pot. The amount of the absorption of nitrogen, phosphorus and magnesium by the biomass of Miscanthus sacchariflorus from the pot on the objects fertilized with organic fertilizers was the highest in the second year of the research, which was a result of mineralization of the applied fertilizers.
Keywords: sewage sludge; composts prepared from sewage sludge; macronutrients; uptake of macronutrients; Miscanthus
Impact of manure and organic fertilizers on the quantity and content yield of heavy metals in spring rape
by Edward Krzywy; Anna Iżewska; (pp. 60-63).
The pot experiment was set up with the split plot method in three repetitions in 2006. The objects of the first factor were the doses of manure and organic fertilizers to the soil in conversion to the brought in nitrogen (85 and 170 kg N·ha-1), the objects of the second factor were the types of fertilizers: manure, sewage sludge and the composts prepared from sewage sludge. The soil used in an experiment was supplied from The Agricultural Experimental Station in Lipnik. The soil was taken from the arable layer, it has the granulometric composition of the light loamy sand.
The content of available phosphorus, potassium and magnesium formed on medium level, the pHKCl of the soil amounted to 5.13. The soil was characterized by 00 contamination of trace elements, which means that it contained the natural content of cadmium, copper, nickel, lead and zinc. Spring rape var. Licosmos was the test plant.
The aim of the research was the assessment of the influence of manure, sewage sludge and compost prepared from sewage sludge on yield quantity of seeds and straw and the content of cadmium, nickel, lead and zinc in spring rape.
The conducted research shows that fertilizers brought into the soil (manure, sewage sludge and compost prepared from sewage sludge) as well as two levels of fertilizing had a significant influence on the yield of the seeds and straw of spring rape. Manure, sewage sludge and compost prepared from sewage sludge played less significant influence on the decreasing or excessive increasing of heavy metals concentration in the seeds of spring rape. The double dose of fertilizers caused higher accumulation of heavy metals in the test plant. The straw of spring rape should be treated as a source of organic matter and the main nutrients for the soil. The highest concentration of copper, manganese, nickel and zinc in the straw of spring rape was noticed after the application of sewage sludge and of cadmium and lead after the application of compost prepared from sewage sludge.
Keywords: manure; sewage sludge; compost prepared from sewage sludge; spring rape; heavy metals
Usability of high porosity ceramics for the separation of oily impurities
by Krzysztof Perkowski; Janusz Sokołowski; Mikołaj Szafran; (pp. 64-67).
Organic impurities fallen to the ground water and to surface waters (rivers, lakes, seas and oceans) contribute to the degradation of the fauna and flora. Taking into account the public welfare, as the natural environment is, studies have been undertaken to develop a cheap and effective system for the purification of water from finely dispersed petroleum derivatives. The idea of the solution proposed consists in using a separator with high porosity ceramics of the pore size up to 100 ¨m, of high water permeability and ability to separate oily impurities of very tiny particle size. To improve the efficiency of the process the affinity of the filtering surface to organic particles was increased by the use of water-repellent media. The process of the separation of oily impurities was enhanced by means of ultrasounds of the 18 kHz frequency and various vibration energies.
Keywords: porous ceramic materials; separation of oily impurities; silico-orgaanic materials; ultrasounds
Solid inorganic peroxy compounds in environmental protection
by Barbara Walawska; Joanna Gluzińska; Korneliusz Miksch; Jolanta Turek-Szytow; (pp. 68-72).
The paper presents a solid inorganic peroxy compounds description (calcium peroxide, magnesium peroxide and sodium percarbonate) focused on the properties and environmental application, particularly for the degradation of polycyclic aromatic hydrocarbons (PAHs) and phenols in soil environment. Modern technological processes require the use of compounds that are safe for the environment, non-toxic, easily degradable to the products, which themselves have no adverse environmental effect. Peroxides, as the chemical compounds, produce an effect on the enzymatic activity of the environment into which they are introduced. A good indicator of the activity of soil, bottom sediment or activated sludge, may be the dehydrogenase activity, which is a reflection of the general physiological state of microorganisms. Peroxides can be applied both in a pure form, as well as in mixtures with certain other groups of compounds. To enhance their efficiency they can be mixed with nitrogen, phosphorus or potassium carrying compounds.
Keywords: Active oxygen; peroxy compounds; environmental protection; PAHs
The influence of the conditions and worktime on the waste vanadic catalyst amount
by Piotr Grzesiak; Rafał Motała; Marcin Grobela; Mieczysław Trypuć; Krzysztof Mazurek; (pp. 73-76).
This paper includes the research results of the vanadic catalyst study that was operated in PCC Rokita S.A. during a gaseous SO3 formation. The physical properties have been studied: mechanical strength, bulk density and grindability during the five-year cycle of the catalyst worktime. The studies presented underline the prediction of the amount of the formed vanadic waste material.
Keywords: vanadium catalyst; waste products
Characteristic of physicochemical properties of Pd/MgO catalysts used in the hydrodechlorination process with CCI4
by Jacek Góralski; Bożena Szczepaniak; Jacek Grams; Waldemar Maniukiewicz; Tadeusz Paryjczak; (pp. 77-80).
The aim of this paper was to investigate the physicochemical properties of palladium catalyst containing basic support MgO which was used in hydrodechlorination reaction with carbon tetrachloride. In order to characterize the investigated sample the catalyst was put to tests of XRD, TOF - SIMS, TG-DTA-MS and TPRH2 measurements, activity tests were also performed. The XRD and TPR results demonstrated the presence of PdOxCly species whose decomposition takes place above 700°C. The calcination of the Pd/MgO catalyst at 700°C resulted in the transformation of PdOxCly to PdO.
Keywords: palladium catalyst; basic properties of MgO; hydrodechlorination; CCl4
ToF-SIMS studies of the surface of Pd/ZrO2-TiO2 catalyst used in the hydrodechlorination process
by Jacek Grams; Jacek Góralski; Joanna Kleczewska; Bożena Szczepaniak; Tadeusz Paryjczak; (pp. 81-85).
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used in order to obtain the information about the surface composition of Pd/ZrO2-TiO2 catalyst and to estimate the changes in the concentration of particular components on its surface during the hydrodechlorination of CCl4. The results demonstrated that the hydrodechlorination process led to the increase in the concentration of chlorine and the drop in the amount of surface accessible palladium, while the quantity of Pd-Cl bounds did not change considerably. It suggested that the presence of ZrO2 protected the surface of the studied catalyst against the formation of PdCl2.
Keywords: ToF-SIMS; palladium; catalysis; hydrodechlorination; ZrO2TiO2
Potassium multiphosphates for food processing
by Barbara Cichy; Stanisław Folek; Halina Makała; (pp. 86-90).
The paper discusses the results of research on the preparation of food grade potassium di- and triphosphates and the application thereof as multiphosphate ingredients of functional additives for meat processing. The research on the process of potassium multiphosphate manufacture was performed with the use of equipment corresponding to that used on an industrial scale, facilitating thereby the transfer of the process conditions to a commercial level. The aim of the work was to obtain potassium di- and triphosphate products readily soluble in water and NaCl solutions, determination of optimum parameters of the manufacturing processes, and an application of the products obtained along with sodium multiphosphates in functional phosphate additives for selected meat products. The research presented here is part of an on-going project.
Keywords: food additive; multiphosphate
Waste release from meat processing
by Zbigniew Wzorek; Michał Konopka; Janusz Cholewa; Grzegorz Klamecki; Tomasz Bajcer; (pp. 91-94).
The aim of our work is model solution management of waste from meat industry, which would lead to zero waste production with the use of cleaner technology. The process will allow to obtain semi-finished products to be then reused for both meat industry and energy recovery. The model will include thermal utilization of meat, meat-bone and other meat industry waste. The ashes with strictly specified properties containing phosphorus components will be used as a potential raw material for the production of phosphoric acid and salts used in meat production. The new technology is going to be developed in one of the biggest meat factories in Poland - DUDA-BIS in Sosnowiec. The strategic aim of the factory is meat processing with zero waste. That would help to avoid problems with meat waste transport and the expensive utilization of waste to meat-bone meal. The reuse of suitably processed meat waste in meat production will permit to lower production costs. This model will satisfy the requirements of BATNEEC - Best Available Technology No Entailing Excessive Costs. This procedure is advantageous also because in the EU market there are 18 million tons of meat by-products1, 2 per year.
Regardless of how the utilization problems could be solved, suitably processed meat industry waste can be treated as a potential substitute for phosphoric raw materials. According to the forecast, 50% of phosphoric raw material deposits used at the moment will be exhausted in the next 60 - 70 years. As a result a necessity for a new source of the raw materials has arisen.
Keywords: meat; meat-bone meal; fat; bones
Oligomerization of hexafluoropropylene oxide in the presence of alkali metal halides
by Egbert Meissner; Agnieszka Wróblewska; (pp. 95-97).
Oligomers of hexafluoropropylene oxide are raw materials for the synthesis of compounds having unique properties such as high chemical and thermal resistance. Two basic parameters have influence on the process of hexafluoropropylene oxide oligomerization: the kind of the catalyst and the solvent. The temperature and pressure influence this process to a lesser extent. The influence of halide ions, the solvent and the temperature on the oligomerization of hexafluoropropylene oxide has been studied.
Keywords: heksafluoropropylene oxide; oligomers of hexafluoropropylene oxide
Research on the influence of parameters on hexafluoropropylene oxide oligomerization in the presence of complex amines
by Egbert Meissner; Agnieszka Wróblewska; (pp. 98-100).
Oligomers of hexafluoropropylene oxide were tested as potential materials for obtaining vari-ous compounds with unique properties, of which most important are chemical and thermal re-sistance. Two basic parameters influence the oligomerization process of hexafluoropropylene oxide: the type of the catalyst and the type of the solvent. Other parameters such as temperature and pressure have significantly less influence. The influence of tertiary amines as catalyst, the type of the solvent, temperature, pressure and catalyst concentration were tested in the process of hexafluoropropylene oxide oligomerization.
Keywords: hexafluoropropylene oxide; oligomers of hexafluoropropylene oxide
Comparison of the methods of the phase transfer catalysis and hydroperoxide in the epoxidation of 1,5,9-cyclododecatriene
by Grzegorz Lewandowski; (pp. 101-104).
The process of the epoxidation of cis, trans, trans-1,5,9-cyclododecatriene (CDT) to 1,2-epoxy-5,9-cyclododecadiene (ECDD) with the 30% aqueous hydrogen peroxide under the phase transfer conditions and with tert-butyl hydroperoxide under the homogeneous conditions was investigated. Onium salts such as Aliquat® 336, Arquad® 2HT, methyltrioctylammonium bromide and the Na2WO4/H3PO4 catalyst system are very active under the phase transfer catalysis (PTC) conditions for the selective epoxidation of cis, trans, trans-1,5,9-cyclododecatiene (PTC method). These catalytic systems were found to be as active and selective as the homogeneous phase system Mo(CO)6/TBHP (hydroperoxide method).
Keywords: epoxidation; 1,5,9-cyclododecatriene; phase transfer catalysis; hydrogen peroxidetert-butyl hydroperoxide
Optimization of the epoxidation process of (1Z,5E,9E)-1,5,9-cyclododecatriene to 1,2-epoxy-(5Z,9E)-5,9-cyclododecadiene with tert-buthyl hydroperoxide — the influence of technological parameters on the hydroperoxide conversion
by Grzegorz Lewandowski; E. Rytwińska; Eugeniusz Milchert; (pp. 105-107).
The optimization studies of the epoxidation process of (1Z,5E,9E)-1,5,9-cyclododecatriene (CDT) with tert-buthyl hydroperoxide (TBHP) over the molybdenum catalyst Mo(CO)6 were performed. The reaction was examined in terms of a uniform-rotatable design. Three factors were analyzed: the reaction time, CDT:TBHP molar ratio, and the molar concentration of the catalyst (Mo(CO)6). According to the design 20 experiments were performed at the constant temperature of 70°C.
Keywords: epoxidationtert-butyl hydroperoxide; (1Z,5E,9E)-1,5,9-cyclododecatriene; 1,2-epoxy-(5Z,9E)-5,9-cyclododecadiene; design of experiments; optimization
Utilization of spent iron catalyst for ammonia synthesis
by Walerian Arabczyk; Urszula Narkiewicz; Zofia Lendzion-Bieluń; Dariusz Moszyński; Iwona Pełech; Ewa Ekiert; Marcin Podsiadły; Rafał Pelka; Roman Jędrzejewski; Izabela Moszyńska; Daniel Sibera; (pp. 108-113).
Several methods of the utilization of spent iron catalyst for ammonia synthesis have been presented. The formation of iron nitrides of different stoichiometry by direct nitriding in ammonia in the range of temperatures between 350°C and 450°C has been shown. The preparation methods of carbon nanotubes and nanofibers where iron catalyst catalyse the decomposition of hydrocarbons have been described. The formation of magnetite embedded in a carbon material by direct oxidation of carburized iron catalyst has been also presented.
Keywords: iron catalyst; iron nitrides; carbon nanotubes; nanofibers
An impact of municipal sewage sludge and wheaten straw on some indicators of soil fertility
by Czesław Wołoszyk; Krzysztof Balcer; (pp. 114-117).
In a two-factor pot experiment the impact of applied diverse doses of municipal sewage sludge and equal dose of wheaten straw, with and without supplemental mineral N and NPK fertilization, on some fertility properties of soil was assessed. The soil used in the experiment was acid brown incomplete soil (good rye complex). The grass — Festulolium — was the test plant, harvested four times and in the second year — common sunflower and blue phacelia. After the harvest of phacelia, the pH (in 1 M KCl), the content of total nitrogen, total carbon and the available forms of P, K and Mg were analyzed.
Fertilization with sewage sludge and straw failed to have a significant influence on the change of the soil pH. However, all doses of sewage sludge + straw, in comparison with the control, significantly increased the content of total carbon (from 31.8 to 37.8%) and total nitrogen (from 34.3 to 52.2%) in the soil. There was significantly more phosphorus available in the soil from all the objects with sewage sludge and straw than in the soil from the control object (from 8.2 to 21.6%), while the content of potassium was higher only in the soil from the object with 1.5% of sewage sludge + straw and magnesium at the highest dose of sewage sludge. The mineral N and NPK fertilization, used against the background of sewage sludge and straw, did not have asignificant impact on the shaping of the analyzed soil fertility indicators.
Keywords: municipal sewage sludge; wheaten straw; soil; total carbon; total nitrogen; phosphorus; potassium; available magnesium
Formation of environmentally friendly chloroorganic compounds technology by sewage and by-products utilization
by Jerzy Myszkowski; Eugeniusz Milchert; Waldemar Paździoch; Robert Pełech; (pp. 118-121).
The processes presented in the study enables the separation and disposal of the chloroorganic compounds as by-products from the vinyl chloride plant by using the dichlorethane method and also from the production of propylene oxide by the chlorohydrine method. The integrated purification method of steam stripping and adsorption onto activated carbon allows a complete removal and recovery of the chloroorganic compounds from waste water. Waste distillation fraction is formed during the production of vinyl chloride. 1,1,2-trichloroethane separated from the above fraction, can be processed to vinylidene chloride and further to 1,1,1-trichloroethane. 2,3-Dichloropropene, 2-chloroallyl alcohol, 2-chloroallylamine, 2-chlorothioallyl alcohol or bis(2-chloroallylamine) can be obtained from 1,2,3-trichloropropane. In the propylene oxide plant the waste 1,2-dichloropropane is formed, which can be ammonolysed to 1,2-diaminopropane or used for the production of β-methyltaurine. Other chloroorganic compounds are subjected to chlorinolysis which results in the following compounds: perchloroethylene, tetrachloromethane, hexachloroethane, haxachlorobutadiene and hexachlorobenzene. The substitution of the milk of lime by the soda lye solution during the saponification of chlorohydrine eliminates the formation of the CaCl2 waste.
Keywords: recycling; chloroorganic compounds; vinyl chloride; propylene oxide
Waste management of half-finished products and thermosetting wastes
by Sławomir Leszczyński; Beata Brzychczyk; (pp. 122-126).
Plastics are the widely used materials and their application increases every year considerably. Therefore, appropriate waste management policy should be used in relation to the utilization or recycling of scrap plastic components. Although most of these materials refer to thermoplastics, a huge widening demand is observed in the field of thermosets. They find a wide range of applications as the dielectric or insulating materials, high-current breaker switches, sensors and other electrical and electronic devices, as well as high-resistant sleeves in mechanical devices. The substantial part of the thermohardening products is used in a car, heavy, light, chemical industry and agriculture as well. The thermohardening wastes contain a large amount of combustible fraction as thermosetting resins, and various materials as a different kind of metals group like ferromagnetic and copper. Therefore, they are potential sources of energy and secondary materials. Application of thermal methods for the utilization of these wastes in the pyrolysis process was investigated. The development of the utilization of these wastes with the possibility of gas and liquid substance recovery as a potential source of energy on a commercial scale is the main aim of this paper.
Keywords: plastic waste; thermosetting waste; pyrolysis utilization
The influence of a hard coal type on the degree of sulphur dioxide removal
by Agnieszka Marcewicz-Kuba; Danuta Olszewska; (pp. 127-129).
In this paper the authors have studied the properties of zeolite and montmorillonite doped with the nickel and cobalt cations in the removal of SO2 from the combustion gases process based on the DESONOX method. Burning coal from the hard coal from the Silesian Coal Basin mine "Julian" and the Lubelskie Coal Basin mine "Bogdanka" with supports only - did not show any reduction of the SO2 emission in the combustion gases.
Keywords: hard coal; montmorillonite; zeolite; DESONOX; catalyst; sulphur dioxide
Photodegradation of organic compounds in water
by Krzysztof Brodzik; Jerzy Walendziewski; Marek Stolarski; (pp. 130-133).
The application of photocatalytic processes for the decontamination treatment of polluted water has inspired very extensive studies. Titanium dioxide with its large band gap energy and appropriate redox potential was found as one of the most promising semiconductors for the photodegradation of pollutants in the water as well as in gas phase. The titania-silica aerogels obtained by a simple co-hydrolysis method was applied in the photodegradation of the model organic compound. Different ageing times and heat treatment temperatures were found to influence both the activity and the textural properties of the photocatalysts. The obtained aerogels are efficient photodegradation catalysts of methylene blue and allow a removal up to 98 and 78% of the model pollutant from 20 and 500 ppm solutions, respectively.
Keywords: Photodegradation; photocatalyst; titania; silica titania; aerogels
The influence of the catalyst worktime on SO2 emission quantity from the sulfuric acid system and the catalyst waste material
by Piotr Grzesiak; Marcin Grobela; Rafał Motała; (pp. 134-137).
The catalytic process of SO2 to SO3 oxidation is the main step of sulfuric (VI) acid formation. The sustained catalyst operating due to its structural and textural modifications could disturb the process course. This paper includes the influence of the vanadic catalyst worktime on SO2 emission and the expected amount of the obtained waste material of the inactivated catalyst.
Keywords: vanadic catalyst; inactivation; SO2 emission; industrial waste material
Industrial wastewater treatment by means of membrane techniques
by Maria Tomaszewska; (pp. 138-142).
The importance of membrane processes in wastewater treatment is continuously growing. Membranes can be used for the separation of liquids, dissolved or suspended solids or solutes in the colloid form. The main features of membrane processes application for the treatment of spent solutions are possibilities of removal or recovery of valuable or harmful components as well as the possibility of closing water systems what reduce fresh water consumption. Very often the use of membrane processes allow to purify wastewater to a degree difficult to achieve by conventional techniques. The possibility of an application of pressure driven techniques such as ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) for oily wastewater treatment, has been presented. The studies on the two-stage treatment of bilge water combining UF and RO or NF have demonstrated a high effectiveness of purification. NF could also be applied to recover glycols from spent coolant liquids. The utilization of membrane distillation for saline wastewater concentration or for the treatment of spent metal pickling solutions was demonstrated.
The potential application of a hybrid process combining photocatalytic degradation of organic matter with membrane separation for the treatment of wastewaters from textile industry has been shown.
Keywords: membrane techniques; wastewater treatment; industrial wastewater
Selection of cutting and washing fluids as a method of waste minimization
by Agnieszka Rymarczyk; Krystyna Mędrzycka; Renata Tomczak-Wandze; (pp. 143-146).
The results of the corrosion test for washing and cutting fluids used in the process of gear-shafts production are presented. The test has been performed according to the DIN 51360-2 (Ford-test) and the PN-92/M-55789 procedures. Three cutting fluids and three washing fluids were chosen and their solutions in tap water (used in practice in the company) were investigated. On the basis of the obtained results it has been stated that the lower the fluid concentration, the stronger corrosion is developed. The concentrations recommended by the producer in the case of cutting fluids are properly chosen. For washing fluids two regions of concentration have been evaluated. The concentration recommended for rinsing is too low for protection against corrosion, while higher concentrations, for the washing process, are properly chosen, and corrosion did not occur.
Keywords: corrosion; cutting fluids
Vegetable oils derivatives as the modifiers of the lubricating properties of water
by Marian Włodzimierz Sułek; Witold Sas; Jan Przondo; (pp. 147-150).
Water has been used as a lubricating medium in a number of applications in tribology. Its insufficient lubricating properties are modified by appropriate additives. The aim of the tribological studies presented in this paper is an application of a mixture containing triglyceride ethoxylates and partial glycerides as well as esters and a block copolymer as additives. All the components are commercially available and relatively cheap. In order to examine the aqueous solutions, two kinds of tests were carried out on a four-ball apparatus: at the fixed load - measurements of the friction coefficient and wear as a function of time and seizure tests which made it possible to determine the scuffing load (Pt), the seizure load (Poz) and the limiting pressure of seizure (poz). Changes in the quantities measured were analyzed as a function of concentrations ranging from 0.001% to 100%. In the fixed load tests the coefficient of friction decreased almost eight-fold, reaching the lowest value of 0.06 at above 0.1% concentration of the additive. Wear decreased over 3.5-fold. In the seizure tests a relatively high efficiency of the additive package was observed at the concentration of the order of the thousandth part of one percent. The compositions reached the maximum anti-seizure capacity at the concentrations of 4 and 10%. It is particularly interesting to note that the stability of the lubricating film being formed was characterized by the scuffing load. The maximum value of Pt was about 4kN high. Summing up, on the basis of the results obtained it may be concluded that the choice of package additives was correct and it effectively modified the lubricating properties of water.
Keywords: Ecological cutting fluids; motion resistance; wear; anti-seizure properties
The risk scale estimation of the agricultural environment pollution by heavy metals using the sequential extraction method
by Janusz Rosada; Joanna Grzesiak; Grzegorz Schroeder; (pp. 151-154).
From among various industrial contaminants which can pollute agricultural environment, heavy metals having the capacity of bioaccumulation deserve special attention. The total composition analysis of the heavy metals content in the polluted soils does not provide enough data about their accessibility to the crops cultivated on these soils. It is very important to have the information about the forms in which the examined element exists, because it decides about its mobility and toxicity for the environment. Using the sequential chemical extraction method of Zeien and Brümmer the fractions of Cu, Pb, Zn, Cd and As in the soils influenced by emissions from the Copper Smelter GŁOGÓW, were investigated. The aim of these investigations was to determine the availability assessment of the mentioned elements to the crops cultivated in this region.
Keywords: copper smelter; heavy metals; soil; pollution; sequential chemical extraction method