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1

Establishment of constitutive model and dynamic parameter analysis of rubber conveyor belt

Chen Hongyue, Liu Siyuan

Journal of Theoretical and Applied Mechanics

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2023

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Vol. 61 nr 2

365--378

EN

A rubber conveyor belt is an essential piece of equipment in coal mine transportation. Its current motion and performance are directly affected by dynamic parameters. In this paper, a constitutive model has been established to study a rubber conveyor belt in order to analyze its dynamic characteristics. The covered rubber was considered as a classical solid model. The wire rope core was used as a Kelvin model, and a generalized constitutive mathematical model was established. Using Matlab, compariso of the fitting curve and the experimental curve was carried out to ensure reliability in an appropriate way. Meanwhile, the influence of different factors on dynamic parameters of rubber conveyor belts was also discussed by controlling the loading frequency and amplitude as well as external temperature. Finally, the experiment with the fitting curve was compared and verified, and the research results can provide a reference for this engineering field.

2

Thermal properties of modified single-base propellants

Gańczyk-Specjalska Katarzyna, Cieślak Katarzyna, Zembrzucka Katarzyna

Materiały Wysokoenergetyczne

|

2021

|

T. 13

59--69

EN

The paper outlines the influence of various plasticizers (centralit I, nitroglycerine and diethylene glycol dinitrate) on the thermal properties of single-base propellants. Simultaneous differential scanning calorimetry and thermogravimetric analysis were used for this research. The basic physicochemical properties of the tested propellants were also determined, such as: geometric parameters, density and dynamic vivacity. Modifiers of the combustible layer were introduced into the pores of the nitrocellulose, based on the geometrical parameters of the propellants. The entire combustible powder layer was modified when the process was carried out in ethanol. All the modifiers used influenced the dependence of dynamic vivacity on the conversion degree. The use of 12.6 phr (part per 100 parts of propellant) of liquid nitroesters or ethanol as a dispersing medium causes a change in the propellants decomposition mechanism, which is related to a change in the structure of nitrocellulose.

PL

W pracy przedstawiono wpływ różnych plastyfikatorów (centralit I, nitrogliceryna i diazotan glikolu dietylenowego) na właściwości termiczne prochów jednobazowych. Do badań wykorzystano jednoczesną analizę skaningowej kalorymetrii różnicowej i termograwimetryczną. Określono również podstawowe właściwości fizykochemiczne badanych prochów takie jak: parametry geometryczne, gęstość i żywość dynamiczną. Modyfikatory warstwy palnej zostały wprowadzone do porów nitrocelulozy, co stwierdzono na podstawie parametrów geometrycznych prochów. Przeprowadzenie procesu w etanolu powoduje zmodyfikowanie całej warstwy palnej prochu. Wszystkie zastosowane modyfikatory wpłynęły na zależność żywości dynamicznej od stopnia przereagowania. Zastosowanie 12,6 phr (część na 100 części paliwa) ciekłych nitroestrów lub etanolu jako medium rozpraszającego powoduje zmianę mechanizmu rozkładu prochów, co związane jest ze zmianą struktury nitrocelulozy.

3

Effects of Metal Oxides on the Thermal Decomposition Kinetics and Mechanisms of HAN/PVA Based Propellants

Hu Song-qi, Liu Xue-li, Liu Lin-Lin, Kang Bo, Zhang Yan

Central European Journal of Energetic Materials

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2021

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Vol. 18, no. 3

322-338

EN

The thermal decomposition processes of HAN/PVA-based propellants have been investigated using a simultaneous thermogravimetric analysis (TGA) – differential scanning calorimetry (DSC), coupled with Fourier-Transform Infrared Spectroscopy (FTIR) and Mass Spectrometry (MS) system. The activation energy (Ea), pre-exponential factor A and reaction mechanism function f(α) of the decomposition processes have been determined by non-isothermal and Malek methods. The results showed that the decomposition process of an HAN/PVA sample occurs mainly in the temperature range 202.2~220.1 °C, with a mass loss, heat release and Ea of about 84.8%, 1474.18 and 88.76 kJ·mol–1, respectively. Of the seven metal oxides studied as catalysts, Al2O3, V2O5 and Fe2O3 have significant catalytic effects on an HAN/PVA-based propellant, in lowering the decomposition temperature, with Ea changing from 88.8 to 83.7, 85.6 and 113.6 kJ·mol–1, respectively. The f(α) of both HAN/PVA and HAN/PVA/Al2O3 samples can be expressed as f(α) = (1 – α)2, whereas f(α) = α or f(α) = α/2 fit well for the HAN/PVA/V2O5 and HAN/PVA/Fe2O3 samples.

4

Temperature influence on the electrode process in the presence of 6-thioguanine and surfactants

Nosal-Wiercińska Agnieszka, Kaliszczak Waldemar, Martyna Marlena, Szabelska Anna, Gołębiowska Beata, Wiśniewska Małgorzata

Physicochemical Problems of Mineral Processing

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2020

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Vol. 56, iss. 6

14--21

EN

The measurements concerning the process of the electroreduction of Bi(III) ions in the presence of 6–thioguanine (6TG) and Triton X-100 as well as Tween 80 in the 2 mol·dm-3 chlorates(VII) demonstrate a dependence of the process rate on temperature. The applied electrochemical techniques (DC polarography, cyclic and SWV voltammetry) allowed to determine the kinetic and thermodynamic parameters as well as their correlation with changes in kinetics of the electrode process. The catalytic activity of 6TG was confirmed by the decrease of overall enthalpies of activation. Different values of ∆𝐻# and ∆𝑆° for Bi(III) electroreduction in the presence of 6–thioguanine as well as Triton X-100 and Tween 80 suggest changes in kinetics of the electrode process towards inhibition.

5

Efficient nitrate adsorption from water by aluminum powder. Kinetic, equilibrium and influence of anion competition studies

Fakhri Y., Kakavandi B., Safaei Z., Asadi A., Mohseni S. M., Golestanifar H.

Environment Protection Engineering

|

2018

|

Vol. 44, nr 3

19--31

EN

The feasibility of aluminum powder (with particle size of 75–150 μm) for nitrate removal from aqueous solutions has been investigated. Adsorption was examined in function of initial nitrate concentration, contact time, pH and influence of other interfering anions. Maximum nitrate removal occurred at equilibrium pH of 10. The kinetics of adsorption of nitrate ions was discussed based on three kinetic models, namely: the pseudo-first order, the pseudo-second order and the intraparticle diffusion model. The experimental data fitted the pseudo-second order kinetic model very well; the rate constant was 4x10–4 g/ (mg·min) at the concentration of NO3- of 100 mg/dm3. The adsorption data followed both Langmuir (R2 = 0.808) and Freundlich (R2 = 0.865) isotherms probably due to the real heterogeneous nature of the surface sites involved in the nitrate uptake. The maximum sorption capacity of aluminum powder for nitrate adsorption was found to be ca. 45.2 mg/g at room temperature. The results indicate that aluminum powder is an interesting alternative for nitrate removal from the water.

6

Adsorption and inhibitive properties of methanol extract of Eeuphorbia Heterophylla for the corrosion of copper in 0.5 M nitric acid solutions

Fouda A. S., Elmorsi M. A., Abou-Elmagd B. S.

Polish Journal of Chemical Technology

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2017

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Vol. 19, nr 1

95--103

EN

The adsorption and the inhibitive properties of methanol extract of Euphorbia heterophylla on copper in 0.5 M HNO3 have been studied by weight loss method at different temperatures (30-50°C), potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. Also, the surface morphology was analyzed by scanning electron microscopy (SEM). It was found that the inhibition efficiency increases with increasing extract doses and decreased with increasing temperature. The polarization data revealed that this extract acts as mixed type inhibitor. The adsorption process was more favored at lower temperatures with larger negative standard free energy. The extract was adsorbed physically on the copper surface followed Frumkin isotherm.

7

Aktywność biologiczna ustabilizowanej drobnej frakcji odpadów komunalnych podczas ich długotrwałej ekspozycji na warunki atmosferyczne

Stegenta S., Kałdun B., Sobieraj K., Białowiec A.

Ochrona Środowiska

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2017

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Vol. 39, nr 4

31--40

EN

One of the accepted technological solutions used in mechanical-biological waste treatment is screening of stabilized undersize fraction (code 190599) through a sieve to separate two fractions with the grain size of 20–80 mm (code 190599) and < 20 mm (code 190503 – compost that fails to comply with requirements). Fraction < 20 mm may be used for landfill remediation as a landfill cover. However, its long-lasting exposure to atmospheric conditions may have an adverse effect on microbial respiration. This phenomenon was verified in the field study and lysimetric experiment aimed to simulate landfill conditions, which lasted 10 weeks (both in winter and summer season). The lysimeters contained stabilized fine fraction, while half of the containers were additionally filled with water to reflect adverse conditions at a landfill site resulting from stagnant pond formation. Both the direct measurements and model studies confirmed a significant increase of microbial activity in hydrated waste samples. During remediation works special care should be taken to avoid stagnant pond formation on the landfill top because of the unfavourable pond conditions that facilitate decomposition of organic matter in the stabilized fine fraction. Therefore, biological stabilization of municipal solid waste should be planned to effectively lower organic matter content and minimize moisture of the under-size fraction. It was demonstrated that activity at the level of AT4 < 2 mgO2/g allowed for safe use of the stabilized fine fraction in restoration process of closed landfills.

PL

Jednym z akceptowanych rozwiązań technologicznych mechaniczno-biologicznego przetwarzania odpadów komunalnych jest wielkościowa waloryzacja ustabilizowanej frakcji podsitowej o kodzie 190599, przez jej przesianie na sicie w celu wydzielenia dwóch frakcji – o uziarnieniu 20÷80 mm (o kodzie 190599) oraz <20 mm (o kodzie 190503 – kompost nieodpowiadający wymaganiom). Frakcja <20 mm może być wykorzystana do rekultywacji składowisk odpadów, jednakże podczas jej długotrwałej ekspozycji na warunki atmosferyczne możliwe są niekorzystne zmiany aktywności oddechowej mikroorganizmów obecnych w tej frakcji. Zjawisko to zweryfikowano w doświadczeniu polowym oraz eksperymencie lizymetrycznym, trwającym 10 tygodni (w sezonie zimowym i letnim), mającym symulować warunki panujące na składowisku. Lizymetry zawierały frakcję podsitową odpadów z procesu stabilizacji, przy czym połowę z nich wypełniono wodą, aby odzwierciedlić niekorzystne warunki w postaci zastoisk wody na powierzchni składowiska. Zarówno bezpośrednie pomiary aktywności oddechowej drobnoustrojów, jak i badania modelowe potwierdziły znacznie większą aktywność mikroorganizmów w nawodnionych próbkach odpadów. Podczas rekultywacji składowiska odpadów należy więc unikać powstawania zastoisk wody na wierzchowinie, ponieważ powstające w nich warunki wpływają na przyspieszenie rozkładu związków organicznych pozostałych w stabilizacie. Biologiczna stabilizacja odpadów komunalnych powinna zatem dążyć do skutecznego zmniejszenia zawartości związków organicznych oraz do ograniczenia wilgotności uzyskanego stabilizatu. Potwierdzono, że stosowanie materiału o aktywności AT4<2 mgO2/g pozwala na bezpiecznie użycie frakcji podsitowej do rekultywacji zamkniętych składowisk.

8

Sorption kinetics of Cd(II) ions on fermented grape marc

Grudić V., Bošković I., Jaćimović Z.

Environment Protection Engineering

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2017

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Vol. 43, nr 4

243--252

EN

The sorption kinetics of Cd(II) ions on the biosorbent which is waste in wine production has been investigated. The sorption process took place relatively quickly, enabling one to achieve equilibrium within a period of 15–20 min only, depending on initial concentration of the sorbate. Kinetic models of pseudo-first and pseudo-second order, model of diffusion in a fluid film and Weber’s and Morris’ intraparticle diffusion model were used to describe the experimental results. The pseudo-second order kinetic model described the sorption process with a high correlation coefficient (R2 = 0.998) better than the other kinetic models. The mass transfer coefficient decreases upon increasing the initial concentration of the solution, which can be explained by the fact that the mechanism of binding of Cd(II) ions to the surface of the sorbent is ion exchange followed by discharge of exchangeable cations from the surface. Characteristic constants in the Weber–Morris model increase upon increasing the initial concentration of the solution.

9

Coal Char Kinetics of Oxidation and Gasification Reactions

Lewtak R., Hercog J.

Chemical and Process Engineering

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2017

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Vol. 38, nr 1

135--145

EN

Experimental investigations and numerical simulations have been conducted in this study to derive and test the values of kinetic parameters describing oxidation and gasification reactions between char carbon and O2 and CO2 occurring at standard air and oxy-fuel combustion conditions. Experiments were carried out in an electrically heated drop-tube at heating rates comparable to fullscale pulverized fuel combustion chambers. Values of the kinetic parameters, obtained by minimization of the difference between the experimental and modeled values of char burnout, have been derived and CFD simulations reproducing the experimental conditions of the drop tube furnace confirmed proper agreement between numerical and experimental char burnout.

10

Dobór modelu i wyznaczanie parametrów kinetycznych aktywności oddechowej odpadów w trakcie procesu tlenowej biostabilizacji frakcji podsitowej odpadów komunalnych

Stegenta S., Kałdun B., Białowiec A.

Rocznik Ochrona Środowiska

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2016

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Tom 18, cz. 1

800--814

PL

Końcowym produktem procesu biostabizacji jest stabilizat, czyli odpad stały, który po biologicznym przetworzeniu, spełnia wymogi rozporządzenia Ministra Środowiska w sprawie mechaniczno-biologicznego przetwarzania zmieszanych odpadów komunalnych (Dz.U. z 2012, poz. 1052). Aby określić stopień stabilizacji odpadu, (w praktyce stopień dekompozycji materii organicznej), stosuje się wskaźniki określające aktywność biologiczną. W polskim prawie przyjęto iż jednym z parametrów wskazującym na stopień stabilizacji odpadu jest aktywność respirometryczna AT4 (rozporządzenie Dz.U. z 2012, poz. 1052). Zużycie tlenu w trakcie procesu rozkładu materii organicznej zawartej w odpadach może mieć charakter równania 0-ego lub 1-ego rzędu. Odpowiednie dopasowanie modelu do reakcji jest kluczowe aby wyznaczyć poprawnie parametry kinetyczne reakcji. Z tego względu wykonano badania, których celem było sprawdzenie stopnia dopasowania 2 modeli matematycznych do krzywej zużycia tlenu dla próbek odpadów będących w różnych fazach procesu biostabilizacji oraz zaproponowanie modelu o najwyższej użyteczności. Eksperyment przeprowadzono w skali technicznej, w instalacji do biostabilizacji odpadów, gdzie stosowany jest biopreparat bakteryjny w celu obniżenia uciążliwości odorowej. Badania wykonano w dwóch wariantach z wykorzystaniem partii odpadów zaszczepionych biopreparatem i odpadów niezaszczepionych. W trakcie procesu biostabilizacji pobierano próbki odpadów w interwałach cotygodniowych. Po pobraniu, próbki odpadów transportowane były do laboratorium, gdzie tego samego dnia rozpoczynano pomiary aktywności oddechowej metodą OxiTop®. Przeprowadzone badania wykazały, iż niezależnie od czasu trwania procesu oraz zastosowania lub niezastosowania inokulacji biopreparatem modelem najlepiej opisującym kinetykę zużycia tlenu jest model I-ego rzędu. Wykazano także, iż dodatek biopreparatu spowodował podwyższenie aktywności oddechowej odpadów w pierwszych 3 tygodniach procesu biostabilizacji.

EN

Final product of waste biostabilization process is stabilized organic fraction. It is a solid waste, after biological process, which perform requirements of actual law regulation (Dz.U. z 2012, poz. 1052). To determine stabilization of waste degree (in practice decomposition of organic matter degree), used indicator which define biological activity. The Polish regulations adopted that one of the parameters indicating the degree of stabilization of waste, is the respiration activity index AT4. Oxygen consumption during organic matter decomposition process, could have 0-order or 1st-orderreaction character. Suitable fit of the model to react is crucial, to correctly determine the kinetic parameters of the reaction. For this reason, experiments, which purposes were to: examine the relevance of two mathematical models, to the oxygen consumption curves, for waste samples that are in various stages of the biostabilization process, and to propose a model of the highest utility, were performed. The study was conducted on an industrial scale, in operating conditions biostabilization plant, where biostimulator was used to reduce odors. Two variants, first using waste with biostimulator and second without biostimulator were tested. During the biostabilization process, samples were collected in weekly intervals. Samples of waste were transported to the laboratory, where respiratory activity was measured. Research has shown that independently of the duration of the process, and the inoculation or without -inoculation of biostimulator, the best fitting model which describes the kinetics of oxygen consumption is the first order reaction model. It was also shown that the addition of biostimulator increase respiration activity of waste during first 3 weeks of biostabilization process.

11

Treatment of milk wastewater using up-flow anaerobic packed bed reactor

Bhuyar K. D., Suke S. G., Dawande S. D.

Polish Journal of Chemical Technology

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2015

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Vol. 17, nr 2

84--88

EN

An up-flow anaerobic packed bed (UAPB) bioreactor has been designed on a laboratory-scale and used for treatment of domestic milk wastewater (MWW). The UAPB bioreactor was operated under mesophilic temperature (37-45°C) and reactor performance evaluated at various organic loading rates of MWW effluent at hydraulic retention times (HRT) of 1, 2, and 3 d based on the removal of organic matter COD, BOD, SS, pH changes and biogas production. The kinetic parameters were estimated using the experimental data to develop a reactor model. Empirical relations were generated for the characteristics like COD, BOD, and SS using modeling equations. This study proved that the UAPB reactor performance is excellent for treating domestic MWW and easily biodegradable dairy wastewater influent. Hence, this system can operate at low costs, making it suited for use in the developing countries and rural areas.

12

Badanie procesu sieciowania jednoskładnikowych żywic epoksydowych ASSET®

Pilawka R., Mąka H., Czulak A.

Przetwórstwo Tworzyw

|

2014

|

[R.] 20, nr 6 (162)

517--521

PL

Przedstawiono wyniki badań procesu sieciowania dwóch komercyjnych jednoskładnikowych żywic epoksydowych oferowanych przez firmę „New Era Materials" o różnej reaktywności. Zmiany zachodzące podczas tego procesu obserwowano śledząc zmiany ciepła właściwego za pomocą różnicowej kalorymetrii skaningowej (DSC) oraz lepkości (reometr naprężeniowy ARES) co pozwoliło określić parametry kinetyczne i dopasować modele kinetyczne autokatalitycznego procesu sieciowania zgodnie z równaniami Sesták-Berggrena i Kamala. Dane uzyskane metodą DSC jak i z krzywych reologicznych umożliwiają wyznaczenie parametrów charakterystycznych oraz kinetycznych procesu sieciowania: stałych szybkości reakcji oraz globalnych rzędów reakcji. Ponadto pozwalają na optymalizację procesu sieciowania poprzez dobór temperatury tego procesu, odpowiednio: dla ASSET®01 temperatury 120°C oraz ASSET®02 170°C.

EN

The results of curing process of two commercial one-component epoxy resin exhibiting various reactivity (product by "New Era Materials", Poland), has been presented. Using differential scanning calorimetry and stress rheometry ARES (viscosity changes) allowed to determine kinetic parameters of curing process, such as: rate constant and global reaction orders. Subsequently, kinetic models of autocatalytic curing process were fitted (Sesták-Berggren and Kamal). Moreover, optimal temperature values crosslinking process, i.e. 120°C and 170°C for ASSET®01 and ASSET®02, respectively has been determined.

13

Badania kinetyki zgazowania węgla kamiennego parą wodną w warunkach podwyższonego ciśnienia

Porada S., Rozwadowski A.

Przemysł Chemiczny

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2014

|

T. 93, nr 3

384-387

PL

Zbadano szybkość wydzielania się gazowych produktów zgazowania węgla kamiennego parą wodną pod ciśnieniem 2 MPa. Obliczono parametry kinetyczne reakcji tworzenia się wodoru i tlenku węgla(II), wydajności głównych produktów gazowych procesu oraz stopień konwersji pierwiastka C w węglu.

EN

Bituminous coal was gasified with steam at 800–1000°C and under 2 MPa to study the reaction course. Kinetic parameters of H₂ and CO formation, yield of the gas products and the degree of C conversion during the gasification of coal were calcd.

14

Determination of kinetic parameters of coal pyrolysis to simulate the process of underground coal gasification (UCG)

Urych B.

Journal of Sustainable Mining

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2014

|

Vol. 13, iss. 1

3--9

EN

Purpose The aim of the research presented in this paper was to determine the values of the kinetic parameters of coal pyrolysis from two areas of the planned experiment, UCG, i.e. the Barbara Experimental Mine of the Central Mining Institute and the Wieczorek Mine. Methods The thermal decomposition of coal analysis used the thermogravimetric technique. The test was carried out in a temperature range of 298-1173 K in a nitrogen atmosphere for three fixed heating rates, β – 5, 10, and 15 K/min. A selection of sample heating rates of coal and reaction environments were designed to reflect the conditions seen during the process of underground coal gasification. The kinetic parameters were determined by using modified Coats-Redfern, Kissinger and Mianowski-Radko methods. Results The values of the activation energy, E, and the pre-exponential factor, A, were determined for a given model of the first order decomposition reaction of coal. The study successfully compared kinetic parameters of the tested coals. Practical implications Designated kinetic parameters may be used to model the process of pyrolysis and – as preliminary data – for installation design of pilot underground coal gasification. Originality/ value The devolatilization of a homogenous lump of coal is a complex issue. Currently, the CFD technique (Computational Fluid Dynamics) is commonly used for the multi-dimensional and multiphase phenomena modelling. The mathematical models, describing the kinetics of the decomposition of coal, proposed in the article can, therefore, be an integral part of models based on numerical fluid mechanics.

15

A numerical approach to predict sulphur dioxide emissions during switchgrass combustion

Peters B., Smuła-Ostaszewska J.

Chemical and Process Engineering

|

2013

|

Vol. 34, nr 1

121--137

EN

The demand for a net reduction of carbon dioxide and restrictions on energy efficiency make thermal conversion of biomass a very attractive alternative for energy production. However, sulphur dioxide emissions are of major environmental concern and may lead to an increased corrosion rate of boilers in the absence of sulfatation reactions. Therefore, the objective of the present study is to evaluate the kinetics of formation of sulphur dioxide during switchgrass combustion. Experimental data that records the combustion process and the emission formation versus time, carried out by the National Renewable Energy Institute in Colorado (US), was used to evaluate the kinetic data. The combustion of switchgrass is described sufficiently accurate by the Discrete Particle Method (DPM). It predicts all major processes such as heating-up, pyrolysis, combustion of switchgrass by solving the differential conservation equations for mass and energy. The formation reactions of sulphur dioxide are approximated by an Arrhenius-like expression including a pre-exponential factor and an activation energy. Thus, the results predicted by the Discrete Particle Method were compared to measurements and the kinetic parameters were subsequently corrected by the least square method until the deviation between measurements and predictions was minimised. The determined kinetic data yielded good agreement between experimental data and predictions.

16

Kinetyka krystalizacji bezwodnego siarczanu sodu i przenoszenie skali procesu

Warmuziński K., Jaschik J., Jaschik M.

Przemysł Chemiczny

|

2012

|

T. 91, nr 7

1445-1448

PL

Przedstawiono wyniki badań doświadczalnych kinetyki krystalizacji wyparnej bezwodnego siarczanu sodu. Badania prowadzono z zastosowaniem trzech geometrycznie podobnych krystalizatorów o pojemności: 0,2, 1 i 5 dm³. Wyznaczano liniową szybkość wzrostu kryształów i efektywną szybkość zarodkowania. Opracowano korelacje potęgowe określające zależność parametrów kinetycznych krystalizacji od przesycenia, gęstości zawiesiny i intensywności mieszania. Określono wpływ wielkości krystalizatora na rozmiar otrzymywanych kryształów.

EN

Anhyd. Na₂SO₄ was crystd. from its aq. soln. in mixed reactors (0.2–5 L) under vacuum evapn. (430 hPa, 80°C) at varying residence time (1135–4012 s), evapn. rate (0.980– 35.433 g/min), suspension d. (22.13–129.63 kg/m³) and stirrer speed (450–1950 rpm) to study the process kinetics and to det. the linear crystal growth and effective nucleation rates. The correlations between kinetic parameters of the crystn. and supersatn., magma d. and mixing intensity were derived from the expt. data. The detd. order of crystal growth rate was about 1.4 for all crystallizers. The exponents in the equations describing the effect of the growth rate, magma d. and stirrer speed on the nucleation rate were 0.85, 1 and 2.5, resp. The scale-up principles to achieve the same median crystal size were developed. Over the range studied, a modest increase in median crystal size with increasing vol. of the crystallizer was obsd. for a const. sp. power input.

17

Maturity of Menilite Shales from Polish Outer Carpathians based on vitrinite reflectance and Rock-Eval pyrolysis data

Waliczek M., Więcław D.

Geology, Geophysics and Environment

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2012

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Vol. 38, no. 4

551--552

EN

Maturity of organic matter is one of the most important parameters characterizing the source rock. The maturation process depends on organic matter properties (kinetic parameters of kerogen) and burial history (temperature and time). The vitrinite reflectance measurements and Rock-Eval pyrolysis are widely used to characterize the maturity of organic matter occurring in the source rock. The purpose of the present study is to determine the thermal maturity of organic material present in Oligocene Menilite Shales from Polish Outer Carpathians based on vitrinite reflectance and Rock-Eval pyrolysis data. These organic-rich rocks are considered as a main source of oils accumulated in Outer Carpathian sequence (Kotarba & Kołtun 2006). Analysis has been performed on eleven claystone samples collected from outcrops of Dukla Unit. Part of them was taken in tectonic windows of Dukla Unit within Magura Unit: Świątkowa, Grybów and Ropa. Microscopic analysis of organic matter in reflected white light and fluorescence has been carried out for each sample. Macerals have been characterized and classified according to their optical properties and morphology. Rock-Eval pyrolysis has been used to determine: a) the amount of free hydrocarbons present in the sample (S1), b) the amount of residual hydrocarbons generated during pyrolysis of organic matter (S2), c) the amount of CO2 generated during pyrolysis of organic matter (S3), d) the temperature of maximum of S2 peak (Tmax), e) the amount of CO2 received during oxidation of residual, carbon (S4). Based on received parameters the source-rock indices were calculated: a) total organic carbon {TOC = [0.83(S1 + S2) + S4]/10}, b) hydrogen index (HI = 100S2/TOC), c) oxygen index (0I = lOOS3/TOC), d) production index [PI = S1/(S1 + S2)]. Reflected white light optical research methods of organic matter enable to find in each studied sample macerals from vitrinite and inertynite group. Two generation of vitrinite has been noticed during the studies. The first type has been represented by vitrinite in situ. The second one has been recognized as a dark, gelified vitrinite, filled in with some mineral or organic association. Inertinite macerals have been represented mostly by detritus material. Macerals from liptynite group have been recognized using fluorescent microscopy. These macerals occur commonly in each sample, what could indicate domination of oil-prone kerogen Type II. The vitrinite reflectance measurements have been carried out for both types of vitrinite. The random reflectance Rr of organic matter varies between 0.45% and 0.9% for first type of vitrinite and from 0.2% to 0.66% for the second one. Measurements of reflectance of vitrinite in situ have indicated that organic matter has reached the maturation stages of hydrocarbon generation corresponding to oil window phase. Values of selected parameters and indices received from Rock-Eval pyrolysis vary: TOC from 1.73 wt. % to 6.4 wt. % (median 4.3 wt. %), HI from 197 mg HC/g TOC to 681 mg HC/g TOC (median 342 mg HC/g TOC) and Tmax from 421°C to 456°C (median 440°C). These data indicate that analysed samples are rich in organic matter, predominantly of oil-prone kerogen Type II. Rock-Eval Tmax temperature values correlate well with reflectance of organic matter for vitrinite in situ; for dark vitrinite this correlation is not visible.

18

Badania kinetyki spalania komunalnych osadów ściekowych w atmosferze wzbogaconej tlenem

Bień J., Gandor M.

Inżynieria i Ochrona Środowiska

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2011

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T. 14, nr 3

233-244

PL

Przedstawiono wyniki badań kinetyki spalania komunalnych osadów ściekowych w modyfikowanej atmosferze, realizowanych z zastosowaniem metodyki opartej na termograwimetrii. Badania termograwimetryczne przeprowadzono jako dynamiczne (nieizotermiczne) i statyczne (quasi-izotermiczne). Badania prowadzono w pięciu atmosferach gazowych, przygotowanych na bazie tlenu oraz ditlenku węgla. Udział tlenu w mieszance stanowił odpowiednio: 20, 40, 60, 80 oraz 100% obj. Eksperyment prowadzony był w zakresie temperatur 873 ÷ 1273 K. Otrzymane doświadczalnie wyniki, w oparciu o przyjęty model kurczącego się rdzenia (SCM), pozwoliły wyznaczyć podstawowe parametry kinetyczne: rząd reakcji n, współczynnik przedeksponencjalny K0, energię aktywacji Ea, oraz przeprowadzić szacowanie reaktywności osadów w szerokim zakresie parametrów. Wykazano przy tym znaczący wpływ stężenia tlenu na pozorną szybkość reakcji, w przeciwieństwie do wpływu temperatury, który okazał się nieznaczny. Zaobserwowano znaczący wpływ współczynnika szybkości nagrzewania na termiczną dekompozycję osadów ściekowych w tej samej atmosferze. Maksymalną szybkość ubytku masy próbki odnotowano przy największym współczynniku nagrzewu. Nie zaobserwowano natomiast znaczącego przesunięcia temperaturowego w kierunku wyższych wartości temperatur wraz ze wzrostem współczynnika nagrzewu, co ma miejsce przy wzroście stężenia tlenu.

EN

The paper presents the results of combustion kinetics of municipal sewage sludge in a modified atmospheres. The studies were investigated by a thermogravimetric analysis. Thermogravimetric tests were carried out as a dynamic (non-isothermal) and static (quasi-isothermal). Tests was conducted in five gaseous atmospheres prepared from oxygen and carbon dioxide. Participation of oxygen in the mixture were as following: 20, 40, 60, 80 and 100% vol. The experiment was conducted in the temperature range 873 ÷ 1273 K. Experimentally obtained results based on the model of the shrinking core (SCM), helped establish the basic kinetic parameters such as: reaction order n, factor K0 and activation energy Ea. The values of activation energy Ea and K0 were, respectively: 45.57 kJ/mol (10.9 kcal/mol) and 0.0127 mg/m2sPa. Values of activation energy Ea of sewage sludge combustion in O2/CO2 atmosphere in the temperature range 873 ÷ 1273 K show that the limiting factor of combustion is the diffusion of oxygen, therefore the combustion reaction takes place here only in the outer layer of the unreacted core. The experimental studies in a wide range of process parameters such as temperature and partial pressure of oxygen helped to create an array of apparent reaction rates as a function of temperature and oxygen concentration in the gas reaction. It has been shown the significant effect of oxygen on the apparent reaction rate, in contrast to the effect of temperature, which was insignificant. The impact of the heating rate on sludge combustion was also investigated. For this purpose, sludge was heated from ambient temperature to a 1000°C at a four different heating rates 10, 20 and 40 K min-1 in the ° variable O2/CO2 atmosphere. With increasing heating rates TG curves get closer and closer to each other. Percentage weight loss was about 65.26% at a heating rate 10 K min-1. At 40 K min-1 percentage loss was 65.97%. From that it could be stated the the heating rate play no role in the loss of material mass. With increasing heating rate is not observed a substantial shift of the peak temperature of the sample weight loss.

19

Stabilność operacyjna tyrozynazy w reaktorze okresowym w obecności rozpuszczalników organicznych

Zynek K., Tomaszewska A., Bryjak J.

Inżynieria i Aparatura Chemiczna

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2010

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Nr 1

121-122

PL

Głównym problemem enzymatycznego utleniania związków fenolowych jest tworzenie wolnych rodników, które są traktowano jako główna przyczyna in-aktywacji samobójczej ryrozynazy. Do badań wykorzystano 4 rozpuszczalniki organiczne mieszające się z wodą i na podstawie analizy kinetyki inaktywacji enzymu w obecności różnych stężeń ko-rozpuszczalników stwierdzono, że etanol i dimetyloformamid, w stężeniu 10%, mogą być zastosowane w bio-transformacjach jako potencjalne stabilizatory wolnych rodników.

EN

Four water miscible organic solvents of different concentrations were tested as potential co-solvents for phenolic compounds conversion with tyrosinase. A main problem in biotransformations with tyrosinase is its suicide inac- tivation that can be caused by free radicals formed by the enzyme during reaction. On basis of inactivation kinetics in the presence of co-solvents it was stated that ethanol and dimethylformamide in 10% concentration could be used as potential free radicals stabilizers.

20

Estimation of hydrous-pyrolysis kinetic parameters for oil generation from Baltic Cambrian and Tremadocian source rocks with Type-II kerogen

Więcław D., Kotarba M. J., Lewan M. D.

Geological Quarterly

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2010

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Vol. 54, No 2

217-226

EN

Determining kinetic parameters for oil generation from a source rock by hydrous pyrolysis requires a considerable amount of sample (kilograms) and laboratory time (several weeks). In an effort to circumvent these requirements, hydrous-pyrolysis (HP) kinetic parameters for oil generation from Upper Cambrian and Tremadocian source rocks of the Baltic region are estimated by two methods: (1) organic sulfur content in kerogen and (2) HP experiments conducted at 330 and 355°C for 72 h. Estimates for the Upper Cambrian source rocks based on organic sulfur contents gave activation energies from 47 to 56 kcal/mole and frequency factors from 1.156 ' 1025>/sup> to 1.078 ' 1028 m.y.-1 . Tremadocian source rocks based on organic sulfur content gave estimated activation energies from 60 to 62 kcal/mole and frequency factors from 1.790 ' 1029 to 1.104 ' 1030 m.y.-1 . The estimates for the Tremadocian source rocks were less affected by thermal maturation because their low kerogen S/(S + C) mole fractions (< 0.018) remained essentially constant. Conversely, the higher kerogen S/(S + C) mole fractions (>>gt; 0.018) of the Upper Cambrian source rocks decreased with thermal maturation and resulted in overestimation of the kinetic parameters. The second method was designed to estimate kinetic parameters based on two HP experiments. The assumption that the maximum yield in calculating the rate constant at 330°C (k330°C could be determined by a second hydrous pyrolysis experiment at 355°C for 72 h proved not to be valid. Instead, a previously established relationship between Rock-Eval hydrogen index and maximum HP yield for Type-II kerogen was used to calculate k330°C from oil yields generated by the HP experiment at 330°C for 72 h assuming a first-order reaction. HP kinetic parameters were determined from relationships between k330°C and the HP kinetic parameters previously reported. These estimated HP kinetic parameters were in agreement with those obtained by the first method for immature samples, but underestimated the kinetic parameters for samples at higher thermal maturities. Applying these estimated HP kinetic parameters to geological heating rates of 1 and 10°C/m.y. indicated that the Upper Cambrian source rocks would generate oil notably earlier than the overlying Tremadocian source rocks. This was confirmed in part by available data from two neighboring boreholes in the Polish sector of the Baltic.