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EN
One of the main toxic components of post quenching salts formed in large quantities during steel hardening processes is BaCl2. This dangerous ingredient can be chemically neutralized after dissolution in water by means of reaction crystallization with solid ammonium sulphate (NH4)2SO4. The resulting size distribution of the ecologically harmless crystalline product - BaSO4 - is an important criteria deciding about its further applicability. Presence of a second component of binary quenching salt mixture (BaCl2-NaCl) in water solution, NaCl, influences the reaction-crystallization process kinetics affecting the resulting product properties. The experimental 39 input-output data vectors containing the information about the continuous reaction crystallization in BaCl2 - (NH4)2SO4 - NaCl - H2O system ([BaCl2]RM = 10-24 mass %, [NaCl]RM = 0-12 mass %, T = 305-348 K and τ = 900-9000 s) created the database for the neural network training and validation. The applicability of diversified network configurations, neuron types and training strategies were verified. An optimal network structure was used for the process modeling.
PL
Przebadano doświadczalnie wpływ stężenia kwasu L(+)-askorbinowe-go (od 30 do 50% mas.) w roztworze zasilającym i średniego czasu przebywania zawiesiny (od 900 do 3600 s) w krystalizatorze laboratoryjnym DT MSMPR na rozkład rozmiarów kryształów witaminy C otrzymywanych w sposób ciągły z roztworów wodno-etanolowych.
EN
An inftuence of L(+)-ascorbic acid (from 30 to 50 mass %) concentra-tion in feed stream and mean residence time of suspension (from 900 to 3600 s) in a iaboratory DT MSMPR crystaHizer on crystal size distribution of vitamin C produced continuously from water-ethanot so-utions was verified experimentally.
EN
Growth kinetics of vitamin C crystals during the batch mass crystallization process in L(+)-ascorbic acid - methanol - ethanol - water system was determined. The linear growth rate values were estimated on the basis of the product crystal size distributions. The kinetic model of the continuous process in a MSMPR crystallizer was adopted for the batch mode description according to Nyvlt's conception, taking the sizedependent growth (SDG) rate effects into consideration. The kinetic parameter values were determined with a Rojkowski hyperbolic SDG model. A good compatibility between the experimental product crystal population density distributions and the SDG model predictions was observed. The interpretation of the kinetic data was presented and discussed.
EN
Effect of L(+)-ascorbic acid concentration in a feeding solution ([MeOH]rm = 20 wt. %) and mean residence time of suspension in a laboratory DT MSMPR crystallizer on the product crystal size distribution as well as on the nucleation and growth rates were investigated. Kinetic parameters have been estimated based on the size-independent growth (SIG) MSMPR model. The exponent values in the equation correlating the linear growth rate and the suspension density with the secondary nucleation rate have been calculated.
PL
Zbadano zależność rozkładu rozmiarów kryształów kwasu L(+)-askorbinowego oraz szybkości ich zarodkowania i wzrostu od jego stężenia w roztworze zasilającym ([MeOH]rm = 20% mas.) oraz średniego czasu przebywania zawiesiny w krystalizatorze laboratoryjnym DT MSMPR. Do obliczeń parametrów kinetycznych procesu zastosowano model kinetyki dla krystalizatora MSMPR zakładający niezależność szybkości wzrostu kryształu od jego rozmiaru (model SIG). Wyznaczono wartości wykładników w równaniu opisującym zależność szybkości zarodkowania wtórnego od liniowej szybkości wzrostu i stężenia kryształów w zawiesinie.
EN
Addition of aliphatic alcohol improves the yield of the technical vitamin C (L(+)-ascorbic acid) purification process via batch crystallization. Simultaneous presence of two alcohols (methanol and ethanol) in the system, in respect of complex physicochemical interactions, modifies the metastable zone width more effectively than it could be achieved by adding these alcohols individually. This essentially influences batch crystallization process time, as well as the supersaturation discharge dynamics (limiting of excessive primary nucleation and agglomeration). Existence of complex, nonlinear relations in L(+)-ascorbic acid-MeOH-EtOH-H2O system inclined the authors towards the elaboration of its neural network's model.
EN
The experimental kinetic data concerning the linear growth rate of L-sorbose crystals in water solutions with addition of methanol or ethanol (batch crystallization process) are presented. The growth rate values were estimated on the basis of the product-crystal size distributions analysis. For the calculation purposes the kinetic models of continuous mass crystallization process in a MSMPR apparatus were adapted: size independent growth (SIG) model and Rojkowski exponential size dependent growth (SDG) model. It is observed that the 15 mass % of MeOH (or EtOH) addition into the solution destined for batch cooling crystallization (55 mass % of L-sorbose) causes the crystal growth rate decreasing - according to a SDG model - from G = 8.81ź10^-8 m s^-1 (water) to G = 2.15ź10^-8 m s^-1 (MeOH) or G = 2.84ź10^-8 m s^-1 (EtOH).
EN
Reaction-crystallization processes of hydroxyapatite precipitation from its diluted water solutions in the DTM-type crystallizers were discussed. A liquid jet-pump, working with an assumed minimal power of the feeding stream, was tested. It was concluded that the product crystal agglomerates within the 76-316 žm size range were obtained. It was observed that with the increase of Ca2+ ions concentration in a feeding solution the agglomeration phenomena are more pronounced, while the increase of the temperature and the enlargement of suspension residence time effectively restrain the agglomeration effects.
EN
The research results concerning a linear growth rate of vitamin C crystals in the L(+)-ascorbic acid - methanol-ethanol - water system are presented. This kinetic parameter of batch crystallization process was calculated on the basis of crystal product population density distribution. The distributions were determined using two different methods, viz. the particle size laser analyzer and conventional mesh analysis.
EN
The reaction-crystallization process of struvite precipitation from diluted water solutions of magnesium, ammonium and phosphate ions in a DTM type crystallizer with the jet-pump, working at the assumed minimal value of feeding stream unit power was discussed. Struvite crystals of a mean size within the range of 12—20 μm were produced. Process kinetic parameters were estimated on the basis of the product-crystals population density distribution.
EN
The potential application of artificial neural networks for the kinetic analysis of complex struvite reaction-crystallization processes in a DTM continuous crystallizer with inner circulation of suspension forced by a liquid-liquid jet-pump was presented, verified and discussed.
EN
The reaction-crystallization process of hydroxyapatite precipitation from its diluted water solutions in a DTM type crystallizer equipped with the jet-pump working under the assumption of minimal power of a jet-pump feeding stream was discussed. It was concluded that crystal agglomerates with a size range of 227-285 mm were obtained.
EN
The results of investigation of the kinetics of barium ions precipitation by means of crystalline ammonium sulfate addition in a reaction-crystallization process have been presented. The experiments were performed in a continuous laboratory DTM crystallizer with inner circulation of suspension forced by a liquid jet-pump device generating ascending flow of medium in a mixing chamber. The influence of barium chloride concentration in a feeding solution on the crystal size distribution of barium sulfate product and on its reaction-crystallization kinetics were investigated. Nucleation and crystal growth rates were elaborated on the basis of the kinetic model of the MSMPR crystallizer, in two versions: a simplified one - making assumption that in the BaSO4 crystals population a size-independent growth (SIG) is fulfilled, and the enhanced one, incorporating the size dependent growth (SDG) phenomena observed in a real system. Rojkowski exponential SDG kinetic model was recognized as the practical design equation which is fitted the best to the experimental data in a whole L range tested. Both test data and the kinetic expressions with their parameter values can be practically utilized for the improvement of constructions of liquid jet-pump DTM crystallizers, recommended for complex, coupled processes of precipitation and crystallization of sparingly soluble salts.
PL
Przedstawiono wyniki badań krystalizacji z reakcją chemiczną strącania jonów baru krystalicznym siarczanem amonu. Proces prowadzono w krystalizatorze o działaniu ciągłym z wewnętrzną cyrkulacją zawiesiny wymuszaną strumienicą o ruchu wstępującym w komorze mieszania. Badano wpływ stężenia chlorku baru w roztworze zasilającym na rozkład rozmiaru kryształów siarczanu baru i kinetykę jego krystalizacji. Do obliczenia szybkości zarodkowania i wzrostu kryształów wykorzystano modele kinetyczne dla krystalizatora MSMPR. W obliczeniach zakładano, że szybkość wzrostu kryształów BaSO4 nie zależy bądź zależy od ich rozmiarów. Stwierdzono, że najlepiej opisującym dane doświadczalne okazał się wykładniczy model SDG Rojkowskiego. Wyniki badań mogą być wykorzystane do doskonalenia konstrukcji krystalizatora DTM ze strumienicą, zalecanego do prowadzenia procesów strącania i krystalizacji trudno rozpuszczalnych soli.
EN
The results of the mass crystallization kinetics of the process of calcium ions precipitation with the use of ammonium dihydrogenphosphate NH4H2PO4 in water under alkaline conditions (pH = 9) are presented. The experiments were carried out in the continuous laboratory DTB MSMPR (Draft Tube Baffle, Mixed Suspension Mixed Product Removal) crystallizer with the internal circulation of the suspension. The influence of calcium ions concentration in the feed stream, the temperature and the residence time on the nucleation and the growth rates of hydroxyapatite crystals formed, was established. The kinetic parameters were evaluated from the crystal size distributions employing selected SDG (Size Dependent Growth) models.
EN
The research results concerning the reaction crystallization processes of hydroxyapatite (HAP) and struvite (MAP) in the two flow jet pump DTM crystallizers with the internal circulation of the suspension are presented. Calcium or/and magnesium ions precipitation from the diluted water solutions was taken into effect by the addition of ammonium dihydrogenphosphate NH4H2PO4 solution in the alkali environment (T = 298 K, pH = 9, t = 900 s). The influence of calcium (0.1 - 1.5 mass %) and magnesium (0.1 - 2.0 mass %) ions concentration in the feeding stream on the resulting product crystal size distribution was investigated. The test results can be utilized in the improvement of the jet pump DTM crystallizers design. This construction is especially recommended for the precipitation of the calcium or/and magnesium ions, as well as the phosphate(V) ions from the diluted solutions or the liquid wastes.
PL
Przedstawiono wyniki badań kinetyki krystalizacji w procesie strącania jonów magnezu z roztworów wodnych za pomocą roztworu diwodorofosforanu(V) amonu. Pomiary przeprowadzono w ciągłym krystalizatorze laboratoryjnym DTB MSMPR. Z rozkładu rozmiarów kryształów produktu wyznaczono parametry kinetyczne procesu krystalizacji strąceniowej struwitu. Do obliczeń, uwzględniających zależność szybkości wzrostu kryształów od ich rozmiarów, wykorzystano model hiperboliczny I Rojkowskiego.
EN
The work presents the results of mass crystallization kinetics experiments during the process of magnesium ions reaction crystallization from aqueous solution with the use of ammonium dihydrogenphosphate (NH4H2P0.4). The experiments were carried out in the computer-controlled continuous laboratory DTB MSMPR crystallizer with the internal circulation of suspension. Kinetic parameters of the process were evaluated after fitting the theoretical Crystal Size Distributions curve, developed on the basis of Rojkowski hyperbolic I SDG model G(L) to various sets of experimental data. The influence of the pH value as well as crystal suspension mean residence time t, on the population density distribution n(L), linear growth rate boundary values (Go and GŤ.), G(L) profile and nucleation rate, B, was examined and discussed.
PL
Przedstawiono wyniki badań kinetyki krystalizacji w procesie strącania jonów wapnia w wodzie za pomocą roztworu diwodorofosforanu(V) amonu w środowisku alkalicznym (pH = 9.0). Pomiary przeprowadzono w ciągłym krystalizatorze laboratoryjnym DTB MSMPR. Z rozkładu rozmiarów kryształów produktu wyznaczono parametry kinetyczne procesu krystalizacji strąceniowej hydroksyapatytu. Do obliczeń uwzględniających zależność szybkości wzrostu kryształów od ich rozmiaru wykorzystano model hiperboliczny Rojkowskiego.
EN
The work presents the results of mass crystallization kinetics experiments during the process of calcium ions precipitation from aqueous solution with the use of ammonium dihydrogenphosphate NH4H2PO4 under alkaline conditions (pH = 9). Experiments were carried out in the continuous laboratory DTB MSMPR crystallizer. The kinetic parameters of the process were evaluated after fitting the theoretical Crystal Size Distributions employing Rojkowski hyperbolic SDG model to experimental data.
EN
The experimental results concerning hydroxyapatite and struvite crystals' growth kinetics while calcium and magnesium ions precipitation from diluted solutions by ammonium dihydrogenphosphate(V) solution addition in alkaline environment are presented. The measurements were clone using continuous laboratory DTB MSMPR crystallizer. The influence of calcium/magnesium ions' concentration in the feeding solution, suspension residence time, temperature (hydroxyapatite) and pH (struvite) on the resulting Crystal Size Distributions (CSDs) courses was investigated. The ln n(L) dependencies' shapes suggested occurrence of the Size Dependent Growth (SDG) kinetics. The parameters' values in the size-dependent crystal growth kinetic equation (Rojkowski hyperbolic II model assumed) were evaluated. Both the experimental data and evaluated dependencies can be practically applied to the design of processes concerned with the removal of ca1cium and/ar magnesium ions from water or diluted solutions.
PL
Przedstawiono wyniki badań wzrostu kryształów hydroksyapatytu i struwitu w procesie strącania jonów wapnia i magnezu z roztworów rozcieńczonych za pomocą roztworu diwodorofosforanu(V) amonu w środowisku alkalicznym. Pomiary przeprowadzono w ciągłym krystalizatorze laboratoryjnym DTB MSMPR. Przebadano wpływ stężenia jonów wapnia lub magnezu w surowcu podawanym do krystalizatora, czasu przebywania zawiesiny w krystalizatorze, temperatury (hydroksyapatyt) i pH (struwit) na rozkład rozmiarów kryształów soli odprowadzanych z krystalizatora. Do obliczeń przyjęto model szybkości wzrostu kryształów uwzględniający zjawisko zależności szybkości wzrostu od rozmiarów kryształów (SDG). Obliczenia przeprowadzono dla modelu hiperbolicznego II SDG Rojkowskiego. Z rozkładu gęstości populacji kryształów produktu obliczono graniczne (maksymalne i minimalne) wartości szybkości wzrostu kryształów hydroksyapatytu i struwitu. Wyniki badań i obliczeń mogą być wykorzystane do projektowania procesu usuwania jonów wapnia i/lub magnezu z wody lub z roztworów rozcieńczonych.
EN
The paper presents the results of the studies carried out on the crystallization process of magnesium ions precipitation in water with the use of ammonium dihydrogenphosphate NH4H2PO4 under alkaline conditions. The experiments were carried out in the continuous crystallizer with an internal circulation of suspension (T = 298 K). The influence of magnesium ions concentration in the raw material, pH, and the residence time on the mean size of magnesium ammonium phosphate hexahydrate crystals (Lm = 5.6 - 45.9 mm) were evaluated. The rates of struvite crystals growth (Gre = 1.0-10"9 - 9.6109 m/s) were evaluated from the crystal size distribution.
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