Ten rock samples consisting of one pyroclastic density current(PDC1)deposit,seven lava flows(LF1–7),and two summit lava domes(LD1,2)were studied to understand the petrogenesis and magma dynamics at Mt.Sumbing.The str...Ten rock samples consisting of one pyroclastic density current(PDC1)deposit,seven lava flows(LF1–7),and two summit lava domes(LD1,2)were studied to understand the petrogenesis and magma dynamics at Mt.Sumbing.The stratigraphy is arranged as LF1,PDC1,LF2,LF3,LF4,LF5,LF6,LF7,LD1,and LD2;furthermore,these rocks were divided into two types.TypeⅠ,observed in the oldest(LF1)sample,has poor MgO and high Ba/Nb,Th/Yb and Sr.The remaining samples(PDC1–LD2)represent typeⅡ,characterized by high MgO and low Ba/Nb,Th/Yb and Sr values.We suggest that type I is derived from AOC(altered oceanic crust)-rich melts that underwent significant crustal assimilation,while typeⅡoriginates from mantle-rich melts with less significant crustal assimilation.The early stage of typeⅡmagma(PDC1–LF3)was considered a closed system,evolving basaltic andesite into andesite(55.0–60.2 wt%SiO_(2))with a progressively increasing phenocryst(0.30–0.48φ_(PC))and decreasing crystal size distribution(CSD)slope(from-3.9 to-2.9).The evidence of fluctuating silica and phenocryst contents(between 55.9–59.7 wt%and 0.25–0.41φ_(PC),respectively),coupled with the kinked and steep(from-5.0 to-3.3)CSD curves imply the interchanging condition between open(i.e.,magma mixing)and closed magmatic systems during the middle stage(LF4–LF6).Finally,it underwent to closed system again during the final stage(LF7–LD2)because the magma reached dacitic composition(at most 68.9 wt%SiO_(2))with abundant phenocryst(0.38–0.45φ_(PC))and gentle CSD slope(from-4.1 to-1.2).展开更多
Crystal shape distribution, i.e. the multidimensional size distribution of crystals, is of great importance to their down-stream processing such as in filtration as well as to the end-use properties including the diss...Crystal shape distribution, i.e. the multidimensional size distribution of crystals, is of great importance to their down-stream processing such as in filtration as well as to the end-use properties including the dissolution rate and bioavailability for crystalline pharmaceuticals. Engineering crystal shape and shape distribution requires knowledge about the growth behavior of different crystal facets under varied operational conditions e.g. supersaturations. Measurement of the facet growth rates and growth kinetics of static crystals in a crystallizer without stirring has been reported previously. Here attention is given to study on real-time characterization of the 3D facet growth behavior of crystals in a stirred tank where crystals are constantly moving and rotating. The measurement technique is stereo imaging and the crystal shape reconstruction is based on a stereo imaging camera model. By reference to a case study on potash alum crystallization, it is demonstrated that the crystal size and shape distributions (CSSD) of moving and rotating potash alum crystals in the solution can be reconstructed. The moving window approach was used to correlate 3D face growth kinetics with supersaturation (in the range 0.04 - 0.12) given by an ATR FTIR probe. It revealed that {100} is the fastest growing face, leading to a rapid reduction of its area, while the {111} face has the slowest growth rate, reflected in its area continuously getting larger.展开更多
The crystal size distribution(CSD)was determined with small angle X-ray scattering technique.Theanticoking property of Ni-catalysts was investigated with the steam reforming of n-heptane in a TG-monitoredflow reacto...The crystal size distribution(CSD)was determined with small angle X-ray scattering technique.Theanticoking property of Ni-catalysts was investigated with the steam reforming of n-heptane in a TG-monitoredflow reactor.The results of this study show that the rate of coking on the supported Ni-catalysts depends main-ly on the percentage content of the large size fraction(25-70nm)of Ni-crystallites,and that the dispersion ofNi-crystallites and the anticoking property of the Ni/α-Al<sub>2</sub>O<sub>3</sub> catalysts were promoted obviously by theLa<sub>2</sub>O<sub>3</sub>-modification method.The variation of the Ni-CSD and the anticoking property of the catalysts were fur-ther tested through different periods of hydrothermal treatment.It is found that the content of the largeNi-crystal size fraction and the coking rate pass correspondingly through a maximum.展开更多
The Panzhihua layered intrusions is generated closely related to the Emeishan LIPs.This paper analyzes the spatial distribution of plagioclase and pyroxene.The quantitative texture analysis of 2209 plagioclase shows t...The Panzhihua layered intrusions is generated closely related to the Emeishan LIPs.This paper analyzes the spatial distribution of plagioclase and pyroxene.The quantitative texture analysis of 2209 plagioclase shows that the characteristic length of plagioclase is 0.54 to 0.96 mm,the intercept variation range is large,from-0.67 to 0.96,and the slope is-1.85 to-1.04,the Aspect Ratio shows from 1.84 to 2.59 and fractal dimension D is 1.908–1.933.The quantitative texture analysis of 2342 pyroxene shows that the characteristic length of pyroxene is 0.38–0.64 mm,the intercept shows from 0.46 to 2.26,The slope ranges from-2.6 to-1.47,the Aspect Ratio value varies from 1.53 to 1.71,the fractal dimension D is 0.93 to 1.13.All the CSDs results of the Panzhihua intrusions indicate that plagioclase and pyroxene form in an open magma system and undergo four replenishment of magma injection.The plagioclase crystals do not grow as the lathlike shape,and the fractal growth leads to complex crystal surface.The plagioclase undergoes deformation compaction during the crystal process,and then is oriented.The pyroxene crystals grow along an approximately triaxial ratio and undergo texture adjustment and small crystal dissolution reabsorption.When all crystals in magma system grows up to 2 mm,the pyroxene undergoes cumulation in the Panzhihua layered intrusions.The plagioclase crystallization time scale is 171.23–304.41 years,representing that the crystallization is the more uniform in central part of the melt.The nucleation density continuously increases during the crystallization process of the magma system.The time scale to reach the final maximum crystal nucleation density is 15.28–58.98 years.展开更多
In manufacturing process, it is necessary to measure change in CSD (Crystal Size Distribution) with time accurately because CSD is one of the most important indices that evaluate quality of products. FBRM (Focused Bea...In manufacturing process, it is necessary to measure change in CSD (Crystal Size Distribution) with time accurately because CSD is one of the most important indices that evaluate quality of products. FBRM (Focused Beam Reflectance Measurement) can measure CLD (Chord Length Distribution) in line, but CLD is different from CSD because of principle of FBRM. However, if CSD is determined beforehand, CLD can be calculated from the CSD with statistical method. First, when crystal shape is defined from the characteristic crystal size, the matrix of each crystal shape which transforms CSD into CLD in a uniform manner is calculated with Monte Carlo analysis. Characteristic crystal size is added to the variables defining chord length in order to avoid complex integrals and apply the change in crystal shape with characteristic crystal size to the transforming matrix. Secondly, CSD and CLD are actually measured in suspension of acetaminophen in ethanol and suspension of L-arginine in water to demonstrate the validity of 2 matrices. Lastly, these matrices are multiplied by some simple CSD models to test the properties of these matrices and demonstrate the utility of this transformation.展开更多
Ultrasonic technology has been intensively studied recently due to its special features. In this paper, an ultrasonic crystallization method was introduced for the preparation of ZnAl-Hydrotalcite-Like compounds (ZnA...Ultrasonic technology has been intensively studied recently due to its special features. In this paper, an ultrasonic crystallization method was introduced for the preparation of ZnAl-Hydrotalcite-Like compounds (ZnAl-HTLcs). Samples with high crystallinity, small particle size and narrow particle size distribution were obtained and fully characterized using conventional techniques of XRD, FT-IR and TGDTA. The results prove that both ultrasonic frequency and ultrasonic power have effects on the sizes of the product particles. By varying the ultrasonic power from 250 W to 88 W, with the ultrasonic frequency fixed at 59 kHz, the median particle size of the samples increased from 0.37 μm to 0.82 μm. By altering the hydrothermal treatment time from 1 h to 5 h at 110 ℃, the median particle size of ZnAl-HTLcs synthesized via ultrasonic crystallization increased from 0.88 μm to 1.11 μm.展开更多
Regarding sugar and salt crystallization with large single crystals,the agglomerate thermodynamics and geometric morphologies,not the dynamics,dominate the particle size distribution(PSD).To consider this issue,a PSD ...Regarding sugar and salt crystallization with large single crystals,the agglomerate thermodynamics and geometric morphologies,not the dynamics,dominate the particle size distribution(PSD).To consider this issue,a PSD design model is proposed for limited large crystal agglomeration.In this model,the agglomeration thermodynamic criticality is determined by estimating the adhesion and dispersion forces between single crystals.The geometric agglomerate morphologies are described by corresponding single crystal units stacking with porosity.By seed well-controlled of population,the key parameters of PSD(D01,D50 and D99)are precisely designed.For erythritol,the model design accuracies are 92%–99%in the 1.2 L and 10 L crystallizers,indicating that it can design PSD at various crystallization scales.Concerning the general research attention to microcrystal agglomeration kinetics(mostly active pharmaceutical ingredients),this model effectively guides the sugar and salt PSD design with limited large crystal agglomeration.展开更多
High purity and ultrafine DAAF(u-DAAF)is an emerging insensitive charge in initiators.Although there are many ways to obtain u-DAAF,developing a preparation method with stable operation,accurate control,good quality c...High purity and ultrafine DAAF(u-DAAF)is an emerging insensitive charge in initiators.Although there are many ways to obtain u-DAAF,developing a preparation method with stable operation,accurate control,good quality consistency,equipment miniaturization,and minimum manpower is an inevitable requirement to adapt to the current social technology development trend.Here reported is the microfluidic preparation of u-DAAF with tunable particle size by a passive swirling microreactor.Under the guidance of recrystallization growth kinetics and mixing behavior of fluids in the swirling microreactor,the key parameters(liquid flow rate,explosive concentration and crystallization temperature)were screened and optimized through screening experiments.Under the condition that no surfactant is added and only experimental parameters are controlled,the particle size of recrystallized DAAF can be adjusted from 98 nm to 785 nm,and the corresponding specific surface area is 8.45 m^(2)·g^(-1)to 1.33 m^(2)·g^(-1).In addition,the preparation method has good batch stability,high yield(90.8%-92.6%)and high purity(99.0%-99.4%),indicating a high practical application potential.Electric explosion derived flyer initiation tests demonstrate that the u-DAAF shows an initiation sensitivity much lower than that of the raw DAAF,and comparable to that of the refined DAAF by conventional spraying crystallization method.This study provides an efficient method to fabricate u-DAAF with narrow particle size distribution and high reproducibility as well as a theoretical reference for fabrication of other ultrafine explosives.展开更多
Crystallization is one of the oldest separation and purification unit operations, and has recently contributed to significant improvements in producing higher-value products with specific properties and in building ef...Crystallization is one of the oldest separation and purification unit operations, and has recently contributed to significant improvements in producing higher-value products with specific properties and in building efficient manufacturing processes. In this paper, we review recent developments in crystal engineering and crystallization process design and control in the pharmaceutical industry. We systematically summarize recent methods for understanding and developing new types of crystals such as co-crystals, polymorphs, and solvates, and include several milestones such as the launch of the first co-crystal drug, Entresto (No- vartis), and the continuous manufacture of Orkambi (Vertex). Conventional batch and continuous processes, which are becoming increasingly mature, are being coupled with various control strategies and the recently developed crystallizers are thus adapting to the needs of the pharmaceutical industry. The development of crystallization process design and control has led to the appearance of several new and innovative crystal- lizer geometries for continuous operation and improved performance. This paper also reviews major recent orogress in the area of process analytical technology.展开更多
The reactive crystallization process of dexamethasone sodium phosphate was investigated in a continuous mixed-suspension, mixed-product-removal(MSMPR) crystallizer. Analyzing experimental data, it was found that the g...The reactive crystallization process of dexamethasone sodium phosphate was investigated in a continuous mixed-suspension, mixed-product-removal(MSMPR) crystallizer. Analyzing experimental data, it was found that the growth of product crystal was size-dependent. The Bransom, CR, ASL, M J2 and M J3 size-dependent growth models were discussed in details. Using experimental steady state population density data of dexamethasone sodium phosphate, parameters of five size-dependent growth models were determined by the method of non-linear least-squares. By comparison of experimental population density and linear growth rate data with those obtained from the five size-dependent growth models, it was found that the MJ3 model predicts the growth more accurately than do the other four models. Based on the theory of population balance, the crystal nucleation and growth rate equations of dexamethasone sodium phosphate were determined by non-linear regression method. The effects of different operation parameters such as supersaturation, magma density and temperature on the quality of product crystal were also discussed, and the optimal operation conditions were derived.展开更多
Citric acid is an important organic substance whose marketing concerns various fields. Nevertheless, until 1997 the scientific literature reported little information about the process of crystallization by cooling thr...Citric acid is an important organic substance whose marketing concerns various fields. Nevertheless, until 1997 the scientific literature reported little information about the process of crystallization by cooling through which the commercial product is obtained. In particular, the available studies were aimed to investigate only the kinetics of nucleation and crystal growth neglecting some effective aspects of the industrial crystallization in mechanically stirred apparatus. In order to fill that sci-tech gap, the Department of Chemical Engineering at the University "La Sapienza" of Rome decided to lead a long and meticulous experimental research on the crystallization in discontinuous (batch) of CAM (citric acid monohydrate) in the allotropic form that is stable at room temperature. Due to the number of people involved in that pioneering work, carried out in the historic laboratories of"La Sapienza" (Faculty of Engineering), and motivated by the publication of related M.Sc. dissertations and research papers, such collective effort was called "School of Industrial Crystallization". Among the graduate students in Chemical Engineering that 17 years ago participated in that fruitful experience there was also the author who, under the supervision of Prof. Barbara Mazzarotta, had the specific task of assessing the effects on CAM of changing the crystallization operating conditions until their optimization; the achievements are briefly illustrated in this paper.展开更多
The research results concerning continuous removal of phosphate (V) ions from solutions containing 1.0 or 0.20 mass % of phosphate (V) ions and 0.2 or 0.5 mg/kg of copper (II) ions using magnesium and ammonium ions ad...The research results concerning continuous removal of phosphate (V) ions from solutions containing 1.0 or 0.20 mass % of phosphate (V) ions and 0.2 or 0.5 mg/kg of copper (II) ions using magnesium and ammonium ions addition are presented. Continuous reaction crystallization of struvite MgNH4PO4 × 6H2O ran both under stoichiometric conditions and at 20% excess of magnesium ions (pH 9, t 900 s). It was concluded, that presence of copper (II) ions in a process system influenced product quality moderately advantageously. Mean size of struvite crystals enlarged by ca. 6% only. Lower concentration of phosphate (V) ions and excess of magnesium ions caused, that products of ca. 9% - 13% larger crystal mean size (up to ca.40mm) were removed from the crystallizer. Presence of struvite crystals and copper (II) hydroxide were detected analytically in the products (Cu in a product varied from 6 to 90 mg/kg). Presence of copper (II) ions favored crystallization of struvite in the form of tubular crystals.展开更多
The Tafresh granitoids are located at the central part of the Urumieh-Dokhtar Magmatic Arc(UDMA)in Iran.These rocks,mainly consisting of diorite and granodiorite,were emplaced during the Early Miocene.They are compose...The Tafresh granitoids are located at the central part of the Urumieh-Dokhtar Magmatic Arc(UDMA)in Iran.These rocks,mainly consisting of diorite and granodiorite,were emplaced during the Early Miocene.They are composed of varying proportions of plagioclase+K-feldspar+hornblende±quartz±biotite.Discrimination diagrams and chemical indices of amphibole phases reveal a calc-alkaline affinity and fall clearly in the crust-mantle mixed source field.The estimated pressure,derived from Al in amphibole barometry,is approximately 3 Kb.The granitoids are I-type,metaluminous and belong to the calc-alkaline series.They are all enriched in light rare earth elements and large ion lithophile elements,depleted in high field strength elements and display geochemical features typical of subduction-related calc-alkaline arc magmas.Most crystal size distribution(CSD)line patterns from the granitoids show a non-straight trend which points to the effect of physical processes during petrogenesis.The presence of numerous mafic enclaves,sieve texture and oscillatory zoning along with the CSD results show that magma mixing in the magma chamber had an important role in the petrogenesis of Tafresh granitoids.Moreover,the CSD analysis suggests that the plagioclase crystals were crystallized in a time span of less than 1000 years,which is indicative of shallow depth magma crystallization.展开更多
Reaction crystallization of struvite in water solutions containing 0.20 mass % of phosphate(V) ions by magnesium and ammonium ions addition was investigated experimentally. Process was carried out in DTM type crystall...Reaction crystallization of struvite in water solutions containing 0.20 mass % of phosphate(V) ions by magnesium and ammonium ions addition was investigated experimentally. Process was carried out in DTM type crystallizer with liquid jet pump device in 298 K assuming stoichiometric conditions. Struvite crystals of mean size Lm 5.2-23.0 μm were produced depending on pH (9-11) and mean residence time of suspension in a crystallizer τ (900-3600 s). Under these conditions linear growth rate of struvite crystals (SIG MSMPR kinetic model) decreased 2-time with the increase in pH and 3-time with the elongation of mean residence time of crystal suspension from 7.11×10-9 m/s (pH 9, τ900 s) to 1.65×10-9 m/s (pH 11, τ3600 s). Nucleation rate varied within the 7.9×108-1.8×1010 1/(sm3) limits. Struvite product of maximal linear size exceeded 100 μm with 10 vol. % of < 3 μm fraction corresponded to pH 9 and τ3600 s.展开更多
Phosphate (V) ions were continuously removed from synthetic wastewater containing inorganic impurities using magnesium and ammonium ions. The product was magnesium ammonium phosphate (V) hexahydrate, struvite, MgNH4PO...Phosphate (V) ions were continuously removed from synthetic wastewater containing inorganic impurities using magnesium and ammonium ions. The product was magnesium ammonium phosphate (V) hexahydrate, struvite, MgNH4PO4 × 6H2O. Research ran in stoichiometric conditions in DT MSMPR type crystallizer with internal circulation of suspension. Increase in process environment pH from 9 to 11 resulted in 3-time decrease of mean struvite crystals size (from 40.1 to12.6mm). Elongation of mean residence time of suspension in a crystallizer up to 3600 s resulted in improvement of the product quality. Mean size of struvite crystals enlarged up to50.2mm. Based on kinetic calculations results (SIG MSMPR model) it was concluded, that linear struvite crystal growth rate varied within 5.04 × 10–9 – 1.69 × 10–8 m/s range, whereas nucleation rate within 1.4 × 107 – 1.7 × 1010 1/(s m3) limits. In solid product, besides struvite, also all impurities present in wastewater were identified analytically as hydroxides, phosphates and other salts.展开更多
基金funded by the Faculty of Geography under the scheme of“Dana Hibah Penelitian Mandiri Dosen Tahun 2023 Tahap 1”。
文摘Ten rock samples consisting of one pyroclastic density current(PDC1)deposit,seven lava flows(LF1–7),and two summit lava domes(LD1,2)were studied to understand the petrogenesis and magma dynamics at Mt.Sumbing.The stratigraphy is arranged as LF1,PDC1,LF2,LF3,LF4,LF5,LF6,LF7,LD1,and LD2;furthermore,these rocks were divided into two types.TypeⅠ,observed in the oldest(LF1)sample,has poor MgO and high Ba/Nb,Th/Yb and Sr.The remaining samples(PDC1–LD2)represent typeⅡ,characterized by high MgO and low Ba/Nb,Th/Yb and Sr values.We suggest that type I is derived from AOC(altered oceanic crust)-rich melts that underwent significant crustal assimilation,while typeⅡoriginates from mantle-rich melts with less significant crustal assimilation.The early stage of typeⅡmagma(PDC1–LF3)was considered a closed system,evolving basaltic andesite into andesite(55.0–60.2 wt%SiO_(2))with a progressively increasing phenocryst(0.30–0.48φ_(PC))and decreasing crystal size distribution(CSD)slope(from-3.9 to-2.9).The evidence of fluctuating silica and phenocryst contents(between 55.9–59.7 wt%and 0.25–0.41φ_(PC),respectively),coupled with the kinked and steep(from-5.0 to-3.3)CSD curves imply the interchanging condition between open(i.e.,magma mixing)and closed magmatic systems during the middle stage(LF4–LF6).Finally,it underwent to closed system again during the final stage(LF7–LD2)because the magma reached dacitic composition(at most 68.9 wt%SiO_(2))with abundant phenocryst(0.38–0.45φ_(PC))and gentle CSD slope(from-4.1 to-1.2).
文摘Crystal shape distribution, i.e. the multidimensional size distribution of crystals, is of great importance to their down-stream processing such as in filtration as well as to the end-use properties including the dissolution rate and bioavailability for crystalline pharmaceuticals. Engineering crystal shape and shape distribution requires knowledge about the growth behavior of different crystal facets under varied operational conditions e.g. supersaturations. Measurement of the facet growth rates and growth kinetics of static crystals in a crystallizer without stirring has been reported previously. Here attention is given to study on real-time characterization of the 3D facet growth behavior of crystals in a stirred tank where crystals are constantly moving and rotating. The measurement technique is stereo imaging and the crystal shape reconstruction is based on a stereo imaging camera model. By reference to a case study on potash alum crystallization, it is demonstrated that the crystal size and shape distributions (CSSD) of moving and rotating potash alum crystals in the solution can be reconstructed. The moving window approach was used to correlate 3D face growth kinetics with supersaturation (in the range 0.04 - 0.12) given by an ATR FTIR probe. It revealed that {100} is the fastest growing face, leading to a rapid reduction of its area, while the {111} face has the slowest growth rate, reflected in its area continuously getting larger.
文摘The crystal size distribution(CSD)was determined with small angle X-ray scattering technique.Theanticoking property of Ni-catalysts was investigated with the steam reforming of n-heptane in a TG-monitoredflow reactor.The results of this study show that the rate of coking on the supported Ni-catalysts depends main-ly on the percentage content of the large size fraction(25-70nm)of Ni-crystallites,and that the dispersion ofNi-crystallites and the anticoking property of the Ni/α-Al<sub>2</sub>O<sub>3</sub> catalysts were promoted obviously by theLa<sub>2</sub>O<sub>3</sub>-modification method.The variation of the Ni-CSD and the anticoking property of the catalysts were fur-ther tested through different periods of hydrothermal treatment.It is found that the content of the largeNi-crystal size fraction and the coking rate pass correspondingly through a maximum.
基金funded by National Basic Research Program of China(Grant No.2011CB808901)the Geological Survey Program of the China Geological Survey(Grant No.1212011220921)。
文摘The Panzhihua layered intrusions is generated closely related to the Emeishan LIPs.This paper analyzes the spatial distribution of plagioclase and pyroxene.The quantitative texture analysis of 2209 plagioclase shows that the characteristic length of plagioclase is 0.54 to 0.96 mm,the intercept variation range is large,from-0.67 to 0.96,and the slope is-1.85 to-1.04,the Aspect Ratio shows from 1.84 to 2.59 and fractal dimension D is 1.908–1.933.The quantitative texture analysis of 2342 pyroxene shows that the characteristic length of pyroxene is 0.38–0.64 mm,the intercept shows from 0.46 to 2.26,The slope ranges from-2.6 to-1.47,the Aspect Ratio value varies from 1.53 to 1.71,the fractal dimension D is 0.93 to 1.13.All the CSDs results of the Panzhihua intrusions indicate that plagioclase and pyroxene form in an open magma system and undergo four replenishment of magma injection.The plagioclase crystals do not grow as the lathlike shape,and the fractal growth leads to complex crystal surface.The plagioclase undergoes deformation compaction during the crystal process,and then is oriented.The pyroxene crystals grow along an approximately triaxial ratio and undergo texture adjustment and small crystal dissolution reabsorption.When all crystals in magma system grows up to 2 mm,the pyroxene undergoes cumulation in the Panzhihua layered intrusions.The plagioclase crystallization time scale is 171.23–304.41 years,representing that the crystallization is the more uniform in central part of the melt.The nucleation density continuously increases during the crystallization process of the magma system.The time scale to reach the final maximum crystal nucleation density is 15.28–58.98 years.
文摘In manufacturing process, it is necessary to measure change in CSD (Crystal Size Distribution) with time accurately because CSD is one of the most important indices that evaluate quality of products. FBRM (Focused Beam Reflectance Measurement) can measure CLD (Chord Length Distribution) in line, but CLD is different from CSD because of principle of FBRM. However, if CSD is determined beforehand, CLD can be calculated from the CSD with statistical method. First, when crystal shape is defined from the characteristic crystal size, the matrix of each crystal shape which transforms CSD into CLD in a uniform manner is calculated with Monte Carlo analysis. Characteristic crystal size is added to the variables defining chord length in order to avoid complex integrals and apply the change in crystal shape with characteristic crystal size to the transforming matrix. Secondly, CSD and CLD are actually measured in suspension of acetaminophen in ethanol and suspension of L-arginine in water to demonstrate the validity of 2 matrices. Lastly, these matrices are multiplied by some simple CSD models to test the properties of these matrices and demonstrate the utility of this transformation.
基金Supported by the Natural Science Funds (20001015) of Xianxi Province.
文摘Ultrasonic technology has been intensively studied recently due to its special features. In this paper, an ultrasonic crystallization method was introduced for the preparation of ZnAl-Hydrotalcite-Like compounds (ZnAl-HTLcs). Samples with high crystallinity, small particle size and narrow particle size distribution were obtained and fully characterized using conventional techniques of XRD, FT-IR and TGDTA. The results prove that both ultrasonic frequency and ultrasonic power have effects on the sizes of the product particles. By varying the ultrasonic power from 250 W to 88 W, with the ultrasonic frequency fixed at 59 kHz, the median particle size of the samples increased from 0.37 μm to 0.82 μm. By altering the hydrothermal treatment time from 1 h to 5 h at 110 ℃, the median particle size of ZnAl-HTLcs synthesized via ultrasonic crystallization increased from 0.88 μm to 1.11 μm.
基金financially supported by the Key 647 Research and Development Project of Hebei 22372601Dthe financial support of Haihe Laboratory of Sustainable Chemical Transformations.
文摘Regarding sugar and salt crystallization with large single crystals,the agglomerate thermodynamics and geometric morphologies,not the dynamics,dominate the particle size distribution(PSD).To consider this issue,a PSD design model is proposed for limited large crystal agglomeration.In this model,the agglomeration thermodynamic criticality is determined by estimating the adhesion and dispersion forces between single crystals.The geometric agglomerate morphologies are described by corresponding single crystal units stacking with porosity.By seed well-controlled of population,the key parameters of PSD(D01,D50 and D99)are precisely designed.For erythritol,the model design accuracies are 92%–99%in the 1.2 L and 10 L crystallizers,indicating that it can design PSD at various crystallization scales.Concerning the general research attention to microcrystal agglomeration kinetics(mostly active pharmaceutical ingredients),this model effectively guides the sugar and salt PSD design with limited large crystal agglomeration.
基金the National Natural Science Foundation of China (Grant No.22105184)Research Fund of SWUST for PhD (Grant No.22zx7175)+1 种基金Sichuan Science and Technology Program (Grant No.2019ZDZX0013)Institute of Chemical Materials Program (Grant No.SXK-2022-03)for financial support。
文摘High purity and ultrafine DAAF(u-DAAF)is an emerging insensitive charge in initiators.Although there are many ways to obtain u-DAAF,developing a preparation method with stable operation,accurate control,good quality consistency,equipment miniaturization,and minimum manpower is an inevitable requirement to adapt to the current social technology development trend.Here reported is the microfluidic preparation of u-DAAF with tunable particle size by a passive swirling microreactor.Under the guidance of recrystallization growth kinetics and mixing behavior of fluids in the swirling microreactor,the key parameters(liquid flow rate,explosive concentration and crystallization temperature)were screened and optimized through screening experiments.Under the condition that no surfactant is added and only experimental parameters are controlled,the particle size of recrystallized DAAF can be adjusted from 98 nm to 785 nm,and the corresponding specific surface area is 8.45 m^(2)·g^(-1)to 1.33 m^(2)·g^(-1).In addition,the preparation method has good batch stability,high yield(90.8%-92.6%)and high purity(99.0%-99.4%),indicating a high practical application potential.Electric explosion derived flyer initiation tests demonstrate that the u-DAAF shows an initiation sensitivity much lower than that of the raw DAAF,and comparable to that of the refined DAAF by conventional spraying crystallization method.This study provides an efficient method to fabricate u-DAAF with narrow particle size distribution and high reproducibility as well as a theoretical reference for fabrication of other ultrafine explosives.
文摘Crystallization is one of the oldest separation and purification unit operations, and has recently contributed to significant improvements in producing higher-value products with specific properties and in building efficient manufacturing processes. In this paper, we review recent developments in crystal engineering and crystallization process design and control in the pharmaceutical industry. We systematically summarize recent methods for understanding and developing new types of crystals such as co-crystals, polymorphs, and solvates, and include several milestones such as the launch of the first co-crystal drug, Entresto (No- vartis), and the continuous manufacture of Orkambi (Vertex). Conventional batch and continuous processes, which are becoming increasingly mature, are being coupled with various control strategies and the recently developed crystallizers are thus adapting to the needs of the pharmaceutical industry. The development of crystallization process design and control has led to the appearance of several new and innovative crystal- lizer geometries for continuous operation and improved performance. This paper also reviews major recent orogress in the area of process analytical technology.
文摘The reactive crystallization process of dexamethasone sodium phosphate was investigated in a continuous mixed-suspension, mixed-product-removal(MSMPR) crystallizer. Analyzing experimental data, it was found that the growth of product crystal was size-dependent. The Bransom, CR, ASL, M J2 and M J3 size-dependent growth models were discussed in details. Using experimental steady state population density data of dexamethasone sodium phosphate, parameters of five size-dependent growth models were determined by the method of non-linear least-squares. By comparison of experimental population density and linear growth rate data with those obtained from the five size-dependent growth models, it was found that the MJ3 model predicts the growth more accurately than do the other four models. Based on the theory of population balance, the crystal nucleation and growth rate equations of dexamethasone sodium phosphate were determined by non-linear regression method. The effects of different operation parameters such as supersaturation, magma density and temperature on the quality of product crystal were also discussed, and the optimal operation conditions were derived.
文摘Citric acid is an important organic substance whose marketing concerns various fields. Nevertheless, until 1997 the scientific literature reported little information about the process of crystallization by cooling through which the commercial product is obtained. In particular, the available studies were aimed to investigate only the kinetics of nucleation and crystal growth neglecting some effective aspects of the industrial crystallization in mechanically stirred apparatus. In order to fill that sci-tech gap, the Department of Chemical Engineering at the University "La Sapienza" of Rome decided to lead a long and meticulous experimental research on the crystallization in discontinuous (batch) of CAM (citric acid monohydrate) in the allotropic form that is stable at room temperature. Due to the number of people involved in that pioneering work, carried out in the historic laboratories of"La Sapienza" (Faculty of Engineering), and motivated by the publication of related M.Sc. dissertations and research papers, such collective effort was called "School of Industrial Crystallization". Among the graduate students in Chemical Engineering that 17 years ago participated in that fruitful experience there was also the author who, under the supervision of Prof. Barbara Mazzarotta, had the specific task of assessing the effects on CAM of changing the crystallization operating conditions until their optimization; the achievements are briefly illustrated in this paper.
文摘The research results concerning continuous removal of phosphate (V) ions from solutions containing 1.0 or 0.20 mass % of phosphate (V) ions and 0.2 or 0.5 mg/kg of copper (II) ions using magnesium and ammonium ions addition are presented. Continuous reaction crystallization of struvite MgNH4PO4 × 6H2O ran both under stoichiometric conditions and at 20% excess of magnesium ions (pH 9, t 900 s). It was concluded, that presence of copper (II) ions in a process system influenced product quality moderately advantageously. Mean size of struvite crystals enlarged by ca. 6% only. Lower concentration of phosphate (V) ions and excess of magnesium ions caused, that products of ca. 9% - 13% larger crystal mean size (up to ca.40mm) were removed from the crystallizer. Presence of struvite crystals and copper (II) hydroxide were detected analytically in the products (Cu in a product varied from 6 to 90 mg/kg). Presence of copper (II) ions favored crystallization of struvite in the form of tubular crystals.
文摘The Tafresh granitoids are located at the central part of the Urumieh-Dokhtar Magmatic Arc(UDMA)in Iran.These rocks,mainly consisting of diorite and granodiorite,were emplaced during the Early Miocene.They are composed of varying proportions of plagioclase+K-feldspar+hornblende±quartz±biotite.Discrimination diagrams and chemical indices of amphibole phases reveal a calc-alkaline affinity and fall clearly in the crust-mantle mixed source field.The estimated pressure,derived from Al in amphibole barometry,is approximately 3 Kb.The granitoids are I-type,metaluminous and belong to the calc-alkaline series.They are all enriched in light rare earth elements and large ion lithophile elements,depleted in high field strength elements and display geochemical features typical of subduction-related calc-alkaline arc magmas.Most crystal size distribution(CSD)line patterns from the granitoids show a non-straight trend which points to the effect of physical processes during petrogenesis.The presence of numerous mafic enclaves,sieve texture and oscillatory zoning along with the CSD results show that magma mixing in the magma chamber had an important role in the petrogenesis of Tafresh granitoids.Moreover,the CSD analysis suggests that the plagioclase crystals were crystallized in a time span of less than 1000 years,which is indicative of shallow depth magma crystallization.
文摘Reaction crystallization of struvite in water solutions containing 0.20 mass % of phosphate(V) ions by magnesium and ammonium ions addition was investigated experimentally. Process was carried out in DTM type crystallizer with liquid jet pump device in 298 K assuming stoichiometric conditions. Struvite crystals of mean size Lm 5.2-23.0 μm were produced depending on pH (9-11) and mean residence time of suspension in a crystallizer τ (900-3600 s). Under these conditions linear growth rate of struvite crystals (SIG MSMPR kinetic model) decreased 2-time with the increase in pH and 3-time with the elongation of mean residence time of crystal suspension from 7.11×10-9 m/s (pH 9, τ900 s) to 1.65×10-9 m/s (pH 11, τ3600 s). Nucleation rate varied within the 7.9×108-1.8×1010 1/(sm3) limits. Struvite product of maximal linear size exceeded 100 μm with 10 vol. % of < 3 μm fraction corresponded to pH 9 and τ3600 s.
文摘Phosphate (V) ions were continuously removed from synthetic wastewater containing inorganic impurities using magnesium and ammonium ions. The product was magnesium ammonium phosphate (V) hexahydrate, struvite, MgNH4PO4 × 6H2O. Research ran in stoichiometric conditions in DT MSMPR type crystallizer with internal circulation of suspension. Increase in process environment pH from 9 to 11 resulted in 3-time decrease of mean struvite crystals size (from 40.1 to12.6mm). Elongation of mean residence time of suspension in a crystallizer up to 3600 s resulted in improvement of the product quality. Mean size of struvite crystals enlarged up to50.2mm. Based on kinetic calculations results (SIG MSMPR model) it was concluded, that linear struvite crystal growth rate varied within 5.04 × 10–9 – 1.69 × 10–8 m/s range, whereas nucleation rate within 1.4 × 107 – 1.7 × 1010 1/(s m3) limits. In solid product, besides struvite, also all impurities present in wastewater were identified analytically as hydroxides, phosphates and other salts.