Numerical investigation of the performance of several static mixers

The performance of six static mixer (Kenics, Inliner, LPD, Cleveland, SMX and ISG) are compared using 3D numerical simulations in laminar creeping flow regime. Numerical pressure drop results are tested against experimental ones, showing overall a good agreement. Besides pressure drop, four criteria (extensional efficiency, stretching, mean shear rate and intensity of segregation) are chosen to compare the static mixers. It appears that Kenics, Inliner, LPD and Cleveland mixers are rather similar. The ISG mixer seems better than this first group of mixers, but pressure drop is too high compared to other advantages. From our numerical results, SMX appears to be the most efficient of the six compared static mixers.     

数值模拟静态混合器结构对PS/CO_2熔体温度的影响

利用专用CFD软件Polyflow对SMX型和Kenics型静态混合器中PS/CO_2发泡溶液进行数值模拟计算,分析比较不同板厚在不同元件个数条件下两种静态混合器消耗的压力损失,以及不同CO_2浓度对静态混合器压力损失的影响;并引入"离散系数"分析比较两种静态混合器出口温度均匀性的变化.数值模拟的结果表明:SMX型静态混合器冷却效果优于Kenics型静态混合器,并且SMX型静态混合器出口温度均匀性高于Kenics型静态混合器.     

Polymerization of 1,3-butadiene with VO(P204)2 and VO(P507)2 activated by alkylaluminum

The oxovanadium phosphonates (VO(P₂₀₄)₂ and VO(P₅₀₇)₂) activated by various alkylaluminums (AlR₃, R = Et, i-Bu, n-Oct; HAlR₂, R = Et, i-Bu) were examined in butadiene (Bd) polymerization. Both VO(P₂₀₄)₂ and VO(P₅₀₇)₂ showed higher activity than those of classical vanadium-based catalysts (e.g. VOCl₃, V(acac)₃). Among the examined catalysts, the VO(P₂₀₄)₂/Al(Oct)₃ system (I) revealed the highest catalytic activity, giving the poly(Bd) bearing M_n of 3.76 × 10⁴ g/mol, and M_w/M_n ratio of 2.9, when the [Al]/[V] molar ratio was 4.0 at 40 °C. The polymerization rate for I is of the first order with respect to the concentration of monomer. High thermal stability of I was found, since a fairly good catalytic activity was achieved even at 70 °C (polymer yield > 33%); the M_n value and M_w/M_n ratio were independent of polymerization temperature in the range of 40-70 °C. By IR and DSC, the poly(Bd)s obtained had high 1,2-unit content (>65%) with atactic configuration. The 1,2-unit content of the polymers obtained by I was nearly unchanged, regardless of variation of reaction conditions, i.e. [Al]/[V], ageing time, and reaction temperature, indicating the high stability of stereospecificity of the active sites.     

Mg-doped poly(?-caprolactone)/siloxane biohybrids

Ionically conducting materials based on a poly(?-caprolactone) (PCL)/siloxane organic/inorganic host framework doped with magnesium triflate (Mg(CF₃SO₃)₂) were synthesized by the sol-gel process. In this matrix short PCL chains are covalently bonded to the siliceous network via urethane linkages. In this study the salt content of samples was identified using the conventional notation n, where n indicates the number of (C(O)(CH₂)₅O) PCL repeat units per Mg²⁺ ion. Xerogels with compositions ranging from n = ∞ to 1 were prepared. The only composition studied that was not entirely amorphous was that prepared with n = 1. Xerogels with n ≥ 7 are thermally stable up to at least 200 °C. The composition with the highest conductivity of the series is that with n = 34 (5.9 × 10⁻⁹ and 9.8 × 10⁻⁷ S cm⁻¹ at 24 and 104 °C, respectively).     

Laminar flow and chaotic advection mixing performance in a static mixer with perforated helical segments

The laminar flow and chaotic mixing characteristics of a high-viscosity fluid in static mixers with staggered perforated helical segments were numerically investigated in the range of Re=0.1-150. The numerical results of pressure drop of Kenics static mixer have a good agreement with the reported data from the literature. The effects of aspect ratio A _r and Reynolds number on the mixing performance of Modified Kenics Static Mixers (MKSM) were evaluated by Darcy friction coefficient, shear rate, stretching rate, and Lyapunov exponent, respectively. The product of f×Re for MKSM linearly increased with the increase of Re, but it was constant under Re<10. The values of shear rate in the first perforated hole of mixing elements gradually became much larger by 1.10%-11.78% than those in the second perforated hole with the increasing Re. With the increase of dimensionless axial mixing length, the stretching rate increased linearly and the sensitivity for initial condition gradually weakened. A larger A _r is beneficial for micro-mixing in creeping flow. The average Lyapunov exponent linearly increases with the increase of Re. The profiles of Lyapunov exponent at different dimensionless perforated diameter (d/W) and perforated spacing (s/W) indicate that the chaotic mixing in MKSM is much more sensitive to d/W than s/W. A dimensionless parameter η taking into account the mixing degree and pressure drop was employed to evaluate the mixing efficiency. The optimization of perforated helical segments with the highest mixing efficiency at Re=100 was d/W=0.55 and s/W=1.2.     

A simplified correlation for fixed bed pressure drop

An experimental study was conducted on the pressure drop characteristics of a variety of vertical packed beds in turbulent flow of air. The materials of different particle diameter, D_p, with a range of sphericity Φ, 0.55 ≤ Φ ≤ 1.00 were used in random loose packing to produce beds of different lengths, L, with a range of porosity, ε, 0.36 ≤ ε ≤ 0.56. In the covered test cases the cross-sectional velocity distribution at the exit plane of the packed beds and the pressure drop ΔP_Bed were measured in a particle Reynolds number range of Re_p, 675 ≤ Re_p ≤ 7772. The particular emphasis of the study was given to determine the influence of ε, Φ, D_p, L, Re_p on ΔP_Bed. In this respect the measurements of ΔP_Bed were compared with the well-known Ergun's Equation and the data were expressed in terms of correlations through introduced dimensionless parameters of pressure coefficient, ΔP^? and exit Reynolds number Re_exit. The proposed correlations of ΔP^? = ΔP^?(εRe_pD_p / L) and Re_exit = Re_exit(Re_pD_p / L) are found to be appropriate for the determination of ΔP_Bed and mean exit velocity, U, respectively with an acceptable fit of experimental data in an error margin less than ± 20%. The methodology is presented in this paper as an alternative approach to the available literature on packed beds.     

The nucleation and crystallization of MgO-B2O3-SiO2 glass

The nucleation and crystallization of MgO-B₂O₃-SiO₂ (MBS) glass were studied by means of a non-isothermal, thermal analysis technique, X-ray diffraction and scanning electron microscopy. The temperature range of the nucleation and the temperature of the maximum nucleation rate for MBS glass were determined from the dependences of the inverse temperature at the DSC peak (1/T_p) and the maximum intensity of the exothermic DSC crystallization peak ((δT)_p) on the nucleation temperature (T_n). For MBS glass the nucleation occurred at 600-750 °C, with the maximum nucleation rate at 700 °C, whereas the nucleation and crystal growth processes overlapped at 700 °C < T ≤ 750 °C. The analyses of the non-isothermal data for the bulk MBS glass using the most common models (Ozawa, Kissinger, modified Kissinger, Ozawa-Chen, etc.) revealed that the crystallization of Mg₂B₂O₅ was three-dimensional bulk with a diffusion-controlled crystal growth rate, that n = m = 1.5 and that the activation energy for the crystallization was 410-440 kJ/mol.     

RAFT polymerization and self-assembly of thermoresponsive poly(N-decylacrylamide-b-N,N-diethylacrylamide) block copolymers bearing a phenanthrene fluorescent α-end group

Phenanthrene α-end-labeled poly(N-decylacrylamide-b-N,N-diethylacrylamide) (PDcA_n-b-PDEA_m) block copolymers consisting in a highly hydrophobic block (n = 11) and a thermoresponsive block with variable length (79 ≤ m ≤ 468) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. A new phenanthrene-labeled chain transfer agent (CTA) was synthesized and used to control the RAFT polymerization of a hydrophobic acrylamide derivative, N-decylacrylamide (DcA). This first block was further used as macroCTA to polymerize N,N-diethylacrylamide (DEA) in order to prepare diblock copolymers with the same hydrophobic block of PDcA (number average molecular weight: M_n = 2720 g mol⁻¹, polydispersity index: M_w/M_n = 1.13) and various PDEA blocks of several lengths (M_n = 10,000-60,000 g mol⁻¹) with a very high blocking efficiency. The resulting copolymers self-assemble in water forming thermoresponsive micelles. The critical micelle concentration (CMC) was determined using Förster resonance energy transfer (FRET) between phenanthrene linked at the end of the PDcA block and anthracene added to the solution at a low concentration (10⁻⁵ M), based on the fact that energy transfer only occurs when phenanthrene and anthracene are located in the core of the micelle. The CMC (∼2 μM) was obtained at the polymer concentration where the anthracene fluorescence intensity starts to increase. The size of the polymer micelles decreases with temperature increase around the lower critical solution temperature of PDEA in water (LCST ∼ 32 °C) owing to the thermoresponsiveness of the PDEA shell.     

Synthesis, characterization and optical properties of cross-linkable poly(phthalazinone ether ketone sulfone)

Cross-linkable poly(phthalazinone ether ketone sulfone) bearing tetrafluorostyrene groups (PPEKS-FSt) has been prepared by copolycondensation reaction for optical waveguide applications. The resulting amorphous polymer exhibits good solubility in some common polar organic solvents (e.g., N,N′-dimethylacetamide, N-methyl-2-pyrrolidinone, chloroform) at room temperature, and can be easily spin-coated into thin films with good optical quality. The glass transition temperature (T_g) and the temperature of 1% weight loss (1% T_d) are 261 °C and 494 °C, respectively, which could be further increased by 31 °C and 14 °C upon thermal cross-linking. The cross-linked polymer thin films exhibit high refractive index (∼1.65, TE mode), high thermo-optic coefficient value (dn/dT) (−1.455 × 10⁻⁴/°C, TE mode), low optical loss (less than 0.24 dB/cm at 1310 nm) and relatively low birefringence (∼0.007).     

Dry catalytic partial oxidation of diesel-fuel distillates into syngas

Volatile compounds distilled below 205 °C from diesel fuel are reformed into synthesis gas by dry catalytic partial oxidation using porous membrane reactors, eliminating complex liquid-fuel injectors and fuel-air mixers, greatly simplifying reformers for applications with solid-oxide fuel cells and NO_x traps. For distillates utilizing 20 wt% of the diesel fuel, 88 mol% of the carbon is converted into CO and 75 mol% of the hydrogen into H₂. Rationale is as follows: Long-chain n-alkanes such as n-hexadecane, with normal boiling point, 286.5 °C, but autoignition temperature, 205 °C, are the least thermally stable hydrocarbons in diesel fuel. If attempts are made to vaporize diesel fuel under oxygen-lean conditions without precautions, long-chain n-alkanes crack at autoignition temperatures forming radicals that initiate polymerization. By eliminating more troublesome compounds by distillation, and by effusing cooler air through porous ceramic membranes to react radicals with oxygen, carbon deposition is largely suppressed. A perovskite catalyst, fed pre-heated air at >900 °C, provides a reservoir of mobile lattice oxygen to react with adsorbed carbon. In continuous runs of 72 h, carbon deposition was negligible in the reactor, on the catalyst, and in the exhaust, except for minor graphite deposited onto walls near the catalytic hot zone.     

Interfacial tension of marine lipids in contact with high pressure carbon dioxide

Interfacial tension (IFT) of fish oil triglycerides (TG) and fatty acid ethyl esters (FAEE) in contact with carbon dioxide (CO₂) was measured according to the pendant drop method at 40, 55 and 70 °C and pressures up to 25 MPa. The IFT of both TG and FAEE decreased substantially with CO₂ pressure. The IFT of FAEE vanished at elevated pressures, whereas that of TG decreased to a fairly constant level of about 2 mN/m. The IFT was correlated using a model taking into account the density, pressure and temperature of CO₂, thereby facilitating the calculation of the ideal pendant drop volume as well as the surface excess concentration of CO₂. In the pressure range studied, the pendant drop volume for FAEE decreased with pressure, whereas for TG it increased at elevated presssures due to the predominant effect of buoyancy. Furthermore, the change in IFT over time was determined at 55 °C for TG in contact with CO₂ at pressures up to 11.4 MPa showing a decrease of IFT over time at low pressures, whereas at higher pressures it remained nearly constant. IFT influences drop formation as well as the disintegration of falling films thereby affecting the performance of separation processes.     

Deep desulfurization of fuels catalyzed by surfactant-type decatungstates using H2O2 as oxidant

Oxidation of dibenzothiphene (DBT) in model oil with H₂O₂ using surfactant-type decatungstates Q₄W₁₀O₃₂ (Q = (CH₃)₃NC₁₆H₃₃, (CH₃)₃NC₁₄H₂₉, (CH₃)₃NC₁₂H₂₅ and (CH₃)₃NC₁₀H₂₁) as catalysts was studied. The surfactant-type decatungstates were synthesized and characterized. The suitable reaction condition of deep desulfurization was suggested: n(DBT):n(catalyst):n(H₂O₂) = 1:0.01:3, 60 °C for 0.5 h, under which the DBT conversion can reach 99.6% with [(CH₃)₃NC₁₆H₃₃]₄W₁₀O₃₂ as catalyst. The length of carbon chains of quaternary ammonium cations played a vital role in the catalytic activity of surfactant-type decatungstates, that is, the longer the carbon chain of quaternary ammonium cation of a catalyst was, the better the activity of this catalyst showed. [(CH₃)₃NC₁₆H₃₃]₄W₁₀O₃₂ exhibited the best catalytic performance and can be recycled for six times without significant decrease in catalytic activity. Using benzothiphene (BT) and 4,6-dimethyldibenzothiphene (4,6-DMDBT) as substrates in model oil, surfactant-type decatungstates also showed high catalytic activity. During desulfurization process, BT conversion can reach 99.6% at 3.25 h, while 99.4% of 4,6-DMDBT conversion reached at 1.25 h, with the temperature of 60 °C under atmospheric pressure. The sulfone can be separated from the oil using N,N-dimethylformamide (DMF) as an extractant, and the sulfur content can be lowered from 1000 to 4 ppm. For real diesel, the sulfur removal can reach 93.5% after five times extraction.     

Impedance analysis of Sr-substituted CePO4 with mixed protonic and p-type electronic conduction

Members of the solid-solution series Ce_1−xSr_xPO_4−δ (x = 0, 0.01, 0.02) with mixed protonic and electronic transport have been synthesized by a nitrate-decomposition method followed by sintering at 1450 °C. Impedance spectroscopy is employed to estimate the bulk electrical conductivity in wet (∼0.03 atm) and dry atmospheres of O₂ and 10%H₂:90%N₂. Conductivity increases with dopant concentration (x), oxygen partial pressure (pO₂) and water vapour partial pressure (pH₂O) reaching ∼3.5 × 10⁻³ S cm⁻¹ at 600 °C for x = 0.02 in wet O₂. Activation energies (E_a) for the bulk conductivity of Ce_0.98Sr_0.02PO_4−δ below 650 °C are 0.44 and 0.78 eV for wet oxidising and wet reducing conditions, respectively. A moderate but positive pO₂⁺ⁿ power-law dependence (n < 1/10) of conductivity is exhibited in the pO₂ range 10^−2.5 to 10⁻¹ atm, consistent with mixed ionic and p-type electronic transport. Thermogravimetric analysis indicates that the Sr-doped materials are stable in a CO₂ atmosphere in the temperature range 25–1200 °C.     

Effect of sintering temperature on ferroelectric properties of 0.94(K0.5Na0.5)NbO3–0.06LNbO3 system

Lead free 0.94(K_0.5Na_0.5NbO₃)–0.06(LiNbO₃) (KNN–LN) system was synthesized by conventional solid state reaction route (CSSRR). The KNN–LN system was calcined at 850 °C for 6 h for the formation of single perovskite phase whereas the sintering was done at 1050 °C, 1080 °C and 1100 °C for 4 h, respectively. The KNN–LN samples sintered at 1080 °C show better properties: room temperature (RT) dielectric constant (?_r) ∼936, dielectric loss (tan δ) ∼0.016 at 1 MHz, a relatively high bulk density (ρ) ∼4.385 g/cm³, which is 97.5% of the theoretical density (TD ∼ 4.51), remnant polarization (P_r) ∼6.4 μC/cm² and coercive field (E_c) ∼9.6 kV/cm have been observed.     

A general correlation for pressure drop in a Kenics static mixer

A new pressure drop correlation in a Kenics static mixer has been developed. Pressure drop data were generated from computational fluid dynamics (CFD) calculations, avoiding the experimental limitations in obtaining comprehensive data enough for developing a reliable pressure drop correlation. Dimensional analysis reveals that the pressure drop characteristic of the Kenics static mixer can be described by three dimensionless groups, i.e., the friction factor, Reynolds number (Re), and aspect ratio of a mixing element (AR). A systematic graphical analysis led to a single master curve governing the pressure drop behavior of the Kenics static mixer, which had never been achieved before. We derived a pressure drop correlation fitting well with the obtained master curve in a general form into which the AR effect on the pressure drop is directly incorporated. Unlike the already existing correlations available in the literature, the correlation proposed in this study can cover the whole range of Re from laminar to turbulence. The reliability of the proposed correlation was validated by the comparison with various pressure drop data reported in the literature.     

Hydrolytic degradation of poly[(R)-3-hydroxybutyric acid] in the melt

Poly[(R)-3-hydroxybutyric acid] [R-P(3HB)] was hydrolyzed in high-temperature and high-pressure water at the temperature range of 180-300 °C and for a period of 360 min. The formation, racemization, and decomposition of 3-hydroxybutyric acids (3HBs) and molecular weight change of R-P(3HB) were investigated. The highest yield of (R)-3-hydroxybutyric acid (R-3HB), ca. 80%, was obtained at 200 °C in the hydrolytic degradation periods of 240-360 min. Too-high hydrolytic degradation temperature such as 300 °C induced the decomposition and racemization of formed 3HBs, resulting in decreased yield of R-3HB. The hydrolytic degradation of R-P(3HB) proceeds homogeneously and randomly via a bulk erosion mechanism. The molecular weight of R-P(3HB) decreased exponentially without formation of low-molecular-weight specific peaks originating from crystalline residues. The hydrolytic degradation rates in the melt estimated from M_n changes were lower for R-P(3HB) than for poly(l-lactide) (PLLA) in the temperature range of 180-220 °C. The activation energy for the hydrolytic degradation (ΔE_h) of R-P(3HB) in the melt (180-250 °C) was 30.0 kcal mol⁻¹, which is higher than 12.2 kcal mol⁻¹ for PLLA in the melt in the temperature range (180-250 °C). This study reveals that hydrolytic degradation of PHB in the melt is an effective and simple method to obtain (R)-3HB and to prepare R-P(3HB) having different molecular weights without containing the specific low-molecular-weight chains, because of the removal of the effect caused by crystalline residues.     

Comparative analysis of different static mixers performance by CFD technique: An innovative mixer

The flow and mixing behavior of two miscible liquids has been studied in an innovative static mixer by using CFD,with Reynolds numbers ranging from 20 to 160. The performance of the new mixer is compared with those of Kenics, SMX, and Komax static mixers. The pressure drop ratio(Z-factor), coefficient of variation(CoV), and extensional efficiency(α) features have been used to evaluate power consumption, distributive mixing, and dispersive mixing performances, respectively, in all mixers. The model is firstly validated based on experimental data measured for the pressure drop ratio and the coefficient of variation. CFD results are consistent with measured data and those obtained by available correlations in the literature. The new mixer shows a superior mixing performance compared to the other mixers.     

Investigation of the intra-particle sintering kinetics of a mainly agglomerated alumina powder by using surface area reduction

An alumina precursor was prepared by the aluminium sulphate (0.20 M) and excess urea reaction in boiling aqueous solution. The precursor was calcined at 900 °C for 2 h and then δ-Al₂O₃ powder having volumetric agglomeration degree of 80% was obtained. Cylindrical compacts having diameter of 14 mm were prepared under 32 MPa by axial pressing using oleic acid as binder. Each compact was fired isothermally at various temperatures between 950 and 1400 °C. The firing time was changed from zero to 2 h. The fired compacts were examined by scanning electron microscopy (SEM) and nitrogen adsorption techniques. The specific surface areas (S/m² g^− 1) of the samples were calculated using the Brunauer, Emmett, and Teller (BET) procedure. The rate constant (k) and mechanism-characteristic parameter (n) were obtained for different temperatures between 950 °C and 1150 °C from the application of the neck-growth sintering rate (NGRM) model on the surface area reduction data. An Arrhenius equation and the parameter n for the sintering were found in the forms of k = (7.648 × 10⁶ h^− 1) exp (− 186,234 J mol^− 1 / RT) and n = 4.0 × 10^− 7 T³-1.7 × 10^− 3 T² + 2.3 T − 1030.8 respectively. The parameter n changes in the interval 0.61 <  n < 1.34 with rising temperature having maximum at about 1025 °C. Based on the SEM images and NGRM data, the intra-particle sintering was discussed.     

Kenics型静态混合器和GK型静态混合器流场的数值模拟及比较

采用计算流体动力学(CFD)的方法,分别计算了Kenics型静态混合器和GK型静态混合器内的流场。数值模拟的结果表明,Kenics型静态混合器内流场的湍动强度大于GK型静态混合器的,导致了Kenics型静态混合器的流体阻力和传热系数大于GK型静态混合器的。GK型静态混合器的压力降大约只是Kenics型静态混合器压力降的0.554~0.579倍,但两者的传热膜系数相差不大。GK型静态混合器具有较强的综合性能。     

The structure of a cyanobiphenyl side chain liquid crystalline poly(silylenemethylene)

The structure of a side chain liquid crystalline poly(silylenemethylene) (-(SiCH₃R-CH₂)-: R=O(CH₂)₁₁O-Ph-Ph-CN, Ph=phenyl) (CN-11) has been studied by X-ray diffraction and differential scanning calorimetry (DSC). The DSC results showed that CN-11 has transitions at ∼92 °C (T₂) and ∼147 °C (T₁) during both cooling and immediate heating. A third transition occurred at ∼50 °C (T₃) during heating after annealing at room temperature. The X-ray fiber pattern of the CN-11 annealed at room temperature showed several wide and small angle reflections which were indexed by a monoclinic unit cell with parameters a=16.8 Å, b=7.42 Å, c=43.6 Å and β=102.1° (b: fiber direction), representing a crystal structure with layer thickness of ∼43 Å. Upon heating at T₃, the crystal structure became less ordered (but somewhat more ordered than smectic A (S_A) and smectic C (S_C)). This was followed by S_A (or S_C) phase at T₂, and ultimately an isotropic state (I) at T₁. The observed layer thickness (∼43 Å) is about ∼1.5 times the most extended side chain length, indicating a double-layer structure with tilted or interdigitated side chains. The X-ray fiber pattern had a four-point pattern at d=4.52 Å, suggesting that the side chains in the crystal are likely to be tilted by 56° from the polymer fiber axis.