Facile synthesis of hierarchical NaX zeolite from natural kaolinite for efficient Knoevenagel condensation

Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.

Chromatin condensation but not DNA integrity of pig sperm is greater in the sperm-rich fraction

Background Protamination and condensation of sperm chromatin as well as DNA integrity play an essential role during fertilization and embryo development.In some mammals,like pigs,ejaculates are emitted in three separate fractions:pre-sperm,sperm-rich(SRF)and post sperm-rich(PSRF).These fractions are known to vary in volume,sperm concentration and quality,as well as in the origin and composition of seminal plasma(SP),with differences being also observed within the SRF one.Yet,whether disparities in the DNA integrity and chromatin condensation and pro-tamination of their sperm exist has not been interrogated.Results This study determined chromatin protamination(Chromomycin A3 test,CMA_(3)),condensation(Dibromobi-mane test,DBB),and DNA integrity(Comet assay)in the pig sperm contained in the first 10 m L of the SRF(SRF-P1),the remaining portion of the sperm-rich fraction(SRF-P2),and the post sperm-rich fraction(PSRF).While chromatin protamination was found to be similar between the different ejaculate fractions(P>0.05),chromatin condensation was seen to be greater in SRF-P1 and SRF-P2 than in the PSRF(P=0.018 and P=0.004,respectively).Regarding DNA integrity,no differences between fractions were observed(P>0.05).As the SRF-P1 has the highest sperm concentra-tion and ejaculate fractions are known to differ in antioxidant composition,the oxidative stress index(OSi)in SP,calcu-lated as total oxidant activity divided by total antioxidant capacity,was tested and confirmed to be higher in the SRF-P1 than in SRF-P2 and PSRF(0.42±0.06 vs.0.23±0.09 and 0.08±0.00,respectively;P<0.01);this index,in addition,was observed to be correlated to the sperm concentration of each fraction(Rs=0.973;P<0.001).Conclusion While sperm DNA integrity was not found to differ between ejaculate fractions,SRF-P1 and SRF-P2 were observed to exhibit greater chromatin condensation than the PSRF.This could be related to the OSi of each fraction.

Controllable Condensation of Aromatics and Its Mechanisms in Carbonization

In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations were used to study the thermal reactions of pyrene,1-methylpyrene,7,8,9,10-tetrahydrobenzopyrene,and mixtures of pyrene with 1-octene,cyclohexene,or styrene.The reactant conversion rates,reaction rates,and product distributions were calculated and compared,and the mechanisms were analyzed and discussed.The results demonstrated that methyl and naphthenic structures in aromatics might improve the conversion rates of reactants in hydrogen transfer processes,but their steric hindrances prohibited the generation of high polymers.The naphthenic structures could generate more free radicals and presented a more obvious inhibition effect on the condensation of polymers compared with the methyl side chains.It was discovered that when different olefins were mixed with pyrene,1-octene primarily underwent pyrolysis reactions,whereas cyclohexene mainly underwent hydrogen transfer reactions with pyrene and styrene,mostly producing superconjugated biradicals through condensation reactions with pyrene.In the mixture systems,the olefins scattered aromatic molecules,hindering the formation of pyrene trimers and higher polymers.According to the reactive molecular dynamics simulations,styrene may enhance the yield of dimer and enable the controlled polycondensation of pyrene.

Supersonic expansion and condensation characteristics of hydrogen gas under different temperature conditions

This paper introduced supersonic expansion liquefaction technology into the field of hydrogen liquefaction.The mathematical model for supersonic condensation of hydrogen gas in a Laval nozzle model was established.The supersonic expansion and condensation characteristics of hydrogen gas under different temperature conditions were investigated.The simulation results show that the droplet number rises rapidly from 0 at the nozzle throat as the inlet temperature increases,and the maximum droplet number generated is 1.339×10^(18)kg^(-1)at inlet temperature of 36.0 K.When hydrogen nucleation occurs,the droplet radius increases significantly and shows a positive correlation with the increase in the inlet temperature,and the maximum droplet radii are 6.667×10^(-8)m,1.043×10^(-7)m,and 1.099×10^(-7)m when the inlet temperature is 36.0 K,36.5 K,and 37.0 K,respectively.The maximum nucleation rate decreases with increasing inlet temperature,and the nucleation region of the Laval nozzle becomes wider.The liquefaction efficiency can be effectively improved by lowering the inlet temperature.This is because a lower inlet temperature provides more subcooling,which allows the hydrogen to reach the thermodynamic conditions required for large-scale condensation more quickly.

Self-aldol condensation of aldehydes over Lewis acidic rare-earth cations stabilized by zeolites

The self-aldol condensation of aldehydes was investigated with rare-earth cations stabilized by[Si]Beta zeolites in parallel with bulk rare-earth metal oxides.Good catalytic performance was achieved with all Lewis acidic rare-earth cations stabilized by zeolites and yttrium appeared to be the best metal choice.According to the results of several complementary techniques,i.e.,temperature-programmed surface reactions,in situ diffuse reflectance infrared Fourier transform spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,the reaction pathway and mechanism of the aldehyde self-aldol condensation over Y/Beta catalyst were studied in more detail.Density functional theory calculations revealed that aldol dehydration was the rate-limiting step.The hydroxyl group at the open yttrium site played an important role in stabilizing the transition state of the aldol dimer reducing the energy barrier for its hydration.Lewis acidic Y(OSi)(OH)2 stabilized by zeolites in open configurations were identified as the preferred active sites for the self-aldol condensation of aldehydes.

Finite-Time Thermodynamic Simulation of Circulating Direct Condensation Heat Recovery on Chillers

A time series model is used in this paper to describe the progress of circulating direct condensation heat recovery of the compound condensing process (CCP) which is made of two water cooling condensing processes in series for a centrifugal chiller in the paper. A finite-time thermodynamics method is used to set up the time series simulation model. As a result, an upper bound of recoverable condensation heat for the compound condensing process is obtained which is in good agreement with experimental result. And the result is valuable and useful to optimization design of condensing heat recovery.

Generalized polynomial chaos expansion by reanalysis using static condensation based on substructuring

This paper presents a new computational method for forward uncertainty quantification(UQ)analyses on large-scale structural systems in the presence of arbitrary and dependent random inputs.The method consists of a generalized polynomial chaos expansion(GPCE)for statistical moment and reliability analyses associated with the stochastic output and a static reanalysis method to generate the input-output data set.In the reanalysis,we employ substructuring for a structure to isolate its local regions that vary due to random inputs.This allows for avoiding repeated computations of invariant substructures while generating the input-output data set.Combining substructuring with static condensation further improves the computational efficiency of the reanalysis without losing accuracy.Consequently,the GPCE with the static reanalysis method can achieve significant computational saving,thus mitigating the curse of dimensionality to some degree for UQ under high-dimensional inputs.The numerical results obtained from a simple structure indicate that the proposed method for UQ produces accurate solutions more efficiently than the GPCE using full finite element analyses(FEAs).We also demonstrate the efficiency and scalability of the proposed method by executing UQ for a large-scale wing-box structure under ten-dimensional(all-dependent)random inputs.

Reducing Condensation Inside the Photovoltaic(PV)Inverter according to the Effect of Diffusion as a Process of Vapor Transport

A photovoltaic(PV)inverter is a vital component of a photovoltaic(PV)solar system.Photovoltaic(PV)inverter failure can mean a solar system that is no longer functioning.When electronic devices such as photovoltaic(PV)inverter devices are subjected to vapor condensation,a risk could occur.Given the amount of moisture in the air,saturation occurswhen the temperature drops to the dewpoint,and condensationmay formon surfaces.Numerical simulation with“COMSOL Software”is important for obtaining knowledge relevant to preventing condensation by using two steps.At first,the assumption was that the device’s water vapor concentration was homogeneous to evaluate the amount of liquid water accumulated on the internal walls of the photovoltaic(PV)inverter box.Second,by considering the effect of external wind velocity onmoisture transport at the air interface to evaluate water vapor transport outdoors and reduce condensation.General factorial designs are utilized for analyzing the nature of the relationship between the vapor condensation response and the variables.Reducing vapor condensation inside the solar inverter by the effect of external wind speed on diffusion as a process of transporting moister air outside the inverter box is the main solution for this problem.During the movement and assessment of the flow of water vapor,the impact of vapor condensation is reduced.The saturation period was determined by using a Boolean saturation indicator.The saturation indicator was set to 1 when saturation was detected(relative humidity greater than or equal to 1)and 0 otherwise.Calculating the flow and dispersion of moist air as a function of wind speed helped solve the problem.

First and Second Law Analysis of a LiBr-Water Absorption Cycle with Recovering Condensation Heat for Generation

In conventional absorption refrigeration systems(ARS),the heat from the condenser is usually rejected by the environment in place to be used in the system,so recuperating this is a good alternative to enhance the system’s performance.For instance,in this paper,an alternative ARS in which LiBr/Water is used as a refrigerant mixture,where part of condensing heat is recovered via the solution heat recovery generator absorption cycle(HR-ARS)was energy and exergy evaluated.The influence of generator,condenser and evaporator temperatures,as well as the efficiency of the solution heat exchanger on the coefficient of performance,exergy performance and exergy destroyed of the HR-ARS system,were analyzed and compared with the traditional ARS system at the same working conditions.The results showed an increase between 5.8%–6.3%on the COP and 3.7%–9.5%in the exergy efficiency when condenser/absorber temperature was reduced from 40℃ to 30℃.However,when the evaporation temperature rose from 5℃ to 15℃,the COP(coefficient of performance)increased by around 8%,although this could be increased by 2.3%–6.3%if the generator temperature decreases from 100℃ to 80℃.Moreover,the COP and exergetic performance for the HR-ARS is more significant at the lowest generator,condenser and evaporator temperatures,as well as at high efficiency in the solution heat exchanger,in comparison to ARS system.Furthermore,the COP and exergy performance for the HR-ARS system was improved by 2.57%to 3.11%and 0.22%to 0.7%,respectively,while the recovering condensation heat for generation is around 1.51%–3.76%lower than with the ARS.It also was found that for all ranges of evaporator and condenser temperatures,the COP for the HR-ARS system is around 3%higher than that obtained with the ARS at the three different generator temperatures here analyzed,while when the solution heat exchanger effectiveness was increased from 0.7–1.0,the total exergy destruction for the HR-ARS resulted be 3.24%–5.01%smaller than the ARS system.Finally,it can be concluded that the components with the most exergy destroyed in the systems(80%to 94%)are the generator and absorber.

New Strategy Leverages Lignin Condensation for Biomass Utilization

There is an old saying in the biorefining industry that“You can make anything from lignin except money.”This bio-based compound is abundant and full of potential,but commercializing it remains a challenge.This may no longer be the case soon with an innovative approach by chemists from the Dalian Institute of Chemical Physics(DICP)of the Chinese Academy of Sciences and their colleagues to harness lignin condensation–often considered a nuisance–for efficient utilization of lignocellulose.

In Tube Condensation:Changing the Pressure Drop into a Temperature Difference for a Wire-on-Tube Heat Exchanger

A theoretical study based on the Penalty factor(PF)method by Cavallini et al.is conducted to show that the pressure drop occurring in a wire-on-tube heat exchanger can be converted into a temperature difference for two types of refrigerants R-134a and R-600a typically used for charging refrigerators and freezers.The following conditions are considered:stratified or stratified-wavyflow condensation occurring inside the smooth tube of a wire-on-tube condenser with diameter 3.25,4.83,and 6.299 mm,condensation temperatures 35℃,45℃,and 54.4℃ and cover refrigerant massflow rate spanning the interval from 1 to 7 kg/hr.The results show that the PF variation is not linear with vapor quality and attains a maximum when the vapor quality is 0.2 and 0.18 for the R-134a and R-600a refrigerants,respectively.The PF increases with the refrigerant massflow rate if the inner diameter and saturation temperature constant,and it decreases on increasing the inner diameter to 6.299 mm for constant refrigerant massflow rate and saturation temperature.The PF for R-600a is higher than that for R-134a due to the lower saturation pressure in thefirst case.Furthermore,a stratifiedflow produces higher PF in comparison to the annularflow due to the effect of the surface tension.

基于均值移动确定性漂移的改进CONDENSATION人脸跟踪

针对视频序列目标跟踪粒子滤波经典CONDENSATION算法用先验转移概率,即采用一阶或二阶AR模型难以有效进行粒子传播的问题,提出了一种改进的CONDENSATION人脸跟踪算法。首先利用高效的均值移动跟踪器以低廉的计算成本初步进行人脸目标跟踪定位,并用此初步跟踪结果来确定CONDENSATION粒子动态传播模型中的确定性漂移部分,然后只需加入一个较小的随机扩散噪声来完成粒子的传播。由于这样所得的粒子点能较为集中地分布在状态的真实区域附近,因而大大提高了粒子的利用效率。人脸跟踪实验表明,该改进算法的性能明显优于原CONDENSATION方法。

Magnesium vapor nucleation in phase transitions and condensation under vacuum conditions

Recent findings related to coagulable magnesium vapor nucleation and growth in vacuum were assessed critically, with emphasis on understanding these processes at a fundamental molecular level. The effects of magnesium vapor pressure, condensation temperature, and condensation zone temperature gradient on magnesium vapor nucleation in phase transitions and condensation from atomic collision and coacervation with collision under vacuum conditions were discussed. Magnesium powder and magnesium lump condensates were produced under different conditions and characterized by scanning electron microscopy （SEM） and energy-dispersive X-ray spectroscopy （EDS）. The right condensation zone temperature approach to the liquid transition primarily improved the magnesium vapor concentration rate. The gas-solid phase transition was primarily inhibited by setting a small condenser temperature gradient. Under the right condensation temperature and temperature gradients, increasing magnesium vapor partial pressure improved crystallization and reduced the oxidation rate.

Amine-grafted on lanthanide metal-organic frameworks:Three solid base catalysts for Knoevenagel condensation reaction

A post-synthetic modification strategy has been used to prepare three solid base catalysts, including Er（btc）（ED）075（H2O）0.25 （2, btc = 1,3,5-benzenetricarboxylates, ED = 1,2-ethanediamine）, Er（btc）（PP）0.55（H20）0.45 （3, PP = piperazine）, and Er（btc）（DABCO）0.15（H2O）0.85 （4, DABCO = 1,4- diazabicyclo[2.2.2]octane）, by grafting three different diamines onto the coordinatively unsaturated Er（III） ions into the channels of the desolvated lanthanide metal-organic framework （Er（otc））. The resulting metal-organic frameworks were characterized by elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and N2 adsorption. Based on its higher loading ratio of the diamine, as well as its greater stability and porosity, catalyst 2 exhibited higher catalytic activity and reusability than catalysts 3 and 4- for the Knoevenagel condensation reaction. The catalytic mechanism of 2 has also been investigated using size-selective catalysis tests.

一种改进的Condensation人脸特征点跟踪算法

Condensation跟踪算法只能完成一些简单的目标跟踪。由于人脸容易出现被遮挡,姿态和表情也经常发生变化,导致人脸特征点极易跟踪失败。针对这些复杂变化,提出一种改进的Condensation人脸特征点跟踪算法。该算法对跟踪的特征点利用增量PCA方法实现特征基和均值的在线更新,同时,加入一个遗忘因子,使得在新样本的更新过程中,考虑了旧样本的存在,更新了均值。实验证明,该算法可以有效地克服复杂变化带来的影响,实现了人脸特征点的准确跟踪。

Numerical investigation of condensation of gasoline vapor with turbulent flow in vertical tubes

To investigate the characteristics of the condensation in gasoline vapor condensation recovery,the condensation process of gasoline vapor with turbulent flow in a vertical tube is simulated based on the gas-liquid two-phase flow model.An effective diffusion coefficient is used to describe mass diffusion among the species of gasoline vapor.Several variables including temperature,pressure,liquid film thickness and the variation of the Nusselt number in the tube are simulated.The effects of the inlet-to-wall temperature difference and the Reynolds number on the condensation rate and the Nusselt number are obtained by modelling.The results show that heat transfer and condensation can be enhanced significantly by increasing the inlet Reynolds number.However,the increase in the inlet-to-wall temperature difference has little effect on the condensation rate.It is also found that the gasoline vapor condensation rate is influenced greatly by the mass transfer resistance.The comparison of results from the model with previous experiments shows a good agreement.

Mathe matical model and calculation for heat transfer during condensation on surfaces of corrugated plates

A mathematical model was established for condensation on surfaces of verticalcorrugated plates based on the mechanism of heat transfer enhancement to thin down the liquid filmdue to surface tension effect between corrugated plate surfaces and liquid films. The relative heattransfer coefficients of condensation on corrugation plates were calculated in contrast withequivalent vertical plane ones. The heat transfer enhancement effects for the main geometricparameters such as pitch, height, corrugation angle, tilt angle, and fillet radii of corrugationswere analyzed to guide the optimization of corrugation structure for application. A two-scalecorrugation is suggested, which can compromise both the enhanced heat transfer effect and adequatecross section area for flows, and it makes the heat transfer coefficient 1 to 2 times more than thatof an equivalent plane one.

Fabrication of amino-functionalized Fe_3O_4@Cu_3(BTC)_2 for heterogeneous Knoevenagel condensation

Metal organic frameworks（MOFs） are an important platform for heterogeneous catalysts.Although MOFs with a smaller particle size exhibit better catalytic performance because of less diffusion limitations,their separation and recycling after catalytic reactions are difficult.The integration of MOFs with magnetic nanoparticles could facilitate their recovery and separation.Especially,the shell thickness of the core-shell structured composites is controllable.In this study,amino-functionalized Fe3O4@Cu3（BTC）2 was fabricated by a stepwise assembly method and its catalytic performance in Knoevenagel condensation was investigated.The results demonstrated that the magnetic hybrid material exhibited a core-shell structure,with a shell thickness of about 2 00 nm.Furthermore,it not only exhibited high catalytic activity,but remarkably,it could also be easily recovered magnetically and recycled without obvious loss of catalytic efficiency after three cycles.

Fe_3O_4@UiO-66-NH_2 core–shell nanohybrid as stable heterogeneous catalyst for Knoevenagel condensation

separation is an attractive alternative to filtration or centrifugation for separating solid catalysts from a liquid phase, Here, core-shell Fe3O4@UiO-66-NH2 nanohybrids with well-defined structures were constructed by dispersing magnets in a dimethylformamide （DMF） solution con- taining two metal-organic framework （MOF） precursors, namely ZrCI4 and 2-aminobenzenetricar- boxylic acid. This method is simpler and more efficient than previously reported step-by-step method in which magnets were consecutively dispersed in DMF solutions each containing one MOF precursor, and the obtained Fe304@UiO-66-NH2 with three assembly cycles has a higher degree of crystallinity and porosiW. The core-shell Fe3O4@UiO-66-NH2 is highly active and selective in Knoevenagel condensations because of the bifunctionality of UiO-66-NH2 and better mass transfer in the nano-sized shells. It also has good recycling stability, and can be recovered magnetically and reused at least four times without significant loss of catalytic activity and framework integrity. The effects of substitution on the reactivity of benzaldehyde and of substrate size were also investigated.