The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl pho...The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.展开更多
The extraction of Nd^3+ and Sm^3+, including the extraction and stripping capability as well as the separation effect of Nd^3+ or Sm^3+, from a sulfuric acid medium, by mixtures of di-(2-ethylhexyl) phosphoric a...The extraction of Nd^3+ and Sm^3+, including the extraction and stripping capability as well as the separation effect of Nd^3+ or Sm^3+, from a sulfuric acid medium, by mixtures of di-(2-ethylhexyl) phosphoric acid (HDEHP, H2A2(0)) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (HEH/EHP, H2L2(0)) were studied. The distribution ratios and synergistic coefficients of Nd^3+ and Sm^3+ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3+ or Nd^3+. The chemical compositions of the extracted complex were determined as Nd.(HA2)2-HL2 and Sm.(HA2)2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.展开更多
Laboratory batch experiments were conducted to study arsenic (As) removal from a naturally contaminated soil using phosphoric acid (H3PO4) and potassium dihydrogen phosphate (KHEPO4). Both H3PO4 and KHEPO4 prove...Laboratory batch experiments were conducted to study arsenic (As) removal from a naturally contaminated soil using phosphoric acid (H3PO4) and potassium dihydrogen phosphate (KHEPO4). Both H3PO4 and KHEPO4 proved to reduce toxicity of the soil in terms of soil As content, attaining more than 20% As removal at a concentration of 200 mmol/L. At the same time, acidification of soil and dissolution of soil components (Ca, Mg, and Si) resulted from using these two extractants, especially H3PO4. The effectiveness of these two extractants could be attributed to the replacement of As by phosphate ions (PO4^3-). The function of H3PO4 as an acid to dissolve soil components had little effects on As removal. KH2PO4 almost removed as much As as H3PO4, but it did not result in serious damage to soils, indicating that it was a more promising extractant. The results of a kinetic study showed that As removal reached equilibrium after incubation for 360 rain, but dissolution of soil components, especially Mg and Ca, was very rapid. Therefore dissolution of soil components would be inevitable if As was further removed. Elovich model best described the kinetic data of As removal among the four models used in the kinetic study.展开更多
Phosphorite ore is a potential resource of rare earths (RE) as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid (WPA) is promising. This study investigated the influence of rotatio...Phosphorite ore is a potential resource of rare earths (RE) as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid (WPA) is promising. This study investigated the influence of rotational speed, extractant concentration, flow ratio and phase contact time on the centrifugal extraction of RE from WPA and the separation of RE from impurities. The results indicate that higher rotational speed, higher extractant concentration and larger flow ratio are beneficial to the extraction of RE and impurities from phosphoric acid. It is found that the phase contact time for efficiently extracting RE and that for iron are of great difference, which provides an effective method for separating RE from iron using the non-equilibrium extraction process in centrifugal contactors. Compared with equilibrium extraction, the separation factor βRE/Fe is enhanced from 0.07 to 17.6.展开更多
There are numerous impurities in wet-process phosphoric acid,among which manganese is one of detrimental metallic impurities,and it causes striking negative effects on the industrial phosphoric acid production and dow...There are numerous impurities in wet-process phosphoric acid,among which manganese is one of detrimental metallic impurities,and it causes striking negative effects on the industrial phosphoric acid production and downstream commodity.This article investigated the adsorption behavior of manganese from phosphoric acid employing Sinco-430 cationic ion-exchange resin.Resorting FT-IR and XPS characterizations,the adsorption mechanism was proved to be that manganese was combined with sulfonic acid group.Several crucial parameters such as temperature,phosphoric acid content and resin dose were studied to optimize adsorption efficiency.Through optimization,removal percentage and sorption capacity of manganese reached 53.12 wt%,28.34 mg·g^-1,respectively.Pseudo-2nd-order kinetic model simulated kinetics data best and the activation energy was evaluated as 6.34 kJ·mol^-1 for the sorption reaction of manganese.In addition,the global adsorption rate was first controlled by film diffusion process and second determined by pore diffusion process.It was found that the resin could adsorb up to 50.24 mg·g^-1 for manganese.Equilibrium studies showed that Toth adsorption isotherm model fitted best,followed by Temkin and Langmuir adsorption isotherm models.Thermodynamic analysis showed that manganese adsorption was an endothermic process with enhanced randomness and spontaneity.展开更多
Desupersaturation is a complex cooling operation that involves hydrodynamic,thermal and mechanical phenomena.This process requires continuous agitation to avoid fouling problems and sludge deposition.The current work ...Desupersaturation is a complex cooling operation that involves hydrodynamic,thermal and mechanical phenomena.This process requires continuous agitation to avoid fouling problems and sludge deposition.The current work aims to investigate the well mixedness in the desupersaturation tank for optimal performance.For this purpose,a multi-fluid CFD study was conducted based on the Euler–Euler modeling approach,considering a multiphase flow involving a liquid phase(phosphoric acid)and a poly-dispersed solid phase,i.e.a sludge with three different sizes where each size is considered as a separate phase.First,the hydrodynamic behavior of the flow within the agitated desupersaturator is analyzed through the investigation of the velocity fields as well as the power and pumping numbers,to determine both the agitator capacity to pump the flow and its power consumption during the operation.Then,in order to assess the mixture homogeneity,we evaluated the solid suspension in the desupersaturation reactor following conventional methods and two new proposed methodologies:the first approach is to evaluate the suspension quality in the mixing system by compartment and the second consists on the assessment of the uniform convergence of the solid concentration.Furthermore,we calculated the time required to achieve a full suspension at different solid concentrations.On other hand,we conducted a detailed analysis of the solid distribution dependency on the impeller rotational speed at different solid volume fraction,which allows a good understanding of the parameters controlling the homogenization in the desupersaturator.展开更多
Kiln phosphoric acid(KPA)technology could produce P2O5 with high purity and has been applied in thermal phosphoric acid industry;however the formation of fouling in the high-temperature rotary kiln restricts the stabl...Kiln phosphoric acid(KPA)technology could produce P2O5 with high purity and has been applied in thermal phosphoric acid industry;however the formation of fouling in the high-temperature rotary kiln restricts the stable and long-term operation.In this paper,the reaction of phosphate ores with gaseous P2O5 was investigated in a high-temperature reactor,and the Ca O-SiO2-P2O5 ternary phase diagram was analyzed to understand the fouling formation mechanism.The results showed that the low-melting-point products,such as Ca(PO3)2and Ca2P2O7,are responsible for the fouling in the KPA process.In addition,a small amount of impurities,e.g.,aluminum and iron,could facilitate the generation of the low-melting-point products and cause serious fouling.Based on the high-temperature SiO2-P2O5 and CaO-SiO2-P2O5 phase diagram analysis,the control of Si/Ca molar ratio(e.g.,Si/Ca=2.0)was found to avoid fouling formation in the kiln.These results could provide the operation parameters of reaction temperature and feeds composition to suppress the fouling in the kiln reactor for the phosphoric acid production in industry.展开更多
As the world's population exponentially grows,so does the need for the production of food,with cereal production growing annually from an estimated 1.0 billion to 2.5 billion tons within the last few decades.This ...As the world's population exponentially grows,so does the need for the production of food,with cereal production growing annually from an estimated 1.0 billion to 2.5 billion tons within the last few decades.This rapid growth in food production results in an ever increasing amount of agricultural wastes,of which already occupies nearly 50%of the total landfill area.For example,is the billions of dry tons of cellulose-containing spent coffee grounds disposed in landfills annually.This paper seeks to provide a method for isolating cellulose nanocrystals(CNCs)from spent coffee grounds,in order to recycle and utilize the cellulosic waste material which would otherwise have no applications.CNCs have already been shown to have vast applications in the polymer engineering field,mainly utilized for their high strength to weight ratio for reinforcement of polymer-based nanocomposites.A successful method of purifying and hydrolyzing the spent coffee grounds in order to isolate usable CNCs was established.The CNCs were then characterized using current techniques to determine important chemical and physical properties.A few crucial properties determined were aspect ratio of 12±3,crystallinity of 74.2%,surface charge density of(48.4±6.2)mM/kg cellulose,and the ability to successfully reinforce a polymer based nanocomposite.These characteristics compare well to other literature data and common commercial sources of CNCs.展开更多
Chiral amino cyclic phosphoric acids, 5-amino-2-hydroxy-4-(4-nitrophenyl)-1,3,2-dioxaphosphorinane 2-oxide and 2-hydroxy-4-(4-methylsulfonylphenyl)-5-phthalimido-1,3,2-dioxaphos phorinane 2-oxide are synthesized in go...Chiral amino cyclic phosphoric acids, 5-amino-2-hydroxy-4-(4-nitrophenyl)-1,3,2-dioxaphosphorinane 2-oxide and 2-hydroxy-4-(4-methylsulfonylphenyl)-5-phthalimido-1,3,2-dioxaphos phorinane 2-oxide are synthesized in good over yields (64.2%and 72.8%respectively) from 2-amino-1-aryl-1,3-propanediols. The different reaction conditions are necessary in hydrolysis reactions of amino cyclic phosphonyl chlorides.展开更多
A hybrid system that consists of a phosphoric acid fuel cell(PAFC),an absorption refrigerator and a refrigeration-space is proposed.The four-heat-source absorption refrigerator,which is driven by the waste heat produc...A hybrid system that consists of a phosphoric acid fuel cell(PAFC),an absorption refrigerator and a refrigeration-space is proposed.The four-heat-source absorption refrigerator,which is driven by the waste heat produced from PAFC,provides cooling for a refrigeration-space.A numerical model is set up to analyze both the steady-state performance and transient performance considering the influences of the electrochemical and thermodynamic irreversibilities.Expressions of the equivalent power output and efficiency of the hybrid system are determined.Moreover,the transient behavior of cold-space temperature is performed and the time to reach a prescribed cold-space temperature is displayed.Thus,the operation regions of the current are optimized at different operating conditions.The results showthat in an appropriate current range,the overall power output and efficiencies of the hybrid system are enhanced.展开更多
In order to study the effect of fused spinel on the properties of phosphoricacid bonded high alumina castables, samples with different contents of fused spinel were prepared.The results show that when the contents of ...In order to study the effect of fused spinel on the properties of phosphoricacid bonded high alumina castables, samples with different contents of fused spinel were prepared.The results show that when the contents of the fused spinel are between 8% and 16% (mass fraction),the castables have good properties. The castables overcome the shortages of the phosphoric acidbonded high alumina castables with bauxite cement as a hardening promoter. The experimentsdemonstrate that most of the service properties of the castables with fused spinel are better thanthose of the normal phosphoric acid bonded castables which use bauxite cement as a hardeningpromoter. The examination of the materials indicates that free MgO inclusions in the spinel powdercan promote the hardening of the castables.展开更多
Cellulose,being as the most abundant nature polymer material and the most promising oil substitute,attracts more and more interests.A new cellulose dissolution system,phosphoric acid(PA)/polyphosphoric acid(PPA) solve...Cellulose,being as the most abundant nature polymer material and the most promising oil substitute,attracts more and more interests.A new cellulose dissolution system,phosphoric acid(PA)/polyphosphoric acid(PPA) solvent,was investigated in this study.It had been found that a larger cellulose solid content could be dissolved quickly in a hypothermic situation.By evaluating the stability of regenerated cellulose film and the formation of anisotropic solution,the dissolution behavior of cellulose was investigated.Wide-angle X-ray diffraction(WAXD) and Fourier transform infrared spectroscopy(FT-IR) were employed to characterize the crystalline structure and morphology of regenerated cellulose.The measurement results revealed a transition from cellulose-Ⅰ of raw cellulose to cellulose-Ⅱ of regenerated cellulose and a decrease of crystallinity of cellulose after dissolved.This was attributed to the interaction between cellulose and acid solvent,which leaded to the breakage of cellulose intra-and inter-molecule hydrogen bonds and the conformation change of cellulose C6-OH.Moreover,the formation process of cellulose liquid crystal solution was illustrated by polarized light microscope(PLM).That may be induced by the rearranging movement of the cellulose macromolecular chains.展开更多
The dynamic competitive adsorption behaviors of different binary organic vapor mixtures on ACF-Ps under different operation conditions were investigated by gas chromatography in this paper. The studied mixtures includ...The dynamic competitive adsorption behaviors of different binary organic vapor mixtures on ACF-Ps under different operation conditions were investigated by gas chromatography in this paper. The studied mixtures included benzene/toluene, toluene/xylene, benzene/isopropylbenzene, ethyl acetate/toluene and benzene/ethyl acetate. Experimental results show that various ACF-Ps, as with ACF-W, can remove both vapors in binary vapor mixtures with over 99% of removal efficiency before the breakthrough point of the more weakly adsorbed vapor. In dynamic competitive adsorption, the more weakly adsorbed vapor not only penetrates early, but also will be displaced and desorbed consequently by stronger adsorbate and therefore produces a rolling up in the breakthrough curve. The ACF-Ps prepared at different temperatures have somewhat different adsorption selectivity. The feed concentration ratio of vapors, the length/diameter ratio and the thick of bed have effect on competitive adsorption. The competitive adsorption ability of a vapor is mainly related to its boiling point. Usually, the higher the boiling point, the stronger the vapor adsorbed on ACF-P.展开更多
Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful s...Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful synthesis of atropisomeric 2-arylindoles using direct amination of indoles with p-quinonediimines in the presence of chiral phosphoric acid as a catalyst.Quinonediimine acts as an aminating reagent through formal polarity inversion of imine.The malonate group on the 2-aryl of 2-indoles was found to be essen-tial for high enantioselectivity of the products.This could be due to the additional interaction between the ester group and the cata-lyst,as well as the intramolecular hydrogen bonding.Our findings provide a new strategy for the asymmetric construction of 2-arylindole atropisomers.展开更多
Catalytic enantioselective alkenylation is an efficient method to construct chiral alkene molecules,but the asymmetric alkenylation of simple alkenes catalyzed by metal-free catalysts remains an elusive challenge.Here...Catalytic enantioselective alkenylation is an efficient method to construct chiral alkene molecules,but the asymmetric alkenylation of simple alkenes catalyzed by metal-free catalysts remains an elusive challenge.Herein,we reported an asymmetric alkenylation of benzoxazinones with diarylethylenes by utilizing a B(C_(6)F_(5))_(3)/chiral phosphoric acid catalyst.A broad of benzoxazinones and diarylethylenes with electron-withdrawing and electron-donating groups were tolerated(up to 95%yield and 97.5:2.5 e.r.)in the methodology under mild reaction conditions.Moreover,the synthetic utility was confirmed by the scaled-up reaction and transformations of the products.The mechanism was preliminarily explored by control reactions,nonlinear effect experiment and DFT calculations.展开更多
Highly enantioselective sulfa-Michael additions(SMA)between 2-alkenyl quinoxalines and aromatic thiols are accomplished using a low loading of chiral phosphoric acid catalyst(1 mol%).It was confirmed by an investigati...Highly enantioselective sulfa-Michael additions(SMA)between 2-alkenyl quinoxalines and aromatic thiols are accomplished using a low loading of chiral phosphoric acid catalyst(1 mol%).It was confirmed by an investigation of a lot of azaarenes that the two C-N units of quinoxalines are indispensable for controlling the reaction enantioselectivities.A series of non-terminal 2-alkenes substituted with aryls or alkyls,even other electro-withdrawing groups such as ketones,esters,or amides,selectively reacted and afforded the desired SMA products(48 examples)in good regioselectivities with high yields(up to 99%)and good ee values(up to 97%).展开更多
It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)throug...It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)through expanding the dimensionality of proton conduction.Three COF-based composites,COF-1@PA,COF-2@PA,and COF-3@PA(PA:phosphoric acid),are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups.With the increase of hydrophilic groups,COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks.powder X-ray diffraction(PXRD),scanning electron microscopy(SEM),and two-dimensional(2D)solid-state nuclear magnetic resonance(NMR)analyses show that PA can not only enter the channels of COF-3,but also insert into its 2D interlayers.This expands the proton conduction pathways from one-dimensional(1D)to three-dimensional(3D),which greatly improves the proton conductivity of COF-3.Meanwhile,the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30(30μL of PA loaded on COF-3).At 150℃,COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1,which is a record of anhydrous proton conductivity reported to date.This work develops a new strategy for increasing the proton conductivity of 2D COF materials.展开更多
In this work,a super-low friction coefficient of 0.003 was found between a silicon nitride ball and a sapphire plate lubricated by phosphoric acid solution.The wear mainly occurred in the running-in period and disappe...In this work,a super-low friction coefficient of 0.003 was found between a silicon nitride ball and a sapphire plate lubricated by phosphoric acid solution.The wear mainly occurred in the running-in period and disappeared after superlubricity was achieved.The friction coefficient was effectively reduced from 0.3 to 0.003 at a constant speed of 0.076 m/s,accompanied by a 12-nm-thickness film.The lubrication regime was indicated to change from boundary lubrication in the running-in period to elastohydrodynamic lubrication in the superlubricity period,which is also supported by the results of the friction coefficient versus sliding speed.In addition,the experimental results showed good agreement with theoretical calculations based on the elastohydrodynamic lubrication theory,suggesting a significant hydrodynamic effect of phosphoric acid on superlubricity.展开更多
The well-defined conformational properties of axially chiral compounds bring extraordinary values to an assortment of bioactive molecules,advanced materials,organocatalysts as well as chiral ligands in asymmetric tran...The well-defined conformational properties of axially chiral compounds bring extraordinary values to an assortment of bioactive molecules,advanced materials,organocatalysts as well as chiral ligands in asymmetric transformations.The demonstrated usefulness and untapped potential of axially chiral structural motifs stimulate increasing efforts to develop novel and efficient approaches for their preparation.In this regard,the chiral phosphoric acids broadly used in asymmetric Brønsted acid catalysis have shown high relevance for atroposelective synthesis as well.Our strong interest in reaction chemistry of atropisomers has established a rewarding research programme in our group.The course of studies will be recounted in this account,with discussion focused on the use of chiral phosphoric acids to catalyze construction of several key axially chiral structures such as BINAM,BINOL,NOBIN,arylquinones,SPINOL,arylpyrrole analogues and axially chiral alkenes.展开更多
基金supported by the Science and Technology Research Project of Henan Province (192102310490 and 212102310505)。
文摘The efficient separation of amphoteric organic compounds from dilute solutions is of great importance in the industrial field. In the present work, the reactive extractions of 4-hydroxypyridine(4-HP) with tributyl phosphate(TBP), di(2-ethylhexyl) phosphoric acid(D2EHPA) and TBP + D2EHPA dissolved in 1-octanol were investigated, respectively. The influences of the initial concentrations of TBP, D2EHPA and TBP + D2EHPA on distribution ratio(D) were discussed, as well as the reactive extraction mechanism were proposed. The obvious intensification effect was observed when the mixture of TBP and D2EHPA was used as extractant. The best extraction conditions were found to be of the molar ratio of D2EHPA and TBP at 2:1 and the equilibrium aqueous pH at 3.50-4.50. D values increased with the increase of the total concentration of TBP and D2EHPA in 1-octanol. Especially, the analysis on the extraction mechanisms clearly indicate(i) TBP in 1-octanol shows negligible reactive extraction toward 4-HP,(ii) D2EHPA in 1-octanol exhibits moderate extraction effect by forming 4-HP:D2EHPA(1:1) and 4-HP:2D2EHPA(1:2) type complexes, while(iii) D2EHPA in TBP/1-octanol demonstrates the maximum distribution ratio with the 4-HP:D2EHPA(1:1) type complex domination. The discussion provides new insights on the mechanism and opens a new way for the intensified extraction of amphoteric organic compounds by using the mixture of multiple extractants in the diluent.
基金the National Natural Science Foundation of China (50674016)the National High Technology Research and Develop-ment Program of China (863 Program) ( 2006AA06Z123)
文摘The extraction of Nd^3+ and Sm^3+, including the extraction and stripping capability as well as the separation effect of Nd^3+ or Sm^3+, from a sulfuric acid medium, by mixtures of di-(2-ethylhexyl) phosphoric acid (HDEHP, H2A2(0)) and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (HEH/EHP, H2L2(0)) were studied. The distribution ratios and synergistic coefficients of Nd^3+ and Sm^3+ in different acidities were also determined. A synergistic extractive effect was found when HDEHP and HEH/EHP were used as mixed extractants for Sm^3+ or Nd^3+. The chemical compositions of the extracted complex were determined as Nd.(HA2)2-HL2 and Sm.(HA2)2-HL2. The extraction equilibrium constants, enthalpy change, and entropy change of the extraction reaction were also determined.
基金This work was supported by the National Natural Science Foundation of China(No.20677080,20477055).
文摘Laboratory batch experiments were conducted to study arsenic (As) removal from a naturally contaminated soil using phosphoric acid (H3PO4) and potassium dihydrogen phosphate (KHEPO4). Both H3PO4 and KHEPO4 proved to reduce toxicity of the soil in terms of soil As content, attaining more than 20% As removal at a concentration of 200 mmol/L. At the same time, acidification of soil and dissolution of soil components (Ca, Mg, and Si) resulted from using these two extractants, especially H3PO4. The effectiveness of these two extractants could be attributed to the replacement of As by phosphate ions (PO4^3-). The function of H3PO4 as an acid to dissolve soil components had little effects on As removal. KH2PO4 almost removed as much As as H3PO4, but it did not result in serious damage to soils, indicating that it was a more promising extractant. The results of a kinetic study showed that As removal reached equilibrium after incubation for 360 rain, but dissolution of soil components, especially Mg and Ca, was very rapid. Therefore dissolution of soil components would be inevitable if As was further removed. Elovich model best described the kinetic data of As removal among the four models used in the kinetic study.
基金the National High Technology Research and Development Program of China (No.2006AA06Z126) for the financial aid
文摘Phosphorite ore is a potential resource of rare earths (RE) as well as phosphate; therefore, the recovery of RE from wet-process phosphoric acid (WPA) is promising. This study investigated the influence of rotational speed, extractant concentration, flow ratio and phase contact time on the centrifugal extraction of RE from WPA and the separation of RE from impurities. The results indicate that higher rotational speed, higher extractant concentration and larger flow ratio are beneficial to the extraction of RE and impurities from phosphoric acid. It is found that the phase contact time for efficiently extracting RE and that for iron are of great difference, which provides an effective method for separating RE from iron using the non-equilibrium extraction process in centrifugal contactors. Compared with equilibrium extraction, the separation factor βRE/Fe is enhanced from 0.07 to 17.6.
文摘There are numerous impurities in wet-process phosphoric acid,among which manganese is one of detrimental metallic impurities,and it causes striking negative effects on the industrial phosphoric acid production and downstream commodity.This article investigated the adsorption behavior of manganese from phosphoric acid employing Sinco-430 cationic ion-exchange resin.Resorting FT-IR and XPS characterizations,the adsorption mechanism was proved to be that manganese was combined with sulfonic acid group.Several crucial parameters such as temperature,phosphoric acid content and resin dose were studied to optimize adsorption efficiency.Through optimization,removal percentage and sorption capacity of manganese reached 53.12 wt%,28.34 mg·g^-1,respectively.Pseudo-2nd-order kinetic model simulated kinetics data best and the activation energy was evaluated as 6.34 kJ·mol^-1 for the sorption reaction of manganese.In addition,the global adsorption rate was first controlled by film diffusion process and second determined by pore diffusion process.It was found that the resin could adsorb up to 50.24 mg·g^-1 for manganese.Equilibrium studies showed that Toth adsorption isotherm model fitted best,followed by Temkin and Langmuir adsorption isotherm models.Thermodynamic analysis showed that manganese adsorption was an endothermic process with enhanced randomness and spontaneity.
文摘Desupersaturation is a complex cooling operation that involves hydrodynamic,thermal and mechanical phenomena.This process requires continuous agitation to avoid fouling problems and sludge deposition.The current work aims to investigate the well mixedness in the desupersaturation tank for optimal performance.For this purpose,a multi-fluid CFD study was conducted based on the Euler–Euler modeling approach,considering a multiphase flow involving a liquid phase(phosphoric acid)and a poly-dispersed solid phase,i.e.a sludge with three different sizes where each size is considered as a separate phase.First,the hydrodynamic behavior of the flow within the agitated desupersaturator is analyzed through the investigation of the velocity fields as well as the power and pumping numbers,to determine both the agitator capacity to pump the flow and its power consumption during the operation.Then,in order to assess the mixture homogeneity,we evaluated the solid suspension in the desupersaturation reactor following conventional methods and two new proposed methodologies:the first approach is to evaluate the suspension quality in the mixing system by compartment and the second consists on the assessment of the uniform convergence of the solid concentration.Furthermore,we calculated the time required to achieve a full suspension at different solid concentrations.On other hand,we conducted a detailed analysis of the solid distribution dependency on the impeller rotational speed at different solid volume fraction,which allows a good understanding of the parameters controlling the homogenization in the desupersaturator.
基金support from the National Key R&D Program of China(2018YFC1900201)the Provincial Key R&D Program of Shanxi(201603D31212003)。
文摘Kiln phosphoric acid(KPA)technology could produce P2O5 with high purity and has been applied in thermal phosphoric acid industry;however the formation of fouling in the high-temperature rotary kiln restricts the stable and long-term operation.In this paper,the reaction of phosphate ores with gaseous P2O5 was investigated in a high-temperature reactor,and the Ca O-SiO2-P2O5 ternary phase diagram was analyzed to understand the fouling formation mechanism.The results showed that the low-melting-point products,such as Ca(PO3)2and Ca2P2O7,are responsible for the fouling in the KPA process.In addition,a small amount of impurities,e.g.,aluminum and iron,could facilitate the generation of the low-melting-point products and cause serious fouling.Based on the high-temperature SiO2-P2O5 and CaO-SiO2-P2O5 phase diagram analysis,the control of Si/Ca molar ratio(e.g.,Si/Ca=2.0)was found to avoid fouling formation in the kiln.These results could provide the operation parameters of reaction temperature and feeds composition to suppress the fouling in the kiln reactor for the phosphoric acid production in industry.
文摘As the world's population exponentially grows,so does the need for the production of food,with cereal production growing annually from an estimated 1.0 billion to 2.5 billion tons within the last few decades.This rapid growth in food production results in an ever increasing amount of agricultural wastes,of which already occupies nearly 50%of the total landfill area.For example,is the billions of dry tons of cellulose-containing spent coffee grounds disposed in landfills annually.This paper seeks to provide a method for isolating cellulose nanocrystals(CNCs)from spent coffee grounds,in order to recycle and utilize the cellulosic waste material which would otherwise have no applications.CNCs have already been shown to have vast applications in the polymer engineering field,mainly utilized for their high strength to weight ratio for reinforcement of polymer-based nanocomposites.A successful method of purifying and hydrolyzing the spent coffee grounds in order to isolate usable CNCs was established.The CNCs were then characterized using current techniques to determine important chemical and physical properties.A few crucial properties determined were aspect ratio of 12±3,crystallinity of 74.2%,surface charge density of(48.4±6.2)mM/kg cellulose,and the ability to successfully reinforce a polymer based nanocomposite.These characteristics compare well to other literature data and common commercial sources of CNCs.
基金Supported by the Science and Technology Fund of Wuhan City(No:996001016G)
文摘Chiral amino cyclic phosphoric acids, 5-amino-2-hydroxy-4-(4-nitrophenyl)-1,3,2-dioxaphosphorinane 2-oxide and 2-hydroxy-4-(4-methylsulfonylphenyl)-5-phthalimido-1,3,2-dioxaphos phorinane 2-oxide are synthesized in good over yields (64.2%and 72.8%respectively) from 2-amino-1-aryl-1,3-propanediols. The different reaction conditions are necessary in hydrolysis reactions of amino cyclic phosphonyl chlorides.
文摘A hybrid system that consists of a phosphoric acid fuel cell(PAFC),an absorption refrigerator and a refrigeration-space is proposed.The four-heat-source absorption refrigerator,which is driven by the waste heat produced from PAFC,provides cooling for a refrigeration-space.A numerical model is set up to analyze both the steady-state performance and transient performance considering the influences of the electrochemical and thermodynamic irreversibilities.Expressions of the equivalent power output and efficiency of the hybrid system are determined.Moreover,the transient behavior of cold-space temperature is performed and the time to reach a prescribed cold-space temperature is displayed.Thus,the operation regions of the current are optimized at different operating conditions.The results showthat in an appropriate current range,the overall power output and efficiencies of the hybrid system are enhanced.
文摘In order to study the effect of fused spinel on the properties of phosphoricacid bonded high alumina castables, samples with different contents of fused spinel were prepared.The results show that when the contents of the fused spinel are between 8% and 16% (mass fraction),the castables have good properties. The castables overcome the shortages of the phosphoric acidbonded high alumina castables with bauxite cement as a hardening promoter. The experimentsdemonstrate that most of the service properties of the castables with fused spinel are better thanthose of the normal phosphoric acid bonded castables which use bauxite cement as a hardeningpromoter. The examination of the materials indicates that free MgO inclusions in the spinel powdercan promote the hardening of the castables.
文摘Cellulose,being as the most abundant nature polymer material and the most promising oil substitute,attracts more and more interests.A new cellulose dissolution system,phosphoric acid(PA)/polyphosphoric acid(PPA) solvent,was investigated in this study.It had been found that a larger cellulose solid content could be dissolved quickly in a hypothermic situation.By evaluating the stability of regenerated cellulose film and the formation of anisotropic solution,the dissolution behavior of cellulose was investigated.Wide-angle X-ray diffraction(WAXD) and Fourier transform infrared spectroscopy(FT-IR) were employed to characterize the crystalline structure and morphology of regenerated cellulose.The measurement results revealed a transition from cellulose-Ⅰ of raw cellulose to cellulose-Ⅱ of regenerated cellulose and a decrease of crystallinity of cellulose after dissolved.This was attributed to the interaction between cellulose and acid solvent,which leaded to the breakage of cellulose intra-and inter-molecule hydrogen bonds and the conformation change of cellulose C6-OH.Moreover,the formation process of cellulose liquid crystal solution was illustrated by polarized light microscope(PLM).That may be induced by the rearranging movement of the cellulose macromolecular chains.
基金supported by Major Natural Science Foundation of Guangdong Provincethe Trans-century Training Programmed Foundation for the Talents of the State Education Ministry of Chinaand the Foundation for the Key Teachers in Chinese University
文摘The dynamic competitive adsorption behaviors of different binary organic vapor mixtures on ACF-Ps under different operation conditions were investigated by gas chromatography in this paper. The studied mixtures included benzene/toluene, toluene/xylene, benzene/isopropylbenzene, ethyl acetate/toluene and benzene/ethyl acetate. Experimental results show that various ACF-Ps, as with ACF-W, can remove both vapors in binary vapor mixtures with over 99% of removal efficiency before the breakthrough point of the more weakly adsorbed vapor. In dynamic competitive adsorption, the more weakly adsorbed vapor not only penetrates early, but also will be displaced and desorbed consequently by stronger adsorbate and therefore produces a rolling up in the breakthrough curve. The ACF-Ps prepared at different temperatures have somewhat different adsorption selectivity. The feed concentration ratio of vapors, the length/diameter ratio and the thick of bed have effect on competitive adsorption. The competitive adsorption ability of a vapor is mainly related to its boiling point. Usually, the higher the boiling point, the stronger the vapor adsorbed on ACF-P.
基金support from the National Key R&D Program of China (2022YFA1503703,2021YFF0701604)the National Natural Science Foundation of China (21825105,22231004,22271135)+1 种基金Guangdong Innovative Program (2019BT02Y335)Shenzhen Science and Technology Program (KQTD20210811090112004,JCYJ20210324120205016,JCYJ20210324105005015).
文摘Indole-based atropisomers are a very important class of axially chiral compounds.However,the atroposelective synthesis of axially chiral 2-arylindole remains largely unexplored.In this study,we report the successful synthesis of atropisomeric 2-arylindoles using direct amination of indoles with p-quinonediimines in the presence of chiral phosphoric acid as a catalyst.Quinonediimine acts as an aminating reagent through formal polarity inversion of imine.The malonate group on the 2-aryl of 2-indoles was found to be essen-tial for high enantioselectivity of the products.This could be due to the additional interaction between the ester group and the cata-lyst,as well as the intramolecular hydrogen bonding.Our findings provide a new strategy for the asymmetric construction of 2-arylindole atropisomers.
基金National Natural Science Foundation of China(Nos.22193011,21971120 and 21933008)National Science&Technology Fundamental Resource Investigation Program of China(No.2018FY201200)for financial support.
文摘Catalytic enantioselective alkenylation is an efficient method to construct chiral alkene molecules,but the asymmetric alkenylation of simple alkenes catalyzed by metal-free catalysts remains an elusive challenge.Herein,we reported an asymmetric alkenylation of benzoxazinones with diarylethylenes by utilizing a B(C_(6)F_(5))_(3)/chiral phosphoric acid catalyst.A broad of benzoxazinones and diarylethylenes with electron-withdrawing and electron-donating groups were tolerated(up to 95%yield and 97.5:2.5 e.r.)in the methodology under mild reaction conditions.Moreover,the synthetic utility was confirmed by the scaled-up reaction and transformations of the products.The mechanism was preliminarily explored by control reactions,nonlinear effect experiment and DFT calculations.
基金supported by the West Light Foundation of the Chinese Academy of Sciences(No.25E0C304)the Sichuan Science and Technology Program(No.2021ZYD0061).
文摘Highly enantioselective sulfa-Michael additions(SMA)between 2-alkenyl quinoxalines and aromatic thiols are accomplished using a low loading of chiral phosphoric acid catalyst(1 mol%).It was confirmed by an investigation of a lot of azaarenes that the two C-N units of quinoxalines are indispensable for controlling the reaction enantioselectivities.A series of non-terminal 2-alkenes substituted with aryls or alkyls,even other electro-withdrawing groups such as ketones,esters,or amides,selectively reacted and afforded the desired SMA products(48 examples)in good regioselectivities with high yields(up to 99%)and good ee values(up to 97%).
基金We are grateful for financial support from the National Natural Science Foundation of China(Nos.21771193 and 22275210)Key Research and Development Projects of Shandong Province(No.2019JZZY010331).
文摘It is of great significance to develop high-temperature anhydrous proton conducting materials.Herein,we report a new strategy to significantly enhance the proton conductivity of covalent organic frameworks(COFs)through expanding the dimensionality of proton conduction.Three COF-based composites,COF-1@PA,COF-2@PA,and COF-3@PA(PA:phosphoric acid),are prepared by PA doping of three COFs with similar pore sizes but different amounts of hydrophilic groups.With the increase of hydrophilic groups,COFs can load more PA because of the enhanced hydrogen–bonding interactions between PA and the frameworks.powder X-ray diffraction(PXRD),scanning electron microscopy(SEM),and two-dimensional(2D)solid-state nuclear magnetic resonance(NMR)analyses show that PA can not only enter the channels of COF-3,but also insert into its 2D interlayers.This expands the proton conduction pathways from one-dimensional(1D)to three-dimensional(3D),which greatly improves the proton conductivity of COF-3.Meanwhile,the confinement effect of 1D channels and 2D layers of COF-3 also makes the hydrogen-bonded networks more orderly in COF-3@PA-30(30μL of PA loaded on COF-3).At 150℃,COF-3@PA-30 exhibits an ultrahigh anhydrous proton conductivity of 1.4 S·cm−1,which is a record of anhydrous proton conductivity reported to date.This work develops a new strategy for increasing the proton conductivity of 2D COF materials.
基金supported by the National Key Basic Research(973)Program of China(No.2013CB934200)the National Natural Science Foundation of China(Nos.51222507,51335005,51321092).
文摘In this work,a super-low friction coefficient of 0.003 was found between a silicon nitride ball and a sapphire plate lubricated by phosphoric acid solution.The wear mainly occurred in the running-in period and disappeared after superlubricity was achieved.The friction coefficient was effectively reduced from 0.3 to 0.003 at a constant speed of 0.076 m/s,accompanied by a 12-nm-thickness film.The lubrication regime was indicated to change from boundary lubrication in the running-in period to elastohydrodynamic lubrication in the superlubricity period,which is also supported by the results of the friction coefficient versus sliding speed.In addition,the experimental results showed good agreement with theoretical calculations based on the elastohydrodynamic lubrication theory,suggesting a significant hydrodynamic effect of phosphoric acid on superlubricity.
文摘The well-defined conformational properties of axially chiral compounds bring extraordinary values to an assortment of bioactive molecules,advanced materials,organocatalysts as well as chiral ligands in asymmetric transformations.The demonstrated usefulness and untapped potential of axially chiral structural motifs stimulate increasing efforts to develop novel and efficient approaches for their preparation.In this regard,the chiral phosphoric acids broadly used in asymmetric Brønsted acid catalysis have shown high relevance for atroposelective synthesis as well.Our strong interest in reaction chemistry of atropisomers has established a rewarding research programme in our group.The course of studies will be recounted in this account,with discussion focused on the use of chiral phosphoric acids to catalyze construction of several key axially chiral structures such as BINAM,BINOL,NOBIN,arylquinones,SPINOL,arylpyrrole analogues and axially chiral alkenes.