To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the character...To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the characteristics of low-tempe rature sulfuric acid deco mposition.When a single monazite was leached using 75 wt% H_(2)SO_(4) solution with phosphoric acid,the size and number of monazite particles in the washing slag gradually decrease with the increase in phosphoric acid content in the leaching solution.The monazite phase can hardly be found in the slag when the phosphoric acid content reaches 70 g/L,which indicates that phosphoric acid is favorable for monazite decomposition.The mixed rare earth concentrate was leached by 75 wt% H_(2)SO_(4) containing 70 g/L phosphoric acid,the mineral compositions of the washing slag are only gypsum and unwashed rare earth sulfuric acid.After cyclic leaching of75 wt% H_(2)SO_(4),the mineral compositions of the primary leaching washing slag are mainly undecomposed monazite,rare earth sulfate and calcium sulfate.However,monazite is not found in the mineral phase of the second and third leaching washing slag.The leaching rates of rare earth and phosphorus gradually increase with the increase in cyclic leaching times.In addition,the phosphoric acid content in the leaching solution increases with the increase in the number of cyclic leaching time.However,the rising trend decreases when the phosphoric acid content reaches 50 g/L by adsorption and crystallization of phosphoric acid.A small amount of water can be used to clean the leaching residue before washing to recover the more soluble phosphorus acid according to the difference of dissolution between phosphoric acid and rare earth sulfuric acid.展开更多
The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalys...The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.展开更多
Phosphoric acid is a key ingredient in fertilizer production and contains many rare earth elements(REEs).Recovering REEs from phosphoric acid can prevent the accumulation of these elements in the soil and help bridge ...Phosphoric acid is a key ingredient in fertilizer production and contains many rare earth elements(REEs).Recovering REEs from phosphoric acid can prevent the accumulation of these elements in the soil and help bridge the gap between supply and demand.In this concern,a new material called Si-6G PAMAMPPAAM dendrimers modified silica gel terminated with phenylphosphonic acid-amide moieties was developed and its ability to adsorb Nd(Ⅲ)and Er(Ⅲ)from the phosphoric acid solution was investigated.K inetics and isotherm of the uptake process were investigated to explo re the so rption characte ristics.The attained results show that both metal ions exhibit the same adsorption performance,and the uptake process is depicted as a chemisorption,monolayer,uniform,and homogeneous process.The equilibrium state is achieved within 120 min,and the maximum uptake capacity is 16.7 mg Nd(Ⅲ)/g,and 14.0 mg Er(Ⅲ)/g.Sorption thermodynamics is an endothermic,spontaneous,and feasible uptake process.Nitric acid(1.0 mol/L)is found to be efficient for adsorbing about 94.3%and 92.5%of neodymium(Ⅲ)and erbium(Ⅲ)respectively,and the prepared Si-6G PAMAM-PPAAM demonstrates excellent stability over five consecutive sorption/desorption cycles.Preliminary tests on commercial phosphoric acid demonstrate that Si-6G PAMAM-PPAAM retains its effective REEs uptake from a complex comm ercial phosph oric acid solution.展开更多
The significance of axial chiral compounds in asymmetric organic catalysis,functional materials,and pharmaceutical useful molecules has encouraged advancements in the atroposelective synthesis of such compounds.Herein...The significance of axial chiral compounds in asymmetric organic catalysis,functional materials,and pharmaceutical useful molecules has encouraged advancements in the atroposelective synthesis of such compounds.Herein,we report the first atroposelective construction of axially chiral N-aryl benzimidazoles catalyzed by a polymer-supported chiral phosphoric acid.A varied library of atropisomers has been synthesized in 30%-96%yield with 58%-98%enantiomeric excess(ee)under a straightforward reaction setup(without the use of molecular sieves).Notably,even after 12 cycles,the immobilized catalyst maintained its reactivity and selectivity(TON>540).展开更多
All-cellulose composites(ACCs)are composites that use non-derivatized cellulose as both the matrix and the reinforcement phase.ACC consists entirely of cellulose,and since the reinforcement phase and the matrix have e...All-cellulose composites(ACCs)are composites that use non-derivatized cellulose as both the matrix and the reinforcement phase.ACC consists entirely of cellulose,and since the reinforcement phase and the matrix have exactly the same chemical properties,they can overcome the problem of poor fiber-matrix adhesion in biocomposites.In this study,ACC was prepared by partially dissolving wood pulp in a cryogenic aqueous phosphoric acid solution,and the effects of dissolution temperature,dissolution time and pressing load on the properties of ACC were investigated.The results showed that a dissolution time of 45 min achieved the optimal reinforcement-matrix ratio.The use of an aqueous ethanol solution at an ethanol mass fraction of 50%as a coagulation bath and a pressing load of 3000 kg during the drying process achieved the best mechanical properties of ACC,with a tensile strength of 49.3 MPa(approximately 210%higher than that of the untreated wood pulp)and an elastic modulus of 1.6 GPa(approximately 122%higher than that of the untreated wood pulp).The composite’s compactness affected ACC’s mechanical properties.The air permeability analysis showed that the barrier performance of ACC was also significantly better than that of the untreated wood pulp.With a pressing load of 3500 kg,the surface water contact angle(WCA)increased to 110.3°(approximately 94%higher than that of the untreated wood pulp),and the air permeability was significantly reduced to 1.1 mm/s,showing its good application prospects in the field of green packaging materials.展开更多
A comprehensive mechanistic study on the chiral phosphoric acid catalyzed an enantioselective asymmetric aza-pinacol rearrangement of 4-chloro-N-(2-(3'-hydroxy-1'-phenylspiro[cyclopentane-1,2'-indolin]-3&#...A comprehensive mechanistic study on the chiral phosphoric acid catalyzed an enantioselective asymmetric aza-pinacol rearrangement of 4-chloro-N-(2-(3'-hydroxy-1'-phenylspiro[cyclopentane-1,2'-indolin]-3'-yl)ethyl)(1a)is investigated at the M06-2X/6-311+G(d,p)level.Our computational results suggest that the whole catalytic cycle proceeds through dehydration of 1a,enantioselective aza-pinacol rearrangement,intramolecular cyclization and catalyst regeneration to deliver the fused indoline product.The aza-pinacol rearrangement is the key stereocontrolling step of the title reaction.The chiral catalyst controls the orientation of the transition states of the enantioselective step through two potential binding sites between the bifunctional chiral phosphate and the aza-ortho-xylylene intermediate.Moreover,theoretical studies identified that the multiple C—H…π,C—H…O,and C—H…N hydrogen bonds and N—H…O^(-)electrostatic interactions between the substrates and the arms as well as functional oxygen anion of the chiral catalyst(R)-4c play a crucial role in determining the stereochemical outcomes.And the strong N—H…O^(-)interaction in the major transition state was found to contribute to the high levels of enantioselectivity.Additionally,the predicted enantiomeric excess(ee)of 89%based on the 6.3 kJ·mol^(–1)energy difference between the enantioselective TS-2-major and TS-2-minor is in agreement with the experimental results of 90%.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
A comparison between the effects of ordinary walnut shell and phosphoric acid modified walnut shell on adsorption of Cr（Ⅵ） was carried out. The experimental results showed that owing to larger surface void of modif...A comparison between the effects of ordinary walnut shell and phosphoric acid modified walnut shell on adsorption of Cr（Ⅵ） was carried out. The experimental results showed that owing to larger surface void of modified walnut shell its adsorption of Cr（Ⅵ） was better. When the temperature was 35 ℃, adsorbent particle size was 1.0-1.6 mm, shaker shock rate was 200 r/min, and dosage of walnut shell was 0.80 g, the Cr（Ⅵ） removal rate reached 99.4%. The fitting of adsorption isotherm and kinetics model showed that, Langmuir isotherm model could reflect the adsorption process of modified walnut shell; and both the adsorption processes of ordinary and modified walnut shells accorded with the pseudo-second-order kinetic equations.展开更多
Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation ex...Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation exchange resin for iron removal from phosphoric acid. The specific surface area and the total exchange capacity of resin were 8.91 m2·g-1 and 5.18 mmol·g-1, respectively. The sorption mechanism was determined by FTIR and XPS and the results indicated that iron was combined with-SO3 H in resin. The removal process was studied as a function of temperature, H3 PO4 content and mass ratio between resin and solution. The unit mass of resin to remove iron was 0.058 g·g-1 resin when the operating parameters were T = 50 ℃, H3 PO4 content = 27.61 wt%and S/L = 0.1, respectively. Kinetics study demonstrated that pseudo-second-order reaction model fits this study best and the calculated activation energy of overall reaction is 29.10 kJ·mol-1. The overall reaction process was mainly controlled by pore diffusion.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
The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H3PO4) offers a promising method for the selective production of levoglucosenone (LGO),a valuable anhydrosugar product.However,the fundamenta...The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H3PO4) offers a promising method for the selective production of levoglucosenone (LGO),a valuable anhydrosugar product.However,the fundamental mechanism for selective LGO formation is unclear.Herein,quantum chemistry calculations and catalytic fast pyrolysis experiments were performed to reveal the formation mechanism of LGO in H3PO4-catalyzed cellulose pyrolysis.H3PO4 significantly decreased the energy barriers of the pyrolytic reactions and altered the competitiveness of the LGO formation pathways,promoting LGO formation.Through different pathways in the non-catalytic and H3P04-catalyzed conditions,LGO is mainly produced from the primary decomposition of glucose units of cellulose and secondary conversion of levoglucosan.The major catalytic formation pathways of LGO comprise similar reactions,with dehydration at the 3-OH+2-H site as the rate-determining step.Importantly,secondary conversion of 1,4;3,6-dianhydro-α-D-glucopyranose is not feasible for LGO formation,in contrast to previous reports.In addition,a high degree of polymerization is beneficial for the selectivity of LGO formation in the catalytic process,because the glycosidic bond is important for the formation of the bicyclic structure (1,5-and1,6-acetal rings).展开更多
This review summarizes the very recent advances in asymmetric reactions catalyzed by chiral phosphoric acids（CPAs）, a family of versatile catalysts that catalyze a broad range of reactions to afford diverse chiral m...This review summarizes the very recent advances in asymmetric reactions catalyzed by chiral phosphoric acids（CPAs）, a family of versatile catalysts that catalyze a broad range of reactions to afford diverse chiral molecules. In the past years, different kinds of chiral phosphoric acids have been designed and developed into a privileged class of catalysts in asymmetric synthesis. A number of remarkable achievements have been made by many groups around the world. Due to length limitation, this review only summarizes those works published from January 2016 to November 2017. Meanwhile, catalytic systems which combine metal catalysts and chiral phosphoric acids will not be discussed in this review.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
The rheological behavior of phosphoric acid-water glass grout in different mixing ratios was studied. Grout made of water glass with Baume degree of 20° and 13.4% phosphoric acid by 1:1 volume ratio is found to b...The rheological behavior of phosphoric acid-water glass grout in different mixing ratios was studied. Grout made of water glass with Baume degree of 20° and 13.4% phosphoric acid by 1:1 volume ratio is found to be more effective in stopping water. Laboratory model test of water shutoff by grouting was conducted. Test results show that the diffusion length and water cutoff effect of the grout are significantly improved as the grout head is raised, due to the dilution of underground water, and it takes the grout longer than its gel time to cut off water.展开更多
The recovery of rare earth elements(REEs)from NdFeB slurry by traditional hydrometallurgy has been limited becuase a large number of REEs are lost during separation together with iron.In this paper,a simple and sustai...The recovery of rare earth elements(REEs)from NdFeB slurry by traditional hydrometallurgy has been limited becuase a large number of REEs are lost during separation together with iron.In this paper,a simple and sustainable method is proposed to efficiently separate and recover REEs and iron from NdFeB slurry.REEs were recovered by one-step selective precipitation in phosphoric acid,and the dissolved iron was recovered by oxalic acid.Phosphoric acid leaching results show that under the conditions of 4 mol/L phosphoric acid,80℃,L/S of 30:1 and 90 min,the leaching efficiencies of Fe and REEs reach 98.76%and1.09%,respectively.While the rest of REEs remained in the leaching residue in the form of REEPO_(4)·nH_(2)O precipitation.Subsequently.the mixed rare earth oxide(rare earth oxalate roasted at 800℃)and FeC_(2)O_(4)·2 H_(2)O are obtained by oxalic acid precipitation with purities of 99.49%and 97.17%from the REEPO4·nH_(2)O dissolving solution and the phosphoric acid leaching solution.Moreover,the phosphoric acid is regenerated while recovering iron,and it can be reused in the phosphoric acid leaching step after removing the impurity C_(2)O_(4)^(2-).In summary,this work provides an efficient and environmentally friendly method for recovering REEs and iron from NdFeB slurry waste.展开更多
Calcium molybdate(CaMoO4)is the main component of powellite and is a predominant intermediate in the pyrometallurgical and hydrometallurgical process of molybdenum.The extraction of Mo from CaMoO4 by a combination of ...Calcium molybdate(CaMoO4)is the main component of powellite and is a predominant intermediate in the pyrometallurgical and hydrometallurgical process of molybdenum.The extraction of Mo from CaMoO4 by a combination of phosphoric acid and hydrochloric acid was investigated.For further understanding of the leaching mechanism,the effects of five key factors were studied to describe the leaching kinetics.The results indicated that the dissolution rate of CaMoO4 was independent of the stirring speed.Mo extraction significantly increased with increasing HCl concentration and temperature,but decreased with increasing particle size.A shrinking core model with surface chemical reaction was found to withstand the dissolution of CaMoO4.The apparent activation energy was calculated to be 70.879 kJ/mol,and a semi-empirical equation was derived for the rate of reaction.展开更多
Solid-liquid extraction of gadolinium was investigated from phosphoric acid medium using commercial amino phosphonic acid resin, Tulsion CH-93. The experimental conditions studied included equilibration time, acid con...Solid-liquid extraction of gadolinium was investigated from phosphoric acid medium using commercial amino phosphonic acid resin, Tulsion CH-93. The experimental conditions studied included equilibration time, acid concentration, mass of the resin, metal concentration, loading and elution. The percent extraction of Gd（Ⅲ） was studied as a function of phosphoric acid （0.05-3 mol/L） using Tulsion CH-93 resin. The corresponding lgD vs. equilibrium pH plot gave straight line with a slope of 1.8. The percent extraction decreased with acid co centration increasing, conforming ion exchange mechanism. Under observed experimental conditions the loading capacity of Tulsion CH-93 for gadolinium was 10.6 mg/g. Among several eluants screened, the quantitative elution of Gd（III） from loaded Tulsion CH-93 was obtained with ammonium oxalate （0.15 mol/L）. The extraction behavior of commonly associated metals with gadolinium was studied as a function of phosphoric acid concentration. Tulsion CH-93 resin showed selective extraction towards heavy rare earths （Lu and Yb） which could be separated from other rare earths at 3 mol/L H3PO4, similar to wet phosphoric acid （3-5 mol/L）. On the other hand Gd（Ⅲ） and other rare earths were studied with chelating resin Tulsion CH-90. Light rare earths were highly extracted and these could be separated from heavy rare earths and Gd.展开更多
Activated carbon was prepared from bamboo by mechanochemical process with phosphoric acid as activating agent.The effects of milling time on the adsorption property and porous structure of the obtained activated car-b...Activated carbon was prepared from bamboo by mechanochemical process with phosphoric acid as activating agent.The effects of milling time on the adsorption property and porous structure of the obtained activated car-bon were discussed.The results showed that phosphoric acid activation assisted by mechanochemical process can slightly improve the adsorption performance of the prepared activated carbon.The iodine,methylene blue adsorption value and the specific surface area of the prepared activated carbons increased from 840.16 mg/g,168 mg/g and 1229.246 m/g to 947.51 mg/g,195 mg/g,and 1265.373 m2/g,respectively.Compared with conventional phosphoric acid activation,the activated carbon produced by mechanochemical process has greater adsorption capacity.展开更多
In order to provide practical fundamental data for rare-earth elements （REEs） recovery from phosphoric acid and to betterunderstand REEs behavior during the phosphoric acid evaporation process, the solubilities of R...In order to provide practical fundamental data for rare-earth elements （REEs） recovery from phosphoric acid and to betterunderstand REEs behavior during the phosphoric acid evaporation process, the solubilities of REEs in phosphoric acid with variousconcentrations of phosphorus at different temperatures were measured. A simple linear model between REEs solubility andphosphoric acid concentration is built and the experimental data are found to fit it very well （R2〉0.94）. Hydrogen-ion concentration isfound to be the predominant factor controlling the solubility of REEs in phosphoric acid. In addition, the solubility of REEs inphosphoric acid is found to sharply decrease with increasing temperature, which can be attributed to the increase of the Gibbs energyof the REEPO4 dissolution reaction or the restraint of the disassociation of phosphoric acid molecules owing to the elevatedtemperature.展开更多
基金support by the National Natural Science Foundation of Inner Mongolia (2022SHZR1885)Natural Science Foundation of Hebei province (E2022402101,E2022402105)。
文摘To completely recover valuable elements and reduce the amount of waste,the impact of phosphoric acid on the decomposition of rare earth,fluorine and phosphorus during cyclic leaching was studied based on the characteristics of low-tempe rature sulfuric acid deco mposition.When a single monazite was leached using 75 wt% H_(2)SO_(4) solution with phosphoric acid,the size and number of monazite particles in the washing slag gradually decrease with the increase in phosphoric acid content in the leaching solution.The monazite phase can hardly be found in the slag when the phosphoric acid content reaches 70 g/L,which indicates that phosphoric acid is favorable for monazite decomposition.The mixed rare earth concentrate was leached by 75 wt% H_(2)SO_(4) containing 70 g/L phosphoric acid,the mineral compositions of the washing slag are only gypsum and unwashed rare earth sulfuric acid.After cyclic leaching of75 wt% H_(2)SO_(4),the mineral compositions of the primary leaching washing slag are mainly undecomposed monazite,rare earth sulfate and calcium sulfate.However,monazite is not found in the mineral phase of the second and third leaching washing slag.The leaching rates of rare earth and phosphorus gradually increase with the increase in cyclic leaching times.In addition,the phosphoric acid content in the leaching solution increases with the increase in the number of cyclic leaching time.However,the rising trend decreases when the phosphoric acid content reaches 50 g/L by adsorption and crystallization of phosphoric acid.A small amount of water can be used to clean the leaching residue before washing to recover the more soluble phosphorus acid according to the difference of dissolution between phosphoric acid and rare earth sulfuric acid.
文摘The catalytic enantioselective electrophilic amination reaction has emerged as a highly efficient method for synthesizing diverse nitrogen-containing chiral molecules,with the development of various asymmetric catalysis systems.Chiral phosphoric acids(CPA)have been widely acknowledged as versatile chiral organocatalysts since it was first discovered in 2004,finding application in catalyzing diverse asymmetric reactions.A comprehensive overview of recent advances in CPA-catalyzed asymmetric electrophilic amination reactions using different N-electrophilic reagents,including azo reagents,aryldiazonium salts,and imine derivatives,is presented.Furthermore,insights into future developments in this field are offered.
文摘Phosphoric acid is a key ingredient in fertilizer production and contains many rare earth elements(REEs).Recovering REEs from phosphoric acid can prevent the accumulation of these elements in the soil and help bridge the gap between supply and demand.In this concern,a new material called Si-6G PAMAMPPAAM dendrimers modified silica gel terminated with phenylphosphonic acid-amide moieties was developed and its ability to adsorb Nd(Ⅲ)and Er(Ⅲ)from the phosphoric acid solution was investigated.K inetics and isotherm of the uptake process were investigated to explo re the so rption characte ristics.The attained results show that both metal ions exhibit the same adsorption performance,and the uptake process is depicted as a chemisorption,monolayer,uniform,and homogeneous process.The equilibrium state is achieved within 120 min,and the maximum uptake capacity is 16.7 mg Nd(Ⅲ)/g,and 14.0 mg Er(Ⅲ)/g.Sorption thermodynamics is an endothermic,spontaneous,and feasible uptake process.Nitric acid(1.0 mol/L)is found to be efficient for adsorbing about 94.3%and 92.5%of neodymium(Ⅲ)and erbium(Ⅲ)respectively,and the prepared Si-6G PAMAM-PPAAM demonstrates excellent stability over five consecutive sorption/desorption cycles.Preliminary tests on commercial phosphoric acid demonstrate that Si-6G PAMAM-PPAAM retains its effective REEs uptake from a complex comm ercial phosph oric acid solution.
基金supported by Shenzhen Science and Technology Research(Nos.JSGG20201103153807021,GXWD20220811173736002,KCXFZ20230731094904009)the Fundamental Research Funds for the Central Universities,Sun Yat-sen University(No.24qnpy060)+2 种基金Natural Science Foundation of Guangdong Province(No.2021A1515110366)National Natural Science Foundation of China(Nos.22302048,82204231,22275146)Shenzhen Key Laboratory of Advanced Functional Carbon Materials Research and Comprehensive Application。
文摘The significance of axial chiral compounds in asymmetric organic catalysis,functional materials,and pharmaceutical useful molecules has encouraged advancements in the atroposelective synthesis of such compounds.Herein,we report the first atroposelective construction of axially chiral N-aryl benzimidazoles catalyzed by a polymer-supported chiral phosphoric acid.A varied library of atropisomers has been synthesized in 30%-96%yield with 58%-98%enantiomeric excess(ee)under a straightforward reaction setup(without the use of molecular sieves).Notably,even after 12 cycles,the immobilized catalyst maintained its reactivity and selectivity(TON>540).
基金Fundamental Research Funds for the Central Universities,China(No.2232023G-04)。
文摘All-cellulose composites(ACCs)are composites that use non-derivatized cellulose as both the matrix and the reinforcement phase.ACC consists entirely of cellulose,and since the reinforcement phase and the matrix have exactly the same chemical properties,they can overcome the problem of poor fiber-matrix adhesion in biocomposites.In this study,ACC was prepared by partially dissolving wood pulp in a cryogenic aqueous phosphoric acid solution,and the effects of dissolution temperature,dissolution time and pressing load on the properties of ACC were investigated.The results showed that a dissolution time of 45 min achieved the optimal reinforcement-matrix ratio.The use of an aqueous ethanol solution at an ethanol mass fraction of 50%as a coagulation bath and a pressing load of 3000 kg during the drying process achieved the best mechanical properties of ACC,with a tensile strength of 49.3 MPa(approximately 210%higher than that of the untreated wood pulp)and an elastic modulus of 1.6 GPa(approximately 122%higher than that of the untreated wood pulp).The composite’s compactness affected ACC’s mechanical properties.The air permeability analysis showed that the barrier performance of ACC was also significantly better than that of the untreated wood pulp.With a pressing load of 3500 kg,the surface water contact angle(WCA)increased to 110.3°(approximately 94%higher than that of the untreated wood pulp),and the air permeability was significantly reduced to 1.1 mm/s,showing its good application prospects in the field of green packaging materials.
基金financially supported by the National Natural Science Foundation of China(21873018,21573036,and21603028)the open project of the Jilin Province Key Laboratory of Organic Functional Molecular Design&Synthesis(130028655)the Northeast Normal University Research Frontier Exploration Program(XDFZ202501)
文摘A comprehensive mechanistic study on the chiral phosphoric acid catalyzed an enantioselective asymmetric aza-pinacol rearrangement of 4-chloro-N-(2-(3'-hydroxy-1'-phenylspiro[cyclopentane-1,2'-indolin]-3'-yl)ethyl)(1a)is investigated at the M06-2X/6-311+G(d,p)level.Our computational results suggest that the whole catalytic cycle proceeds through dehydration of 1a,enantioselective aza-pinacol rearrangement,intramolecular cyclization and catalyst regeneration to deliver the fused indoline product.The aza-pinacol rearrangement is the key stereocontrolling step of the title reaction.The chiral catalyst controls the orientation of the transition states of the enantioselective step through two potential binding sites between the bifunctional chiral phosphate and the aza-ortho-xylylene intermediate.Moreover,theoretical studies identified that the multiple C—H…π,C—H…O,and C—H…N hydrogen bonds and N—H…O^(-)electrostatic interactions between the substrates and the arms as well as functional oxygen anion of the chiral catalyst(R)-4c play a crucial role in determining the stereochemical outcomes.And the strong N—H…O^(-)interaction in the major transition state was found to contribute to the high levels of enantioselectivity.Additionally,the predicted enantiomeric excess(ee)of 89%based on the 6.3 kJ·mol^(–1)energy difference between the enantioselective TS-2-major and TS-2-minor is in agreement with the experimental results of 90%.
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Supported by National Natural Science Foundation of China(51168013)National Key Technology Support Program(2014BAC04B03)~~
文摘A comparison between the effects of ordinary walnut shell and phosphoric acid modified walnut shell on adsorption of Cr（Ⅵ） was carried out. The experimental results showed that owing to larger surface void of modified walnut shell its adsorption of Cr（Ⅵ） was better. When the temperature was 35 ℃, adsorbent particle size was 1.0-1.6 mm, shaker shock rate was 200 r/min, and dosage of walnut shell was 0.80 g, the Cr（Ⅵ） removal rate reached 99.4%. The fitting of adsorption isotherm and kinetics model showed that, Langmuir isotherm model could reflect the adsorption process of modified walnut shell; and both the adsorption processes of ordinary and modified walnut shells accorded with the pseudo-second-order kinetic equations.
基金Supported by the National Basic Research Program of China(2016YFD0200404)
文摘Iron element is one of the main impurities in wet-process phosphoric acid and it has a significant impact on the subsequent phosphorus chemical products. This paper studied the feasibility of using Sinco-430 cation exchange resin for iron removal from phosphoric acid. The specific surface area and the total exchange capacity of resin were 8.91 m2·g-1 and 5.18 mmol·g-1, respectively. The sorption mechanism was determined by FTIR and XPS and the results indicated that iron was combined with-SO3 H in resin. The removal process was studied as a function of temperature, H3 PO4 content and mass ratio between resin and solution. The unit mass of resin to remove iron was 0.058 g·g-1 resin when the operating parameters were T = 50 ℃, H3 PO4 content = 27.61 wt%and S/L = 0.1, respectively. Kinetics study demonstrated that pseudo-second-order reaction model fits this study best and the calculated activation energy of overall reaction is 29.10 kJ·mol-1. The overall reaction process was mainly controlled by pore diffusion.
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.
基金the National Natural Science Foundation of China(51576064,51776070)Beijing Nova Program(Z171100001117064)+2 种基金Beijing Natural Science Foundation(3172030)grants from the Fok Ying Tung Education Foundation(161051)Fundamental Research Funds for the Central Universities(2018QN057,2018ZD08)for financial support。
文摘The catalytic fast pyrolysis of cellulose impregnated with phosphoric acid (H3PO4) offers a promising method for the selective production of levoglucosenone (LGO),a valuable anhydrosugar product.However,the fundamental mechanism for selective LGO formation is unclear.Herein,quantum chemistry calculations and catalytic fast pyrolysis experiments were performed to reveal the formation mechanism of LGO in H3PO4-catalyzed cellulose pyrolysis.H3PO4 significantly decreased the energy barriers of the pyrolytic reactions and altered the competitiveness of the LGO formation pathways,promoting LGO formation.Through different pathways in the non-catalytic and H3P04-catalyzed conditions,LGO is mainly produced from the primary decomposition of glucose units of cellulose and secondary conversion of levoglucosan.The major catalytic formation pathways of LGO comprise similar reactions,with dehydration at the 3-OH+2-H site as the rate-determining step.Importantly,secondary conversion of 1,4;3,6-dianhydro-α-D-glucopyranose is not feasible for LGO formation,in contrast to previous reports.In addition,a high degree of polymerization is beneficial for the selectivity of LGO formation in the catalytic process,because the glycosidic bond is important for the formation of the bicyclic structure (1,5-and1,6-acetal rings).
基金Financial support from the National Natural Science Foundation of China (No. 21772046)the Recruitment Program of Global Experts(1000 Talents Plan)+1 种基金the Natural Science Foundation of Fujian Province(No. 2016J01064)Program of Innovative Research Team of Huaqiao University (No. Z14X0047)are gratefully acknowledged
文摘This review summarizes the very recent advances in asymmetric reactions catalyzed by chiral phosphoric acids（CPAs）, a family of versatile catalysts that catalyze a broad range of reactions to afford diverse chiral molecules. In the past years, different kinds of chiral phosphoric acids have been designed and developed into a privileged class of catalysts in asymmetric synthesis. A number of remarkable achievements have been made by many groups around the world. Due to length limitation, this review only summarizes those works published from January 2016 to November 2017. Meanwhile, catalytic systems which combine metal catalysts and chiral phosphoric acids will not be discussed in this review.
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.
基金Projects(41472278,41202220)supported by the National Natural Science Foundation of ChinaProject(20120022120003)supported by the Research Fund for the Doctoral Program of Higher Education,China+1 种基金Project(2652012065)supported by the Fundamental Research Funds for the Central Universities,ChinaProject supported by Beijing Higher Education Young Elite Teacher Program,China
文摘The rheological behavior of phosphoric acid-water glass grout in different mixing ratios was studied. Grout made of water glass with Baume degree of 20° and 13.4% phosphoric acid by 1:1 volume ratio is found to be more effective in stopping water. Laboratory model test of water shutoff by grouting was conducted. Test results show that the diffusion length and water cutoff effect of the grout are significantly improved as the grout head is raised, due to the dilution of underground water, and it takes the grout longer than its gel time to cut off water.
基金Project supported by the Key Research and Development of Gansu Province,China(17JR7GA014)the National Natural Science Foundation of China(52075234)。
文摘The recovery of rare earth elements(REEs)from NdFeB slurry by traditional hydrometallurgy has been limited becuase a large number of REEs are lost during separation together with iron.In this paper,a simple and sustainable method is proposed to efficiently separate and recover REEs and iron from NdFeB slurry.REEs were recovered by one-step selective precipitation in phosphoric acid,and the dissolved iron was recovered by oxalic acid.Phosphoric acid leaching results show that under the conditions of 4 mol/L phosphoric acid,80℃,L/S of 30:1 and 90 min,the leaching efficiencies of Fe and REEs reach 98.76%and1.09%,respectively.While the rest of REEs remained in the leaching residue in the form of REEPO_(4)·nH_(2)O precipitation.Subsequently.the mixed rare earth oxide(rare earth oxalate roasted at 800℃)and FeC_(2)O_(4)·2 H_(2)O are obtained by oxalic acid precipitation with purities of 99.49%and 97.17%from the REEPO4·nH_(2)O dissolving solution and the phosphoric acid leaching solution.Moreover,the phosphoric acid is regenerated while recovering iron,and it can be reused in the phosphoric acid leaching step after removing the impurity C_(2)O_(4)^(2-).In summary,this work provides an efficient and environmentally friendly method for recovering REEs and iron from NdFeB slurry waste.
基金Project(2017M610766)supported by China Postdoctoral Science FoundationProject(FRF-BD-17-010A)supported by the Fundamental Research Funds for the Central Universities,China
文摘Calcium molybdate(CaMoO4)is the main component of powellite and is a predominant intermediate in the pyrometallurgical and hydrometallurgical process of molybdenum.The extraction of Mo from CaMoO4 by a combination of phosphoric acid and hydrochloric acid was investigated.For further understanding of the leaching mechanism,the effects of five key factors were studied to describe the leaching kinetics.The results indicated that the dissolution rate of CaMoO4 was independent of the stirring speed.Mo extraction significantly increased with increasing HCl concentration and temperature,but decreased with increasing particle size.A shrinking core model with surface chemical reaction was found to withstand the dissolution of CaMoO4.The apparent activation energy was calculated to be 70.879 kJ/mol,and a semi-empirical equation was derived for the rate of reaction.
文摘Solid-liquid extraction of gadolinium was investigated from phosphoric acid medium using commercial amino phosphonic acid resin, Tulsion CH-93. The experimental conditions studied included equilibration time, acid concentration, mass of the resin, metal concentration, loading and elution. The percent extraction of Gd（Ⅲ） was studied as a function of phosphoric acid （0.05-3 mol/L） using Tulsion CH-93 resin. The corresponding lgD vs. equilibrium pH plot gave straight line with a slope of 1.8. The percent extraction decreased with acid co centration increasing, conforming ion exchange mechanism. Under observed experimental conditions the loading capacity of Tulsion CH-93 for gadolinium was 10.6 mg/g. Among several eluants screened, the quantitative elution of Gd（III） from loaded Tulsion CH-93 was obtained with ammonium oxalate （0.15 mol/L）. The extraction behavior of commonly associated metals with gadolinium was studied as a function of phosphoric acid concentration. Tulsion CH-93 resin showed selective extraction towards heavy rare earths （Lu and Yb） which could be separated from other rare earths at 3 mol/L H3PO4, similar to wet phosphoric acid （3-5 mol/L）. On the other hand Gd（Ⅲ） and other rare earths were studied with chelating resin Tulsion CH-90. Light rare earths were highly extracted and these could be separated from heavy rare earths and Gd.
文摘Activated carbon was prepared from bamboo by mechanochemical process with phosphoric acid as activating agent.The effects of milling time on the adsorption property and porous structure of the obtained activated car-bon were discussed.The results showed that phosphoric acid activation assisted by mechanochemical process can slightly improve the adsorption performance of the prepared activated carbon.The iodine,methylene blue adsorption value and the specific surface area of the prepared activated carbons increased from 840.16 mg/g,168 mg/g and 1229.246 m/g to 947.51 mg/g,195 mg/g,and 1265.373 m2/g,respectively.Compared with conventional phosphoric acid activation,the activated carbon produced by mechanochemical process has greater adsorption capacity.
基金Project(51674036)supported by the National Natural Science Foundation of ChinaProject(Z161100004916108)supported by the Beijing Nova Program,China
文摘In order to provide practical fundamental data for rare-earth elements （REEs） recovery from phosphoric acid and to betterunderstand REEs behavior during the phosphoric acid evaporation process, the solubilities of REEs in phosphoric acid with variousconcentrations of phosphorus at different temperatures were measured. A simple linear model between REEs solubility andphosphoric acid concentration is built and the experimental data are found to fit it very well （R2〉0.94）. Hydrogen-ion concentration isfound to be the predominant factor controlling the solubility of REEs in phosphoric acid. In addition, the solubility of REEs inphosphoric acid is found to sharply decrease with increasing temperature, which can be attributed to the increase of the Gibbs energyof the REEPO4 dissolution reaction or the restraint of the disassociation of phosphoric acid molecules owing to the elevatedtemperature.
