Intensified reactive extraction of 4-hydroxypyridine with di(2-ethylhexyl) phosphoric acid in 1-octanol by using tributyl phosphate

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.

Adsorption equilibrium and kinetics studies of divalent manganese from phosphoric acid solution by using cationic exchange resin

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.

CFD investigation of the agitation in the desupersaturation during the wet-process phosphoric acid(WPPA)process

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.

The fouling properties of SiO2-CaO-P2O5 system in high-temperature rotary kiln phosphoric acid process

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.

Isolation of Thermally Stable Cellulose Nanocrystals from Spent Coffee Grounds via Phosphoric Acid Hydrolysis

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.

Performance Optimization of a Phosphoric Acid Fuel Cell/Absorption Refrigerator Hybrid System

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.

The Structure Development of Cellulose Dissolved in the Phosphoric Acid/Polyphosphoric Acid Solvent

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.

STUDIES ON THE DYNAMIC COMPETITIVE ADSORPTION OF ORGANIC VAPORS ON THE ACTIVATED CARBON FIBERS ACTIVATED WITH PHOSPHORIC ACID

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.

Quinoxaline-specific enantioselective sulfa-michael reaction catalyzed by chiral phosphoric acid

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%).

Expanding the dimensionality of proton conduction enables ultrahigh anhydrous proton conductivity of phosphoric acid-doped covalent-organic frameworks

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.

Hydrodynamic effect on the superlubricity of phosphoric acid between ceramic and sapphire

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.

Chiral Phosphoric Acid Catalyzed Asymmetric Synthesis of Axially Chiral Compounds

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.

Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

Chiral spirocyclic phosphoric acids(SPAs)are introduced in 2010 and have been versatile catalysts capable of promoting a wide range of asymmetric organocatalytic reactions,such as multi-component reactions,Friedel–Crafts reactions,Pictet–Spengler reactions,Fischer indolizations,cycloaddition reactions,desymmetrization reactions,dearomatization reactions,conjugate addition reactions and rearrangement reactions,etc.Moreover,a diverse range of applications in metal-organic cooperative catalysis,organic photoredox catalysis,total synthesis,materials science and molecular recognition are beautifully illustrated.This account summarizes the past decade's advances in this field and highlights the selected but not comprehensive significant achievements.

Influences of additives on phosphoric acid treatment of titanium dioxide as a novel white pigment

Titanium dioxide is a photocatalytically active substance used as a white pigment for cosmetics.In sunlight,titanium dioxide catalyzes decomposition of a certain amount of sebum on the skin by ultraviolet radiation.Herein,a novel white pigment for use in cosmetics was developed from titanium dioxide and phosphoric acid at pH=4 with and without glycerin,sodium lactate,lactic acid,and urea.The chemical composition,powder properties,photocatalytic activity,color phase,and smoothness of the samples were studied.Addition of glycerin led to a decline in the intensity of the X-ray diffraction(XRD)peak of TiO_(2) relative to that of the other samples.The particle size of the materials prepared with and without additives was 0.3μm;however,extensive aggregation was observed in the obtained materials.The photocatalytic activity of TiO_(2) was inhibited by phosphoric acid treatment.The materials prepared with sodium lactate,lactic acid,and glycerin exhibited higher photocatalytic activity than that prepared without additives.The obtained materials showed a high reflectance in the range of visible light,and the L^(*)values in L^(*)a^(*)b^(*) color space were high(where L^(*)defines lightness,a^(*) denotes the red/green value,and b^(*) the yellow/blue value).These results indicate that the samples prepared in this work are suitable for use as white pigments.

Leaching isomorphism rare earths from phosphorite ore by sulfuric acid and phosphoric acid

Most of the phosphorite deposits in the world contain isomorphism rare earths(RE) which are considerably difficult to be leached into solution in the wet phosphoric acid process. In this work, a systematic study of leaching RE using sulfuric acid, phosphoric acid, mixed acid and two-step leaching of phosphoric acid and sulfuric acid was performed. The aims are to illuminate the main factors that inhibit RE leaching and to provide insights into the further enrichment of RE in the wet phosphoric acid solution. The results indicate that H_2SO_4 is not an effective acid for leaching isomorphism RE from phosphorite ore.The low RE leaching efficiency attributes to the RE cocrystallized and encapsulated by phosphogypsum(PG) as well as the precipitation of RE by RE sulfates or phosphates. High concentration of H_3PO_4 can enhance the dissolution and diffusion of RE ions. Hence, the optimized leaching mode of improving RE leaching efficiency is to adequately dissolve phosphorite ores in high concentration of H_3PO_4 solution and then add H_2SO_4 to crystallize PG.The effect of co-crystallization or encapsulation of PG on RE can be decreased due to the crystallizing mode of PG in the bulk solution instead of on the interface of solid reactants. RE leaching efficiency can be high up to 65% by the optimized leaching mode.

Enantioselective three-component Ugi reaction catalyzed by chiral phosphoric acid

A catalytic enantioselective three-component Ugi reaction was developed.SPINOL-derived phosphoric acid with bulky 2,4,6-tricyclohexylphenyl groups at the 6,6′positions was found to be the best catalyst to affordα-amino amide derivatives in good to excellent yields(62%to 99%)and enantiocontrol(81%to>99%enantiomeric excess).This asymmetric reaction was applicable well to an array of aliphatic aldehydes.The gram-scale synthesis,modification of dapsone,and enantioselective synthesis of(R)-Lacosamide underline the general utility of this methodology.Influence of dihedral angles and substituents of the chiral phosphoric acids on the enantioselectivity was also discussed in this article.

One-step separation and recovery of rare earth and iron from NdFeB slurry via phosphoric acid leaching

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.

Preparation of activated carbon from sunflower straw through H_(3)PO_(4) activation and its application for acid fuchsin dye adsorption

With the development circular economy, the use of agricultural waste to prepare biomass materials to remove pollutants has become a research hotspot. In this study, sunflower straw activated carbon (SSAC) was prepared by the one-step activation method, with sunflower straw (SS) used as the raw material and H3PO4 used as the activator. Four types of SSAC were prepared with impregnation ratios (weight of SS to weight of H3PO4) of 1:1, 1:2, 1:3, and 1:5, corresponding to SSAC1, SSAC2, SSAC3, and SSAC4, respectively. The adsorption process of acid fuchsin (AF) in water using the four types of SSAC was studied. The results showed that the impregnation ratio significantly affected the structure of the materials. The increase in the impregnation ratio increased the specific surface area and pore volume of SSAC and improved the adsorption capacity of AF. However, an impregnation ratio that was too large led to a decrease in specific surface area. SSAC3, with an impregnation ratio of 1:3, had the largest specific surface area (1 794.01 m2/g), and SSAC4, with an impregnation ratio of 1:5, exhibited the smallest microporosity (0.052 7 cm3/g) and the largest pore volume (2.549 cm3/g). The adsorption kinetics of AF using the four types of SSAC agreed with the quasi-second-order adsorption kinetic model. The Langmuir isotherm model was suitable to describe SSAC3 and SSAC4, and the Freundlich isotherm model was appropriate to describe SSAC1 and SSAC2. The result of thermodynamics showed that the adsorption process was spontaneous and endothermic. At 303 K, SSAC4 showed a removal rate of 97.73% for 200-mg/L AF with a maximum adsorption capacity of 2 763.36 mg/g, the highest among the four types of SSAC. This study showed that SAAC prepared by the H3PO4-based one-step activation method is a green and efficient carbon material and has significant application potential for the treatment of dye-containing wastewater.

Synthesis,Characterization and Application of Some Axially Chiral Binaphthyl Phosphoric Acids in Asymmetric Mannich Reaction

Two novel chiral Brønsted acids 3b and 3c were prepared without involving the complexity of Suzuki coupling.Catalyst 3c bearing two additional hydroxyl groups at 3 and 3'positions of axially chiral 1,1-binaphthalene-2,2'-diol phosphoric acid was applied in a model Mannich reaction to affordβ-amino ester in high yield(92%)and enantiomeric excess(91%)at low reacting temperature of−40℃.In addition,thoseβ-amino ester derivatives with high yields and excellent enatioselectivities were obtained in the presence of catalyst 3c under the above condition.