High-performance and robust high-temperature polymer electrolyte membranes with moderate microphase separation by implementation of terphenyl-based polymers

Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.

Design and manufacture of emulsion liquid membrane based on various amine extractants for separation and extraction of succinic acid from fermentation broth

The aim of this study was to design a new emulsion liquid membrane(ELM)system for the separation of succinic acid from aqueous solutions.The concentration of succinic acid varied from 20 to 60 mmol·L^(-1).The prepared ELM system includes tributylamine(TBA)as a carrier,commercial kerosene as a solvent,Span 80 as a surfactant,and Na2CO3as a stripping agent.In order to control the membrane swelling,different values of cyclohexanone were added to the membrane phase.The effect of various empirical variables on the extraction of the succinic acid such as acid concentration in the feed solution,initial feed concentration,carrier concentration,the stirring speed of the extraction,Na2CO3,surfactant,and cyclohexanone concentrations,and treat ratio in the ELM system.The best result was obtained when TBA was used as the carrier.The final acid extraction efficiency was independent of pH variations of the aqueous feed solution.The extraction of succinic acid solution with a concentration of 40 mmol·L^(-1)was improved by increasing the treat ratio 1:7-1:3,stripping phase concentration 0.5-1.5 mol·L^(-1),stirring speed 300-500 r·min^(-1)and cyclohexanone concentration in the membrane phase 1.2-1.6 mol·L^(-1).No considerable effect on the extraction rate was observed for the carrier concentration in the membrane phase.But,the surfactant concentration in the feed phase showed a dual effect on the extraction efficiency.

Separation of galena and chalcopyrite using the difference in their surface acid corrosion characteristics

Galena(PbS)and chalcopyrite(CuFeS_(2))are sulfide minerals that exhibit good floatability characteristics.Thus,efficiently separating them via common flotation is challenging.Herein,a new method of surface sulfuric acid corrosion in conjunction with flotation separation was proposed,and the efficient separation of galena and chalcopyrite was successfully realized.Contact angle test results showed a substantial decrease in surface contact angle and a selective inhibition of surface floatability for corroded galena.Meanwhile,the contact angle and floatability of corroded chalcopyrite remained almost unaffected.Scanning electron microscope results confirmed that sulfuric acid corrosion led to the formation of a dense oxide layer on the galena surface,whereas the chalcopyrite surface remained unaltered.X-ray photoelectron spectroscopy results showed that the chemical state of S^(2-)on the surface of corroded galena was oxidized to SO_(4)^(2-).A layer of hydrophilic PbSO4was formed on the surface,leading to a sharp decrease in galena floatability.Meanwhile,new hydrophobic CuS_(2),CuS,and Cu_(1-x)Fe_(1-y)S_(2-z)species exhibiting good floatability were generated on the chalcopyrite surface.Finally,theoretical analysis results were further verified by corrosion–flotation separation experiments.The galena–chalcopyrite mixture was completely separated via flotation separation under appropriate corrosion acidity,corrosion temperature,and corrosion time.A novel approach has been outlined in this study,providing potential applications in the efficient separation of refractory copper–lead sulfide ore.

One-step crosslinking preparation of tannic acid particles for the adsorption and separation of cationic dyes

In this study,a new tannic acid adsorbent(ethylene glycol diglycidyl ether crosslinked tannic acid,TAEGDE)for adsorptive removal of dyes from water was prepared using EGDE as a cross-linking agent.The resultant TA-EGDE was in particulate form with rough surface morphology and a diameter ranging from 10 to 30μm.The adsorption performance of the TA-EGDE was evaluated in a flow-through mode using water samples contaminated with methylene blue(MB)and two-component mixed dyes,respectively.The TA-EGDE provided adsorption capacity up to 721.8 mg·g^(-1)at 65°C for MB.It showed a high removal efficiency(99%)of MB(50 mg·L^(-1))from the water sample and could recovery 90%of the adsorbed MB by eluting with acidic ethanol aqueous solution.The excellent adsorption of MB and neutral red on the TA-EGDE may be the result of the synergy of electrostatic interaction andπ-πinteraction.Furthermore,the TA-EGDE could separate dyes from water samples contaminated with twocomponent mixed dyes with a separation coefficient ranging from 1.8 to 36.5.The anionic TA-EGDE would be an effective adsorbent to remove and recycle dyes from the contaminated water.

Selective depression effect in flotation separation of copper-molybdenum sulfides using 2,3-disulfanylbutanedioic acid

2,3-disulfanylbutanedioic acid（DMSA） was found to be a selective depressant in the flotation separation of coppermolybdenum sulfides.The flotation results suggest that a low dosage of DMSA has a strong depression effect on chalcopyrite in the p H range between 4 and 12.At p H 6,the recoveries of molybdenum are up to 85%,75%,and 80% while those of chalcopyrite are 15%,5%,and 20% respectively when flotation tests are carried out with single minerals,mixed minerals and molybdenum-bearing copper concentrates.Adsorption isotherms measurement indicates that DMSA adsorbs more strongly on chalcopyrite than on molybdenite.The frontier orbital calculation reveals that the two S atoms of DMSA molecule are active centers for the adsorption of the DMSA molecule on chalcopyrite surface.Fermi level calculation shows that chalcopyrite can obtain electrons from the DMSA molecule while molybdenite cannot.

Depression effect of pseudo glycolythiourea acid in flotation separation of copper-molybdenum

Pseudo glycolythiourea acid（PGA） was synthesized and used as depressant for flotation separation of Cu and Mo.The results indicate that a low amount of PGA has strong depression effect on chalcopyrite.Mo grade of 26.17% and recovery of 89.83% were achieved with rougher and scavenger one time and cleaners twice,while the recovery of Mo was deceased by 2% when Na2S was used as depressant.Measurement on adsorption of PGA on the mineral surface indicates that PGA and xanthate were adsorbed on mineral surface by competition,and PGA was adsorbed on chalcopyrite surface much stronger than on molybdenite surface.FTIR results indicate a chemical absorption process for PGA on chalcopyrite surface and a physical adsorption process on molybdenite surface.The frontier orbital calculation shows that the S atom is an active center,and the depression of PGA can be explained with the Fermi level of energy based on the electrochemical mechanism.

Separation of W and Mo from their peroxoacids solutions by thermal decomposition

A separation method for W and Mo from peroxoacids solution by thermal decomposition wasstudied. Thermal decomposition of peroxotungstic acid and peroxomolybdic acid was investigated respectively. The results confirmed that peroxomolybdic acid showed a preferable stability compared with peroxotungstic acid. This thermal stability difference was the basic principle of theseparationof W and Mo. Experiments were performed to study the effects of temperature, stirring speed, free acid concentration and Mo concentration on the separation efficiency. The results indicated that peroxotungstic acid decomposed into tungstic acid（H2WO4） and precipitated selectively,while Mo was rejected in aqueous solution,realizing good separation of W and Mo. The separation factorof W and Moreached 112 under the studied conditions, which indicated that this method has potential for use in separating W and Mo.

4-Pyrazolecarboxylic Acid-based MOF-5 Analogs Framework with High Adsorption and Separation of Light Hydrocarbons

One porous framework [Zn4（μ4-O）（μ4-4-pca）3]·2（DEF）·2（H2O）（1, 4-H2Pca = 4-pyrazolecarboxylic acid, DEF = N,N-diethylformamide） with MOF-5 type topology has been synthesized solvothermally. Significantly, this compound exhibits high capacity of C2 hydrocarbons. C2H2 capacity could compare with the highest value of the reported MOFs, far exceeding that of MOF-5, as well as the high selectivity adsorption of C2s over C1.

Extraction Separation of Germanium with Hydroxamic Acid HGS98

The extraction separation of germanium from indium raffinate in hydrometallurgical zinc process was discussed. The conditions and mechanism of the extraction with hydroxamic acid HGS98 have been investigated in detail. The results show that u sing 2% (mass fraction) hydroxamic acid HGS98 and 5% D 2EHPA as synergist, germanium is extracted (1 stage) over 99% in 5 min at phase ratio ( V o∶ V a) of 1∶5 from indium raffinate with original acidity. Then, using 2 mol·L -1 NH 4F as strip liquor, the stripping recovery is over 98% in 15 min at phase ratio of 1∶1. This process has the following advantages:easy to operate, high recovery and selectivity, and lower investment cost. It provides a new way to recover rare metal-germanium from metallurgical spent residues.

Rare Earth Separation with 1-Hexyl-4-Ethyloctyl Isopropylphosphonic Acid Extractant

A new extractant 1 hexyl 4 ethyloctyl isopropylphosphonic acid (HHEOIPP or HA) in heptane was employed to extract rare earths from hydrochloric acid medium. The dependence of extraction distribution ratio on equilibrium aqueous pH and the concentration of extractant were investigated. On the basis of slope analysis, it was proposed that two different kinds of extracted species were formed. For rare earth elements (La～Ho) the extracted species was LnA 3(HA) 3 and for heavy rare earth elements (Er～Lu) the species was LnClA 2(HA) 3. The steric hindrance plays an important role in forming the species. The extraction constants and separation factors of the adjacent rare earths were calculated too. Compared with HDEHP and HEH/EHP, HHEOIPP is a valuable extractant with high separation selectivity. The “tetrad effect” between K ex and atomic number was observed.

L-LACTIC ACID FERMENTATION IN A ROTATING-DISC CONTACTOR WITH SIMULTANEOUS PRODUCT SEPARATION BY ION-EXCHANGE

A rotating disk contactor（RDC）was designed to perform L-lactic acid fermentation with afilamentous fungi,Rhizopus oryzae,which was immobilized on the surfaces of the rotating discs.Thebioreactor was operated using repeated-batch method as well as continuous feeding method.Ananionic resin,D354,slightly basic in nature and of high selectivity and capacity was chosen for lacticacid separation.A coupled process of L-lactic acid fermentation and ion-exchange separation wasevaluated experimentally.The results indicated that the pH value of the fermentation broth could bemaintained at about 3-3.5 without any addition of alkali.The conversion ratio of glucose to L-lacticacid was about 0.7 g·g-1 and the fermentation rate reached as high as 62.5 g·h-1·m-2.

Primary beneficiation of tantalite using magnetic separation and acid leaching

Primary beneficiation was successfully performed prior to dissolution of manganotantalite （sample A） and ferrotantalite （sample C） samples obtained from two different mines in the Naquissupa area, Mozambique. Magnetic separation removed the majority of iron and titanium, whereas H2SO4 leaching removed a large portion of thorium and uranium in these samples. Analytical results indicated that 64.14wt% and 72.04wt% of the total Fe and Ti, respectively, and -2wt% each of Nb205 and Ta205 were removed from sample C （ferrotantalite） using the magnetic separation method, whereas only 9.64wt% and 8.66wt% of total Fe203 and TiO2, respectively, and -2wt% each of NbEOs and Ta2O5 were removed from sample A （manganotantalite）. A temperature of 50℃ and a leaching time of 3 h in the presence of concentrated HESOa were observed to be the most appropriate leaching conditions for removal of radioactive elements from the tantalite ores. The results obtained for sample A under these conditions indicated that 64.14wt% U3O8 and 60.77wt% ThO2 were leached into the acidic solution, along with 4.45wt% and 0.99wt% of Nb2O5 and Ta2O5, respectively.

Cascade sulfidation and separation of copper and arsenic from acidic wastewater via gas-liquid reaction

Copper and arsenic in acidic wastewater were separated by cascade sulfidation followed by replacement of arsenic in theprecipitates by copper in the solution which was realized by recycling precipitates obtained in the first stage into the initial solution.The effects of reaction time,temperature and H2S dosage on copper and arsenic removal efficiencies as well as the effects of solid-toliquidratio,time and temperature on the replacement of arsenic by copper were investigated.With20mmol/L H2S at50°C within0.5min,more than80%copper and nearly20%arsenic were precipitated.The separation efficiencies of copper and arsenic werehigher than99%by the replacement reaction between arsenic and copper ions when solid-to-liquid ratio was more than10%at20°Cwithin10min.CuS was the main phases in precipitate in which copper content was63.38%in mass fraction.

Studies of benzyl hydroxamic acid/calcium lignosulphonate addition order in the flotation separation of smithsonite from calcite

Flotation separation of smithsonite from calcite is difficult due to their similar surface properties.In the present study,a reagent scheme of depressant calcium lignosulphonate(CLS) and collector benzyl hydroxamic acid(BHA) was introduced in the flotation of smithsonite from calcite.Microflotation tests revealed that the efficient flotation of smithsonite from calcite could only be obtained with the addition order of BHA before CLS,which was opposite to the widely-used order that adding depressant prior to the collector.The zeta potential measurements indicated that BHA selectively adsorbed onto smithsonite surface,then not allowed the CLS adsorption onto the smithsonite surface rather than calcite surface because of the steric hindrance,thereby the smithsonite surface remained hydrophobic while calcite surface became more hydrophilic after the addition of CLS.As a result,the calcite flotation was completely depressed while the smithsonite flotation recovery was still in high value,leading to the optimal flotation separation performance.

Study of Transport and Separation of Rare Earth Ions through the Emulsion Liquid Membrane of Bis(2,4,4-trimethylpentyl)phosphinic Acid-Span 80-Toluene

It is indicated from a study of transport of rare earth ions through the emulsion liquid mem- brane of bis(2,4,4-trimethylpentyl)phosphinic acid-Span 80-toluene that transporting rare earth ions com- pletely and rapidly was realized under the optimum experimental conditions:1.0×10^(-3)～3.0×10^(-3)mol/L bis(2,4,4-trimethylpentyl)phosphinic acid and 2%～4%(W/V)Span 80 in toluene solution as membrane phase,0.50～2.0 mol/L HCl as inner phase,rare earth ion solutions with pH 3.5～5.0 as outer phase.Ac- cording to the differences of transport behavior for rare earth ions,it is possible to separate rare earth ions from mixed solutions of rare earth ions by this liquid membrane system.

Efficient Separation of Butyric Acid by an Aqueous Two-phase System with Calcium Chloride

One of the bottlenecks for bioproduction of butyric acid as bulk chemical is the difficulty in separating butyric acid from the fermentation broth,compared with the petroleum-based chemical synthesis method.In the present work,a novel separation methodology was developed based on an aqueous two-phase system with inor-ganic salts.Calcium chloride was screened out for effective separation of butyric acid from butyric acid-water-salt systems.Within appropriate concentration range of butyric acid and salt,butyric acid was enriched in the upper phase and most of calcium ions remained in the lower phase.This"salting out"effect is very efficient to separate butyric acid from the simulated butyrate fermentation broth,which consists of butyric acid and acetic acid with concentration ratio of 4︰1,so that the final ratio of butyric acid/acetic acid in the upper phase is improved to 9.87. The aqueous two-phase system was used to separate butyric acid from the actual fermentation broth with satisfac-tory result.

Carboxymethyl-β-cyclodextrin for Chiral Separation of Amino Acids Derivatized with Fluorescene-5-isothiocyanate by Capillary Electrophoresis and Laser-induced Fluorescence Detection

A method using carboxymethyl-b-cyclodextrin (CM-b-CD) as selector for chiral separation of amino acids by capillary electrophoresis and laser-induced fluorescence detection was studied. Resolution was better than that obtained by b-CD or HP-b-CD.

Dialkyl phosphinic acids:Synthesis and applications as extractant for nickel and cobalt separation

Three kinds of dialkylphosphinic acids(DAPAs),i.e.dihexylphophinic acid(DHPA),di-(2,4,4-trimethylpentyl) phosphinic acid(DTMPPA)and didecylphophinic acid(DDPA),were synthesized through free radical addition reaction.The influence of the types of initiator,reation time and reaction temperature on the yield of DAPAs were investigated.The products were characterized by NMR and MS.By using DHPA,DTMPPA and DDPA(10%in kerosene)as extractants,the extraction of Co2 +and Ni2 +in sulphate medium at different equilibrium pH values were measured.The results show that the maximum yield of DHPA, DTMPPA and DDPA can all be achieved at about 130℃under the initiation of di-tert-butyl peroxide(DTBP).All the extraction of cobalt with respect to DHPA,DDPA and DTMPPA precedes that of nickel.The difference in pH1/2 value(defined as the pH at which 50%metal extraction occurs)between cobalt and nickel increases in the following sequence from large to small:DHPA,DDPA and DTMPPA,which indicates that the separation ability for cobalt and nickel ascends from DHPA,DDPA to DTMPPA.

Separation and Purification of Dodecanedioic Acid from Its Homologous Compounds by Falling Film Crystallization

Separation and purification of dodecanedioic acid (DDDA) from its homologous compounds were studied experimentally by falling film crystallization (FFC). The influences of various operation parameters, including crystallizing time, flow rate of melt and temperature of glycerine bath, on purity of DDDA and crystallizing rate were investigated. Over 99% (by mole) DDDA was obtained for a feed composition of 96% (by mole). The main factors affecting the separation efficiency are flow rate of melt and temperature of glycerine bath. The crystallizing layer of DDDA was further purified by sweating and blasting. A set of optimized operation data are provided for better understanding the mechanism of heat and mass transfer in FFC, and for further industrial application of DDDA purification process.

Acid Separation, Catalytic Oxidation and Coagulation for ATC Waste Liquid Treatment

It is difficult to treat 2-amino-thiazoline-4-carboxylic acid （ATC） waste liquid effectively at present for its characteristics of high chemical oxygen demand （COD）, high salinity and low biodegradability. In order to solve this problem, this paper presents several kinds of physical-chemical treatment unit techniques, including acid separation, catalytic oxidation and coagulation. First of all, acid separation was adopted to precipitate relevant organics at isoelectric point. When the temperature and pH value of acid separation were controlled at about 5 ℃ and 2.2 respectively, the COD removal rate could reach 27.600. Secondly, oxidation was used to break chemical constitution of refractory organics. The optimal reaction parameters of catalytic oxidation should be 20 ℃, pH adjusted to 5.0 and [Fe2+] 300 mg/L. Then with 500 H2O2 added and after one-hour reaction, the COD removal rate could achieve about 5200. Finally, coagulation was adopted to remove a portion of refractory organics, and 1500 polymeric molysite flocculant was the best for the coagulation, and the COD removal rate could reach about 1500. Therefore, the proposed feasible process of physical-chemical pretreatment for ATC waste liquid could have about 7000 COD removed in total.