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1.
The removal of nickel from aqueous solutions streams has been investigated using an artificial amorphous crandallite‐type compound, CaAl3(OH)6(HPO4)(PO4) (Ca‐crandallite), synthesized in our laboratory. Equilibrium ion‐exchange isotherms in an aqueous medium of Ca2+/Ni2+ at different pH values at 293 K have been determined. The experimental equilibrium data were satisfactorily correlated using a Langmuir‐type empirical equation. At low pH values, the hydrogen ion competes with the heavy metal cation and the percentage removal of metal declines. It was found that the operating capacity of Ca‐crandallite with respect to the metal ion increased with the pH of the solution, in accordance with a second‐degree polynomial equation. However, the pH should not be allowed to rise to levels at which chemical precipitation as nickel hydroxide would occur, with 7.00 the highest value tested. Taking into account the variation of operating capacity with pH, the system exhibited a unique separation factor, namely all the experimental points can be described by a unique isotherm in a dimensionless form. The Ca‐crandallite showed a high capacity, 2.176 meq g?1, for the exchange of Ni(II) from nickel nitrate solutions and the rate of exchange of metal increases with increasing solution temperature due to the enhancement of effective intraparticle diffusivity. Copyright © 2005 Society of Chemical Industry  相似文献   

2.
Certain tannin-containing agricultural wastes, such as peanut skin, are highly efficient ion exchange materials for the removal of cupric ion from aqueous waste solutions. Concentrations of Cu2+ as high as 200–1000 ppm can be reduced to less than 0.5 ppm by pouring the waste solution through a short column of peanut skin. The column packing can take up greater than 10% of its weight in copper, even from 50 ppm solution. Complete regeneration of the packing is readily achieved by eluting the Cu2+ from the column with 0.1 N HCl. The ion exchange process is pH dependent, with optimum removal of copper from solution occuring in the 5–7 pH range. Two hydrogen ions are liberated into solution for each Cu2+ attached to the peanut skin, so pH decreases as reaction continues, inhibiting the reactions. Thus, a continuous column process would be more efficient than a stepwise batch process.  相似文献   

3.
The present study has been undertaken to investigate a process that might remove inorganic mercury from mine waste water streams by use an ion exchange resin system. A number of commercial resins have been evaluated as ion exchangers and the mercury content of the waste water, ranging from 70 to 90 ppm, is reduced to a permitted level of 34 ppb. Dowex XZS‐1, a strong cationic ion exchanger in a gel Form, has the most pronounced selectivity for mercury. The loaded resin was regenerated efficiently using HCl solutions, due to increased competition between Hg and hydronium ions and formation of an HgCl 4 2− ionic complex. © 2000 Society of Chemical Industry  相似文献   

4.
Synthesis of two unconventional ion exchange resins and their behaviour on the mercury sorption experiments were investigated.The ion exchange resins were obtained by the quaternization reaction of 4-vinylpyridine:divinylbenzene copolymer, gel-type, by two ways namely, the nucleophilic substitution of the pyridine matrix with 2-chloroacetamide and the nucleophilic addition of protonated copolymer to acrylamide.Comparative sorptions of Hg2+ ions on the synthesized pyridine resins by batch experiments in mono- and binary system were analyzed. Mercury retention experiments aimed to study the influence of the solution concentration, contact time and solution pH. The removal of Hg2+ ions from aqueous solutions depends on the pH values, the amount of the retained mercury increased with the pH value.The studied strong base pyridine anion exchange resins presented a good selectivity for the Hg2+ ions during the competitive sorption of Hg2+/Cu2+, Hg2+/Zn2+ and Hg2+/Fe3+ at metal cations ratio of 1:1.  相似文献   

5.
《Ceramics International》2022,48(20):29770-29781
The substituted (Ca2+/Cu2+), and co-substituted (Cu2+/Zn2+), (Cu2+/Sr2+), and (Sr2+/Mn2+) β-tricalcium phosphate (β-TCP)-based Ca3-2x(MˊMˊˊ)x(PO4)2 (M = Zn2+, Cu2+, Mn2+ and Sr2+) solid solutions have been synthesized using solid-state route. The powder X-ray diffraction study shows the formation of β-TCP-type structure as the main phase in all solid solutions. The crystal structures and chemical compositions were approved using Fourier-transform infrared (FT-IR) absorption spectra and energy-dispersive X-ray spectrometry (EDX) data, respectively. The unit cell parameters and volume of as-synthesized samples directly depend on the radius of the incorporated ions. The limits of the single-phase solid solutions were found based on the possible occupation of the crystal sites in β-TCP structure. For the divalent ions with small radii, such as Cu2+ or Zn2+, the limit composition was found as Ca2.5710.429–xMˊˊx(PO4)2 for Mˊ and Mˊˊ – Cu2+ and Zn2+. The enlargement of the unit cell by incorporation of Sr2+ allows to extend the limit of solid solutions up to Ca2.5Sr0.5–xx(PO4)2 for Mˊ – Cu2+ or Mn2+. The antibacterial properties were studied on 4 bacteria (S. aureus, P. aeruginosa, E. coli and E. faecalis) and 1 fungus (C. albicans). It has been showed that co-doped Ca2.5Sr0.25Cu0.25(PO4)2 sample exhibits the highest antimicrobial activity resulting in 92%, 96% and 96% inhibition growth rate for S. aureus, P. aeruginosa and E. faecalis, respectively. The antimicrobial properties are strongly related to the occupation of the crystal sites in the β-TCP structure by doping ions.  相似文献   

6.
In this work, Ba0.9Sr0.1TiO3, Ba0.7Sr0.3TiO3, Ba0.5Sr0.5TiO3, Ba0.5Ca0.25Sr0.25TiO3 and Ba0.5Ca0.5TiO3 have been synthesized to evaluate the influence of mono and co-substitution of A-site dopants (Sr2+ and Ca2+) on the structural, electrical and optical properties of BaTiO3 ceramics. Sr2+ added samples showed a tetragonal structure which became slightly distorted with increasing Sr2+ concentration and finally achieved a cubic structure for x?=?0.50. Ba0.5Ca0.5TiO3 also retained their tetragonality with limited solubility. Presence of second phase, CaTiO3 demonstrated the fact of restricted solubility. The concurrent effect of Sr2+ and Ca2+ didn't alter the tetragonal structure. Sr2+ substitution enhanced the apparent density as well as grain size which stimulated the domain wall motion and improved dielectric properties. However, the ferroelectric nature of Ba1-xSrxTiO3 was poor due to the redistribution of point defect at grain boundary. The optical band gap was found to be reduced from 3.48?eV to 3.28?eV with increasing Sr2+ content. Co-substitution of cations improved the electrical property significantly. The highest value of dielectric constant was found to be ~547 for Ba0.5Ca0.25Sr0.25TiO3 ceramics. Both Ba0.5Ca0.25Sr0.25TiO3 and Ba0.5Ca0.5TiO3 had developed P-E loop having lower coercive field and moderate optical band gap energy. Co-doping with Sr2+ and Ca2+ was a good approach enhancing materials electrical as well as optical property.  相似文献   

7.
In this study, a series of red-emitting Ca3Sr3(VO4)4:Eu3+ phosphors co-doped with La3+ was prepared using the combustion method. The microstructures, morphologies, and photoluminescence properties of the phosphors were investigated. All Ca3Sr3(VO4)4:Eu3+, La3+ samples synthesized at temperatures greater than 700 ℃ exhibited the same standard rhombohedral structure of Ca3Sr3(VO4)4. Furthermore, the Ca3Sr3(VO4)4:Eu3+, La3+ phosphor was effectively excited by near-ultraviolet light of 393 nm and blue light of 464 nm. The strong excitation peak at 464 nm corresponded to the 7F05D2 electron transition of Eu3+. The strong emission peak observed at 619 nm corresponded to the 5D07F2 electron transition of Eu3+. Co-doping with La3+ significantly improved the emission intensity of Ca3Sr3(VO4)4:Eu3+ red phosphors. The optimum luminescence of the phosphor was observed at Eu3+ and La3+ concentrations of 5% and 6%, respectively. Moreover, co-doping with La3+ also improved the fluorescence lifetime and thermal stability of the Ca3Sr3(VO4)4:Eu3+ phosphor. The CIE chromaticity coordinate of Ca3Sr3(VO4)4:0.05Eu3+, 0.06La3+ was closer to the NTSC standard for red phosphors than those of other commercial phosphors; moreover, it had greater color purity than that of all the samples tested. The red emission intensity of Ca3Sr3(VO4)4:0.05Eu3+, 0.06La3+ at 619 nm was ~1.53 times that of Ca3Sr3(VO4)4:0.05Eu3+ and 2.63 times that of SrS:Eu2+. The introduction of charge compensators could further increase the emission intensity of Ca3Sr3(VO4)4:Eu3+, La3+ red phosphors. The phosphors synthesized herein are promising red-emitting phosphors for applications in white light-emitting diodes under irradiation by blue chips.  相似文献   

8.
Bench-scale investigations indicate that NO, NO2, hematite (α-Fe2O3), maghemite (γ-Fe2O3), and HCl promote the conversion of gaseous elemental mercury (Hg0) to gaseous oxidized mercury (Hg2+) and/or particle-associated mercury (Hg[p]) in simulated coal combustion flue gases. In this investigation, the effects of NOx, α-Fe2O3, γ-Fe2O3, and HCl on Hg transformations were evaluated by injecting them into actual coal combustion flue gases produced from burning subbituminous Absaloka and lignitic Falkirk coals in a 7-kW down-fired cylindrical furnace. A bituminous Blacksville coal known to produce an Hg2+-rich combustion flue gas was also burned in the system. The American Society for Testing and Materials Method D6784-02 (Ontario Hydro method) or an online Hg analyzer equipped to measure Hg0 and total gaseous mercury (Hg[tot]) was used to monitor Hg speciation at the baghouse inlet (160–195 °C) and outlet (110–140 °C) locations of the system. As expected, the baseline Blacksville flue gas was composed predominantly of Hg2+ (Hg2+/Hg[tot]=0.77), whereas Absaloka and Falkirk flue gases contained primarily Hg0 (Hg0/Hg[tot]=0.84 and 0.78, respectively). Injections of NO2 (80–190 ppmv) at 440–880 °C and α-Fe2O3 (15 and 6 wt.%) at 450 °C into Absaloka and Falkirk coal combustion flue gases did not significantly affect Hg speciation. The lack of Hg0 to Hg2+ conversion suggests that components of Absaloka and Falkirk combustion flue gases and/or fly ashes inhibit heterogeneous Hg0–NOx–α-Fe2O3 reactions or that the flue gas quench rate in the 7-kW system is much different in relation to bench-scale flue gas simulators.An abundance of Hg2+, HCl, and γ-Fe2O3 in Blacksville flue gas and the inertness of injected α-Fe2O3 with respect to heterogeneous Hg0 oxidation in Absaloka and Falkirk flue gases suggested that γ-Fe2O3 catalyzes Hg2+ formation and that HCl is an important Hg0 reactant. The filtration of Absaloka and Falkirk combustion flue gases at 150 °C through fabric filters with ≈60 g/m2 γ-Fe2O3 indicated that about 30% of the Hg0 in Absaloka and Falkirk flue gases was converted to Hg2+ and/or Hg(p). HCl injection (100 ppmv) into the Absaloka combustion flue gas converted most of the Hg0 to Hg2+, whereas HCl injection into the Falkirk flue gas converted most of the Hg0 and Hg2+ to Hg(p). Additions of γ-Fe2O3 and HCl did not have a synergistic effect on Hg0 oxidation. The filtration of Absaloka and Falkirk flue gases through much greater fabric filter loadings of 475 g/m2 γ-Fe2O3 essentially doubled the baghouse Hg[tot] removal efficiency to about 50%. Results from this investigation demonstrate the importance of evaluating potential Hg0 reactants and oxidation catalysts in actual coal combustion flue gases.  相似文献   

9.
The performance of V2O5/TiO2-based commercial SCR catalyst for the oxidation of gaseous elemental mercury (Hg0) with respect to reaction conditions was examined to understand the mechanism of Hg0 oxidation on SCR catalyst. It was observed that a much larger amount of Hg0 adsorbed on the catalyst surface under oxidation condition than under SCR condition. The activity of commercial SCR catalyst for Hg0 oxidation was negligible in the absence of HCl, regardless of reaction conditions. The presence of HCl in the reactant gases greatly increased the activity of SCR catalyst for the oxidation of Hg0 to oxidized mercury (Hg2+) such as HgCl2 under oxidation condition. However, the effect of HCl on the oxidation of Hg0 was much less under SCR condition than oxidation condition. The activity for Hg0 oxidation increased with the decrease of NH3/NO ratio under SCR condition. This might be attributed to the strong adsorption of NH3 prohibiting the adsorption of HCl which was vital species promoting the oxidation of Hg0 on the catalyst surface under SCR condition.  相似文献   

10.
Mercury species, mass flows and processes in a cement plant   总被引:2,自引:0,他引:2  
The aim of the study was to evaluate the behaviour of mercury in the cement clinker production process. Simultaneous measurements of mercury in all important materials and gas streams were performed in three sampling periods on about 300 solid samples and about 80 samples taken from gas streams. Mercury species in flue gases at characteristic parts of the process were measured as total Hg(t), particulate Hg(p), elemental Hg0(g) and reactive Hg2+(g) mercury. Based on the results of measurements, mercury mass flows and mass balances of the whole and in certain parts of the process were evaluated. It was shown that the process comprises many mercury cycles which are strongly dependent on the operating conditions and technological specifics. Cycling of mercury causes a significant enrichment of mercury inside the process. In the annual mercury input of about 27 kg, raw materials accounted near by 60% and fuels about 40% (i.e. petrol coke 31%, waste tyres 10% and waste oil 0.4%). The annual emission of mercury represented 40-70% of the inputs, while cement clinker only contained about 10%. The difference between inputs and outputs (11-45%) obtained in the annual mass balance could be assigned to mercury recycling and significant enrichment inside the process, as well as variability between spot measurements. The parts of the process with the highest mercury mass flows and the lowest material/gas flows were identified. Such points represent an opportunity to remove a significant amount of mercury from the process at low material flows and to improve mercury control. Mercury was mainly emitted in gaseous form with 92% (direct mode) or 89% (combined mode) as Hg(g) on average, of which about 2/3 was as Hg2+(g), and about 1/3 as Hg0(g). Only a small part (the rest) was emitted as particulate Hg(p). Shares of individual mercury species in the last sampling period were 65.7% Hg2+(g), 34.0% Hg0(g) and 0.3% Hg(p) on average. Ratios between individual mercury forms were found to be related to operating modes. The quantities of Hg(t), Hg(g) and Hg2+(g) emitted were higher when operating with the raw mills off (direct mode). It was seen that the efficiency of Hg removal was strongly related to the dust removal efficiency. Bag filters very efficiently removed all mercury species.  相似文献   

11.
《分离科学与技术》2012,47(8):1244-1250
Adsorbent for strontium (Sr2+) ion removal was prepared from orange waste generated in an orange juice factory. The orange juice residue (OJR) was treated with lime water to prepare saponified orange juice residue (SOJR). The energy dispersive X-ray (EDX) spectroscopic analysis revealed that substitution of Ca2+ ions in SOJR by Sr2+ ions takes place during the adsorption process. The adsorption of Sr2+ ions onto SOJR was fast and strongly pH dependent. Maximum adsorption occurred at pH higher than 5. The adsorption isotherm study showed maximum adsorption capacity of SOJR for Sr2+ ion was 833.4 mmol/kg. Equimolar amount of Ca2+ was found to be released from SOJR during Sr2+ adsorption also indicating that adsorption of Sr2+ on SOJR takes place according to the Ca2+ substitution reaction by cation exchange mechanism. Thus, the adsorption gel prepared in this study can be a promising adsorbent to remove Sr2+ from aqueous solution.  相似文献   

12.
ABSTRACT

The ion exchange behavior of three sodium micas (phlogopite, Ward's Sci.; phlogopite, Suzorite Inc., biotite, Ward's Sci.) towards Li+, K+, Rb+, Cs+, Mg2+. Ca2+, Sr2+, Ba2+, Pb2+ Hg2+, Co2+, Cu2+ Cd2+ and Zn2+ ions has been studied. The ion exchange isotherms of alkali, alkaline earth and some other divalent cations were determined and concentration equilibrium constants as a function of metal loading and temperature were analyzed. Sodium micas exhibit high affinity for heavy alkali metals with the selectivity order Rb+ > Cs+ > K+. By studying the cesium uptake in the presence of NaNO3, CaCl2, NaOH, NaOH+KOH, HNO3 electrolytes (in the range of 0.01–6 M) it was found that sodium micas could remove cesium efficiently in neutral and alkaline media, which make them promising for certain types of nuclear waste treatment.  相似文献   

13.
Phase pure sample of the microporous copper silicate CuSH–1Na has been obtained by simplified hydrothermal method without using additives (H2O2 and Na2HPO4). Ion exchange of Na+ by Cs+, Ca2+ and Sr2+ ions showed that the structure can suffer partial replacement of the charge compensating cations. Ion exchange with Cs+ resulted in distinct dehydration while the ion exchange with Sr2+ increased the total amount of water. Water content in the Ca-exchanged sample is comparable to the as-synthesized sodium phase. Raman spectroscopy revealed that the divalent cations as Ca2+ and Sr2+ induce stronger local structural deformations than the monovalent Cs+. These structural changes have been also followed by the refined lattice distortions. Magnetic analyses showed that CuSH–1Na presents a very weak ferromagnetic interaction along the Cu2+ chains with a nearly vanishing Curie–Weiss temperature. This magnetic coupling is associated with super-super-exchange interactions through Cu–Na–O–Na–Cu paths. Antiferromagnetic coupling, attributed to inter-chains super-super-exchange interactions, competes with the ferromagnetic one and prevails at the lowest temperature.  相似文献   

14.
《Ceramics International》2020,46(7):9240-9248
The effects of Sr2+ substitution for Ba2+ on phase structure, microstructure, dielectric and electric properties for Ba4-xSrxSmFe0.5Nb9.5O30 (x = 0, 1, 2, 3 and 4) ceramics were systematically researched. X-ray diffraction patterns show that Ba4-xSrxSmFe0.5Nb9.5O30 (x = 0, 1, 2 and 3) ceramics are tetragonal tungsten bronze compound with a space group of P4bm, while the sample for x = 4 is an orthorhombic structure compound. The result can be corroborated by the analysis of Raman spectroscopy. As the Sr2+ contents increase from 0 to 3, the full width at half maximum of Raman lines of all samples increase gradually, indicating that the degree of lattice distortion increase. All tetragonal tungsten bronze ceramics exhibited a broad permittivity peaks, accompanied by frequency dispersion, indicating all samples are relaxor. The electrical properties of BSSFN ceramics were further studied by complex impedance spectroscopy. XPS spectrum shows that Fe2+ and Fe3+ coexist in Ba4-xSrxSmFe0.5Nb9.5O30 ceramics, and their proportion varies with the concentration of Sr2+.  相似文献   

15.
A series of quaternary nitride solid solutions with a general formula of Sr1?xCaxLiAl3N4:0.5%Eu2+ was synthesized by a solid‐state reaction method. The experimental results showed that a proper amount of Ca‐doping can improve the crystallinity and the photoluminescence properties of the produced phosphors. Rietveld refinement showed that the volume of the unit cell shrank with the increase of Ca substitution for Sr, which resulted in a red shift of the emission spectra from 654 to 665 nm under blue excitation at 475 nm. Rietveld refinement and CASTPE calculations suggested that Ca2+ ions prefer to occupy the smaller Sr(I) sites in the crystal lattice, which increases the amount of Eu2+ ions in Sr(II) sites and enables the tuning of the chromaticity coordinates of the obtained phosphors. The thermal stability of the produced phosphors is better than that of commercial Sr2Si5N8:Eu2+ phosphor. The experimental results qualify the solid‐solution Sr1?xCaxLiAl3N4:0.5%Eu2+ for consideration as a potential candidate for application in white LEDs.  相似文献   

16.
A series of new apatite phosphors Ca5.95−xSrxLa4(SiO4)2(PO4)4O2:0.05Eu2+ (x = 0-5.95) were prepared with the solid-state method. The variations of the occupation rate and cell parameters were investigated in detail, demonstrating that the phosphors are pure phases and that the different occupation rates of La3+, Ca2+, and Sr2+ ions are due to the different electrostatic bond strengths. The reflectance and photoluminescence excitation spectra prove that the phosphors can be efficiently excited with near-ultraviolet (n-UV) light. The broad redshift (50 nm) in the photoluminescence spectra is attributed to the increase in the crystal field splitting when the Ca2+ ion is replaced by the larger Sr2+ ion. At 150°C, the obtained phosphors maintain an emission intensity of ~67%-77% of that at room temperature (25°C), which indicates relatively the high performance of apatite phosphors in the temperature-dependence experiment. Because of the substitution of the small Ca2+ ion by the large Sr2+ ion, the emission color changes from green to yellow. Finally, a series of self-made light emitting diodes lamps were fabricated by coating the Ca5.95−xSrxLa4(SiO4)2(PO4)4O2:0.05Eu2+ phosphors with commercial blue and red phosphors on an n-UV chip (λex = 370 nm). The self-made white-emitting lamps display a continuous changing correlated color temperature (4053-9353 K) or commission international de L'eclairgae (from [0.29, 0.28] to [0.38, 0.37]), implying that the series apatite phosphors have great potential to meet the different requirements of applications.  相似文献   

17.
《分离科学与技术》2012,47(5):931-948
Abstract

The selectivity mechanism of transport of Na+, Ca2+ and Mg2+ through commercial monovalent‐cation permselective membranes is investigated in batch electrodialysis experiments with synthetic salt solutions containing monovalent and divalent cations. The role of hydration energy, steric effect, kinetic effect as well as effects of permselectivity of cation exchange membrane has been elucidated with electrodialysis of single solutions (NaCl, CaCl2, MgCl2). The mechanism of interferences is investigated in (Na+/Ca2+, Na+/Mg2+, Ca2+/Mg2+ and Na+/Ca2+/Mg2+) mixtures.  相似文献   

18.
《分离科学与技术》2012,47(10):1638-1646
Sodium tripolyphosphate crosslinked chitosan was prepared and immobilized with pentamine moieties. The samples obtained were characterized by elemental analysis and FT-IR. The adsorption behavior of the samples was studied towards Hg2+ using batch and column methods. The adsorption depended on the pH of the medium and was explained to proceed via complex formation and/or ion exchange mechanisms. The uptake capacity was found to be 4.7 mmol/g at pH = 2. Selective separation of Hg2+ from a solution containing Pb2+, Cu2+, Ca2+, Zn2+, Fe3+, and Mg2+ was achieved at pH = 1. The values of the kinetics and the thermodynamic parameters of the uptake process were reported. The flow rate of 3 mL/min in column experiments was found to be the most preferable rate. The regeneration of the loaded resin was performed using 0.5 M potassium iodide.  相似文献   

19.
The starch-stabilized Ag nanoparticles were successfully synthesized via a reduction approach and characterized with SPR UV/Vis spectroscopy, TEM, and HRTEM. By utilizing the redox reaction between Ag nanoparticles and Hg2+, and the resulted decrease in UV/Vis signal, we develop a colorimetric method for detection of Hg2+ ion. A linear relationship stands between the absorbance intensity of the Ag nanoparticles and the concentration of Hg2+ ion over the range from 10 ppb to 1 ppm at the absorption of 390 nm. The detection limit for Hg2+ ions in homogeneous aqueous solutions is estimated to be ~5 ppb. This system shows excellent selectivity for Hg2+ over other metal ions including Na+, K+, Ba2+, Mg2+, Ca2+, Fe3+, and Cd2+. The results shown herein have potential implications in the development of new colorimetric sensors for easy and selective detection and monitoring of mercuric ions in aqueous solutions.  相似文献   

20.
This paper describes the results from an experimental study of the purification of LiHCO3 solution which is used to produce high-purity Li2CO3 by ion exchange. Generally, there are some amounts of Ca2+ and Mg2+ in the LiHCO3 solution whose contents exceed the requirements to produce qualified high-purity Li2CO3, so they need to be removed from the solution. There are many methods available to remove divalent metal ions from solutions, among which the ion exchange is the most simple and efficient one. Investigations of the performance of the chelating resin Amberlite IRC747 for its adsorption for Ca2+ and Mg2+ in LiHCO3 solutions were conducted. Batch studies showed that the SDM-A model could describe the adsorption isotherm data well, and the Kannan particle diffusion model could describe the exchange kinetics properly. The study for column operation showed that breakthrough points of Ca2+ and Mg2+ both advanced with increasing the feed flow rate, and the penetration function model could describe the effluent curves adequately. HCl and LiOH of 1 mol·L− 1 respectively were used to regenerate resins with good effect. This study will provide the basic reference for process operation and the reactor design to purify the LiHCO3 solution by ion exchange.  相似文献   

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