Elucidating the enhancement of kaolinite flotation by iron content through density functional theory: A study on sodium oleate adsorption efficiency

This study delves into the intricate relationship between iron(Fe)content in kaolinite and its impact on the adsorption behavior of sodium oleate.The effects of different iron concentrations on adsorption energy,hydrogen bond kinetics and adsorption efficiency were studied through simulation and experimental verification.The results show that the presence of iron in the kaolinite structure significantly improves the adsorption capacity of sodium oleate.Kaolinite samples with high iron content have better adsorption properties,lower adsorption energy levels and shorter and stronger hydrogen bonds than pure kaolinite.The optimal concentration of oleic acid ions for achieving maximum adsorption efficiency was identified as 1.2 mmol/L across different kaolinite samples.At this concentration,the adsorption rates and capacities reach their peak,with Fe-enriched kaolinite samples exhibiting notably higher flotation recovery rates.This optimal concentration represents a balance between sufficient oleic acid ion availability for surface interactions and the prevention of self-aggregation phenomena that could hinder adsorption.This study offers promising avenues for optimizing the flotation process in mineral processing applications.

Flotation behavior and adsorption mechanism of(1-hydroxy-2-methyl-2-octenyl) phosphonic acid to cassiterite

The flotation behavior and adsorption mechanism of novel（1-hydroxy-2-methyl-2-octenyl） phosphonic acid（HEPA） to cassiterite were investigated by micro-flotation tests, zeta potential measurements, FTIR determination and density functional theory（DFT） calculation. The flotation results demonstrated that HEPA exhibited superior collecting performance compared with styrene phosphonic acid（SPA）. The cassiterite recovery maintained above 90% over a wide pH range of 2-9 with 50 mg/L HEPA. The results of zeta potential measurement and FTIR detection indicated that the adsorption of HEPA onto cassiterite was mainly attributed to the chemisorption between HEPA monoanions and Sn species on mineral surfaces. The DFT calculation results demonstrated that HEPA monoanions owned higher HOMO energy and exhibited a better affinity to cassiterite than SPA, which provided very clear evidence for the stronger collecting power of HEPA presented in floatation test and zeta potential measurement.

Flotation and adsorption of quaternary ammonium cationic collectors on diaspore and kaolinite

The flotation and adsorption behaviors of dodecyltrimethylammonium chloride（DTAC） and cetyltrimethylammonium chloride（CTAC） on diaspore and kaolinite were studied.Solution depletion methods were used to determine adsorption isotherms.Fluorescence probe test along with Zeta potential measurement was also conducted for further investigation into the adsorption of quaternary amines at the mineral-water interface.The results show that the flotation recovery of kaolinite decreases with an increase in pH when DTAC and CTAC are used as collectors,while diaspore is on the contrary.As the carbon chain length of the collectors increases,the flotation recoveries of minerals increase.However,the increment rate of kaolinite is significantly lower than that of diaspore.In the low surfactant concentration range,the cationic surfactants adsorb readily on diaspore surfaces just due to electrostatic interactions.As for kaolinite surfaces,ion exchange process also exists.With a further increase in surfactant concentration,the adsorption was ascribed to the hydrophobic association of chain-chain interactions.Micro-polarity of mineral surfaces study shows that CTAC has a better hydrophobic characteristic than DTAC.Larger aggregates are formed with CTAC on diaspore than on kaolinite in the same solution concentration.The results also indicate that the chain length of cationic surfactants has a greater influence on the adsorption of diaspore than on kaolinite,which is consistent with the flotation result.

An in situ ATR-FTIR study of mixed collectors BHA/DDA adsorption in ilmenite-titanaugite flotation system

This paper researched the enhanced flotation separation performance of ilmenite and titanaugite using the mixed collector benzhydroxamic acid/dodecylamine(BHA/DDA).The interface assembly mechanism was mainly investigated through in situ attenuated total reflectance Fourier transform infrared(ATRFTIR)spectroscopy combined with the two-dimensional correlation spectroscopy(2D-COS)and X-ray photoelectron spectroscopy(XPS).It has been found that BHA/DDA mixed collectors successfully separate ilmenite from titanaugite at a molar ratio of 8:1.Zeta potential experiments suggested that,in the presence of mixed collector system,the BHA-DDA complex adsorbed on the ilmenite surface via the chemically adsorbed BHA and the electrostatically adsorbed DDA,however,the complex adsorbed on the surface of titanaugite unstably.According to in situ ATR-FTIR combined with 2D-COS and XPS results,the interface assembly mechanism of BHA/DDA is summarized as:the function group of BHA molecules first binds to the metal sites on minerals to form bidentate ligand,then DDA co-adsorbed with BHA on the surface of minerals through hydrogen bonding.DDA may change the adsorption modes of some BHA on the ilmenite surface from four-membered ring to five-membered ring,while the modes on the titanaugite surface is true opposite.Finally,recommended adsorption configurations of the BHA/DDA complex on the two mineral surfaces are proposed.

Flotation performance and adsorption mechanism of novel 1-(2-hydroxyphenyl)hex-2-en-1-one oxime flotation collector to malachite

A novel collector 1-(2-hydroxyphenyl)hex-2-en-1-one oxime(HPHO)was synthesized from 2-hydroxy acetophenone and butyraldehyde.Its flotation performance and adsorption mechanism to malachite were investigated by flotation test,zeta potential,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis techniques.Compared with benzohydroxamic acid(BA),1-(2-hydroxyphenyl)ethan-1-one oxime(HPEO)and sodium isobutyl xanthate(SIBX),HPHO exhibited excellent collecting power to malachite without additional reagents,such as Na2S regulator and methyl isobutyl carbinol(MIBC)frother.Results of zeta potential indicated that HPHO was coated on malachite surfaces through a chemisorption process.FTIR and XPS data gave clear evidence for the formation of Cu−oxime complex on malachite surfaces after HPHO adsorption through the linkage between C=C,—OH,N—OH group and Cu species.

Flotation behavior and adsorption mechanism of fine wolframite with octyl hydroxamic acid

Flotation behavior and adsorption mechanism of octyl hydroxamic acid(OHA)on wolframite were investigated through flotation experiments,adsorption tests,zeta-potential measurements,infrared spectroscopy and solution chemistry calculations.Results of flotation and adsorption experiments show that the maximum values of flotation recovery and adsorption capacity occur around p H 9.In term of the solution chemistry calculations,the concentration of metal hydroxamate is greater than that of metal tungstate and metal hydroxyl,and metal hydroxamate compounds are identified to be the main species on wolframite surface at p H region of 8-10,contributing to the increase of OHA adsorption and flotation performance.Results of zeta-potential and IR spectra demonstrate that OHA adsorbs onto wolframite surface by chemisorptions.Hydroxamate ions can bond with Mn_2+/Fe_2+cations of wolframite surface,forming metal hydroxamate compounds,which is a key factor in inducing the hydrophobicity of wolframite under the conditions of maximum flotation.

Insights into the influence of temperature on the adsorption behavior of sodium oleate and its response to flotation of quartz

Temperature affects the flotation of quartz in the calcium/sodium oleate(Na OL)system,while there is a lack of understanding of its potential mechanism.Therefore,in this work,the flotation response of quartz to temperature was investigated via micro-flotation experiments,interface property analyses,and theoretical calculations.Flotation results demonstrated that increasing temperature contributed to higher flotation recovery of quartz,which enhanced the removal of quartz from hematite.Surface tension results revealed that higher temperatures lowered the critical micelle concentration(CMC)and surface tension of the Na OL solution,and thus enhanced its surface activity.Solution chemistry calculations and X-ray photoelectron spectroscopy(XPS)measurements confirmed that the increased content of Ca(OH)+achieved by increasing temperatures enhanced the adsorption amounts of calcium species(acting as activation sites)on the quartz surface.Dynamic light scattering(DLS)measurements verified that the association degree of RCOOàto form(RCOO)22àwas strengthened.Furthermore,adsorption density measurements and molecular dynamics(MD)simulations confirmed that increasing the temperature facilitated Na OL adsorption toward the surface of the quartz,which was attributed to the stronger interaction between Na OL and the calcium-activated quartz surface at higher temperatures.As a result,quartz flotation was improved by increasing temperatures.Accordingly,a possible adsorption model was proposed.

Adsorption behavior and mechanism of copper ions in the sulfidization flotation of malachite

Malachite is one of the main minerals used for the industrial enrichment and recovery of copper oxide resources, and copper ions are unavoidable metal ions in the flotation pulp. The microflotation, contact angle, and adsorption experiments indicated that pretreatment with an appropriate concentration of copper ions could improve the malachite recovery, and the addition of excess copper ions reduced the hydrophobicity of the malachite surface. The results of zeta potential tests indicated that sodium sulfide and butyl xanthate were also adsorbed on the surface of malachite pretreated with copper ions. X-ray photoelectron spectroscopy(XPS) results indicated that —Cu—O and —Cu—OH bonds were formed on the surface of the samples. After pretreatment with an appropriate concentration of copper ions, the number of —OH groups on the mineral surface decreased, whereas the number of Cu—S groups on the mineral surface increased, which was conducive to the sulfidization of malachite. After adding a high concentration of copper ions, the —OH groups on the mineral surface increased, whereas the number of Cu—S groups decreased, which had an adverse effect on the sulfidization flotation of malachite. Time-of-flight secondary ion mass spectrometry showed that pretreatment with copper ions resulted in a thicker sulfidization layer on the mineral surface.

Adsorption mechanism of N-laurel-1,3-diaminopropane in a hematite-quartz flotation system

The strong collecting performance of N-laurel-1,3-diaminopropane（ND13） with respect to quartz encouraged us to study its separation of hematite and quartz mixtures in a laboratory cell flotation test The results show that the best separation results can be achieved when the pulp pH is 7.27 and 58.3 mg/L collector plus 6.67 mg/L depressant are added to the mixture.Products with 58.45%,62.78%and 63.72% iron grades can be achieved respectively when mass ratio of hematite to quartz is 2：3,1：1,and 3：2.The adsorption mechanism of ND13 on a quartz surface was investigated by zeta-potential and X-ray photoelectron spectroscopy measurements.The results reveal that electrostatic and hydrogen bonding adsorption take place between ND13 and the quartz surface,and that ND13 mainly interacts with the oxygen atoms on the quartz surface.

Flotation and adsorption of quaternary ammonium salts collectors on kaolinite of different particle size

The flotation behaviors of decyltrimethylammonium (103C), dodecyltrimethylammonium chloride (DTAC), tetradecyltrimethylammonium chloride (TTAC) and cetyltrimethylammonium chloride (CTAC) on kaolinite of different particle size fraction were studied. The adsorbed amount and adsorption isotherms of collectors on kaolinite were determined for painstaking investigation into the adsorption of quaternary amines at kaolinite-water interface by ultraviolet spectrophotometer methods. The flotation results show that the flotation recovery of kaolinite of different particle fraction increases with an increase in pH when 103C, DTAC, TTAC and CTAC are used as collectors. As the concentration of collectors increases, the flotation recovery increases. Particle size of kaolinite has a strong effect on flotation. The flotation recovery of fine kaolinite decreases with the carbon chain of quaternary ammonium salts collectors increasing, while coarse kaolinite is on the contrary. The adsorbed amount tests and adsorption isotherms show that adsorbed amount increases when the particle size of kaolinite increases or when the carbon chain length of quaternary ammonium salts increases. Within the range of flotation collector concentration, the longer the hydrocarbon chain, the more probable to be absolutely adsorbed by fine kaolinite particles and then the lower the collector concentration in the bulk, which leds to lower flotation recovery.

Flotation behavior and adsorption mechanism of salicylhydroxamic acid in artificial mineral anosovite

Flotation is often employed to separate valuable natural minerals and gangue minerals.However,few studies have been conducted on artificial mineral flotation.Anosovite,the primary mineral in titanium slag,is a typical artificial mineral that can be enriched by flotation.In the present work,flotation behavior and adsorption mechanism of anosovite in salicylhydroxamic acid(SHA)solution were studied.The influence of pH and SHA dosage on anosovite flotability was investigated.Micro-flotation test results show that a pH range of 7–8.5 is available for SHA to collect anosovite.A maximum recovery of 93.26%can be obtained with SHA dosage of only 4×10.5 mol/L.In addition,TOC,zeta potential,FTIR,SEM-EDS,and XPS analyses were used to study the adsorption mechanism.Results demonstrated that SHA adsorption is governed by chemisorption.XPS studies further suggested that chemical adsorption occurred at the Ti sites on the anosovite surface.

Predominating stable adsorption and direct electrochemistry of glucose oxidase on carbon nanotubes by oxygen-containing groups

Stable adsorption and direct electrochemistry of glucose oxidase （COx） occurred on nitric acid （HNO3）-treated multi-walled carbon nanotubcs （MWNTs） instead of as-received MWNTs, demonstrating the critical roles of oxygen-containing groups in stable adsorption and direct electrochemistry of GOx on carbon nanotubcs （CNTs）.

Adsorption and flotation mechanism of a ketoxime-dithiocarbonate surfactant to chalcopyrite

The adsorption mechanism of O-isopropyl-S-[2-(hydroxyimino) propyl] dithiocarbonate ester(IPXPO) to chalcopyrite was investigated by using contact angle, in-situ atomic force microscopy(in-situ AFM), cyclic voltammetry(CV) and X-ray photoelectron spectroscopy(XPS). The results of contact angle and in-situ AFM demonstrated that IPXPO adsorbed on chalcopyrite increases surface hydrophobicity and roughness. It was found by CV experiments that a layer passive film was formed. The results of XPS spectra further revealed that the thiol S atom, oxime N atom, and O atom in the IPXPO molecule might react with copper atoms to form Cu-S, Cu-N, and Cu-O bonds, respectively. An artificial mixed minerals flotation test indicated that under the condition of pH=6.79 and IPXPO initial concentration 5×10^(-5)mol/L, the flotation recovery of chalcopyrite reached about 90%, while for pyrite only 25%, suggesting that IPXPO is an excellent collector for flotation separation and enrichment of chalcopyrite.

Adsorption mechanism of styryl phosphonate ester as collector in ilmenite flotation

A styryl phosphonate ester(SPE) collector was used to improve the flotation performance of ilmenite, and the adsorption mechanism and model were revealed and established, respectively. Microflotation tests showed that SPE exhibited a stronger collecting ability for ilmenite than the traditional collector styrene phosphonic acid(SPA). Zeta potential measurements revealed that both SPE and SPA could negatively shift the zeta potential of ilmenite, while SPE had more effects than SPA, suggesting the stronger adsorption of SPE. The analysis of X-ray photoelectron spectroscopy confirmed the chemisorption of SPA and SPE onto the Fe/Ti sites of ilmenite. According to frontier orbital theory, the chemical activities of SPE are greater than those of SPA. The partial densities of states analysis indicated that the PO—H groups of the collectors could interact with the Ti/Fe atoms of the ilmenite surface to generate a stable four-membered ring. The bonding model of the collector and(104) ilmenite surface showed that the adsorption energy of SPE was higher than that of SPA. Overall, SPE presented a better collecting ability and interaction effect for ilmenite flotation than SPA, and had the potential to replace SPA in the industry.

Adsorption behavior of Pb^(2+) and Cd^(2+) ions on bauxite flotation tailings

The adsorption behavior of Pb2+ and Cd2+ ions on bauxite flotation tailings was investigated to demonstrate the adsorptivity of the bauxite flotation tailings.The adsorption percentage of Pb2+ and Cd2+ ions as a function of adsorbent dosage,solution pH value and shaking time were determined by batch experiments.The maximum adsorption percentage of 99.93% for Pb2+ ions and 99.75% for Cd2+ ions were obtained by using bauxite flotation tailings as adsorbent.The methods,such as zeta potentials,specific surface area measurements and the analysis of adsorption kinetics,were introduced to analyze the adsorption mechanisms of the Pb2+ ions on bauxite flotation tailings.The isoelectric point of bauxite flotation tailings shifts from 3.6 to 5.6 in the presence of Pb2+ ions.The specific surface area of bauxite flotation tailings changes from 12.57 to 20.63 m2/g after the adsorption of Pb2+ ions.These results indicate that a specific adsorption of the cation species happens on the surface of bauxite flotation tailings.Adsorption data of Pb2+ ions on the surface of bauxite flotation tailings can be well described by Langmuir model,and the pseudo-second-order kinetic model provides the best correlation for the adsorption data of Pb2+ and Cd2+ ions on bauxite flotation tailings.

Effects of Particle Size and Chain Length on Flotation and Adsorption of Quaternary Ammonium Salts onto Kaolinite

Effects of particle size and chain length on flotation of quaternary ammonium salts (QAS) onto kaolinite have been investigated by mico-flotation tests. The two kinds of quaternary ammonium salts [RN(CH3)3] with different chain lengths, dodecyltrimethylammonium chloride (DTAC) and cetyltrimethylammonium chloride (CTAC) were used as collectors for kaolinite in different particle size fractions (0.075–0.01 mm, 0.045–0.075 mm, 0–0.045 mm). The anomalous flotation behavior of kaolinite have been further explained based on crystal structure considerations by adsorption tests and molecular dynamics (MD) simulation. The results show that the flotation recovery of kaolinite in all different particle size fractions decreases with an increase in pH when DTAC and CTAC are used as collectors. As the concentration of collectors increases, the flotation recovery increases. The longer the carbon chain of QAS is, the higher the recoveries of coarse kaolinite (0.075–0.01 mm and 0.045–0.075 mm) are. But the flotation recovery of the finest kaolinite (0–0.045 mm) decreases with chain lengths of QAS collectors increasing, which is consistent with the flotation results of unsifted kaolinite (0–0.075 mm). It is explained by the froth stability related to the residual concentration of QAS collector. In lower residual concentration, the froth stability becomes worse. Within the range of flotation collector concentration, it's easy of CTAC to be completely adsorbed by kaolinite in the particle size fraction (0–0.045 mm), which led to lower flotation recovery. Moreover, it is interesting that the particle size of kaolinite is coarser, the flotation recovery is higher. The anomalous flotation behavior of kaolinite is rationalized based on crystal structure considerations. The results of MD simulations show that the (001) kaolinite surface has the strongest interaction with DTAC, compared with the (001), (010) and (110) surfaces. On the other hand, when particle size of kaolinite is altered, the number of basal planes and edge planes is changed. It is observed that the finer kaolinite particles size become, the greater relative surface area of edges is, and the more the number of edges is. It means that fine kaolinite particles have more edges to adsorb less cationic colletors than that of coarse kaolinite particles, which is responsible for the poorer floatability of fine kaolinite.

ADSORPTION MECHANISMS OF HS-IONS ON SULPHIDE MINERAL SURFACES RELATED TO Na_2S-INDUCED FLOTATION

The adsorption mechanisms of HS- ions existing in air-saturated alkaline solutions on sulphide minerals （including pyrite, arsenopyrite, chalcopyrite and galena） were investigated. The measurement of adsorption density, solvent extraction-chemical analysis of neutral sulphur at the surfaces, measurements of pulp potential and voltammogram, and flotation tests were done. Both the electrochemical and non-electrochemi cal adsorption models of HS- ions were established. The former was observed and resulted in the formation of neutral sulphur （S°）when the pyrite and arsenopyrite were chosen, and hence renders the surfaces hy drophobic and induced the two minerals flotation. It is called Na2S-induced flotation. On the other hand, the latter took place and did not produce S° when the chalcopyrite and galena were selected, and hence de presses the collectorless flotation of the two minerals. The adsorptions of HS- ions were mainly influenced by potentials, pH and the electron structures of the mineral surfaces.

Flotation and adsorption of novel Gemini decyl-bishydroxamic acid on bastnaesite:Experiments and density functional theory calculations

Rare earth element is an important strategic metal,but the supply of high purity rare earth ores is growing slowly,which is in sharp contradiction with the rapidly growing demand.Froth flotation has been confirmed to be an effective method to separate bastnaesite from its gangue minerls.However,the traditional collectors are facing serious problems in flotation separation of minerals,requiring the addition of excess depressant and regulator in the flotation process.Herein,we proposed and synthesized novel Gemini hydroxamic acids Octyl-bishydroxamic acid(OTBHA),Decyl-bishydroxamic acid(DCBHA)and Dodecyl-bishydroxamic acid(DDBHA)as the collectors in bastnaesite-barite flotation system.The effect of different carbon chain lengths on the molecular properties were explored by density functional theory(DFT)calculations.DCBHA possessed a stronger reactivity compared with OCBHA and DDBHA.The flotation results verified the consistency of the computational calculation about the performance prediction of Gemini hydroxamic acids.Compared with OCBHA and DDBHA,DCBHA displayed superior collecting affinity toward bastnaesite,and did not float barite.Zeta potential results showed that the presence of DCBHA increased the potential of bastnaesite,while it had almost no effect on barite,indicating DCBHA had a stronger affinity for bastnaesite.Then,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analyses indicated that the adsorption mechanism was due to two hydroxamate groups of DCBHA co-anchored on bastnaesite surface by forming five-membered hydroxamic―(O―O)―Ce complexes.In addition,atomic force microscopy(AFM)clearly observed that DCBHA uniformly aggregated on bastnaesite surface,which increased surface contact angle and improved the hydrophobicity of bastnaesite.

Boron separation by adsorption and flotation with Mg-Al-LDHs and SDBS from aqueous solution

Layered double hydroxides(LDHs)have been shown to be effective adsorbents for boron.However,solid-liquid separation is still a problem when separating boron from industrial radioactive waste liquid.In this research,three types of Mg-Al-LDHs including Mg-Al-LDH(NO_(3)^(-)),Mg-Al-LDH(Cl^(-))and Mg-Al-LDH(SO_(4)^(2-))were applied to adsorb boron,and moreover sodium dodecylbenzenesulfonate(SDBS)was used to float the LDH particles from aqueous solution after boron adsorption.The results showed that 60 min was sufficient for the equilibrium adsorption of the three LDHs.The boron adsorption capacity of three LDHs was determined as follows:Mg-Al-LDH(NO_(3)^(-))>Mg-Al-LDH(Cl^(-))>Mg-Al-LDH(SO_(4)^(2-)),and was 2.0,0.98 and 0.2 mmol·g^(-1),each ranging from 0 to 80 mmol·L^(-1)with the initial boron concentration.The efficiency of boron removal by Mg-Al-LDH(NO_(3)^(-))and SDBS can reach up to 89.7%.Furthermore,the boron flotation mechanism of SDBS and LDHs has been studied,since SDBS as a flotation agent can react with LDHs and penetrate into the interlayer of LDHs in addition to electrostatic attraction.Therefore,LDHs in solution can be floated onto the foam layer to be separated from the solution,and the clarified solution was obtained.The method is simple and promising for boron removal from aqueous solution.

Adsorption behavior and mechanism of Bi(Ⅲ) ions on rutile-water interface in the presence of nonyl hydroxamic acid

The adsorption behavior and mechanism of Bi（Ⅲ） ions on the rutile-water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy（XPS）. According to the results of micro-flotation, Bi（Ⅲ） ions could largely improve the rutile flotation recovery（from 62% to 91%）, and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH-ions, which determined that Bi（Ⅲ） ions were capable of activating rutile flotation. The adsorption of Bi（Ⅲ） ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi（Ⅲ） ions. Based on the adsorption mechanism of Bi（Ⅲ） ions, it was deduced that firstly Bi（Ⅲ） ions occupied the vacancies of the original Ca^2＋, Mg^2＋ and Fe^2＋ ions on the rutile surface; secondly Bi（Ⅲ） ions covered on the rutile surface in the form of hydroxides.