Single and competitive adsorption affinity of heavy metals toward peanut shell-derived biochar and its mechanisms in aqueous systems

Converting peanut shells into biochar by pyrolysis was considered an environmentally friendly and efficient method for agricultural solid waste disposal.The properties of peanut shell-derived biochar(PBC)under different temperature and its adsorption capacity of heavy metals were investigated.It was found that PBC400 exhibited the highest cumulative capability for heavy metals elimination in single solute because of its high specific surface area and rich functional groups.Furthermore,the competitive adsorption revealed that PBC had a substantial difference in adsorption affinity from diverse heavy metal ions,sorption capacity decreased as Pb2+>Cu2+>Cd2+>Ni2+>Zn2+,which was lower than in a single solute.The adsorption process using selected biochar was optimized with respect to p H,reaction time,adsorbent dose,and initial concentration of heavy metals.The kinetic data was well fitted with PSO model,and the Langmuir model was adopted for adsorption equilibrium data in both cases of single solutes and mixed solutes for all heavy metals,which indicated that the removal course was primarily explained by monolayer adsorption,and chemical adsorption occupied an important role.Therefore,peanut shells derived biochar could be a potential and green adsorbent for wastewater treatment.

Binary competitive adsorption of naphthalene compounds onto an aminated hypercrosslinked macroporous polymeric adsorbent

An aminated hypercrosslinked macroporous polymeric adsorbent was synthesized and characterized. Adsorption isotherms for 1 amino 2 naphthol 4 sulfonic acid(1, 2, 4 acid) and 2 naphthol obtained from various binary adsorption environments can be well fitted by Freundlich equation, which indicated a favorable adsorption process in the studied range. Adsorption for 1, 2, 4 acid was an endothermic process in comparison with that for 2 naphthol of an exothermic process. 2 naphthol molecules put a little influence on the adsorption capacity for 1, 2, 4 acid. However, the adsorption to 1, 2, 4 acid depressed that to 2 naphthol in a large extent for the stronger electrostatic interaction between 1, 2, 4 acid and adsorbent. The predominant mechanism can be contributed to the competition for adsorption sites. And the simultaneous environment was confirmed to be helpful to the selective adsorption towards 1,2,4 acid based on the larger selectivity index.

Effect of Competitive Adsorption between Sodium Tripolyphosphate and Naphthalene Superplasticizer on Fluidity of Cement Paste

The adsorption amount, ξ-potential of cement particles and fluidity of cement paste were tested to research the competitive adsorption between naphthalene superplasticizer （FDN） and STPP. The experimental results showed that the presence of STPP could significantly improve the fluidity of cement paste and reduce the fluidity loss with FDN. There existed a competitive adsorption between STPP and FDN. STPP and calcium ions formed complexes; they preferentially adsorbed onto surface of cement particles and preempt adsorption points of FDN; and it reduced adsorption amount of FDN. In the absence of STPP, saturation adsorption amount of FDN was 5.93 mg/g; but when the dosage of STPP was 0.1%, it reduced to 4.3 mg/g （about 72.5%）. The adsorption amount of FDN was reduced by STPP, but ξ-potential of cement particles enhanced and fluidity of cement paste increased because of strong negative charge effect of the complexes. Adsorption of the complexes would delay Ca^2＋ into liquid and inhibit formation of active adsorption points. Then, content of FDN in liquid increased with the addition of STPP and ξ-potential of cement particles became stable. In this way, fluidity loss of cement paste reduced.

Preparation of Fe3O4-octadecyltrichlorosilane for Removal of Methyl Orange and Methylene Blue:Influence of p H and Ionic Strength on Competitive Adsorption

Fe3O4-octadecyltrichlorosilane（Fe3O4-OTS）was synthesized and used to remove dyes in a competitive system.Fe3O4-OTS was prepared by slow hydrolysis of OTS in cyclohexane on the surface of Fe3O4obtained through coprecipitation method.Scanning electron microscope（SEM）,energy dispersive spectrometer（EDS）,and contact angle analyzer（CA）were used to analyze the properties of Fe3O4-OTS.Methyl orange（MO）and methylene blue（MB）were selected as model molecules to study the influence mechanism of p H and ionic strength on competitive adsorption.The results of EDS and CA indicated that Fe3O4 was modified successfully with OTS on the surface.Silicon appeared and carbon content increased obviously on the surface of adsorbent.Contact angle of adsorbent increased from 0~o to 107~o after being modified by OTS.Fe3O4-OTS showed good separation for MO and MB in competitive system,which has potential to separate dyes in sewage.Separation factor（β~OB）changed from 18.724 to 0.017,when p H changed from 7 to 12,revealing that MO and MB could be separated almost thoroughly by Fe3O4-OTS.p H could change the surface charge of Fe3O4-OTS and structure of dyes,and thus change the interactions of competitive system indirectly.Even though hydrophobic interaction was enhanced,ionic strength reduced the difference of electrostatic interaction between dyes and Fe3O4-OTS.So it is unfavorable to separate dyes with opposite charges when ionic strength increases.These findings may provide theoretical guidances to separate two-component dye pollutants.

Competitive adsorption and mobility sequence of heavy metals in urban soils of southeastern China

Heavy metals can be introduced into urban soils at the same time. Therefore, their selective retention and competitive adsorption by the soils become of major importance in determining their availability and movement throughout the soil. In this study, the availability and mobility of six heavy metals in eight urban soils collected from different cities of Zhejiang Province, southeastern China were assessed using distribution coefficients（Kd） and retardation factor（Rf）. The results showed that there were great differences in the Kd and Rfamong the tested soils. The adsorption sequences were Cr〉Pb〉Cu〉Cd〉Zn〉Ni, and the Kd decreased with increasing levels of metal addition. Ni generally has the lowest Rf values followed closely by Cd, and Zn whereas Cr and Pb reached the highest values. The results suggest that Ni and Zn have the highest mobility associated to the lowest adsorption, Cr and Pb present the opposite behavior. Correlation analysis indicates that soil pH, CaCO3 content, and cation exchange capacity （CEC） are key factors controlling the solubility and mobility of the metals in the urban soils.

Mechanism transformation of cyclohexene-thiophene competitive adsorption in FAU zeolite

Competition of hydrocarbon compounds with sulfides in gasoline has caused a not very high selectivity of sulfides in adsorption desulfurization so far,resulting in a reduction of catalyst lifetime as well as more sulfur oxide emissions.Tostudy the whole competitive process changing with the increase of the loading,the dynamic competition adsorption mechanism of cyclohexene and thiophene in siliceous faujasite(FAU)zeolite was analyzed by the Monte Carlo simulation.The results showed that with the increase of the loading,thiophene and cyclohexene had different performances before and after the inflection point of 40 molecule/UC.The adsorbates were distributed ideally at optimal sites during the stage that occurred before the inflection point,which is called the“optimal-displacement adsorption”stage.When approaching the inflection point,the competition became apparent and the displacement appeared accordingly,some thiophene molecules at S sites(refers to the sites inside the supercages)were displaced by cyclohexene.After the inflection point,the concentration of adsorbates at W sites(refers to the 12-membered ring connecting the supercages)was significantly reduced,whereas the adsorbates at S sites got more concentrated.The stage some cyclohexene molecules displaced by thiophene and inserted into the center of the supercage can be named as the“insertion-displacement adsorption”stage,and both the adsorption behavior and the competitive relationship became localized when the adsorption amount became saturated.This shift in the competitive adsorption mechanism was due to the sharp increase of interaction energy between the adsorbates.Besides,the increase in temperature and ratio of Si/Al will allow the adsorbates,especially thiophene molecules to occupy more adsorption sites,and it is beneficial to improve the desulfurization selectivity.

Competitive Adsorption between Bovine Serum Albumin and Collagen Observed by Atomic Force Microscope

Atomic force microscopy (AFM) was used to study the competitive adsorption betweenbovine serum albumin (BSA) and type Ⅰ collagen on hydrophilic and hydrophobic silicon wafers.BSA showed a grain shape and the type Ⅰ collagen displayed fibril-like molecules with relativelyhomogeneous height and width, characterized with clear twisting (helical formation). These AFMimages illustrated that quite a lot of type Ⅰ collagen appeared in the adsorption layer on hydrophilicsurface in a competitive adsorption state, but the adsorption of BSA was more preponderant than thatof type Ⅰ collagen on hydrophobic silicon wafer surface. The experiments showed that theinfluence of BSA on type Ⅰ collagen adsorption on hydrophilic surface was less than that onhydrophobic surface.

The Competitive Adsorption Characteristics of Welan Gum and Superplasticizer in Cement Mortar

Welan gum has been widely used in oil cement and grouting materials for its excellent rheological properties and anti-bleeding,and most of all,being friendly to the environment.However,when welan gum was added,the fluidity of mortar decreased sharply,so it should be used together with a superplasticizer to enable good workability.With its powerful charge density in the molecular structure,the competitive adsorption between welan gum and other admixtures happened remarkably during the addition process.Consequently,we experimentally studied on the bleeding rate and rheological properties of cement slurry,fluidity and mechanical properties of mortar with welan gum mixed with superplasticizer,aiming at understanding the competitive adsorption phenomenon by application of welan gum mixed with superplasticizer.By measuring the hydration heat and zeta potential,the mechanism of interaction of welan gum with superplasticizer was deduced and explained.The results showed that it could ensure a good dispersion effect when welan gum is mixed with the two kinds of superplasticizer.Welan gum had little impact on the naphthalene superplasticizer,but did have a substantial influence on polycarboxylate.In practice,adding welan gum after PCE acted with cement for 2 min could effectively avoid the competitive adsorption and then achieve better performance.On this viewpoint for mortar with PCE,new delay release welan gum needs further research and development.

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.

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb（II） and Cu（II） ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 tool. L^-1 CaC12 as background electrolyte. The desorption isotherms of Pb（lI） and Cu（II） were similar to the adsorption isotherms, which can be fitted well by Freundlich equation （R2 〉 0.96）. The soil in the three sites had greater sorption capacities for Pb（II） than Cu （II）, which was affected strongly by the soil characteristics. In the binary metal solution containing 1 ： 1 molar ratio of Pb（II） and Cu（II）, the total amount of Pb（II） and Cu（lI） adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared （FT-IR） spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.

Study of CH_(4)and CO_(2)competitive adsorption on shale in Yibin,Sichuan Province of China

Shale gas is an unconventional gas source with substantial development potential.In this study,Longmaxi Formation shale from the Silurian system in Yibin,Sichuan Province was collected for characterizing total organic carbon(TOC),clay mineral content,and other reservoir properties.The pore structure of shale was analyzed by field-emission scanning electron microscopy and low-temperature N_(2) adsorption–desorption method.Isothermal adsorption experiments for CH_(4)and CO_(2)mixtures in shale samples were performed.The second Virial coefficient was used to calculate for the compressibility factor of the gas mixture.The influencing factors of gas adsorption capacity of shale were analyzed.Finally,the CH_(4)and CO_(2)adsorption capacities and selection of shale samples were investigated.Under low pressure,the total gas mixture capacity of shale samples was positively correlated with pressure.When the pressure increased to a certain extent,the growth trend of gas mixture adsorption capacity of shale samples decreased.The mixed gas adsorption volume is high at 50℃ for all the proportion.Given the same temperature and pressure,the CO_(2)adsorption of shale samples is higher than the CH_(4)adsorption.In competitive adsorption,shale prefers to adsorb CO_(2).Therefore,CO_(2)is easier to be adsorbed by shale and this causes CH_(4)to be released from the adsorption site.

Competitive and cooperative adsorption behaviors of phenol and aniline onto nonpolar macroreticular adsorbents

The adsorption behaviors of phenol and aniline on nonpolar macroreticular adsorbents(NDA100 and Amberlite XAD4) were investigated in single or binary batch system at 293K and 313K respectively in this study. The results indicated that the adsorption isotherms of phenol and aniline on both adsorbents in both systems fitted well Langmuir equation, which indicated a favourable and exothermic process. At the lower equilibrium concentrations, the individual amount adsorbed of phenol or aniline on macroreticular adsorbents in single-component systems was higher than those in binary-component systems because of the competition between phenol and aniline towards the adsorption sites. It is noteworthy, on the contrast, that at higher concentrations, the total uptake amounts of phenol and aniline in binary-component systems were obviously larger than that in single-component systems, and a large excess was noted on the adsorbent surface at saturation, which is presumably due to the cooperative effect primarily arisen from the hydrogen bonding or weak acid-base interaction between phenol and aniline.

BINARY COMPETITIVE AND COOPERATIVE ADSORPTION OF AROMATIC COMPOUNDS ON POLYMERIC RESINS

The adsorption behaviors of 2-naphthalenesulfonic acid and aniline on a conventional macroporous resin Amberlite XAD4 and the other two newly-developed hypercrosslinked resins NDA101 and NDAI00 were investigated in a single or binary batch system at 293 K and 313 K, respectively. All the adsorption isotherms of 2-naphthalenesulfonic acid and aniline on the test resins in both systems can fit well with the Langmuir equation, indicating that the adsorption is a favorable process. At the identical equilibrium concentration, the amount of aniline adsorbed on polymeric resins in the single system is higher than that in the binary system because of the competitive adsorption between 2-naphthalenesulfonic acid and aniline on the resin surface. However, the uptake amount of 2-naphthalenesulfonic acid in the binary system is markedly larger than that in the single system, which is presumably due to the cooperative effect arisen from the electrostatic interaction between 2-naphthalenesulfonic acid and aniline adsorbed on the resin surface. The simultaneous adsorption system was proven to be helpful for the selective adsorption toward 2-naphthalenesulfonic acid due to its larger selective index.

Effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils

Glyphosate （GPS） is a non-selective, post-mergence herbicide that is widely used throughout the world. Due to the similar molecular structures of glyphosate and phosphate, adsorption of glyphosate on soil is easily affected by coexisting phosphate, especially when phosphate is applied at a significant rate in farmland. This paper studied the effects of phosphate on the adsorption of glyphosate on three different types of Chinese soils including two variable charge soils and one permanent charge soil. The results indicated that Freundlich equations used to simulate glyphosate adsorption isotherms gave high correlation coefficients（0.990-0.998） with K values of 2751, 2451 and 166 for the zhuanhong soil（ZH soil, Laterite）, red soil（ RS, Udic Ferrisol） and Wushan paddy soil（WS soil, Anthrosol）, respectively. The more the soil iron and aluminum oxides and clay contained, the more glyphosate adsorbed. The presence of phosphate significantly decreased the adsorption of glyphosate to the soils by competing with glyphosate for adsorption sites of soils. Meanwhile, the effects of phosphate on adsorption of glyphosate on the two variable charge soils were more significant than that on the permanent charge soil. When phosphate and glyphosate were added in the soils in different orders, the adsorption quantities of glyphosate on the soils were different, which followed GPS-soil 〉 GPS-P-soil = GPS-Soil-P 〉 P-soil-GPS, meaning a complex interaction occurred among glyphosate, phosphate and the soils.

Spectroscopic and macroscopic studies of the adsorption of arsenate and phosphate on polynuclear aluminum organomineral precipitates

Aluminum organic coprecipitates play important roles in the transport of oxyanions in soil environment.A new polynuclear aluminum organomineral precipitate(Al13-oxalate precipitate) was prepared to investigate the adsorption behavior of arsenate and phosphate on noncrystalline aluminum precipitates.Important thermodynamic parameters for adsorption reaction were evaluated using macroscopic adsorption data and equations.The result showed that,the adsorption reaction basically is a diffusion process.FTIR spectroscopic studies have provided evidence for the formation of two different types of complexes in substrate,protonated bidentate and deprotonated bidentate complexes at pH 4 and pH≥6,respectively.The classic competitive adsorption and XPS studies both indicated that phosphate has stronger chemical interaction with substrate than arsenate.The findings of XPS studies revealed that the precipitate substrate can act as Lewis acid when adsorbing oxyanions.

Diffusion and Adsorption of Tetralin Hydrocracking Reaction on Different Zeolites by Molecular Simulation

Three different zeolite catalysts with different pore sizes(MFI-type,BEA-type,and FAU-type zeolites)have been prepared.The influence of different zeolite catalysts on reactivity and product shape selectivity of tetralin is investigated.Clear differences are observed in the reactivity of tetralin and distribution of products achieved by different catalysts.The diffusion and adsorption behavior of the reactant tetralin and its intermediates,n-butylbenzene and 1-methylindane under the reaction conditions are simulated using molecular simulation methods.Upon combining simulation results and experimental observations,it is shown that the difference in diffusion coefficient and competitive adsorption capacity can explain the reactivity of tetralin and the selectivity of products.The steric hindrance of the MFI-type zeolite mainly limits the key step of ring opening of tetralin,leading to lower selectivity of ring-opening products.n-Butylbenzene molecules can diffuse sufficiently fast in the large pores of FAU-type zeolite and the weak adsorption capacity of n-butylbenzene leads to its insufficient cracking.In addition,it also explains the reason that the BEA-type zeolite has the best BTX selectivity,because it can satisfy both good ring-opening activity and sufficient butylbenzene cracking depth.

Synthesis of highly active Cu(Ⅰ)-Y(Ⅲ)-Y zeolite and its selective adsorption desulfurization performance in presence of xylene isomers

A bimetal-exchanged NaY zeolite(Cu(Ⅰ)-Y(Ⅲ)-Y)with a desirable adsorptive desulfurization(ADS)performance was prepared and characterized by means of X-ray diffraction,specific surface area measurements,X-ray fluorescence spectrometer,X-ray photoelectron spectroscopy,thermal gravity analysis and Fourier transform infrared spectroscopy.The effect of Y(Ⅲ)ions on ADS in the presence of the xylenes was investigated.Results indicated that the ADS performance of Y(Ⅲ)-Y is higher than that of most reported CeY.The Y(Ⅲ)-based Cu(Ⅰ)-Y(Ⅲ)-Y demonstrated the higher breakthrough loading than those of reported Ce(Ⅲ)/Ce(Ⅳ)-based transition metal Y zeolites,showing that Y(Ⅲ)ions play a promoting role in improving the ADS selectivity.For Cu(Ⅰ)-Y(Ⅲ)-Y,a new strong S-M interaction(S stands for sulfur,while M stands for metal)active site was formed,which might be caused by the synergistic effect between Cu(Ⅰ)and Y(Ⅲ).The Cu(Ⅰ)-Y(Ⅲ)-Y,which combined the advantages of Cu(I)-Y and Y(Ⅲ)-Y,is a kind of promising adsorbent.The breakthrough loading decreased in the order of Cu(Ⅰ)-Y(Ⅲ)-Y>Y(Ⅲ)-Y>Cu(Ⅰ)-Y,and the effect of xylene isomers on the sulfur removal was in the order of ortho-xylene>meta-xylene>para-xylene,which exhibited the same trend with the bond order of xylenes.

The effect of the density difference between supercritical CO_(2) and supercritical CH_(4) on their adsorption capacities: An experimental study on anthracite in the Qinshui Basin

Deep unmineable coals are considered as economic and effective geological media for CO_(2) storage and CO_(2) enhanced coalbed methane(CO_(2)-ECBM) recovery is the key technology to realize CO_(2) geological sequestration in coals. Anthracite samples were collected from the Qinshui Basin and subjected to mercury intrusion porosimetry, low-pressure CO_(2) adsorption, and high-pressure CH_(4)/CO_(2) isothermal adsorption experiments. The average number of layers of adsorbed molecules(ANLAM) and the CH_(4)/CO_(2) absolute adsorption amounts and their ratio at experimental temperatures and pressures were calculated. Based on a comparison of the density of supercritical CO_(2) and supercritical CH_(4), it is proposed that the higher adsorption capacity of supercritical CO_(2) over supercritical CH_(4) is the result of their density differences at the same temperature. Lastly, the optimal depth for CO_(2)-ECBM in the Qinshui Basin is recommended. The results show that:(1) the adsorption capacity and the ANLAM of CO_(2) are about twice that of CH_(4) on SH-3 anthracite. The effect of pressure on the CO_(2)/CH_(4) absolute adsorption ratio decreases with the increase of pressure and tends to be consistent.(2) A parameter(the density ratio between gas free and adsorbed phase(DRFA)) is proposed to assess the absolute adsorption amount according to the supercritical CO_(2)/CH_(4) attributes. The DRFA of CO_(2) and CH_(4) both show a highly positive correlation with their absolute adsorption amounts, and therefore, the higher DRFA of CO_(2) is the significant cause of its higher adsorption capacity over CH_(4) under the same temperature and pressure.(3) CO_(2) adsorption on coal shows micropore filling with multilayer adsorption in the macro-mesopore, while methane exhibits monolayer surface coverage.(4) Based on the ideal CO_(2)/CH_(4) competitive adsorption ratio, CO_(2) storage capacity, and permeability variation with depth, it is recommended that the optimal depth for CO_(2)-ECBM in the Qinshui Basin ranges from 1000 m to 1500 m.

SINGLE AND BINARY ADSORPTION PERFORMANCE OF SALICYLIC ACID AND 5-SULFOSALICYLIC ACID ONTO HYPERCROSSLINKED POLYMERIC ADSORBENTS

Single and binary adsorption behaviors of salicylic acid and 5-sulfosalicylic acid onto hypercrosslinked polymeric adsorbents,i.e.NDA-101 and NDA-99 were investigated.The Freundlich model can successfully describe all the adsorption isotherms tested,which indicates a favorable and exothermic adsorption process.The adsorption of salicylic acid relies on π-π interaction,while the electrostatic interaction further influences the adsorption of 5-sulfosalicylic acid onto NDA-99.The adsorptive capacity of salicylic acid on NDA-99 decreases but increases on NDA-101 with 5-sulfosalicylic acid as the background component in a binary solute system.The amount of 5-sulfosalicylic acid adsorbed was decreased with the increase in initial concentration of salicylic acid on both adsorbents.The competition for the adsorption sites is considered to be predominant in the solid-to-liquid interaction process.The adsorption selectivity of salicylic acid onto NDA-101 is higher than onto NDA-99 by more than an order of magnitude.Thus,combination technique involving NDA-101 followed by NDA-99 can be effectively applied to separate and recover salicylic acid and 5-sulfosalicylic acid from wastewater.

Adsorption Characteristics of the Powdered Activated Carbon on Pesticide in the Water

The adsorption characteristics of the powdered activated carbon on four kinds of pesticides （ dichlorvos, chlorothalonil, lindane and chlorphyrifos） were studied, and the influential factors of adsorption effect were discussed. Results showed that the powdered activated carbon could effectively remove the above four kinds of pesticides. It was rapid adsorption period before 30 min, and removal rate has reached 90%. Adsorption kinetics of the powdered activated carbon on pesticides corresponded with quasi-two-level kinetic equation, and both Freundlich and Langmuir adsorption isotherms could simulate the adsorption process of the activated carbon on pesticide well. Competitive adsorption between small-molecule organics in the water diverting from Yellow River and Desticides on microDore of the activated carbon would occur.