Adsorption and removal of antimony from aqueous solution by an activated Alumina
Antimony removal from model acid solutions by electrodeposition
Separation and Purification Technology 37(2004)107–116Antimony removal from model acid solutionsby electrodepositionA.Sava¸s Koparal a ,∗,R.Özgür a ,Ü.Bakir Ö˘g ütveren a ,H.Bergmann baEnvironmental Engineering Department,Anadolu University,Cevre Muhendisligi Bolumu,26470,Eskisehir,Turkeyb Anhalt University of Applied Sciences,Bernburger Str.55,06366Köthen,GermanyReceived 30August 2002;received in revised form 3September 2003;accepted 4September 2003AbstractThe aim of this work is to investigate the feasibility of the removal of antimony from model acid solutions simulating copper electrorefining and spent lead/lead oxide acid battery solutions by an electrochemical method.Although some data are available for advanced treatment methods such as adsorption,ion exchange and electrothermal methods,electrodeposition of antimony has not been studied extensively,yet.The data obtained from this work show that the electrodeposition of antimony on a copper electrode from acid solution is attainable and 100%removal is achieved practically depending on the effects of applied potential,current density and concentrations of acid and antimony.©2003Elsevier B.V .All rights reserved.Keywords:Acid recovery;Antimony removal;Battery wastes;Copper electrorefining solutions;Electrodeposition1.IntroductionAntimony is a common impurity in copper elec-trorefining and electrowinning from sulphate solu-tions.Many battery electrodes also contain some antimony that can be dissolved during the lifetime and deposited affecting the charge behaviour of the battery.Although some data exist from copper refin-ing processes,there is no detailed information about antimony deposition [1,2].Heavy metals such as antimony,copper,nickel,etc.,can be removed from acid solutions by conventional∗Corresponding author.Tel.:+90-222-3350580x6406;fax:+90-222-3239501.E-mail address:askopara@.tr (A.S.Koparal).and newly emerging metal treatment and recovery methods [3].The conventional treatment methods based on precipitation are utilised for relatively non-selective treatment and always generate a sludge con-taining heavy metals,requiring disposal management.Newly-emerging treatment and recovery methods are evaporative recovery,ion exchange,membrane sepa-ration,reductive electrolysis,differential precipitation,extractive metallurgy and selective adsorption [3,4].Among these methods reductive electrolysis is well established for certain metal recovery applications [5,6].The removal of a metal by electrodeposition at source seems to be attractive due to the potential for a one-step clean method of metal recycle.The theory of electrolytic reduction (i.e.electrode-position)is basically an oxidation–reduction,which1383-5866/$–see front matter ©2003Elsevier B.V .All rights reserved.doi:10.1016/j.seppur.2003.09.001108 A.S.Koparal et al./Separation and Purification Technology 37(2004)107–116takes place at the surface of conductive electrodes in a chemical medium under the influence of an applied potential [7].At the cathode,the main reaction is reduction of metal,as given in Eq.(1).M 2++2e →M(1)and,in aqueous media,the reduction of the hydrogen ion or water occurs simultaneously (Eq.(2)).2H ++2e →H 2(2)At the anode,the corresponding oxidation takes place and hydrogen ions and oxygen are formed in accordance with Eq.(3).H 2O →2H ++12O 2+2e(3)The recovery of metal ion constituents along with other materials from disposable or spent batteries is a developing area for the application of electrodepo-sition [7].There is one example for the recovery of lead from spent batteries [8].The lead in the batter-ies is dissolved in an acid electrolyte and deposited on the cathode in a tank reactor.Only trivalent antimony among the metal ion impurities present in the elec-trolyte is co-deposited with the lead.Another example is using crushed batteries and separating metal pieces from electrolytic pastes [9].The sludge is solubilized in an alkaline and acid process respectively,andtheFig.1.Electrochemical cell used in electrodeposition of antimony.purified solution is subjected to electrowinning.Cal-cium sulphate is the only solid waste.Electrical en-ergy requirement for the whole process is reported to be 0.5kWh kg −1.Recently,work has been done for antimony removal from spent lead/lead oxide batteries using divided and undivided cells and carbon cloth,lead,platinum,titanium,copper and graphite particle electrodes [10].The best results have been achieved in divided cell on copper electrode due to the prevention of the oxidation of trivalent antimony at the anode.The lowest energy consumption and remaining anti-mony concentration are reported to be as 15kWh m −3and 0.15mg l −1,respectively.In this study,cathodic reduction of antimony from H 2SO 4solutions has been carried out in a divided cell containing copper or carbon cloth electrodes,exam-ining the form of antimony deposited on cathode and the effects of parameters such as current density,ini-tial antimony and acid concentrations.2.ExperimentalElectrochemical deposition has been applied to re-move and recover antimony from aqueous H 2SO 4so-lutions.A reactor with a volume of 200cm 3,a height of 70mm and a diameter of 60mm is used as shown in Fig.1.Anode and cathode chambers are separated by a ceramic cup filled with agar jelly.Either carbonA.S.Koparal et al./Separation and Purification Technology 37(2004)107–116109Fig.2.Polarisation curves on copper cathode:(A)H 2SO 4of 4%;(B)H 2SO 4of 36%;(C)5mg Sb l −1in H 2SO 4of 36%.cloth with a surface area of 55cm 2or a copper sheet with a surface area of 120cm 2is used as the cathode.A power supply (Statron;16V ,6.4A),a digital volt-meter (OGSM 3900)and a magnetic stirrer to pro-vide homogeneity in the solution (Electro-Mag)are used in the experiments.The remaining trivalent an-timony concentration in the solution is determined by atomic absorption spectrometer (Varian Spectra AA 251).Deposited antimony at the surface of the elec-trode was examined by a X-ray diffraction (XRD)ap-paratus (Rigaku Rint 2200,Monochromatic Cu K ␣radiation,λ=1.5406Åand scanning speed 2◦min −1for 2θ).A solution of 100cm 3of H 2SO 4of either 36%or 20%containing trivalent antimony with concen-trations of 1500and 3500mg l −1has been used as a model solution.Percentage removal efficiency and energy consump-tion as kWh g −1have been calculated using the equa-tions Eqs.(4)and (5).removal (%)=C 0−CC 0×100(4)energy consumption =I ×V ×t ×10−3C(5)where C 0is the initial Sb concentration,C the remain-ing Sb concentration,I the current passing reactor in ampere,V the potential applied to the reactor in volt,t the time in hour,and C the concentration difference.Arithmetic mean of the results obtained by repeating the experiments three times has been given as a datum.Since current density is an important factor affect-ing the efficiency and energy consumption of an elec-trochemical system,current densities of 1,2,3and 5mA cm −2are examined.The very high sulphuric acid concentration,com-pared to the antimony concentration,is a problem for detailed kinetic studies because hydrogen evolution overlaps the main reaction as can be seen from Fig.2that is a representative picture of polarisation curves (EG&G Instruments potentiostat)on copper cathode with different acid concentrations.3.Results and discussionIn this study,the copper electrode was seen to be more effective than the carbon cloth for the removal of antimony even if the current density was as low as110 A.S.Koparal et al./Separation and Purification Technology 37(2004)107–116Fig. 3.The variation of residual concentration with time at carbon cloth:(A-1)1mA cm −2,(A-2)2mA cm −2,(A-3)3mA cm −2,(A-4)5mA cm −2;and copper electrodes (B-1)1mA cm −2,(B-2)2mA cm −2,(B-3)3mA cm −2,(B-4)5mA cm −2(initial concentration:3500mg l −1,H 2SO 4of 20%).1mA cm −2as can be seen from Fig.3.At a current density of 2mA cm −2on the copper electrode,the fi-nal concentration of 105mg l −1for antimony with the removal efficiency of 97%has been achieved with ini-tial concentration of 3500mg l −1in 3h whereas 6h were required for the same removal efficiency with carbon cloth electrode.The energy consumption val-ues were 0.03and 0.20kWh g −1,respectively.Qualitative data from XRD analysis shows that the deposited antimony is elemental antimony and an-timony oxide when the copper electrode is used as shown in Fig.4.Two different concentrations of H 2SO 4which are widely encountered are examined and the effect of the acid concentration on the removal efficiency is shown in Fig.5.It can be seen from this figure that the re-moval rate of antimony is slightly higher with 20%H 2SO 4than that with 36%H 2SO 4.Energy consump-tion values are not different in these two cases until maximum removal is achieved as can be seen in Fig.6.The variation of current efficiency with the concen-tration of H 2SO 4has been shown in Fig.7.As can be seen from this figure,slightly better current effi-ciency values are observed when H 2SO 4concentration is 20%.Besides current efficiency,the final concentra-tion of the metal which is related with the initial con-centration is important in terms of process feasibility.Thus,two different initial concentrations of 1500and 3500mg l −1for antimony are examined.The higher the initial concentration,the larger is the amount of antimony removed per unit time,the smaller is the en-ergy consumed per gram of antimony,and the current efficiency is higher at the same removal efficiency of for example 99%as shown in Table 1.Several potential differences have been applied to obtain required current densities from 1to 5mA cm −2.These potential differences have been 2–2.8V with higher concentration of 3500mg l −1Sb and H 2SO 4of 36%in which the conductivity of solution was higher,whereas they have been 2.2–3.3V with lower concen-tration of 1500mg l −1Sb and H 2SO 4of 20%in which the conductivity of solution was lower.This explains the lower specific energy consumption with higher an-timony concentration.The behaviour of the polarisa-tion curves for both lower and higher H 2SO 4concen-trations were similar as can be seen in Fig.2.There-fore,hydrogen overlapping can also be a problem for the H 2SO 4concentration of 20%.Thus,it can be said for the Sb and H 2SO 4system that polarisation curves cannot be suitable to explain the kinetic behaviour of the system.An increase in current density results in an increase in removal efficiency and energy consumption as can be seen from Figs.8and 9.The removal efficiency of 93%for the current density of 1mA cm −2is achieved in 5h with an energy consumption value of 0.1kWhA.S.Koparal et al./Separation and Purification Technology 37(2004)107–116111F i g .4.Q u a l i t a t i v e a n a l y s i s o f a n t i m o n y .112A.S.Koparal et al./Separation and Purification Technology 37(2004)107–1160204060801001201234567Time (h)R e m o v a l E f f i c i e n c y (%)Fig.5.The variation of removal efficiency with time using copper electrode (initial concentration:3500mg l −1,current density:1mA cm −2).per gram of antimony removed.The removal effi-ciency is 99%in 5h at 2mA cm −2with an energy consumption value of 0.43kWh g −1.It means that an increase of 6%in removal efficiency due to an increase00,20,40,60,811,21,412345Time (h)E n e r g y C o n s u m p t i o n (k W h /g )Fig.6.The variation of energy consumption with time using copper electrode (initial concentration:3500mg l −1,current density:1mA cm −2).in current density corresponds to an increase of more than four times in energy consumption.However,the removal efficiency of 99%is achieved producing a so-lution of 35mg l −1at 1mA cm −2in 7h with an energyA.S.Koparal et al./Separation and Purification Technology 37(2004)107–116113010203040506070809010000,511,522,533,544,5Time (h)C u r r e n t E f f i c i e n c y (%)Fig.7.The variation of current efficiency with time using copper electrode (initial concentration:3500mg l −1,current density:5mA cm −2).Table 1Experimental results obtained in electrodeposition of antimony using copper electrodes Initial concentration of Sb (mg l −1)Time (h)Cell voltage (V)Remaining concentration of Sb (mg l −1)Removal efficiency (%)Current efficiency (%)Energy consumption (kWh g −1)15000150000.2523784.2530.003560.5318188.0280.0839*******.3150.1950321699.080.4093235000350000.25136661.0900.001970.5103770.4520.014741 2.855284.2310.0320629497.3180.0687432699.2120.3158042099.463.1158H 2SO 4of 20%,5mA cm −2.0204060801001201234567Time (h)R e m o v a l E f f i c i e n c y (%)Fig.8.The variation of removal efficiency with time at different current densities using copper electrode (initial concentration:3500mg l −1,H 2SO 4of 20%).114A.S.Koparal et al./Separation and Purification Technology 37(2004)107–1160,050,10,150,20,250,30,350,40,450,501234567Time (h)E n e r g y C o n s u m p t i o n (k W h /g )Fig.9.The variation of energy consumption with time at different current densities using copper electrode (initial concentration:3500mg l −1,H 2SO 4of 20%).0500100015002000250030003500400001234567Time (h)R e m a i n i n g C o n c e n t r a t i o n (m g /L)Fig.10.Concentration–time relationship at 1mA cm −2(H 2SO 4of 20%).Table 2Mass transfer coefficients (k m )for the electrodeposition of antimony using copper electrodes Current density3500mg Sb l −11500mg Sb l −1Time (h)k m (×10−6m s −1)Time (h)k m (×10−6m s −1)1mA cm −20–0–1 1.0430.5 4.39920.9941 3.1783 1.0772 3.034 1.1673 3.0185 1.24642.49861.569A.S.Koparal et al./Separation and Purification Technology 37(2004)107–116115Table 2(Continued )Current density3500mg Sb l −11500mg Sb l −1Time (h)k m (×10−6m s −1)Time (h)k m (×10−6m s −1)5mA cm −20–0–0.258.710.2517.080.5 5.630.59.791 4.2751 6.2682 4.18625.2553 3.78342.9905001000150020002500300035004000012345Time (h)R e m a i n i n g C o n c e n t r a t i o n (m g /L )Fig.11.Concentration–time relationship at 5mA cm −2(H 2SO 4of 20%).consumption value of 0.2kWh g −1.Thus,the removal efficiency or the energy consumption may need to be selected for optimisation.Concentration–time relationships for two current densities can be seen in Figs.10and 11.From these figures,a first-order relation between time and concen-tration in a batch reactor represented with the equa-tion (C initial /C final )=e −k L aθ(where θis the reaction time)can be seen.Therefore,mass transfer coeffi-cients have been calculated and tabulated in Table 2.From Table 2,the lower the initial concentration and the higher the current density,the larger are the mass transfer coefficients as expected.These results can also be seen from Figs.10and 11.Therefore,all results ob-tained before have been approved by the mass transfer coefficients.4.ConclusionsIt is concluded from this study that antimony has been removed from H 2SO 4solutions of two differ-ent concentrations representing copper electrorefin-ing and spent battery solutions.The concentration of the acid is found not to be significantly effec-tive on the efficiency of the process.Energy con-sumption is less than enough compared to those of the other processes showing that this process can be accepted as more economically applicable.The H 2SO 4solution after treatment may also be reused since the full removal of antimony is practically achieved.However,efficiency and economy of the system will have to be investigated by studying with real116 A.S.Koparal et al./Separation and Purification Technology37(2004)107–116wastewaters from copper electrorefining and spent lead/lead oxide acid battery. 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从水中去除重金属离子和染料的农业固体废物吸附剂综述说明书
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磁性壳聚糖凝胶微球对水中Pb(Ⅱ)的吸附性能
中国环境科学 2018,38(4)：1364~1370 China Environmental Science 磁性壳聚糖凝胶微球对水中Pb(Ⅱ)的吸附性能蒲生彦1,2,3*,王可心1,2,马慧1,2,杨曾1,2,候雅琪1,2,陈虹宇1,2(1.成都理工大学,地质灾害防治与地质环境保护国家重点实验室,四川成都 610059；2.成都理工大学,国家环境保护水土污染协同控制与联合修复重点实验室,四川成都 610059；3.香港理工大学,土木及环境工程学系,中国香港)摘要：以壳聚糖为原材料,通过原位共沉淀法和柠檬酸钠交联法制备了一种新型多孔磁性壳聚糖凝胶微球吸附剂CS-citrate/Fe3O4.利用扫描电镜(SEM)、透射电镜(TEM)、傅里叶红外光谱(FTIR)、热重分析(TG)对吸附剂进行了表征.结果表明,吸附剂内部具有发达的孔隙结构,并均匀分布有平均直径为(4.79±1.09) nm的Fe3O4纳米颗粒;吸附剂中引入Fe3O4后,仍存在羟基、氨基和羧基等功能基团,且吸附剂磁性良好可用于磁场分离;吸附剂对Pb(II)的吸附等温线和动力学研究表明,吸附过程以化学吸附为主,最大吸附容量可达178.25mg/g.关键词：多孔结构；生物质吸附剂；磁性壳聚糖；凝胶微球；重金属中图分类号：X703 文献标识码：A 文章编号：1000-6923(2018)04-1364-07Adsorption properties ofmagnetic chitosan hydrogelmicrospheres to Pb(II) from aqueous solutions. PU Sheng-yan1,2,3*, WANG Ke-xin1,2, MA Hui1,2, YANG Zeng1,2, HO U Ya-qi1,2, CHEN Hong-yu1,2 (1.State Key Laboratory of Geological Prevention and Geological Environment Protection, Chengdu University of Technology, Chengdu 610059, China；2.State Environmental Protection Key Laboratory of Synergetic Control and Joint Remediation for Soil & Water Pollution, Chengdu University of Technology, Chengdu 610059, China；3.Department of Civil and Environment Engineering, The Hong Kong Polytechnic University, Hong Kong, China). China Environmental Science, 2018,38(4)：1364~1370Abstract：In this study, the magnetic porous chitosan hydrogel microsphere was fabricated by a combination of in situ-coprecipitation and sodium citrate crosslinking technique using chitosan as raw material. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TG) were conducted for the characterization of this novel adsorbent. The hydrogel microsphere present a well developed porous inner structure and the Fe3O4nanoparticles with an average diameter of (4.79±1.09) nm dispersed uniformly. The functional group of chitosan, the hydroxyl, amino and carboxyl groups, remained after the introduction of the Fe3O4, and the magnetic adsorbent could be separated by the addition of external magnetic field. The adsorption isotherm and kinetic study for the Pb () removal from the aquatic environment indicatingⅡthat the adsorption process was dominated by the chemical adsorption and the maximum adsorption capacity was calculated as 178.25mg/g.Key words：porous structure；biomass adsorbent；magnetic chitosan；hydrogel microsphere；heavy metal重金属在生物物质循环和能量交换中不能被分解破坏,只能改变其物理化学形态或转移其存在位置,加之重金属在环境中的迁移转化几乎涉及了所有可能的物理、化学和生物过程,因而治理难度很大[1].伴随现代工业的快速发展,重金属废水已成为对环境污染最严重的工业废水之一[2].现有重金属废水处理技术,如离子交换法、电解法、化学沉淀法等常规方法普遍存在处理工艺复杂,运行成本高,对低浓度重金属废水处理效果差的问题[3].相比之下,吸附法则具有适用范围广、反应速度快、可适应不同反应条件、环境友好等优点,受到了研究人员的高度关注[4].近年,研究较多的吸附材料有活性炭[5]、沸石[6]、膨润土[7]等.这些吸附剂对废水中重金属有一定的去除效果,但吸附完成后难以与水体分离,容易造成环境收稿日期：2017-09-18基金项目：国家自然科学基金资助项目(51408074,41772264)* 责任作者, 教授, pushengyan@4期蒲生彦等：磁性壳聚糖凝胶微球对水中Pb(Ⅱ)的吸附性能 1365二次污染.与非生物质吸附剂相比,生物质基吸附剂富含大量吸附功能基团,对重金属离子有很强的吸附能力和较高吸附容量,而且具有资源丰富,可再生易降解,环境友好成本低的优点,较为适合水中重金属离子的富集与分离[8-9].常见的天然高分子吸附剂,如:壳聚糖[10]、纤维素[11]、木质素[12]等,其中以壳聚糖及其衍生物研究最为活跃.壳聚糖是一种成本低廉,环境友好的天然生物高分子,其分子主链上大量氨基、羟基等官能团可络合金属离子,且这些官能团具有良好的反应性,可功能化改性[13].若将壳聚糖赋予磁性后,采用磁分离技术可使吸附剂回收和再生变得简易[14].目前,磁性壳聚糖吸附剂的制备方法有原位共沉淀法[15]、微乳液法[16]和水热法[17]等,其中原位共沉淀法通过溶液中的化学反应直接得到均一的材料,相比其他方法制备过程简单且环境友好,是应用最普遍的方法之一[18].目前已有的原位共沉淀法包括电喷雾技术[19],静电液滴(ESD)技术[20]和反向共沉淀法[21]等.本研究采用原位共沉淀法结合柠檬酸钠交联制备了一种新型多孔磁性壳聚糖凝胶微球,在对其微观结构、物化性能进行充分表征的基础上,选取Pb(II)作为目标污染物考察了该凝胶微球的吸附性能,以期能为水中重金属富集去除提供一种新的思路和方法.1 材料与方法1.1 材料试剂:壳聚糖(Chitosan,CS,脱乙酰度80%~ 95%)购于上海阿拉丁生化科技股份有限公司;冰醋酸、氢氧化钠、柠檬酸钠购于成都科龙化学试剂厂;六水合氯化铁、四水合氯化亚铁和硝酸铅购于志远化学试剂厂;实验用水均采用超纯水.仪器:KW-400恒温水浴振荡器,上虞佳星仪器厂;SCIENTZ-50F冷冻干燥机,宁波新芝生物科技股份有限公司;GGX-9火焰原子吸收分光光度计,北京海光仪器有限公司.1.2 多孔磁性壳聚糖凝胶微球的制备将0.8g壳聚糖溶于24mL 2%的乙酸溶液中,机械搅拌30min,使得壳聚糖充分溶解;之后向溶液中加入2mL摩尔比为2:1的Fe3+/Fe2+混合溶液,继续搅拌30min,溶液由亮黄色变为棕红色后,将混合溶液用蠕动泵滴入NaOH/柠檬酸钠混合浸泡液(NaOH 1.25mol/L, 柠檬酸钠0.1mol/L)中,静置陈化10h;磁分离后用超纯水多次洗涤,除去残余的NaOH和柠檬酸钠,冷冻干燥30h.无磁壳聚糖凝胶微球(CS)在不加Fe3+/Fe2+混合溶液的条件下以相同方法制得作为实验对照组.1.3 表征方法采用德国Sigma300型扫描电子显微镜(SEM)观察样品表面形貌,采用日本FEI Tecnai-G20型透射电子显微镜(TEM)观察样品内部形貌,采用美国Nicolet-1170SX型傅里叶红外光谱仪(FTIR)进行红外谱图分析,采用美国STA6000型热重分析仪(TGA)考察在壳聚糖凝胶微球中引入Fe3O4纳米颗粒的热力学效应.1.4 对Pb(II)的静态吸附实验将0.05g磁性壳聚糖凝胶微球投加到50mL200mg/L的Pb(II)溶液中,在25℃下恒温振荡(150r/min),测定吸附量q随时间t的变化情况.吸附量采用公式(1)进行计算.()/tq c c V M=− (1) 式中:c0和c t为在Pb(II)溶液的初始浓度和吸附t时间后的浓度,mg/L;V为Pb(II)溶液的体积,L;M为吸附剂的投加量,g.2 结果与讨论2.1 多孔磁性壳聚糖凝胶微球制备首先,壳聚糖溶液与Fe3+/Fe2+(摩尔比为2:1)经螯合作用形成Fe3+-CS-Fe2+混合溶胶,然后,将混合溶胶通过蠕动泵滴入NaOH/柠檬酸钠混合浸泡液形成凝胶微球.在此过程中,发生Fe3+/Fe2+原位共沉淀反应生成Fe3O4纳米颗粒,壳聚糖和柠檬酸钠发生交联反应.最后,将制得吸附剂用于水中重金属离子的静态吸附,并利用外加磁场将吸附剂分离回收,从而达到回收再利用,减少二次污染的目的.多孔磁性壳聚糖凝胶微球制备及重金属吸附实验流程如图1所示.本实验所制得的磁性壳聚糖凝胶微球平均1366 中国环境科学 38卷粒径约为(2.91±0.65)mm,将其冷冻干燥处理后平均粒径约为(2.42±0.51)mm,干燥后平均粒径约减小16.8%,冷冻干燥后凝胶微球较好地保留原有圆球状形态及内部多孔结构.图1 磁性壳聚糖凝胶微球制备与重金属吸附实验流程Fig.1 Schematic illustration of preparation of magnetic chitosan hydrogel microspheres and its adsorption process2.2 多孔磁性壳聚糖凝胶微球吸附剂表征图2(a)~(d)为不同放大倍数下多孔磁性壳聚糖凝胶微球吸附前后外观扫描电镜图,由图可知多孔磁性壳聚糖凝胶微球为形态良好、表面光滑的球型结构,在吸附后吸附剂表面粗糙,覆盖有Pb(II)的结晶产物,孔道堵塞严重;图2(e)和(f)为多孔磁性壳聚糖凝胶微球和壳聚糖凝胶微球的内部结构扫描电镜图.由图可知,与壳聚糖凝胶微球内部紧密的结构相比,磁性壳聚糖凝胶微球内部具有良好的多孔结构,增大了吸附剂的比表面积,有利于吸附作用发生.图2 壳聚糖凝胶微球和磁性壳聚糖凝胶微球SEMFig.2 SEM characterization results of chitosan hydrogel microsphere and magnetic chitosan hydrogel microspheres磁性壳聚糖凝胶微球(a)吸附前外观,×30;(b)吸附前外观,×300;(c)吸附后外观,×30;(d)吸附后外观,×300;(e)内部结构SEM 图,×250;(f) 壳聚糖凝胶微球内部结构SEM 图,×7004期蒲生彦等：磁性壳聚糖凝胶微球对水中Pb(Ⅱ)的吸附性能 1367为深入了解多孔磁性壳聚糖凝胶微球中Fe3O4纳米颗粒的形态,对样品进行了TEM分析.由图3可知,Fe3O4纳米颗粒在壳聚糖微球内部分布较均匀,未出现明显团聚现象,其平均粒径约为(4.79 ±1.09)nm(图3(b)).图3 磁性壳聚糖凝胶微球TEM图Fig.3 TEM characterization results of magnetic chitosanhydrogel microspheres(a)TEM图;(b)Fe3O4纳米颗粒粒径分布图图4为壳聚糖凝胶微球及吸附前后多孔磁性壳聚糖凝胶微球红外光谱图.壳聚糖、柠檬酸钠和Pb(II)之间的相互作用会影响特征峰的位置和强度,在壳聚糖凝胶微球的光谱中,1082cm-1, 1027cm-1两处为C-OH键的伸缩振动吸收峰, 1383cm-1处为伯醇组-C-O键的伸缩振动吸收峰.1425cm-1处为C-N键的伸缩振动峰.壳聚糖固有的O-H和N-H伸缩振动峰出现在3444cm-1附近,在多孔磁性壳聚糖凝胶微球的两个光谱中也可观察到这一较宽的吸收峰.在吸附前多孔磁性壳聚糖凝胶微球的光谱中,1648cm-1处的N-H 伸缩振动吸收峰移动到1640cm-1处.由于柠檬酸钠的交联和Fe3O4与壳聚糖之间的弱相互作用,导致酰胺峰强度降低.在吸附前、后磁性壳聚糖凝胶微球光谱中,586cm-1处出现了Fe3O4的特征吸收峰,对应的是Fe-O的伸缩振动峰,说明磁性纳米颗粒Fe3O4已成功嵌入吸附剂中.而吸附了Pb(II)的凝胶微球光谱图4(b)和(d)中,1383cm-1和1425cm-1处特征吸收峰形状发生变化表明Pb(II)离子和壳聚糖发生络合反应,同时说明多孔磁性壳聚糖凝胶微球的羟基、氨基和羧基可以高效吸附金属阳离子.图4 吸附前后壳聚糖凝胶微球和磁性壳聚糖凝胶微球的红外谱Fig.4 FTIR spectra of pure chitosan hydrogelmicrospheres, and magnetic hydrogel chitosanmicrospheres before and after adsorption(a)壳聚糖凝胶微球Cs;(b) 壳聚糖凝胶微球/吸附后Cs/Pb;(c)磁性壳聚糖凝胶微球Cs-citrate/Fe3O4;(d) 磁性壳聚糖凝胶微球/吸附后Cs-citrate/Fe3O4/Pb通过热重分析表征了壳聚糖凝胶微球中引入的Fe3O4纳米颗粒的热力学效应.图5为壳聚糖凝胶微球和多孔磁性壳聚糖凝胶微球的热重曲线图.图5 磁性壳聚糖凝胶微球的热重分析曲线Fig.5 Thermo gravimetric curves of magnetic chitosanhydrogel microspheres由热重分析曲线可知,壳聚糖凝胶微球重量损失发生在3个阶段.第一阶段,当温度升至90℃左右,吸附剂中的自由水及通过氢键形成的结合水减少;第二阶段,在90~320℃范围内,壳聚糖发生分解;第三阶段,壳聚糖发生碳化分解,1368 中国环境科学 38卷在800℃时所对应的重量为热解最终产物残余碳.多孔磁性壳聚糖凝胶微球在25~120℃的范围内脱去自由水和结合水;在320℃时壳聚糖完全分解;在600℃时,Fe3O4与碳反应生成单质铁;在800℃时残余重量为碳和单质铁.多孔磁性壳聚糖凝胶微球的分解起始温度比壳聚糖凝胶微球高,说明Fe3O4的存在有效地提高了吸附剂的热稳定性.2.3 吸附时间和初始浓度对吸附效果的影响图6(a)讨论了在0~840min内壳聚糖凝胶微球和多孔磁性壳聚糖凝胶微球对Pb(II)吸附量的变化.图6 时间和初始浓度对Pb(II)吸附的影响Fig.6 Influence of time and initial concentration on adsorption of Pb(II)可以看出,壳聚糖凝胶微球的吸附作用主要发生在0~120min内,在120min后达到吸附平衡,平衡吸附量为16.1mg/g.多孔磁性壳聚糖凝胶微球对Pb(II)的吸附与壳聚糖凝胶微球呈现相同的变化趋势,但平衡吸附量达到了45.3mg/g,为壳聚糖凝胶微球的2.8倍,这是磁性复合吸附剂的高度多孔结构提供了较大的比表面积,使更大数目的活性基团与Pb(II)接触产生的结果.吸附剂吸附量在0~120min内升高较快,说明Pb(II)与多孔磁性壳聚糖凝胶微球的基团发生螯合反应,被成功地吸附到样品表面上,使得溶液中Pb(II)浓度下降.随着吸附反应的进行,吸附到多孔磁性壳聚糖凝胶微球的Pb(II)逐渐占据了大部分活性基团,导致活性基团的数目下降,在120min时吸附量趋于平衡.本研究将铅离子初始浓度设置为100、200、300、400、500mg/L对多孔磁性壳聚糖凝胶微球的吸附性能进行了考察(图6(b)).多孔磁性壳聚糖凝胶微球对不同初始浓度Pb(II)的吸附呈现类似的变化趋势,随着初始浓度增大,多孔磁性壳聚糖凝胶微球对Pb(II)的吸附量逐渐增大.2.4 吸附动力学及吸附等温线表1 Pb(II)吸附动力学方程的拟合Table 1 Fitting results of lead ions adsorption kinetics equations准一级动力学准二级动力学初始浓度(mg/L) q exp(mg/g)k1(min-1)(×10-2) q cal(mg/g) R2k2(min-1)(×10-2)q cal(mg/g) R2 100 30.88 0.805 16.53 0.794 0.163 31.34 0.9983 200 45.73 1.976 23.52 0.845 0.263 46.23 0.9995 300 64.97 0.799 23.34 0.562 0.136 65.40 0.9990 400 89.16 2.003 51.94 0.799 0.123 90.01 0.9994 500 105.99 1.651 35.39 0.775 0.182 106.61 0.9999 2.4.1 吸附动力学采用准一级和准二级动力学模型对动力学数据进行拟合,计算出相应的速4期 蒲生彦等：磁性壳聚糖凝胶微球对水中Pb(Ⅱ)的吸附性能 1369率常数,研究其吸附过程的动力学行为并探讨吸附机理.所用拟合方程的线性表达式如下: e e 1ln()ln t q q q k t −=− (2)22e e /1/()/t q k q t q =+ (3)式中:q t 为t 时刻吸附剂对Pb(II)的吸附量,mg/g;q e为平衡吸附量,mg/g;k 1为准一级速率常数,min -1; k 2为准二级速率常数,mg/(g ⋅min).q e 、k 2可分别由截距和直线斜率求得.分析结果见表1和图7.准一级动力学相关系数最高为0.845,而准二级动力学相关系数均高于0.99,因此准二级动力学方程能更好地描述整个吸附过程.这证实了多孔磁性壳聚糖凝胶微球吸附剂对Pb(II)的吸附为化学吸附,比表面积是吸附的重要影响因素.l n (q e-q t )图7 吸附动力学曲线 Fig.7 Absorption kinetic curve2.4.2 吸附等温线 使用Langmuir 和Freundlich 吸附等温线模型来解释吸附机理. Langmuir 方程假设吸附过程为单层吸附,线性表达式如下:e e m e m /1/()/c q kq c q =+ (4) 式中:q e 表示吸附质的吸附量,mg/g;c e 表示其在溶液中的平衡浓度,mg/L;b 为Langmuir 吸附平衡常数,L/mg;q m 为在吸附剂上单层形成的最大吸附能力,mg/g.c e/q e (g /L )c e (mg/L)图8 等温吸附曲线 Fig.8 Sorption isothermFreundlich 等温线是用于描述非均相表面的经验方程,它的线性表达式如下:e F e ln ln (1/)ln q K n c =+ (5) 式中:K F 是Freundlich 常数;1/n 为吸附指数.将Pb(II)起始浓度范围为100~500mg/L 的5组吸附实验数据进行吸附等温线拟合,结果见图8和表2. Langmuir 模型和Freundlich 模型均具有良 好的拟合度,且后者线性拟合相关系数更高,大于0.95,可能是由于吸附剂表面基团分布不均,导致吸附过程呈现非均质吸附特性.吸附指数1/n 的值为0.3749,有报道称1/n <1表明吸附容易进行[22].相较其他生物质基吸附材料吸附铅离子研究,如甘蔗渣对铅最大吸附量为41.32mg/g [23],改性木质素磺酸钠对铅最大吸附量为55.22mg/ g [24],N -(2-磺乙基)壳聚糖对铅最大吸附量为1370 中国环境科学 38卷99.79mg/g [25],本研究中磁性壳聚糖微球对铅的吸附容量178.25mg/g 均大于上述吸附材料.表明磁性壳聚糖微球对Pb(II)具有良好的吸附效果.表2 Pb(II)吸附等温线拟合参数Table 2 Fittingof lead ions adsorption isotherm equationsLangmuir 等温吸附 Freundlich 等温吸附q m (mg/g)178.25K F (mg/g) 3.2541 k 0.0093 1/n 0.3749R 20.9219 R 2 0.95363 结论3.1 采用原位共沉淀法和柠檬酸钠交联法制备得到的多孔磁性壳聚糖凝胶微球内部孔隙丰富,比表面积大,磁性良好,可外加磁场分离.Fe 3O 4纳米颗粒在壳聚糖基质中分布均匀,增加了吸附剂的热稳定性.3.2 多孔磁性壳聚糖凝胶微球对水中Pb(II)具有良好的吸附性能,约在2h 达吸附平衡,当Pb(II)初始浓度从100mg/L 增加到500mg/L 时,平衡吸附量从30.88mg/g 增加到105.99mg/g.3.3 吸附剂对水中Pb(II)的吸附过程满足准二级动力学方程,并较好的符合Freundlich 等温吸附方程,最大吸附容量可达178.25mg/g.参考文献：[1] 唐 黎,李秋华,陈 椽,等.贵州普定水库沉积物重金属分布及污染特征 [J]. 中国环境科学, 2017,37(12):4710-4721. [2] 范小杉,罗 宏.工业废水重金属排放区域及行业分布格局 [J].中国环境科学, 2013,33(4):655-662.[3] Fu F, Wang Q. 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Potential of chitin/chitosan -bearing materialsfor uranium recovery: An interdisciplinary review [J].Carbohydrate Polymers, 2011,84(1):54-63.[14] Feng Y , Gong J, Zeng G , et al. Adsorption of Cd (II) and Zn (II)from aqueous solutions using magnetic hydroxyapatite nanoparticles as adsorbents [J]. Chemical Engineering Journal, 2010,162(2):487-494.[15] Kim D K, Zhang Y , V oit W, et al. Synthesis and characterizationof surfactant -coated superparamagneticmonodispersed iron oxide nanoparticles [J]. Journal of Magnetism and Magnetic Materials, 2001,225(1/2):30-36.[16] Gupta A K, Gupta M. Synthesis and surface engineering of ironoxide nanoparticles for biomedical applications [J]. Biomaterials, 2005,26(18):3995-4021.[17] Li G , Jiang Y , Huang K, et al. Preparation and properties ofmagnetic Fe 3O 4-chitosan nanoparticles [J]. Journal of Alloys and Compounds, 2008,466(1/2):451-456.[18] 宋艳艳,孔维宝,宋 昊,等.磁性壳聚糖微球的研究进展 [J]. 化工进展, 2012,31(2):345-354.[19] Liu Z, Bai H, Sun D D. Facile fabrication of porous chitosan/TiO 2/Fe 3O 4 microspheres with multifunction for water purifications [J]. NEW Journal of Chemistry, 2011,35(1):137-140.[20] Wang C, Yang C, Huang K, et al. Electrostatic droplets assisted insitu synthesis of superparamagnetic chitosan microparticles for magnetic -responsive controlled drug release and copper ion removal [J]. Journal of Materials Chemistry B. 2013,1(16): 2205-2212.[21] 程三旭,李克智,齐乐华,等.反向共沉淀法制备纳米Fe 3O 4及其粒径控制 [J]. 材料研究学报, 2011,(5):489-494.[22] Bulut Y , Gozubenli N, Aydin H. Equilibrium and kinetics studies foradsorption of direct blue 71from aqueous solution by wheat shells [J]. Journal of Hazardous Materials, 2007,144(1/2):300-306.[23] 王珏珏,张越非,池汝安,等.改性木质素磺酸钠对铅离子的吸附行为研究 [J]. 武汉工程大学学报, 2017,39(1):12-18.[24] 涂艳梅,杨汉培,聂 坤,等.磺乙基化与传统壳聚糖对比研究其对水体中铅有效性降低效应 [J]. 环境科技, 2016,29(2):1-6.[25] 王春云,闫新豪,符纯美.基于甘蔗渣生物吸附重金属污染物的研究 [J]. 当代化工. 2017,(1):61-63.作者简介：蒲生彦(1981-),男,甘肃酒泉人,教授,博士,主要从事水土污染协同控制、土壤地下水污染预警与环境基准相关的研究.发表论文30余篇.。
生物活性玻璃降解过程
| 50 |Smile Dental Journal | Volume 7, Issue 2 - 2012ABSTRACTThe development of new materials and methods to substitute lost parts or tissues to restore function and esthetics has been the goal and objective of human civilizations throughout history. Different materials have been proposed and applied to determine their biocompatibility and usefulness, avoiding any ejection, or at times unfavorable responses to foreign materials. With the new advances in the usage of different materials that can be used to restore bony defects, ranging from allografts to xenografts, the need was always to have synthetic material that can be used in such applications with unlimited supply. Bioactive glasses today are used widely in medical and dental fields. Bioactive glasses were used to coat dental implants, used as an antibiotic carrier, and used to restore periodontal defects. When applied to periodontal defects, it was found to be comparable to demineralized freeze-dried bone (DFDBA). The dissolution process is critical to all biomaterials because the cascade of events that will eventually lead to the induction or conduction of bone is dependent on the early chemical interaction between the biomaterials and the surrounding tissues. The bioactive glass possesses extra advantages over other available materials, such as risk free of disease transmission, unlimited supply and mechanical integrity. This article reviews the process of dissolution of Bioactive glasses when they interact with tissues at the time of placement until the complete resolution.KEYWORDSBioactive glasses, Dissolution, Silanol, Osteoconductive.Dissolution Process of Bioactive GlassesAhmad Akroof DDS, MSAl-Adan Dental Center, Head of Periodontal Unit – Kuwaitdntst999@INTRODUCTIONBioactive glasses are made usually of 45% SiO 2, 24.5% CaO, 24.5% Na 2O, and 6% P 2O 2; percentages are by weight.1 In addition to the previous composition, different compositions were also formulated to test the different reactivity rates of the bioactive materials.2 Some researchers have incorporated some porous polymers to bioactive glasses that mimic the bone/ cartilage interface. Others added CaF2 and Al2O3 to the bioactive glasses ceramics.3 New shapes were also developed such as the 45S5 Bioglass ® fiber network form.4MECHANISMThere are 11 steps for the interaction of bioactive glasses to bone as follows:1. Formation of Si-OH (silanol) bonds via cation exchange with H + or H 3O + ions from solution.2.Break-up of the silica network (Si-O-Si bonds) and the continued formation of Si-OH (silanols) at the glass solution interface.3.Condensation and repolymerisation of a SiO 2-rich layer on the surface, depleted in alkalis and alkali-earth cations.4.Migration of Ca+ and PO 4-3 groups to the surface forming a CaO-P 2O 5-rich film on top of the SiO 2-rich layer.5.Crystallization of the amorphous film byincorporation of OH- and CO 3-2 anions from solution to form solution to form a mixed hydroxyl carbonate apatite (HCA) layer.6.Adsorption and desorption of biological growth factors, in the HCA layer (continues throughout the process) to activate differentiation of stem cells.7. Action of macrophages to remove debris from the site allowing sells to occupy the space.8. Attachment of stem cells on the bioactive surface.9. Differentiation of stem cells to form bone growing cells, such as osteoblasts.10. Generation of extra cellular matrix by the osteoblasts to form bone.11. Crystallization of inorganic calcium phosphate matrix to enclose bone cells in a living composite structure.5It’s also established that the bioactive materials react chemically with the surrounding tissues and fluids.6CLINICAL APPLICATIONSIn vitro , extensive amount of studies have explored the behavior of bioactive glasses in different type ofsolutions. The amount of dissolution also depends on the particle size, type and powder form fraction.7 Others also indicated the effect of incorporating different elements such as Zinc to the alloys of Glass-ceramics for dental restorations.8 It was noticed that even though the amount of zinc was 1% of the dental alloy (high gold content), but it exhibited anomalous behavior because of the zinc incorporation in the oxide layer on the surface.8 Alsoother study concluded that sintering of the bioactive glass in 900C for 2 hours formed the most calcium phosphate layer after immersion in body simulated fluids.9 On the other hand, Roman et al.10 concluded that the additionSmile Dental Journal | Volume 7, Issue 2 - 2012 | 51|contain bone morphogenic proteins that are exposedwithin the bone matrix. Those BMP’s will in turn induce the pleuripotential stem cells to differentiate into osteoblasts and eventually to the production of new bone 25. Different human histological studies proved the formation of new attachment apparatus in the intrabony defects.25Others have used it to fill an extraction site to fill the defect and concluded completely filled sockets with mineralized tissue.26,27 Another study also confirmed the significant improvement when bioactive glass was used to fill extracted teeth sockets.28 Others have used the bioactive glass for sinus elevation procedures and found a significant formation of mineralized tissue in the chamber for future implant placement.29,30 Also, the bioactive glass was tried to treat bony defects around implants in dogs.31 In medical uses, the bioactive glass increased tissue strength when used to treat closed skin wounds in dogs.32CONCLUSIONOvertime, the need for materials to replace lost tissue was and still is a primary concern of dental researchers. Different materials have been developed and used. Some of the materials were not as safe and effective as they should have been in the past; that is why a new concept of bioactive materials based on glass-ceramics was developed. The bonding between the material and the tissues surrounding it has now proved its success clinically and these materials are used routinely in clinical settings on a daily basis.REFERENCES1. Ducheyne P . Bioceramics: material characteristics versus in vivobehavior. J Biomed Mater Res. 1987;21(A2 Suppl):219-36.2. Clark AE, Hench LL, Paschall HA. The influence of surface chemistryon implant interface histology: a theoretical basis for implant materials selection. J Biomed Mater Res. 1976;10(2):161-74.3. De Maeyer EA, Verbeeck RM. X-ray diffractometric determination ofcrystalline phase content in bioactive glasses. J Biomed Meter Res. 2001;57(3):467-72.4. De Diego MA, Coleman NJ, Hench LL. Tensile properties ofbioactive fibers for tissue engineering applications. J Biomed Mater Res. 2000;53(3):199-203.5. Jones JR, Sepulveda P , Hench LL. Dose-dependent behavior ofbioactive glass dissolution. J Biomed Mater Res. 2001;58(6):720-6.6. Ducheyne P , Cuckler JM. Bioactive ceramic prosthetic coatings. ClinOrthop. 1992;(276):102-14.7. Sepulveda P , Jones JR, Hench L. In vitro dissolution of melt-derived 45S5 and sol-gel derived 58S bioactive glass. Journal ofBiomedical materials research. 2002;301-11.8. Clare AG. Drescher H. Rheinberger V . Hoeland W . Glass scienceand technology-glastechnisc Berichite. 2000;73:278-85.9. Clupper DC, Mecholsky JJ Jr, LaTorre GP , Greenspan DC.Bioactivity of tape cast and sintered bioactive glass-ceramic in simulated body fluid. Biomaterials. 2002;23(12):2599-606.10. Roman J, Salinas AJ, Vallet-Regi M, Oliveira JM, Correia RN,Fernandes MH. Role of acid attack in the in vitro bioactivity of a glass-ceramic of the 3CaO.P2O5-CaO.SiO2-CaO.MgO.2SiO2 system. Biomaterials. 2001;22(14):2013-9.11. Serro AP , Fernandes AC, Saramago B, Fernandes MH. In vitromineralization of a glass-ceramic of the MgO-3CaO x P2O5-SiO2 system: wettability studies. J Biomed Mater Res. 2002;61(1):99-108.of hydroxyl apatite to the glass-ceramic will favor apatite formation in vitro . Serro et al.11 concluded that a calcium phosphate layer was formed at the surface of bioactive –glass ceramic (MgO-3CaO. P2O5-SiO 2) after one week of immersion in either simulated body fluids or Hank’s balanced salt solution. Others found such layer form as early as one hour of immersion in either serum containing solution or buffer solution supplemented with plasma.12 In addition to the calcium phosphate formation, excavation of the Bioactive Glass particle can also be observed in serum containing solutions.13In vivo , when any implanted material contact blood, blood coagulation or thrombus formation is the end result.14 Such behavior is not acceptable when designing materials intended to be implanted as prosthetic devices.14 The birth of bioactive glasses took another trend in which they can bond chemically to bone and induce its formation without inducing harmful effects during implantation.15 Since bone is continually remodeled by the actions of osteoblasts and osteoclats.16 Some studies looked at the effect of bioactive glass and osteoblasts. Xynos et al. observed the up regulation of osteoblasts gene expression when treated with Bioglass.17 Itala et al.18 concluded that cell attachment of osteoblasts increased and more surface reactivity occurred if the bioactive glass was micro roughened. Studies have also confirmed that the behavior of bioactive glasses in the body as osteoconductive (does not stimulatebone formation if bone forming sells are not present).19 Bioactive glass was also used to coat dental implants.20 Others suggested the use of bioactive glass as an antibiotic carrier.21Systemic antibiotics don’t always reach sufficientconcentrations for the bony tissues because of the poor blood flow to the areas. In return, higher doses are required to reach the therapeutic level to reach theaffected region. Currently, the local drug-delivery systems are an important topic in the medical and dental fields at this time.22 Meseguer-Olmo et al.23 concluded that the usage of bioactive glasses in an animal model as a carrier for gentamicin sustained a good concentration that was always above the minimum inhibitoryconcentration level throughout the 12 week study with the bony growth on the defect. Currently such studies will lead to the future introduction of commerciallyavailable bioactive glasses that can be used as carriers for antibiotics that can be used widely in the fields of medicine and dentistry.Bioactive glasses are used widely today in medical and dental applications. Bioactive glass is used in dental application as a bone substitute material inrestoring periodontal defects.24 When applied to restore periodontal defects, bioactive glass was comparable to the demineralized freezed dried bone (DFDBA) which is usually processed from cadavers.24 DFDBA particles| 52 |Smile Dental Journal | Volume 7, Issue 2 - 201212. Kaufmann EA, Ducheyne P , Radin S, Bonnell DA, CompostoR. Initial events at the bioactive glass surface in contact with protein-containing solutions. J Biomed Mater Res. 2000;52(4):825-30.13. Radin S, Ducheyne P , Falaize S, Hammond A. In vitrotransformation of bioactive glass granules into Ca-P shells. J Biomed Mater Res. 2000;49(2):264-72.14. Baier RE, Dutton RC. Initial events in interactions of blood witha foreign surface. J Biomed Mater Res. 1969;3(1):191-206.15. Ducheyne P, Cuckler JM. Bioactive ceramic prosthetic coatings. Clin Orthop. 1992;(276):102-14.16. Dziak R. Biochemical and molecular mediators of bonemetabolism. Journal of Periodontology. 1993;64(5):407-15.17. Xynos ID, Edgar AJ, Buttery LD, Hench LL, Polak JM. Gene-expression profiling of human osteoblasts following treatment with the ionic products of Bioglass 45S5 dissolution. J Biomed Mater Res. 2001;55(2):151-7.18. Itala A, Ylanen HO, Yrjans J, Heino T , Hentunen T , Hupa M,Aro HT . (2002) Characterization of microrough bioactive glass surface: surface reactions and osteoblast responses in vitro . J Biomed Mater Res. 2002;62(3):404-11.19. Ducheyne P . Bioceramics: material characteristics versus in vivobehavior. J Biomed Mater Res. 1987;21(A2 Suppl):219-36.20. Schrooten J, Van Oosterwyck H, Vander Sloten J, Helsen JA.(1999) Adhesion of new bioactive glass coating. J Biomed Mater Res. 1999;44(3):243-52.21. Griffon DJ, Dunlop DG, Howie CR, Gilchrist T , Salter DM, HealyDM. Early dissolution of a morsellised impacted silicate-free bioactive glass in metaphyseal defects. J Biomed Mater Res. 2001;58(6):638-44.22. Otsuka M, Matsuda Y , Kokubo T , Yoshihara S, NakamuraT ,Yamamuro T . Drug release from a novel self-settingbioactive glass bone cement containing cephalexin and its physicochemical properties. J Biomed Mater Res. 1995;29:33–8.23. L. Meseguer-Olmo, M. J. Ros-Nicolás, M. Clavel-Sainz, V .Vicente-Ortega, M. Alcaraz-Baños, A. Lax-Pérez, D. Arcos, C. V . Ragel, M. Vallet-Regí. Biocompatibility and in vivo gentamicin release from bioactive sol–gel glass implants. J Biomed Mater Res. 2002;61(3):458-65.24. Lovelace TB, Mellonig JT , Meffert RM, Jones AA, NummikoskiPV , Cochran DL. Clinical evaluation of bioactive glass in the treatment of periodontal osseous defects in humans. J Periodontol. 1998;69(9):1027-35.25. Alexandrina L. Dumitrescu. Chemicals in surgical periodontaltherapy: Bone grafts and bone graft substitutes in periodontal therapy. 2011; Edition IX. London, New York: Springer.26. Novaes J. Papalexiou V . Luczyszyn SM. Muglia VA. Souza SL.Taba JM. Immediate implant in extraction socket with acellular dermal matrix graft and bioactive glass: a case report. Implant Dentistry. 2002;11(4):343-8. 27. Sy IP . Alveolar ridge preservation using a bioactive glassparticulate graft in extraction site defects. Gen Dent. 2002;50(1):66-8.28. Throndson RR, Sexton SB. Grafting mandibular third molarextraction sites: a comparison of bioactive glass to anongrafted site. Oral Surg Oral Med Oral Pathol Oral Radiol Endod. 2002;94(4):413-9.29. Cordioli G. Mazzocco C. Schepers E. Majzoub Z. Maxillarysinus floor augmentation using bioactive glass and autogenous bone with simultaneous implant placement. Clinical Oral implants Reasearch. 2001;12(3):270-8,.30. Leonetti JA. Rambo HM. Throndson RR. Osteotome sinuselevation and implant placement with narrow size bioactive glass. Implant Dentistry. 2000;9(2):177-82,.31. Hall EE, Meffert RM, Hermann JS, Mellonig JT , CochranDL. Comparison of bioactive glass to demineralized freeze-dried bone allograft in the treatment of intrabony defects around implants in the canine mandible. J Periodontol. 1999;70(5):526-35.32. Gillette RL, Swaim SF , Sartin EA, Bradley DM, Coolman SL.Effects of a bioactive glass on healing of closed skin wounds in dogs. Am J Vet Res. 2001;62(7):1149-53.。
有机污染物的化学去除英文
有机污染物的化学去除英文Chemical removal is one of the most efficient and widely used methods for the removal of organic pollutants from the environment. It is a process that uses chemicals to break down or remove organic contaminants from the air, water, and soil. Chemical removal can be accomplished through a variety of mechanisms, including adsorption, oxidation, reduction, and catalyst destruction.Adsorption is a process in which adsorbates – molecules that are attracted to a solid surface – are removed from a solution by binding to that solid surface. Adsorption isoften used to remove pollutants from contaminated water. Activated carbon is commonly used as an adsorbent, as it has an extremely large surface area and is able to bind to a wide range of organic pollutants.Oxidation is another chemical removal process that uses strong oxidizing agents such as chlorine, ozone, and hydrogen peroxide to break down organic pollutants. This process is commonly used in wastewater treatment plants to break down organic material, such as sugars, oils, and fats.Reduction is another chemical removal process that uses reducing agents such as sodium, iron, and chlorine dioxide to break down organic pollutants. This process is often used to reduce chlorinated organic compounds, such as chloroform and dichlorobenzene, in water and soil.Catalyst destruction is an effective way to remove organic pollutants from the environment. Catalysts are substances that promote the chemical reaction of organicpollutants, allowing them to be broken down into their component parts and removed from the environment.Chemical removal is an effective solution for theremoval of organic pollutants from the environment. By using adsorption, oxidation, reduction, and catalyst destruction, organic pollutants can be broken down or removed from the air, water, and soil. Chemical removal also eliminates the health risks associated with the presence of these pollutants,making it an attractive option for pollution control.。
含锑废水深度处理技术研究与中试示范
第43卷第 8 期2023年8月Vol.43 No.8Aug.，2023 工业水处理Industrial Water TreatmentDOI：10.19965/ki.iwt.2023-0042含锑废水深度处理技术研究与中试示范陈韬1，付广义1，钟宇1，李琼花1，2，田石强1，成应向1（1.湖南省环境保护科学研究院，水污染控制技术湖南省重点实验室，湖南长沙410004；2.长沙理工大学化学化工学院，湖南省电力运输材料保护重点实验室 &湖南省细胞化学重点实验室，湖南长沙410004）[ 摘要]以某锑制品厂混凝沉淀处理后的低浓度含锑废水为吸附对象，在小试中通过单因素实验得到最佳吸附条件，再通过动态化吸附和再生实验确定深度处理磁分离技术的最佳工艺参数。
该技术使出水的锑质量浓度能稳定达到排放标准（5 μg/L）。
小试结果表明，在铁基Fenton改性磁性吸附剂（AFS350）投加2.0 g/L，吸附1.0 h，搅拌速度200 r/min的条件下，出水锑的质量浓度降为0.004 mg/L。
中试结果表明，AFS350投加3 g/L，搅拌速度300 r/min，吸附2.0 h后，锑的去除率高达98.91%。
此工艺技术实现了磁性吸附材料全自动分离回收及再生利用，同时具有较高的经济效益和可持续发展的潜力，为工业含锑废水的深度处理提供了一种可行方案。
［关键词］水处理技术；磁性吸附材料；含锑废水［中图分类号］X703 ［文献标识码］B ［文章编号］1005-829X（2023）08-0179-06Research and pilot-scale demonstration of advanced treatmenttechnology for antimony-containing wastewater CHEN Tao1，FU Guangyi1，ZHONG Yu1，LI Qionghua1，2，TIAN Shiqiang1，CHENG Yingxiang1（1.Hunan Reasearch Academy of Environmental Sciences，Hunan Provincial Key Laboratory of Water Pollution Control Technology，Changsha 410004，China；2.Changsha University of Science and Technology，School of Chemistry and Chemical Engineering，Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation & Hunan Provincial Key Laboratory of Cytochemistry，Changsha 410004，China）Abstract：The low concentration antimony-containing wastewater from an antimony product plant after coagulation and precipitation treatment was used as the adsorption object，and the optimal adsorption conditions were obtained by single-factor experiments. Then，the optimal process parameters of the magnetic separation technology for deep treatment were determined by dynamicized adsorption and regeneration experiments. The technology enabled the effluent antimony mass concentration to reach the discharge standard（5 μg/L）stably. The results of the experiments showed that the mass concentration of antimony was reduced to 0.004 mg/L under the conditions of iron-based Fenton-modified magnetic adsor‑bent（AFS350） dosing of 2.0 g/L，adsorption for 1.0 h and stirring speed of 200 r/min. The results of the pilot test showed that the removal rate of antimony after AFS350 dosing of 3 g/L，stirring speed of 300 r/min and adsorption for 2.0 h was up to 98.91%. This process technology achieves fully automatic separation and recovery and recycling of magnetic adsorp‑tion materials，and at the same time had high economic efficiency and sustainable development potential，providing a fea‑sible solution for the deep treatment of industrial antimony-containing wastewater.Key words：water treatment technology；magnetic adsorption material；antimony-containing wastewater锑是一种有毒类金属，其化学结构类似于砷，表现出金属和非金属的性质〔1〕。
畜禽粪便中残留抗生素研究进展
畜禽粪便中残留抗生素研究进展尤心雨1李正昊1姜华1*傅留义2（1齐鲁工业大学（山东省科学院）食品科学与工程学院，山东济南250353；2山东爱福地生物科技有限公司，山东济宁272000）摘要畜禽粪便中残留的抗生素是目前比较常见的新型污染物，未经动物体代谢的大部分抗生素会随排泄物排出体外。
大多数畜禽粪便未经处理就排入土壤，这些畜禽粪便是造成土壤中抗生素积累的主要因素之一。
本文阐述了我国畜禽粪便中残留抗生素的种类及情况，分析了畜禽粪便中残留抗生素对环境的影响，并介绍了畜禽粪便中残留抗生素的去除方法，具体包括生物降解、物化降解、吸附技术、热化学技术等，以期为减少我国畜禽粪便中残留抗生素提供参考。
关键词畜禽粪便；残留抗生素；土壤；去除方法中图分类号X713文献标识码A文章编号1007-5739（2023）18-0166-05DOI ：10.3969/j.issn.1007-5739.2023.18.041开放科学（资源服务）标识码（OSID ）：Research Progress on Residual Antibiotics in Livestock and Poultry ManuresYOU Xinyu 1LI Zhenghao 1JIANG Hua 1*FU Liuyi 2(1College of Food Science and Engineering,Qilu University of Technology (Shandong Academy of Sciences),Jinan Shandong 250353;2Shandong Aifudi Biological Co.,Ltd.,Jining Shandong 272000)Abstract The residual antibiotics in livestock and poultry manures are currently a common new type of pollutant,and most antibiotics that have not been metabolized by animals will be excreted from the body with the manures.Most animal manures are discharged into the soil without treatment.These animal manures are one of the main factors for the accumulation of antibiotics in the soil.This paper expounded the types and situation of residual antibiotics in livestock and poultry manures in China,analyzed the impact of residual antibiotics in livestock and poultry manures on theenvironment,and introduced the removal methods of residual antibiotics in livestock and poultry manures,including biodegradation,physicochemical degradation,adsorption technology,thermochemical technology,etc.,so as to provide references for reducing residual antibiotics in livestock and poultry manures in China.Keywordsanimal manure;residual antibiotic;soil;removal method基金项目山东省农业重大应用技术创新项目（SD2019ZZ006）；2022年度山东省重点扶持区域引进急需紧缺人才项目（2022820）。
吸附热力学的英文
吸附热力学的英文English:Adsorption thermodynamics refers to the study of the heat effects involved in the process of adsorption, which is the accumulation of gas, liquid, or dissolved substances on the surface of a solid or a liquid. It encompasses the analysis of the energy changes, such as the heat of adsorption, enthalpy, and entropy, that occur during the adsorption process. The investigation of adsorption thermodynamics is crucial in understanding the physical and chemical properties of adsorbents and adsorbates, as well as in the design and optimization of adsorption processes in various industries. By studying the thermodynamics of adsorption, researchers and engineers can gain insights into the efficiency, selectivity, and performance of different adsorbents, ultimately leading to the development of more effective adsorption systems for environmental remediation, gas purification, and separation processes.中文翻译:吸附热力学指的是研究吸附过程中涉及的热效应，吸附是指气体、液体或溶解物质在固体或液体表面的积聚。
吸附条件对食用油中苯并（a）芘吸附脱除的影响
分析检测吸附条件对食用油中苯并（a）芘吸附脱除的影响张诗琪1,2，刘孟洁2，赵洲桥2，韩立娟1,2,3*，张维农1,2,3(1.大宗粮油精深加工教育部重点实验室，湖北武汉 430023；2.武汉轻工大学 食品科学与工程学院，湖北武汉 430023；3.湖北省油脂精细化工工程技术研究中心，湖北武汉 430023）摘 要：将醋酸纤维素负载在活性炭表面得到的改性活性炭应用于食用油中苯并（a）芘的吸附脱除，以吸附脱除率为衡量指标，从吸附剂用量、吸附温度和时间方面对吸附条件进行优化。
结果表明，在吸附剂添加量为油重的0.8%，110 ℃下吸附30 min的条件下，改性活性炭对苯并（a）芘的脱除率高达100%。
关键词：食用油；苯并（a）芘；吸附脱除Effect of Adsorption Conditions on the Adsorption and Removal of Benzo(a)pyrene in Edible OilZHANG Shiqi1,2, LIU Mengjie2, ZHAO Zhouqiao2, HAN Lijuan1,2,3*, ZHANG Weinong1,2,3(1.Key Laboratory for Deep Processing of Major Grain and Oil, Ministry of Education, Wuhan 430023, China;2.College of Food Science and Engineering, Wuhan Polytechnic University, Wuhan 430023, China;3.Hubei FineChemical Engineering Technology of Oil and Fat Research Center, Wuhan 430023, China) Abstract: Activated carbon modified with cellulose acetate loaded on the surface of activated carbon is applied to the adsorption and removal of benzo(a)pyrene in edible oil. The adsorption and removal rate is used as a measure, and the adsorption conditions are optimized from the amount of adsorbent, adsorption temperature, and time. The results showed that the optimal adsorption conditions were as follows: the amount of adsorbent added was 0.8% of the oil weight, and the removal rate of benzo(a)pyrene was as high as 100% after 30 minutes of adsorption at 110 ℃.Keywords: edible oil; benzo(a)pyrene; adsorption removal苯并芘为多环芳烃的代表性物质，根据其苯环的稠合位置可分为1,2-苯并芘、3,4-苯并芘、4,5-苯并芘等10多种物质，前两种有强致癌性，而4,5-苯并芘致癌作用较弱。
电化学吸附英文
电化学吸附英文Electrochemical AdsorptionElectrochemical adsorption is a fundamental process in many important applications, such as energy storage, catalysis, and environmental remediation. This process involves the interaction between a solid surface and dissolved species, leading to the accumulation of the latter on the former. The driving force behind this phenomenon is the interplay between electrical and chemical forces, which can be harnessed to achieve desirable outcomes.At the heart of electrochemical adsorption is the concept of the electrical double layer, which describes the distribution of ions and charged species at the interface between a solid surface and a liquid electrolyte. This double layer, which can be several nanometers thick, is composed of an inner layer of specifically adsorbed ions and an outer layer of more diffusely distributed ions. The potential difference across this double layer, known as the surface potential, plays a crucial role in determining the extent and nature of the adsorption process.One of the key factors that influence electrochemical adsorption isthe surface charge of the solid material. Depending on the pH of the solution and the point of zero charge (PZC) of the solid, the surface can be positively or negatively charged. This surface charge, in turn, affects the adsorption of ions and molecules from the solution. For example, if the surface is positively charged, it will preferentially adsorb anions from the solution, while a negatively charged surface will attract cations.The strength of the adsorption interaction is also influenced by the chemical nature of the adsorbate and the adsorbent. Specific interactions, such as hydrogen bonding, ion-dipole interactions, and van der Waals forces, can all contribute to the overall adsorption energy. Additionally, the morphology and surface area of the adsorbent material can play a significant role in the adsorption capacity and kinetics.One of the key applications of electrochemical adsorption is in the field of energy storage. In electrochemical capacitors, also known as supercapacitors, the storage of energy is achieved through the reversible adsorption and desorption of ions at the electrode-electrolyte interface. The high surface area of the electrode materials, combined with the rapid kinetics of the adsorption process, allows for the development of high-power energy storage devices with long cycle life.Another important application of electrochemical adsorption is in the area of catalysis. Many catalytic processes, such as fuel cell reactions and electrochemical water splitting, involve the adsorption of reactants and intermediates on the catalyst surface. The controlled adsorption of these species can enhance the catalytic activity and selectivity, leading to improved efficiency and performance.Environmental remediation is yet another field where electrochemical adsorption plays a crucial role. The removal of heavy metals, organic pollutants, and other contaminants from water and wastewater can be achieved through the adsorption of these species onto electrode materials. The ability to tune the surface properties of the adsorbent, as well as the application of an external electric field, can enhance the selectivity and efficiency of the adsorption process.In addition to these well-established applications, electrochemical adsorption is also being explored in emerging fields, such as electrochemical sensors, energy harvesting, and biomedical applications. The versatility and tunability of this process make it a valuable tool in the development of innovative technologies.To further advance the understanding and application of electrochemical adsorption, ongoing research is focused on several key areas. These include the development of novel adsorbent materials with tailored surface properties, the investigation of thefundamental mechanisms governing the adsorption process, and the optimization of the operating conditions and system design for various applications.In conclusion, electrochemical adsorption is a complex and multifaceted phenomenon that underpins a wide range of important technologies. By harnessing the interplay between electrical and chemical forces, researchers and engineers can harness the power of this process to address pressing challenges in energy, environment, and beyond. As our understanding of electrochemical adsorption continues to deepen, we can expect to see even more innovative applications emerge in the years to come.。
水中锑去除文献综述
• 谷壳：pH2,谷壳投加量为1.0g，10min平衡，去除率92%
• 羟基磷灰石粉末，吸附符合Langmuir方程 • 水合氧化物：pH6~7，吸附容量： MnOOH>Al(OH)3>Fe(OH)3，在0.4mol/L的CH3COONa条件 下 • 其中吸附剂研究水浮莲、河中啥子（SiO2,CaCO3）
• 反应快，吸附时间为20min，pH范围广为3-8之间；巯基功能化混合吸附剂吸附容量为 108mg/g
•谢谢
锑和锑的性能
• 锑（Sb）： 银白色有光泽硬而脆的金属,原子序数51，相对原子质量121.8，常见有+3、+5。其中Sb(III)的毒性是Sb(V)的10倍 以上。 锑的氧化物的毒性小于锑的硫化物的毒性。锑是被证实对人体和生物体有毒性和致癌性的重金属元素，长期接触低 含量的锑和锑化合物之后，将会导引发慢性结膜炎、慢性咽炎等疾病。 在pH2-11时，Sb(III)以中性络合物 Sb(OH)3存在，Sb(V)以带负点离子 Sb(OH)6-形式存在。 • 国内外处理方法： 沉淀法、吸附法（无机矿物吸附剂、活性炭吸附剂、有机吸附剂、）调节pH值、电化学法、混凝法、离子交换法。 锑的应用： 印刷、交通、能源、化工、机械、冶金、医药、仪表和电子。包括在塑料、阻燃剂、催化剂、油漆、颜料和玻璃器
Journal of Hazardous Materials 299 (2015) 520–528
Optimized cementation condition is obtained at 60 ◦C for 120 min and stirring rate of 600 rpm with Cu/Sb(III) stoichiometric ratio of 6 in 3 mol L−1 HCl. 去除率达99%
The Principles of Adsorption
The Principles of AdsorptionAdsorption is a critical process in many industries, from water purification to pharmaceuticals and beyond. In essence, it involves the attraction of molecules or particles to a surface or interface. Understanding the principles of adsorption is essential to optimizing these processes and achieving desired results.First, it is essential to understand the various types of adsorption. There are two main types: physical adsorption and chemical adsorption. Physical adsorption involves the attraction of molecules to a surface through van der Waals forces, while chemical adsorption involves a more significant interaction, with the formation of chemical bonds between the surface and adsorbing species.The strength of adsorption is determined by several factors, including temperature, pressure, and the nature of the adsorbent and adsorbate. The higher the temperature and pressure, the more significant the adsorption, but at some point, saturation can occur, and further adsorption becomes impossible. The nature of the adsorbent and adsorbate is also crucial. For example, an adsorbent with a high specific surface area will have a more significant capacity for adsorption, while a polar adsorbate will be more attracted to a polar surface.In addition to these factors, the kinetics of adsorption must also be considered. The rate of adsorption depends on the concentration of the adsorbate at the interface, the surface area of the adsorbent, and the mass transfer rate of the adsorbate to the interface.The principles of adsorption are applied in various ways in different industries. In water purification, activated carbon is used as an adsorbent to remove impurities such as chlorine and pesticides from drinking water. In the pharmaceutical industry, adsorption is used in the purification of drugs and the removal of impurities or contaminants. In the oil and gas industry, adsorption is utilized in processes such as natural gas purification and carbon dioxide capture.One area of particular interest in adsorption research is the development of new materials with improved adsorption properties. For example, graphene and other two-dimensional materials have been shown to have excellent adsorption capacity due to their high surface area. Metal-organic frameworks (MOFs) are also promising materials, with a high degree of tunability and the ability to target specific species for adsorption.In conclusion, understanding the principles of adsorption is essential for optimizing processes and achieving desired results in various industries. Factors such as temperature, pressure, the nature of the adsorbent and adsorbate, and the kinetics of adsorption all contribute to the strength and capacity of adsorption. Continued research and development of new materials with improved adsorption properties will further enhance the applications and effectiveness of this critical process.。
弗雷德盐去除锑矿矿坑废水中的锑
弗雷德盐去除锑矿矿坑废水中的锑*王宁宁1,3,胡容2,曹建新1,3,章兴华3,陆洋2(1.贵州大学化学与化工学院,贵州贵阳550025;2.贵州省分析测试研究院;3.贵州省绿色化工与清洁能源技术重点实验室)摘要:用盐-(羟)氧化物法合成了弗雷德盐,应用其层间阴离子交换反应特性对贵州省东峰锑矿矿坑废水中的锑做了去除实验。
用弗雷德盐除锑,可在中性及碱性区域始终保持对锑的去除率≥97%,矿坑废水中的残余锑量为24.4~32μg/L ,低于GB 30770—2014《锡、锑、汞工业污染物排放标准》中0.3mg/L 一个数量级。
在中性及碱性条件下弗雷德盐是以层间Cl -对废水中的阴离子Sb (OH )6-进行交换。
关键词:弗雷德盐;矿坑废水;除锑;离子交换中图分类号:TQ135.31文献标识码:A文章编号:1006-4990(2018)05-0054-05Removal of antimony in mine drainage by Friedel 忆s saltsWang Ningning 1,Hu Rong 2,Cao Jianxin 1,3,Zhang Xinghua 3,Lu Yang 2(1.School of Chemistry and Chemical Engineering ,Guizhou University ,Guiyang 550025,China ;2.Guizhou Academy of Testing and Analysis ;3.Key Laboratory for Green Chemical and Clean Energy Technology of Guizhou Province )Abstract :A Ca-Al layered double hydroxide (Friedel ′s salt )was synthesized with the oxide ⁃salt decomposition and co ⁃pre ⁃cipitation method.The interlayer anionic exchange characteristics of Friedel ′s salt was applied to carry out an experiment for removing antimony in drainage of Guizhou Province Dongfeng Mine.In the case of the neutral and alkaline conditions ,the re ⁃moval rate of antimony in drainage always kept over 97%,and the residual antimony concentrations in the treatment drainage were as low as 24.4~32μg/L ,which was an order of magnitude lower than 0.3mg/L in the Emission Standards of Pollutants for Stannum ,Antimony and Mercury Industry (GB 30770—2014).In both neutral and alkaline conditions ,the main mecha ⁃nisms of antimony removal by Friedel ′s salt were the ion exchange of interlayer Cl -with Sb (OH )6-.Key words :Friedel ′s salt ;mine drainage ;antimony removal ;ion exchange2015年中国锑产量约占世界锑产量的76.7%。
Lab-10-Adsorption1
If None of the antibodies have been identified then a weak reacting cell can be used assuming that only one antibody may be reacting with it.
5. Confirming the specificity of an antibody by showing that it can be adsorbed only to red cells of a particular blood group phenotype.
Adsorption: Separating Multiple Antibodies
Anti-S
Anti-e
Anti-e
Anti-e Anti-e
Anti-e Anti-S Anti-e
Anti-e
Anti-S Anti-S
Adsorption techniques are useful in such situations as:
1. Separating multiple antibodies present in a single serum.
Specimen
Serum or plasma containing antibody to be adsorbed.
Reagents
Red cells (eg, autologous or allogeneic) that carry the antigen corresponding to the antibody specificity to be adsorbed.
某锑矿含重金属废水的处理
某锑矿含重金属废水的处理谭峥铮【摘要】对锑矿废水处理常用工艺进行比选后,采用石灰-铁盐联合化学中和沉淀法处理该类型废水.工程实际运行结果表明,通过该工艺处理后,出水水质可达到《污水排放综合标准》(GB8978-1996)中一级标准的要求,锑的浓度符合《工业废水中锑污染物排放标准》(DB43/350-2007)中限值.该工艺处理效果稳定可靠,运行操作简单,出水水质达标.【期刊名称】《湖南有色金属》【年(卷),期】2013(029)004【总页数】4页(P53-56)【关键词】锑矿废水;化学沉淀法;石灰-铁盐联合法;除砷;除锑【作者】谭峥铮【作者单位】湖南省环境保护科学研究院,湖南长沙410004【正文语种】中文【中图分类】X703根据美国地质调查局2010年的报告，中国生产的锑占全球的88.9%。
我国现已探明有储量的矿区111处，分布于18个省区。
湖南省的锑矿总储量排名全国第一，省内更有著名的“世界锑都”冷水江。
矿山开发以及锑矿冶炼在拉动当地经济发展的同时，也带来了巨大的环境破坏。
锑是一种有毒元素，持续接触会给心脏和肝脏带来伤害，吸入高含量的锑时可导致锑中毒，长期接触有致癌性。
锑矿开采和冶炼过程中产生的含重金属废水严重威胁着周边居民的饮用水安全和水环境。
因此，对锑矿的含重金属废水治理刻不容缓。
1 锑矿废水的性质湖南某锑矿采用坑采工艺，年产锑矿石2万t。
该矿为采选一体型企业，其废水来源主要由矿坑疏干水和选矿废水组成。
矿坑疏干水被抽出矿坑后，先送往选矿车间进行利用，多余部分未经处理直接外排。
选矿废水也未经处理直接外排。
经现场调查，废水最大排水量为1 100 t/d，矿坑疏干水和选矿废水均为间歇式排放。
该矿废水的主要污染因子为Sb、As、Pb、COD。
拟建一套废水处理设施，经处理后的出水需达到《污水排放综合标准》(GB8978－1996)中一级标准的要求，锑的排放需要达到《工业废水中锑污染物排放标准》(DB43/350－2007)的要求。
The Science of Adsorption and Adsorbent Materials
The Science of Adsorption andAdsorbent MaterialsAdsorption is a process by which molecules or particles of a gas, liquid or dissolved solid adhere to the surface of another substance. The substance that the molecules adhere to is called the adsorbent, and the molecules that adhere to it are known as the adsorbate. Adsorption is a crucial process in many industrial processes, including gas and liquid separations, purification, and catalysis. Adsorbent materials, therefore, play a key role in these processes, making them essential materials in a wide range of industries.Adsorbent MaterialsAdsorbent materials are substances that are designed to adsorb certain molecules or particles from a fluid or gas. They can be natural, such as activated carbon, silica gel, and zeolite, or synthetic, like mesoporous silica, Metal-Organic Frameworks (MOFs) and other advanced materials.Activated carbon, for instance, is widely used as an adsorbent material due to its high surface area and porosity. Its porous carbon structure provides a large surface area for adsorption, and its ability to retain a wide range of molecules makes it useful in various applications, such as air and water purification. Silica gel, on the other hand, is a synthetic adsorbent material composed of porous, amorphous silica particles. It has a high surface area, excellent stability, and can be modified to target specific molecules or particles for adsorption.MOFs, which are a type of advanced material, are a highly versatile class of porous materials, offering unparalleled tunability in their synthesis. They are made of metal ions or clusters that are linked by organic molecules, forming porous structures with high surface areas. MOFs can be designed to target specific molecules, resulting in high selectivity and efficiency in adsorption processes.Adsorption MechanismsAdsorption can occur through several mechanisms, including physical adsorption, chemical adsorption, and physisorption. Physical adsorption is the result of weak intermolecular forces, such as van der Waals forces, between the adsorbate and adsorbent molecules. Chemical adsorption, on the other hand, occurs when covalent or ionic bonds form between the adsorbate and adsorbent molecules. Physisorption is a type of physical adsorption that involves the transfer of electrons between the adsorbate and adsorbent.The choice of adsorbent material and the adsorption mechanism depend on the type of molecules or particles being adsorbed and the application. For example, in gas separations, physical adsorption is often used to adsorb molecules based on their size, shape, or polarity. In catalysis, on the other hand, chemical adsorption is the preferred mechanism since it involves strong chemical bonds between the reactants and catalyst.Applications of Adsorbent MaterialsAdsorbent materials have numerous applications in various industries, and their versatility and specificity make them useful in a wide range of processes. Some applications include:Air and Water Purification: Activated carbon, zeolite, and silica gel are commonly used to adsorb organic and inorganic impurities from air or water.Gas Separation: Adsorbent materials such as zeolite and MOFs are used in gas separations, where they can isolate specific gases based on their size, shape, or polarity.Catalysis: MOFs and other advanced materials are utilized as catalysts in chemical reactions due to their high surface area, tunable porosity, and ability to target specific molecules.Drug Delivery: Mesoporous silica and other nanoparticles have applications in drug delivery systems, where they can selectively adsorb specific drugs and release them in a controlled manner.ConclusionAdsorption is an essential process for many industrial applications, and adsorbent materials play a vital role in these processes. The design, synthesis, and application of adsorbent materials are continually improving, offering higher selectivity, efficiency, and specificity. As new advanced materials are developed, the range and scope of potential applications for adsorbent materials will increase further, making them an important area of research in the field of materials science.。
Antimony Compounds Flame Retardant Properties
Antimony Compounds Flame Retardant PropertiesAntimony compounds have been widely used as flame retardants in various industries due to their excellent properties in inhibiting or delaying the ignition and spread of fire. Antimony trioxide (Sb2O3) is one of the most commonly used antimony compounds in flame retardant applications. However, concerns have been raised about the potential health and environmental risks associated with the use of antimony compounds. In this article, we will explore the flame retardant properties of antimony compounds and the potential risks they pose.Antimony compounds are effective flame retardants due to their ability to release water and carbon dioxide when exposed to high temperatures. This reaction helps to dilute the concentration of flammable gases and reduce the heat generated during combustion. Antimony compounds also act as char-forming agents, which means they can form a protective layer of char on the surface of the material, preventing further combustion. This char layer acts as a barrier between the flame and the material, slowing down the spread of fire.Antimony trioxide is the most commonly used antimony compound in flame retardant applications, particularly in plastics, textiles, and building materials. It is often used in combination with other flame retardants, such as halogenated compounds, to enhance its flame retardant properties. The use of antimony trioxide has been regulated in some countries due to concerns about its potential health and environmental risks. In the European Union, for example, the use of antimony trioxide in certain products has been restricted due to its classification as a carcinogen.One of the main concerns about the use of antimony compounds as flame retardants is their potential toxicity. Antimony trioxide has been classified as a possible human carcinogen by the International Agency for Research on Cancer (IARC). Studies have also shown that exposure to antimony compounds can cause respiratory, gastrointestinal, and skin irritation. In addition, antimony compounds can accumulate in the environment and pose a risk to wildlife and ecosystems.Despite these concerns, antimony compounds continue to be used as flame retardants due to their effectiveness and low cost. However, there is growing interest in developing alternative flame retardants that are less toxic and more environmentally friendly. Some of the alternative flame retardants being explored include phosphorus-based compounds, nitrogen-based compounds, and mineral-based compounds.In conclusion, antimony compounds have excellent flame retardant properties and have been widely used in various industries. However, their potential health and environmental risks have raised concerns, leading to regulations and efforts to develop alternative flame retardants. It is important for manufacturers and consumers to be aware of the potential risks associated with the use of antimony compounds and to consider alternative flame retardants when possible.。
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INTRODUCTION Excessive release of toxic metals into the environment due to industrialization has created a great global concern during recent years. Antimony, one of the toxic metals is also a nonessential element and is comparable in its toxicity to arsenic and bismuth. The word production of antimony is
To cite this article: Yan‐Hua Xu, Akira Ohki & Shigeru Maeda (2001): Adsorption and removal of antimony from aqueous solution by an activated Alumina, Toxicological & Environmental Chemistry, 80:3-4, 133-144 To link to this article: /10.1080/02772240109359004
The adsorption of Sb(V) ions from aqueous solutions onto commercially available activated alumina (AA) was investigated. AA has a much higher adsorption capacity than presently used adsorbents. Sb(V) ions are likely adsorbed through electrostatic attraction and/or specific adsorption mechanism, while the optimum pH is found in the range of 2.8-4.3. The Sb(V) ions adsorption capacities increase with increasing temperature. The addition of nitrate, acetate, arsenite, chloride, and silicate ions affected Sb(V) ions adsorption only slightly, while the coexisting ascorbate, arsenate, phosphate, sulfate, EDTA, tartrate, and citrate ions substantially depressed Sb(V) ions adsorption. Keywords: Antimony; adsorption; removal; activated alumina
Toxicological & Environmental Chemistry
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ADSORPTION AND REMOVAL OF ANTIMONY FROM AQUEOUS SOLUTION BY AN ACTIVATED ALUMINA 1. Adsorption Capacity of Adsorbent and Effect of Process Variables
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Adsorption and removal of antimony from aqueous solution by an activated Alumina
Yan‐Hua Xu , Akira Ohki & Shigeru Maeda
a a b a
Department of Bioengineering, Faculty of Engineering, Kagoshima University, 1–21–40, Korimoto, Kagoshima, 890–0065, Japan
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Toxicological and Environmental Chemistry, Vol. 80, pp. 133-144 Reprints available directly from the publisher Photocopying permitted by license only
YAN-HUA XU, AKIRA OHKI* and SHIGERU MAEDA
Department of Bioengineering, Faculty of Engineering, Kagoshima University, 1-21-40, Korimoto, Kagoshima 890-0065, Japan
© 2001 OP A (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group.
* Corresponding author. E-mail: ohki@apc.kagoshima-u.ac.jp. 133
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about 68,000 tones per year [1]. It has been extensively used in lead alloys, catalyst, battery grids, bearing metal, ceramics and primers, etc. The most prominent use of antimony is as flame-retardant in plastics and textiles. In Japan, the water quality standards for items requiring surveillance for drinking water in 1992 and environmental water in 1993 stipulate that the concentration of antimony is 2 ug/1 or less. Recently, the number of cases detected exceeding the water quality standards has been increasing throughout Japan [2]. Unfortunately, antimony is not as well characterized as arsenic [3]. Also, there are only a very limited studies specifically aimed at antimony removal from aqueous systems, although some procedures have been proposed for the preconcentration and enrichment of antimony from various matrices [4-7]. Adsorption on solid surfaces is the most versatile and widely used technique for the removal of low concentrations of toxic substances from aqueous solutions. But the adsorption of antimony from aqueous system has only been reported on natural zeolites [8], sand [9], rice husks [10], and a chemically bonded adsorbent [11]. These methods have shortcomings in efficiency or cost, thus, the development of new simple and efficient methods for antimony removal from aqueous systems is urgently needed. Activated alumina is a conventional adsorbent and has been successfully used for many toxic anions removal because of its high capacity and rate of adsorption, favorable chemical and physical strengths, and steady supply. Furthermore, it can be expected that the clear and definite composition of this adsorbent will assist the study for the adsorption mechanism of antimony. It has been found that antimony(V) is the predominant inorganic antimony species in water system [1]. In the present study, the adsorption and removal of antimonic ions (Sb(V) ions) from aqueous solution has been investigated by using a kind of commercially available activated alumina (AA) as the adsorbent, which was employed without any pretreatment. Batchwise adsorption tests were carried out with special emphasis on the role of process variables such as the amount of adsorbent, pH of the system, Sb(V) concentration, operation temperature and coexisting anions. A column operation, desorption experiments, regeneration and reuse of the adsorbent were also demonstrated and will be reported subsequently.