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.

EFFECT OF pH ON THE ADSORPTION OFp-AMINOBENZOIC ACID ON POLYSTYRENE-BASED ADSORBENTS

In the present study the adsorptive properties of p-aminobenzoic acid with hypercrosslinked and multi-functional polymeric adsorbents at different solution pHs were systematically investigated in accordance with the particular physicochemical characteristics of the aromatic amphoteric compound involving both Lewis acid and Lewis base functional groups. It was found that the equilibrium adsorption data of the three polymeric adsorbents fitted well in the Langmuir and Freundlich isotherm equations. Studies at various pH levels indicate that the capacity of the adsorbents for adsorption of the ionic forms of adsorbate is less than that for the corresponding neutral species. At pH 3.78, the adsorption capacities of the three adsorbents are the highest. Whereas the adsorption property of multi-functional polymeric adsorbent NJ-99 is the largest, which may be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of p-aminobenzoic acid. The trend of the adsorption capacities of the three adsorbents towards p-aminobenzoic acid with the solution pH is in accord with the dissociation curve of the neutral molecular p-aminobenzoic acid. The adsorption forces include π-π interaction, hydrogen-bonding interaction and electrostatic attraction or repulsion when there exist the molecular and ionic adsorbing species at different pHs in aqueous solution.

ADSORPTION OF PHENYLACETIC ACID ON MACROPOROUS POLYMERIC ADSORBENTS

Several macroporous polymeric adsorbents (NDA-999, XAD-8, X-5 and XAD-2) were employed in the study to adsorb phenylacetic acid from aqueous solution. Effect of salt and ambient temperature on adsorption was studied using NDA-999 adsorbent and the adsorption process conforms to Freundlich抯 model reasonably. Adsorption dynamics were conducted in batch experiments in order to make clear the mechanism of adsorption process. It is proved that the squared driving force mass transfer model can be adopted to elucidate the process. The treatment process of industrial wastewater containing high strength of phenylacetic acid was proposed for cleaner production of phenylacetic acid.

Adsorption thermodynamics and kinetic investigation of aromatic amphoteric compounds onto different polymeric adsorbents

The adsorption behavior ofp-aminobenzoic acid and o-aminobenzoic acid onto the different polymeric adsorbents was systematically investigated as a function of the solution concentration and temperature. Experimental results indicated that the equilibrium adsorption data of the four polymeric adsorbents fitted well in the Freundlich isotherm. The adsorption capacity of multi-functional polymeric adsorbent NJ-99 was the highest, which might be attributed to the strong hydrogen-bonding interaction between the amino groups on the resin and the carboxyl group of aminobenzoic acid. The adsorption capacity of o-aminobenzoic acid onto any adsorbent was higher than p-aminobenzoic acid. Thermodynamic studies suggested the exothermic, spontaneous physical adsorption process. Adsorption kinetics results showed that the adsorption followed the pseudo-second-order kinetics model and the intraparticle mass transfer process was the rate-controlling step.

PROPERTIES AND THERMODYNAMICS OF ADSORPTION OF BENZOIC ACID ONTO XAD-4 AND A WATER-COMPATIBLE HYPERCROSSLINKED ADSORBENT

The adsorption behavior of benzoic acid onto a water-compatible hypercrosslinked polymeric adsorbent NJ-8 wascompared with that onto macroporous Amberlite XAN-4. This paper focuses on the static equilibrium adsorption behaviors,the adsorption thermodynamics and the column dynamic adsorption profiles. Five isotherm models are used to fit the results.This shows that the Freundlich equation can give a perfect fit. The specific surface area of NJ-8 is about as high as that ofAmberlite XAD-4, but the adsorbing capacity for benzoic acid on NJ-8 is about 14.9%-64.8% higher than that on AmberliteXAD-4, which is attributed to its microporous mechanism and partial polarity. The negative values of the adsorptionenthalpy are indicative of an exothermic process. Both enthalpy and free energy changes of adsorption manifest a physicalsorption process. The negative values of the adsorption entropy indicate that adsorption is well consistent with the restrictedmobilities and the configurations of the adsorbed molecules on the surface of the studied adsorbents with superficialheterogeneity. Both adsorbents were used in mini-column experiments to demonstrate the higher breakthrough adsorbing capacity of the hypercrosslinked polymeric adsorbent NJ-8 to benzoic acid, as compared with that of Amberlite XAD-4.

Kinetic and Thermodynamic Studies of Acid Scarlet 3R Adsorption onto Low-cost Adsorbent Developed from Sludge and Straw

A low-cost adsorbent was prepared from sludge and straw by pyrolysis in a dried state with the surface area of the adsorbent of 829.49 ma. g-l, micropore volume of 0.176 cm2·g-1 and average pore radius of 5.0 nm. The kinetic, equilibrium isotherm and thermodynamic characteristics of trisodium 1-（1-naphthylazo）-2-hydroxynaphthalene- 4＇,6,8-trisulphonate （acid scarlet 3R） onto the adsorbent from sludge and straw were investigated. The results indicated that the pseudo second order adsorption was the predominant adsorption mechanism of acid scarlet 3R. Thus, the adsorption phenomenon was suggested as a chemical process. The adsorption data were fitted better with Langmuir model than Freundlich model, indicating that the adsorption of acid scarlet 3R belonged to the monolayer adsorption and mainly occurred in micropores.

Preparation and Characterization of a Novel Spherical Cellulose Adsorbent for Reduction Adsorption of Trichloroacetic Acid

A novel spherical cellulose adsorbent has been prepared by homogeneous graft polymerization of N,N＇-methylenebisacrylamide （MBA） onto cellulose in an ionic liquid, 1-N-butyl-3-methylimidazolium chloride （BMIMC1）, which was then partially amine methylated through Mannich reaction to get bifunctionalized materials containing both amide and sulphinate moities. Factors affecting the attachment of functional groups were investigated. The adsorbent was characterized by Elemental Analysis （EA）, Fourier Transform Infrared Spectroscopy （FTIR） and Scanning Electron Microscope （SEM）. Cellulose adsorbent was then tested for its potential applications in the reduction adsorption oftrichloroacetic acid （TCAA） from aqueous solutions.

SURFACE-ENHANCED RAMAN SPECTRA OF p-AMINOBENZOIC ACID ADSORBED ON Ag2CO3 COLLOIDS

It was observed that the p-aminobenzoic acid(PABA)molecules adsorbed on A92CO3 colloids exhibited strong SERS effect,the enhancement factor is estimated at 10~7—10~8 The mechanism of SERS effect on PABA adsorbed on the colloids was discussed.

AN ADSORB MODEL OF ORGANIC ACID ON BASIC ZEOLITE NAX

The adsorb model of formic acid on NaX derived from TPD was discussed. It was showed that the adsorb sites were various exposed framework O2- centers bearing different basic intensity and spatial resistance. The h-peak was attributed to O2- near S-III in supercage and l-peak to O2- near S-II in beta-cage of faujusite zeolite. The model can explain the experimental results. Meanwhile, a relative standard of basic intensity based on TPD of formic acid was founded.

TREATMENT OF SORBIC ACID MANUFACTURING WASTEWATER BY HYPERCROSSLINKED POLYMERIC ADSORBENT (NDA-150)

The treatment of sorbic acid manufacturing wastewater by NDA-150 resin was investigated. The experiments show that this process is suitable for the treatment of sorbic acid manufacturing wastewater. About 98% sorbic acid and 50% CODcr were removed under optimal operating conditions, and 70% of sorbic acid in sorbic acid manufacturing wastewater was reclaimed. This process makes it possible to recover valuable materials from the wastewater and to improve the quality of effluent water.

ADSORPTION OF BENZOIC ACID AND P-NITROBENZOIC ACID ON A NEW HYPERCROSSLINKED PHENOL GROUP PST ADSORBENT

A comparison of the adsorption of benzoic acid and p-nitrobenzoic acid on the new hypercrosslinked polymeric adsorbent AM-1, with that by macroporous Amberlite XAD-4, including the equilibrium adsorption isotherms, the dynamic adsorption behaviors through column and the adsorption thermodynamics were studied. Results show that Freundlich equation gives a fitting adsorption isotherm. The specific surface of AM-1 is only 67% of that of Amberlite XAD-4, but the adsorption capacities on AM-1 are much higher about 125%~166% than that on Amberlite XAD-4, which is contributed to the micropore mechanism and polarity. The negative values of the adsorption enthalpy are indicative of an exothermic process. Enthalpy and free energy changes of adsorption both manifest a physic-sorption process. The negative values of the adsorption entropy indicate that the adsorption is well consistent with the restricted mobilities and the configurations of the adsorbed benzoic acid molecules on the surface of studied adsorbents with superficial heterogeneity. Both adsorbents were used in mini-column experiments for adsorbing benzoic acid expecting to elucidate the higher breakthrough adsorption capacity of the new hypercrosslinked polymeric adsorbent AM-1 as compared with that of Amberlite XAD-4.

沙柳木粉基高效吸附材料对煤矿废水中Fe(Ⅱ)和Mn(Ⅱ)作用特性及机理

针对煤矿酸性废水中含有较高质量浓度铁离子和锰离子的问题,以沙柳木粉为主要原料,遵循农林废弃物提取再利用原则,经过NaOH、Na2SO3等溶液处理后获得脱木素木粉(DWF),通过微波辅助-原位合成的手段,制备了一种针对煤矿废水中Fe(Ⅱ)和Mn(Ⅱ)的吸附剂(AA-DWFPAM)。借助扫描电子显微镜(SEM)、N_(2)吸附-脱附、傅里叶变换红外光谱(FTIR)和红外热重联用(TG-FTIR)对产物的微观结构、反应机理、热稳定性进行了分析,探讨了AA-DWF-PAM的最佳吸附条件、吸附动力学、吸附等温线,研究了AA-DWF-PAM对Fe(Ⅱ)和Mn(Ⅱ)的吸附特性和吸附机理。表征实验结果表明:AA-DWF-PAM整体存在较多孔洞并呈现网状结构,且比表面积(BET)为150.83 m^(2)/g,说明改性后的吸附剂具有较大的比表面积,能够为Fe(Ⅱ)和Mn(Ⅱ)吸附提供较多位点和空间;此外,AA-DWF-PAM热解气态产物主要有H_(2)O、CO_(2)以及少量CO,裂解温度较高,其结构稳定性较强。吸附特性实验研究表明:AA-DWF-PAM用量为4 g/L、溶液pH=4、吸附时间达到200 min,以及Fe(Ⅱ)、Mn(Ⅱ)初始质量浓度为100 mg/L和80 mg/L时,为AA-DWFPAM的最佳吸附条件;经过计算得知,AA-DWF-PAM更接近于伪二级动力学假设,吸附主要控制过程为化学过程,且吸附过程更符合Langmuir方程的单层分子吸附,Fe(Ⅱ)和Mn(Ⅱ)的理论最大吸附量分别为192.29 mg/g和123.65 mg/g;通过Materials Studio对吸附过程进行分子模拟和量子化学计算得知,吸附过程中—NH_(2)、—COOH以及—OH官能团起到静电吸附作用。因此,合理利用农林废弃物,为煤矿酸性废水治理提供了新途径,开发的AA-DWF-PAM吸附剂,能够有效处理煤矿酸性废水中的铁锰离子。

弱酸性蓝AS 染料排放的废盐制碳基吸附剂及利用

将染料弱酸性蓝AS(AS)生产排放的含盐废水喷雾干燥后制成废盐,再将其有机污染物煅烧制备成类活性炭吸附剂(LAC),用于AS染料生产过程中产生的洗涤废水的吸附脱色净化,同时回收粗盐NaCl可循环用于AS工业生产的盐析过程。对LAC进行吸附过程动力学、热力学研究,并研究AS染料废水溶液初始浓度、温度及pH对吸附性能的影响。在40 mg/L的AS染料废水中,温度为318 K的条件下,平衡吸附量为29.22 mg/g。在酸性及温度较高时吸附能力较强。Langmuir等温线方程能更好拟合吸附实验结果。另外,采用一锅混合法,添加四水合乙酸镁对LAC进行改性,改性后的吸附剂LACMg0.75比表面积较LAC提升了近5倍,饱和吸附量能够达到550.02 mg/g,较LAC提升了接近20倍。

ZSM-5分子筛对典型涂装VOCs的吸附性能及机理研究

通过水热法成功合成了一系列宽硅铝比(50、100、150、300、500、800、1500、3000)的ZSM-5分子筛,旨在研究其对涂装行业典型挥发性有机物(volatile organic compounds,VOCs)的吸附规律。同时,结合分子筛表面的酸性位点,以解析硅铝比对分子筛吸附性能的影响机制。实验结果表明,丙酮的吸附能力主要受自身极性、支链结构和分子筛表面酸位点的影响。而乙酸丁酯、苯乙烯、对二甲苯、苯、甲苯的吸附性能会同时受到自身的分子量、分子直径、极性、分子结构和官能团的影响,分子量和分子直径大、极性强且具有支链结构的VOCs更容易被ZSM-5分子筛吸附。这6种VOCs中,ZSM-5分子筛对丙酮的吸附效果最好,硅铝比对其吸附性能的影响也最大。这是因为丙酮比其他VOCs更容易吸附在Lewis酸位点上,硅铝比的改变会影响酸位点的数量。低硅铝比的分子筛由于具有较多的酸位点,更适用于丙酮的吸附。

多孔活性炭吸附去除阿散酸的研究

阿散酸常被用作饲料添加剂进入动物机体,大部分未被动物机体代谢,会随排泄物进入环境,造成砷污染。本文以榛子壳为原料,用四种活化剂制备了活性炭,经过筛选以ZnCl2为活化剂,600℃下热解制得的多孔活性炭AC(Zn-600)吸附能力最强。当pH=6.0,阿散酸初始浓度为500 mg·L^(-1),接触30min,AC(Zn-600)对阿散酸的饱和吸附量可达131.3 mg·g^(-1),温度升高有利于吸附的发生。AC(Zn-600)中含有较多含氧官能团,存在大量微孔,主要以孔隙吸附、静电、氢键和π-π与阿散酸作用,阿散酸在AC(Zn-600)上的吸附以化学吸附为主,Langmuir等温吸附模型和准一级动力学模型更适合描述吸附过程。

吸附剂表征及改性对棕榈油中3-氯丙醇酯和缩水甘油酯脱除效果的影响

为探究吸附法脱除精炼油脂中3-氯丙醇酯(3-MCPDE)和缩水甘油酯(GEs)的效果,以精炼棕榈油为原料,采用3种类型吸附剂(活性炭、活性白土、凹凸棒土)对其中的3-MCPDE和GEs进行吸附脱除,测定不同吸附剂的3-MCPDE和GEs脱除率,对吸附剂进行表征,分析其固有特性与脱除率的相关性,并研究了酸碱改性方法对吸附剂吸附脱除3-MCPDE和GEs效果的影响。结果表明:3种吸附剂及其酸碱改性后均未对3-MCPDE起到有效吸附脱除效果,而不同吸附剂对GEs表现出了不同的吸附脱除效果;9种活性炭(添加量1%)对GEs的脱除率为6.50%~98.57%,其中有2种活性炭可以有效地将GEs控制在1.00 mg/kg以内;9种活性白土(添加量0.1%)对GEs的脱除率为11.56%~83.72%;3种凹凸棒土(添加量0.5%)对GEs的脱除率为40.86%~69.64%,脱除效果均不理想;相关性分析表明,GEs脱除率与活性炭的pH呈极显著负相关(p<0.01),与活性炭比表面积、介孔面积和介孔容积均呈显著正相关(p<0.05),与活性白土的pH、平均孔径呈极显著负相关(p<0.01),与活性白土的活性度呈显著正相关(p<0.05);酸改性有利于活性炭和活性白土对GEs吸附脱除,而碱改性不利于其对GEs吸附脱除。实际生产中可选择低pH、孔隙发达的活性炭或低pH、活性度高、孔隙发达的活性白土,另外可进行适当的酸改性,以达到较好脱除油脂中GEs的目的。

羟基磷灰石复合腐植酸及其对Mn(Ⅱ)的去除

以硝酸钙和磷酸氢铵为原料,采用化学沉淀法成功合成羟基磷灰石(HAP),并将其与腐植酸(HA)复合,制备出复合吸附剂HAP-HA。通过傅里叶变换红外光谱(FT-IR)、比表面积及孔径分析、差热-热重分析(TGDSC)及扫描电镜(SEM)等方法对样品进行表征。结果表明:腐植酸成功负载到羟基磷灰石上;HAP-HA孔径主要分布在3~5 nm,比表面积较大,且具有较好的稳定性;HAP-HA表面粗糙不平、孔隙较多,这增大了比表面积,为重金属离子提供了大量的活性位点。以Mn(Ⅱ)为目标污染物,将Mn(Ⅱ)的去除率作为指标,通过吸附实验考察吸附剂HAP-HA对污染物的吸附性能。结果表明:在常温、pH为8.0、投加量为0.15 g、吸附时间为150 min的条件下,吸附剂HAP-HA对Mn(Ⅱ)的去除率最高,可稳定达到99.0%以上;该吸附过程符合Freundlich等温吸附模型。同时,对吸附后的吸附剂进行脱附及再生吸附实验,以NaOH溶液作为洗脱剂可取得较好的脱附效果,脱附效率可达78.1%,再生循环吸附6次后HAP-HA仍具有良好的吸附性能。

腐植酸改性木屑对Cu^(2+)的吸附性能

以松木屑为原料,腐植酸为改性剂,制备出改性木屑吸附剂并研究其对废水中Cu^(2+)的吸附性能。采用FT-IR、SEM、XPS、XRD、BET、Zeta等手段对相关物质进行表征。结果表明改性木屑中含有羟基和羧基,有更好的孔隙结构,更加有助于吸附Cu^(2+)。探索吸附过程中吸附温度、溶液pH值、Cu^(2+)初始质量浓度和吸附时间对吸附效果的影响;探究吸附过程动力学、热力学变化。实验结果表明:吸附时间为20 min,温度为45℃,pH值为5时吸附效果最佳,吸附率为98.68%,吸附量为157.89 mg/g。该吸附剂对Cu^(2+)的吸附过程符合拟二级动力学模型,Freundlich吸附等温线模型能很好地描述该吸附行为。改性木屑吸附剂经过4次再生后,对Cu^(2+)的吸附率为77.59%。

L-赖氨酸功能化纤维素对模拟苹果汁中铅的吸附特性研究

本研究采用微米级微晶纤维素(microcrystalline cellulose,MCC)和纳米级纤维素纤维(cellulose nanofiber,CNF)为基质,L-赖氨酸为接枝单体,制备了L-赖氨酸功能化纤维素基铅吸附剂,探究吸附剂在果汁中的吸附性能及果汁中糖类与有机酸对吸附性能的影响。结果表明,以单一铅体系为目标溶液,L-赖氨酸功能化高碘酸钠氧化的微晶纤维素(L-lysine functionalized sodium periodate-oxidized MCC,L-g-POCM)与L-赖氨酸功能化四甲基哌啶体系氧化的纳米纤维素纤维(L-lysine functionalized TEMPO-oxidized CNF,L-g-TOCF)对铅(20 mg L^(-1))有较好的吸附效果,吸附效率分别高达77.36%和96.16%。偏中性的糖类对吸附效果的影响属于较弱的竞争吸附,高酸性的有机酸则属于较强的竞争吸附,且L-g-TOCF受影响程度较小。在pH小于4时,L-g-TOCF的吸附性能被抑制,低至7.54%,而在pH大于4时,最高可达92.18%,因此,L-g-TOCF在低酸类果汁的重金属去除中有良好的前景。

醋酸改质钢渣制备高钙基吸附材料及动力学研究

为提高钢渣的资源综合利用并减少钢铁冶炼过程排放的CO_(2),采用浸出-高温烧结工艺对转炉钢渣进行改质。通过浸出过程,将含钙组分制备成钙基吸附材料,同时富集回收浸出渣含铁组分。考察了浸出参数对钙基吸附剂组成的影响,为探究钢渣颗粒中钙的浸出过程,采用收缩核模型对钢渣颗粒在弱酸性溶液中的浸出速率进行了分析。研究了浸出渣经高温改质物相结构变化,并分析铁元素转变规律。此外,通过使用XRD和SEM分析钙基材料的物相结构。最后,测算钙基材料的吸附性能。结果表明,浸出温度和醋酸浓度对钙基材料中CaO含量影响较大。在较大的粒径下,最佳的浸出参数为酸浓度1 mol/L、固液比1∶10、浸出温度70℃以及时间2 h,此条件下CaO含量最高达86.3%。动力学结果表明,在搅拌条件下,钙浸出过程由内扩散控制。在40~70℃内,钙浸出过程的速率控制步骤未发生变化,仍由内扩散控制。制备的钙基材料CaO纯度较高,且CO_(2)吸附量随着CaO含量增加而增大,在常压条件下最高可达60.6 mg/g。对浸出渣高温改质后,Ca_(2)Fe_(2)O_(5)相转变成了尖晶石相(Fe_(3)O_(4)、MgFe_(2)O_(4)),钙铁元素得到了很好的分离和富集回收。