Revealing the effect of preparation parameters on zeolite adsorption performance for low and medium concentrations of ammonium

The effect of preparation parameters on the performance of zeolite for ammonium(20–300 mg N/L) adsorption from simulated wastewater is reported. It was found that the ratios of Na_2O/SiO_2 and Si/Al had a more important influence than crystallization time on zeolite adsorption properties. Relatively low Na_2O/SiO_2 ratios were beneficial for fabrication of zeolites with high proportions of micropore area and volume, which led to the surface adsorption mechanism being dominated by surface free energy and pore effects. However,with decreasing Si/Al ratios, the effect of ion-exchange was more prominent due to the high negative surface potential of zeolite. In addition, the concentration of weak acid sites on the zeolites was increased with lower ratios of Na_2O/SiO_2 and Si/Al, which may promote ammonium removal. Therefore, the most effective zeolite for ammonium removal, which was fabricated at Na_2O/SiO_2= 1.375, Si/Al = 4 and crystallization time of 48 hr, exhibited the cooperative effects of adsorption, ion-exchange and a large amount of weak acid sites. The maximum ammonium adsorption capacity(35.06 ± 0.98 mg/g) and the removal efficiency(94.44% ± 4.00%) were obtained at the dosage of 4.0 g/L zeolite NaX at ammonium concentrations of 300 mg N/L and 20 mg N/L, respectively. The Freundlich isotherm and pseudo-first-order kinetics models provided excellent fitting for the ammonium adsorption process. In addition, zeolite NaX showed about 1.23–3.2 times the ammonium adsorption capacity of clinoptilolite. The stable and efficient reusability of zeolite NaX after five regeneration cycles demonstrated that this adsorbent has considerable potential for practical industrial applications.     

Cadmium sorption by sodium and thiourea-modified zeolite-rich tuffs

In the present investigation, two zeolite-rich tuffs from Guaymas and El Cajon(State of Sonora), which were conditioned with a sodium chloride solution and subsequently modified with a thiourea solution, were chosen to evaluate the removal of Cd from aqueous systems. The zeolitic materials were characterized by scanning electron microscopy and X-ray diffraction. The surface area was also determined. The experiments were performed in a batch system, and the influences of p H, contact time between phases, and the concentration of Cd in the solution on the adsorption by sodium or thiourea-modified zeolite-rich tuff were investigated. It was found that the efficiency of Cd ion removal from aqueous solutions is influenced by the p H of the aqueous systems. The Cd adsorption kinetic data were well fitted to a pseudo-second-order model in all cases. The Langmuir and Langmuir–Freundlich isotherms adequately described the Cd sorption behavior by the zeolite from El Cajon pretreated with Na Cl and the zeolite from Guaymas modified with thiourea, respectively.     

Inhibitive effects of chlortetracycline on performance of the nitritation-anaerobic ammonium oxidation (anammox) process and strategies for recovery

The short-and long-term effects of chlortetracycline(CTC) on the nitritation-anaerobic ammonium oxidation(anammox) process were evaluated. The half maximal inhibitory concentration of CTC in the batch tests of the nitritation-anammox process was 278.91 mg/L at an exposure time of 12 hr. The long-term effects of CTC on the process were examined in a continuous-flow nitritation-anammox reactor. Within 14 days, the nitrogen removal rate significantly decreased from 0.61 to 0.25 kg N/m~3/day with 60 mg/L CTC in the influent.The performance suppressed by CTC barely recovered, even after CTC was removed from the influent. Furthermore, the inhibition of CTC also reduced the relative abundance of ammonium oxidizing bacteria(AOB) and anaerobic ammonium oxidizing bacteria(An AOB)in the reactor, resulting in both a decreased amount of and an imbalance between AOB and An AOB. When fresh anammox sludge was reseeded into the nitritation-anammox reactor,the nitrogen removal rate recovered to 0.09 ± 0.03 kg N/m~3/day.     

Adsorption behavior of ammonium by a bioadsorbent – Boston ivy leaf powder

The adsorption behaviors of ammonium ions from aqueous solution by a novel bioadsorbent, the Boston ivy (Parthenocissus tricuspidata) leaf powder (BPTL) were investigated. The SEM images and FT-IR spectra were used to characterize BPTL. The mathematical models were used to analyze the adsorption kinetics and isotherms. The optimum pH range for ammonium adsorption by BPTL was found to be 5–10. The adsorption reached equilibrium at 14 hr, and the kinetic data were well fitted by the Logistic model. The intraparticle di usion was the main rate-controlling step of the adsorption process. The high temperature was favorable to the ammonium adsorption by BPTL, indicating that the adsorption was endothermic. The adsorption equilibrium fitted well to both the Langmuir model and Freundlich model, and the maximum monolayer adsorption capacities calculated from Langmuir model were 3.37, 5.28 and 6.59 mg N/g at 15, 25 and 35°C, respectively, which were comparable to those by reported minerals. Both the separation factor (RL) from the Langmuir model and Freundlich exponent (n) suggested that the ammonium adsorption by BPTL was favorable. Therefore, the Boston ivy leaf powder could be considered a novel bioadsorbent for ammonium removal from aqueous solution.     

Removal efficiency of fluoride by novel Mg-Cr-Cl layered double hydroxide by batch process from water

The fluoride ion removal from aqueous solution using synthesized Mg-Cr-Cl layered double hydroxide has been reported.Mg-Cr-Cl was characterized by X-ray powder diffraction,Fourier-transform infrared,thermo-gravimetric analysis,differential thermal analysis,and scanning electron microscope.Adsorption experiments were carried out in batch mode as a function of adsorption dosages,contact time,pH,and initial fluoride concentration to get optimum adsorption capacity.The adsorption kinetic study showed that the adsorption process followed first order kinetics.The fluoride removal was 88.5% and 77.4% at pH 7 with an adsorbent dose of 0.6 g/100 mL solution and initial fluoride concentration of 10 mg/L and 100 mg/L,respectively.The equilibrium was established at 40 min.Adsorption experiment data were fitted well with Langmuir isotherm with R 2 = 0.9924.Thermodynamic constants were also measured and concluded that the adsorption process was spontaneous and endothermic in nature.The removal percentage decreased slowly with increasing pH.This process is suitable for industrial effluents.The regeneration of the material is not possible.     

A comparative study and evaluation of sulfamethoxazole adsorption onto organo-montmorillonites

Three organo-montmorillonites were prepared using surfactants, and their adsorption behaviors toward sulfamethoxazole（SMX） were investigated. The surfactants used were cetyltrimethyl ammonium bromide（CTMAB）, 3-（N,N-dimethylhexadecylammonio） propane sulfonate（HDAPS） and 1,3-bis（hexadecyldimethylammonio）-propane dibromide（BHDAP）. The properties of the organo-montmorillonites were characterized by X-ray diffraction, scanning electron microscopy and N2adsorption–desorption isotherm measurements. Results showed that the interlayer spacing of montmorillonite was increased and the surface area as well as the morphology were changed. Batch adsorption experiments showed that the surfactant loading amount had a great effect on the adsorption of SMX. The adsorption process was p H dependent and the maximum adsorption capacity was obtained at p H 3 for HDAPS-Mt, while CTMAB-Mt and BHDAP-Mt showed a high removal efficiency at 3–11. The adsorption capacity increased with the initial SMX concentration and contact time but decreased with increasing solution ionic strength.Kinetic data were best described by the pseudo second-order model. Equilibrium data were best represented by the Langmuir model, and the Freundlich constant（n） indicated a favorable adsorption process. The maximum adsorption capacity of SMX was 235.29 mg/g for CTMAB-Mt, 155.28 mg/g for HDAPS-Mt and 242.72 mg/g for BHDAP-Mt. Thermodynamic parameters were calculated to evaluate the spontaneity and endothermic or exothermic nature. The adsorption mechanism was found to be dominated by electrostatic interaction,while hydrophobic interaction played a secondary role.     

Adsorption of dyes onto activated carbon prepared from olive stones

Activated carbon was produced from olive stones（OSAC） by a physical process in two steps. The adsorption character of this activated carbon was tested on three colour dyes molecules in aqueous solution： Methylene blue（MB）, Rhodamine B（RB） and Congo Red（CR）. The adsorption equilibrium was studied through isotherms construction at 30℃, which were well described by Langmuir model. The adsorption capacity on the OSAC was estimated to be 303 mg/g, 217 mg/g and 167 mg/g respectively for MB, RB and CR. This activated carbon has a similar adsorption properties to that of commercial ones and show the same adsorption performances. The adsorption kinetics of the MB molecule in aqueous solution at different initial concentrations by OSAC was also studied. Kinetic experiments were well fitted by a simple intra-particle diffusion model. The measured kinetics constant was influenced by the initial concentration and we found the following correlation： Kid = 1.55 C0^0.51.     

Influence of moderate pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing activated carbon

A novel adsorbent based on iron oxide dispersed over activated carbon(AC) were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing AC were determined. Two series of ACs, non-oxidized and oxidized carbon modified by iron(denoted as AC-Fe and AC/OFe), resulted in a maximum impregnated iron of 4.03% and 7.56%, respectively. AC/O-Fe showed 34.0%–46.6% higher phosphate removal efficiency than the AC-Fe did. This was first attributed to the moderate pre-oxidation of raw AC by nitric acid, achieved by dosing Fe(II) after a pre-oxidation, to obtain higher iron loading, which is favorable for phosphate adsorption. Additionally, the in-situ formed active site on the surface of carbon, which was derived from the oxidation of Fe(II) by nitric acid dominated the remarkably high efficiency with respect to the removal of phosphate. The activation energy for adsorption was calculated to be 10.53 and 18.88 kJ/mol for AC-Fe and AC/OFe, respectively. The results showed that the surface mass transfer and intra-particle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.     

Ammonium sulfide-assisted hydrothermal activation of palygorskite for enhanced adsorption of methyl violet

Herein,palygorskite(PAL)was activated via a simple hydrothermal process in the presence of ammonium sulfide,and the effects of activation on the microstructure,physico-chemical feature and adsorption behaviors of PAL were intensively investigated.The hydrothermal process evidently improved the dispersion of PAL crystal bundles,increased surface negative charges and built more active –Si–O-groups served as the new"adsorption sites".The adsorption property of the activated PAL for Methyl Violet(MV)was systematically investigated by optimizing the adsorption variables,including p H,ionic strength,contact time and initial MV concentration.The activated PAL exhibited a superior adsorption capability to the raw PAL for the removal of MV(from 156.05 to 218.11 mg/g).The kinetics for MV adsorption followed pseudo second-order kinetic models,while the isotherm and thermodynamics results showed that the adsorption pattern well followed the Langmuir model.The structure analysis of PAL before and after adsorption demonstrated that electrostatic interaction and chemical association of –X–O-are the prominent driving forces for the adsorption process.     

Phosphate removal from domestic wastewater using thermally modified steel slag

This study was performed to investigate the removal of phosphate from domestic wastewater using a modified steel slag as the adsorbent. The adsorption effects of alkalinity, salt, water,and thermal modification were investigated. The results showed that thermal activation at 800℃ for 1 hr was the optimum operation to improve the adsorption capacity. The adsorption process of the thermally modified slag was well described by the Elovich kinetic model and the Langmuir isotherm model. The maximum adsorption capacity calculated from the Langmuir model reached 13.62 mg/g. Scanning electron microscopy indicated that the surface of the modified slag was cracked and that the texture became loose after heating. The surface area and pore volume did not change after thermal modification. In the treatment of domestic wastewater, the modified slag bed(35.5 kg) removed phosphate effectively and operated for 158 days until the effluent P rose above the limit concentration of 0.5 mg/L. The phosphate fractionation method, which is often applied in soil research, was used to analyze the phosphate adsorption behavior in the slag bed. The analysis revealed that the total contents of various Ca–P forms accounted for 81.4%–91.1%, i.e., Ca10–P 50.6%–65.1%, Ca8–P 17.8%–25.0%,and Ca2–P 4.66%–9.20%. The forms of Al–P, Fe–P, and O–P accounted for only 8.9%–18.6%. The formation of Ca10–P precipitates was considered to be the main mechanism of phosphate removal in the thermally modified slag bed.     

臭氧/沸石工艺处理水中硝基苯的机理探讨

考察了臭氧在H型沸石上吸附与分解情况,发现臭氧在H型沸石上发生了吸附与分解,并且吸附过程与脱附过程是不可逆的,其脱附速率很快.在吸附分解平衡后,臭氧在H型沸石上的吸附分解量与进水臭氧浓度成正比.而在1×10^-3 mol/L Na⁺存在条件下,被Na⁺交换的H型沸石基本不吸附分解臭氧.考察不同阳离子和不同型号沸石对臭氧/沸石工艺去除硝基苯的影响,发现Ca²⁺的影响最大,另外Na型沸石和NH₄型沸石在降解硝基苯的过程中,硝基苯的去除效率逐渐提高,并且Na型沸石中的Na⁺发生溶出,表明盐析效应影响臭氧扩散进入沸石孔道进行自分解和催化分解的能力.脱铝后的H型沸石没有体现降解硝基苯的效果.最后在pH 3.0时,H型沸石也能吸附分解一部分臭氧,说明H⁺的影响不如其它阳离子.     

NaCl改性沸石对水中氨氮的吸附机制

通过颗粒强度测定、扫描电镜分析（SEM）、X射线能谱分析（EDS）和零电点测定（pHPZC）考察改性前后沸石表面特性的变化,考察pH值、沸石投加量、初始氨氮浓度以及温度对吸附过程的影响,并通过吸附等温式和吸附动力学对吸附机制进行描述.经过NaCl改性后的沸石的颗粒强度明显增大,表面更加粗糙,孔径增大,钠离子通过交换作用进入到沸石内部.pH值为7,沸石投加量为8g/L,温度为35℃时吸附效果最好,平衡吸附量（qe）与氨氮初始浓度呈正相关性.Langmuir等温线比Freundlich等温线更适合描述实验数据,最大饱和吸附量为13.210mg/g.吸附动力学符合准二级动力学模型.实验表明NaCl改性沸石能够有效去除水中的氨氮.     

改性人造沸石处理含黄玉铬洁(Ⅵ张焕)祯地下水的实验研究

为了提高人造沸石对地下水中铬(Ⅵ)的去除能力,采用氯化铝对人造沸石进行改性。确定最佳改性条件:20%氯化铝溶液,液固比12 mL/g,室温下以180 r/min振荡改性8 h;最佳除Cr(Ⅵ)条件:pH值为4～8,液固比为33.3 mL/g,室温下水浴恒温振荡2 h。改性沸石对铬(Ⅵ)的吸附符合Langmuir及Freundlich等温线方程,由Langmuir吸附等温线可得其吸附容量为5.624 mg/g。在最佳反应条件下,水样中铬(Ⅵ)浓度可由5 mg/L下降到0.026 mg/L,低于0.05 mg/L,满足GB/T 14848—93《地下水环境质量标准》Ⅲ类标准。     

载镁活化天然沸石处理高氟水实验研究

为了提高沸石对氟的吸附能力,采用氯化镁对活化天然沸石进行改性,分析了除氟剂的性能,确定了除氟剂改性的最佳条件:10%氯化镁溶液,固液比1∶4,pH=7.0,室温以300 r/min的速度振荡改性3h。最佳除氟条件:pH=7.0,室温以300 r/min的速度搅拌反应1.5 h。吸附剂对F-的吸附过程符合Langmuir及Freundlich等温线方程,由D-R模型拟合可知,除氟剂对氟的吸附为物理吸附过程。在最佳反应条件下,水样中氟浓度由2 mg/L降低到0.78 mg/L,符合GB5949-2006《生活饮用水卫生标准》(≤1 mg/L)。     

沸石的改性及其对氨氮吸附特征

为研究不同改性方法及其组合顺序对天然沸石吸附NH₄+效率的影响及其吸附特征,选择盐、高温、酸3种改性方法进行不同组合. 结果显示,改性组合顺序对天然沸石的吸附性能影响较明显,最佳改性组合顺序为“盐+酸+高温”,其改性后的沸石在初始ρ(NH₄+)为15、30和50 mg/L下对NH₄+的去除率分别为87%、92%和94%. 采用Langmuir和Freundlich 2种方程来拟合“盐+酸+高温”改性后沸石的吸附行为,表明其更符合Langmuir模型,R2为0.998 5,其最大吸附量(q_max)为8.23 mg/g,并且其吸附过程符合一级动力学方程, R 2为0.998 1. 扫描电子显微镜(SEM)和比表面积(BET)分析结果表明,沸石经最优组合改性后表面形态明显变化,比表面积增大.      

生物絮凝剂与改性沸石复配处理猪场废水厌氧消化液的响应面优化

采用响应面分析法(RSM)对红平红球菌所产发酵液与聚合氯化铝(PAC)复配处理高岭土悬浊液及发酵液与改性沸石复配处理猪场废水厌氧消化液的过程进行了优化.设定的响应值分别为絮凝率和絮体粒径,COD和氨氮去除率.实验分别拟合了关于絮凝率,絮体粒径,COD去除率和氨氮去除率的二次模型,决定系数(R2)分别为0.8933,0.8353,0.7819和0.8343,表明拟合情况良好.根据响应值的分布情况,确定高岭土悬浊液的最佳絮凝条件为发酵液3.7mL/L,PAC 49mg/L,pH值8.7,CaCl224mg/L, 反应时间15min,相应絮凝率和絮体粒径分别为96.3%和0.67mm;猪场废水厌氧消化液的最佳絮凝条件为发酵液4.5mL/L,改性沸石12g/L,pH值8.3,CaCl216mg/L,反应时间55min,相应COD,氨氮去除率分别为87.9%和86.9%.     

氧化铁改性沸石对Se(Ⅳ)的吸附性能及试验废物再利用研究

为解决天然沸石去除废水中Se（Ⅳ）能力低的问题,采用氯化铁对天然沸石进行改性,制备表面负载氧化铁的改性沸石,即氧化铁改性沸石,并将其应用于去除水体中Se（Ⅳ）.首先对比天然沸石和氧化铁改性沸石的结构特征,研究二者对Se（Ⅳ）溶液的吸附特性,并通过X射线荧光光谱（XRF）、X射线衍射图谱（XRD）、扫描电镜（SEM）和氮气吸附孔径分布测试（BET）对二者进行表征;其次进行吸附试验,考虑接触时间、pH、吸附剂投加量、初始溶液反应浓度的影响,并通过天然沸石和氧化铁改性沸石的吸附动力学及吸附等温线对吸附的机理进行阐述.结果表明:①氧化铁改性沸石表面形成细碎的球状颗粒,分布在沸石的表面.②氧化铁改性沸石能够高效地吸附水体中的Se（Ⅳ）,且在pH为3时吸附效率最高,其对Se（Ⅳ）溶液的去除率最高达97.7%,其理论最大吸附量为46.901 mg/g.③氧化铁改性沸石对Se（Ⅳ）的吸附过程符合准二级动力学模型和Langmuir等温吸附模型.④添加负载Se（Ⅳ）后的氧化铁改性沸石土壤均达到富硒土壤标准（>0.4 mg/kg）.研究显示,氧化铁改性沸石吸附Se（Ⅳ）的效果较好,显著优于天然沸石的吸附效果,且吸附Se（Ⅳ）废水后的废弃氧化铁改性沸石还可应用于土壤改良方向.      

稻壳基A型沸石的表征及其对NH_3-N的吸/脱附动力学研究

以稻壳的煅烧灰分为原料,采用水热合成法制得稻壳沸石,运用SEM、XRD和FTIR表征了稻壳沸石的结构特性,并通过静态平衡吸附实验研究了稻壳沸石对NH3-N的吸附特性。结果表明:实验条件下可获得结晶度高、晶型较好的A型单晶沸石,降低晶化温度有利于A型沸石的生成。初始浓度为25,50,100 mg/L时稻壳沸石的最大吸附量分别为3.36,5.16,8.39 mg/g,吸附过程遵循伪二级吸附动力学模型。碱当量MNa OH/AN对NH3-N从稻壳沸石上的脱附影响较大,MNaOH/AN为0.85、8.47和42.4时伪二级模型拟合的饱和脱附值分别为7.46,16.21,19.96 mg/g,与实测值基本接近,NH3-N从稻壳沸石上的脱附主要受化学作用控制,过程遵循伪二级脱附动力学模型。     

改性沸石对焦化废水中COD的去除研究

本文研究了沸石经NaCl、NaOH、HDTMA（溴化十六烷基三甲胺）改性后对焦化废水中的COD的去除效果。比较得出HDTMA改性沸石对COD的去除能力较好．而且废水的色度明显减小。接着进一步研究了该废水处理过程中的影响因素，包括吸附时间、烘干温度、改性剂HDTMA的浓度、pH值等。结果表明，HDTMA改性沸石处理焦化废水可使其COD的浓度降低至150mg／L以下，达到污水综合排放二级标准。     

天然沸石吸附低浓度氨氮废水的研究

采用浙江某地天然沸石吸附废水中低浓度氨氮,研究了pH、天然沸石投加量对吸附的影响,分析了吸附等温线和吸附动力学,并进行了动态吸附和脱附研究。结果表明,pH对天然沸石吸附有较大影响,吸附的最佳pH为8.0;随着天然沸石投加量的增加,氨氮的去除率逐渐增大,但吸附量随之减小。Freundlich方程比Langmuir方程更好地描述氨氮在天然沸石上的吸附行为,且此吸附是优惠吸附。假二级方程很好地拟合吸附动力学实验数据,吸附速率常数k2随着天然沸石投加量的增大而增大。装填105g天然沸石吸附柱处理含氨氮20mg/L废水的水量为15L,出水氨氮浓度小于5mg/L。用含氯化钠和氢氧化钠的溶液作为脱附剂,脱附率为95.5%。