Development of metal organic fromwork-199 immobilized zeolite foam for adsorption of common indoor VOCs

Reticulated foam shaped adsorbents are more efficient for the removal of volatile organic compounds(VOCs),particularly from low VOC-concentration indoor air streams. In this study composite structure of zeolite and metal organic frameworks(MOFs),referred as ZMF,has been fabricated by immobilization of fine MOF-199 powder on foam shaped Zeolite Socony Mobil-5(ZSM-5)Zeolitic structure,referred as ZF. The ZMF possess a uniform and well-dispersed coating of MOF-199 on the porous framework of ZF. It shows higher surface area,pore volume,and VOCs adsorption capacity,as compared to ZF-structure.Post-fabrication changes in selective adsorption properties of ZMF were studied with three common indoor VOCs(benzene,n-hexane,and cyclohexane),using gravimetric adsorption technique. The adsorption capacity of ZMF with different VOCs follow the order of benzene n-hexane cyclohexane. In comparison with MOF-199 and ZF,the composite structure ZMF shows improvement in selectivity for benzene from other two VOCs. Further,improvement in efficiency and stability of prepared ZMF was found to be associated with its high MOF loading capacity and unique morphological and structural properties. The developed composite structure with improved VOCs removal and recyclability could be a promising material for small to limited scale air pollution treatment units.     

Removal of Cs from water and soil by ammonium-pillared montmorillonite/Fe3O4 composite

To remove cesium ions from water and soil, a novel adsorbent was synthesized by following a one-step co-precipitation method and using non-toxic raw materials. By combining ammonium-pillared montmorillonite (MMT) and magnetic nanoparticles (Fe₃O₄), an MMT/Fe₃O₄ composite was prepared and characterized. The adsorbent exhibited high selectivity of Cs⁺ and could be rapidly separated from the mixed solution under an external magnetic field. Above all, the adsorbent had high removal efficiency in cesium-contaminated samples (water and soil) and also showed good recycling performance, indicating that the MMT/Fe₃O₄ composite could be widely applied to the remediation of cesium-contaminated environments. It was observed that the pH, solid/liquid ratio and initial concentration affected adsorption capacity. In the presence of coexisting ions, the adsorption capacity decreased in the order of Ca^2 + > Mg^2 + > K⁺ > Na⁺, which is consistent with our theoretical prediction. The adsorption behavior of this new adsorbent could be expressed by the pseudo-second-order model and Freundlich isotherm. In addition, the adsorption mechanism of Cs⁺ was NH₄⁺ ion exchange and surface hydroxyl group coordination, with the former being more predominant.     

新型多孔材料MOF-199脱除噻吩硫化物

采用水热法合成新型多孔材料MOF-199,利用XRD、77K下N2吸附等温线和SEM表征其结构.运用固定床吸附穿透曲线考察了模型燃油类型对MOF-199吸附分离噻吩的影响.结果表明,MOF-199在脂肪和芳香模型油中的饱和吸附容量分别为1.96wt%和1.85wt%,超过相关文献报道.MOF-199在含溶解水和纯混合模型油中噻吩硫的饱和吸附容量分别为2.15wt%和1.62wt%,脱硫吸附容量降低了25%. 运用活性炭分层填装吸附柱技术可使MOF-199饱和吸附容量达到2.12wt%.     

Reversibly enhanced aqueous solubilization of volatile organic compounds using a redox-reversible surfactant

Surfactant-enhanced remediation (SER) is an effective method for the removal of volatile organic compounds (VOCs) from contaminated soils and groundwater. To reuse the surfactant the VOCs must be separated from the surfactant solutions. The water solubility of VOCs can be enhanced using reversible surfactants with a redox-acive group, (ferrocenylmethyl)dodecyldimethylammonium bromide (Fcl2) and (ferrocenylmethyl)tetradecanedimethylammonium bromide (Fcl4), above and below their critical micelle concentrations (CMC) under reducing (I⁺) and oxidative (I²⁺) conditions. The CMC values of Fcl2 and Fcl4 in I⁺ are 0.94 and 0.56 mmol/L and the solubilization of toluene by Fcl2 and Fcl4 in I⁺ for toluene is higher than the solubilization achieved with sodium dodecyl sulfate, cetyltrimethylammonium bromide and Trition X-114. The solubilization capacity of the ferrocenyl surfactants for each tested VOCs ranked as follows: ethylbenzene > toluene > benzene. The solubilities of VOCs by reversible surfactant in I⁺ were 30% higher than those in I²⁺ at comparable surfactant concentrations. The effects of Fcl4 concentrations on VOCs removal efficiency were as follows: benzene > toluene > ethylbenzene. However, an improved removal efficiency was achieved at low ferrocenyl surfactant concentrations. Furthermore, the reversible surfactant could be recycled through chemical approaches to remove organic pollutants, which could significantly reduce the operating costs of SER technology.     

硅藻土复合材料净化室内空气的实验研究

利用硅藻土复合材料对室内空气中三种主要污染物甲醛、氨和苯进行了净化研究,比较了普通硅藻土和硅藻土复合材料对三种污染物的去除效果。测试了硅藻土复合材料的平衡吸附量,及其在空气流速、净化时间和吸附剂量条件下对污染物去除率的影响。结果表明:硅藻土复合材料的净化性能优于普通硅藻土,对甲醛、氨和苯的平衡吸附量分别为132μg/g、95μg/g和87μg/g,最佳去除率分别为67%、91%和53%,吸附剂量在一定范围内改变对硅藻土复合材料的净化效率影响不大,而空气流速和净化时间存在最佳值。     

金属有机框架ZIF-8/聚二乙烯基苯纳米复合材料的合成及其吸附VOCs的性能

在常温常压下的甲醇溶液体系中,将COOH功能化的介孔材料聚二乙烯基苯(PDVB)与微孔材料金属有机框架(MOFs)ZIF-8进行复合,获得了一种新型的多孔纳米复合材料ZIF-8/PDVB,采用XRD、FTIR、SEM和氮气吸附-脱附等方法对ZIF-8/PDVB进行表征,并考察了其吸附甲苯、乙酸乙酯的性能.XRD谱图表明,所合成的ZIF-8以晶体形式存在;FTIR和XRD的结果表明,ZIF-8与PDVB的复合是通过Zn2+与PDVB上的COOH形成配位,未配位饱和的Zn~(2+)再与2-甲基咪唑进行配位,从而形成纳米复合材料ZIF-8/PDVB;SEM结果显示,ZIF-8晶体分散在PDVB的表面上;氮气吸附-脱附表征结果显示,ZIF-8/PDVB的比表面积达到1301 m~2·g~(-1),材料同时具有介孔与微孔结构.吸附性能评价结果表明,ZIF-8/PDVB对甲苯、乙酸乙酯均具有优良的吸附性能,ZIF-8/PDVB在吸附VOCs性能上显示出潜在的巨大优势.     

北京某小学室内外VOC浓度及有毒害物种识别

采用美国EPA推荐的TO14/15方法定量分析了北京市某小学室内外夏季观测的空气样品,得到82种挥发性有机物（VOCs）的浓度水平及组成特征,对其中可能危害儿童健康的有毒有害物质进行了识别.结果表明,室内总VOCs浓度高于室外,烷烃是含量最丰富物种,平均占室内外空气中定量VOCs总浓度的32.8%.室内外VOCs组成相似,异戊烷、苯、甲苯、丙醛、丙烯和二氯甲烷为浓度优势物种,受到室外源的影响较大,室内的对二氯苯、环己烷及间二氯苯较为特征,前2种物质室内/室外浓度比例平均值分别为65.8和10.5,间二氯苯室内平均浓度为2.02×10^-9（体积分数）,而室外浓度低于检测限,这3种物质可能来自室内源. 1, 3-丁二烯、氯乙烯、苯和氯甲烷4种物质在学校室内、室外及儿童家中都超过1×10^-6的癌症风险值,平均风险值分别为1.3×10^-5、 6.4×10^-6、 5.1×10^-6和3.3×10^-6,小学室外、室内及儿童家中的累积癌症风险超过1×10^-6的癌症风险值24～39倍.丙烯醛未确认具有致癌性,但具有毒有害性,在室内外及儿童家中超过基准浓度13～72倍.     

Fluoride removal by Al, Ti, and Fe hydroxides and coexisting ion effect

Batch experiments were conducted to evaluate fluoride removal by Al,Fe,and Ti-based coagulants and adsorbents,as well as the effects of coexisting ions and formation of aluminum–fluoride complexes on fluoride removal by co-precipitation with alum(Al_2(SO_4)_3·18H_2O).Aluminum sulfate was more efficient than the other coagulants for fluoride removal in the pH range between 6 and 8.Nano-crystalline TiO_2 was more effective for fluoride removal than Al and Fe hydroxides in a pH range of 3–5.Coexisting anions in water decreased the removal of fluoride in the order:phosphate(2.5 mg/L) arsenate(0.1 mg/L) bicarbonate(200 mg/L) sulfate(100 mg/L) = nitrate(100 mg/L) silicate(10 mg/L) at a pH of 6.0.The effect of silicate became more significant at pH 7.0.Calcium and magnesium improved the removal of fluoride.Zeta-potential measurements determined that the adsorption of fluoride shifted the PZC of Al(OH)_3 precipitates from 8.9 to 8.4,indicating the chemical adsorption of fluoride at the surface.The presence of fluoride in solution significantly increased the soluble aluminum concentration at pH 6.5.A Visual MINTEQ modeling study indicated that the increased aluminum solubility was caused by the formation of AlF~(2+),AlF~(+2),and AlF_3complexes.The AlF_x complexes decreased the removal of fluoride during co-precipitation with aluminum sulfate.     

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes

Iron oxide(FeO)coated by natural organic matter(NOM)is ubiquitous.The associations of minerals with organic matter(OM)significantly changes their surface properties and reactivity,and thus affect the environmental fate of pollutants,including nutrients(e.g.,phosphorus(P)).In this study,ferrihydrite/goethite-humic acid(FH/GE–HA)complexes were prepared and their adsorption characteristics on P at various p H and ionic strength were investigated.The results indicated that the Fe O–OM complexes showed a decreased P adsorption capacity in comparison with bare Fe O.The maximum adsorption capacity(Q_(max))decreased in the order of FH(22.17 mg/g)FH-HA(5.43 mg/g)GE(4.67 mg/g)GE-HA(3.27 mg/g).After coating with HA,the amorphous FH–HA complex still showed higher P adsorption than the crystalline GE–HA complex.The decreased P adsorption observed might be attributed to changes of the Fe O surface charges caused by OM association.The dependence of P adsorption on the specific surface area of adsorbents suggests that the Fe O component in the complexes is still the main contributor for the adsorption surfaces.The P adsorptions on Fe O–HA complexes decreased with increasing initial p H or decreasing initial ionic strength.A strong dependence of P adsorption on ionic strength and p H may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the Fe O component and P.Therefore,previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils,especially in humic-rich areas.     

Breakthrough CO2 adsorption in bio-based activated carbons

In this work, the effects of different methods of activation on CO₂ adsorption performance of activated carbon were studied. Activated carbons were prepared from biochar, obtained from fast pyrolysis of white wood, using three different activation methods of steam activation, CO₂ activation and Potassium hydroxide (KOH) activation. CO₂ adsorption behavior of the produced activated carbons was studied in a fixed-bed reactor set-up at atmospheric pressure, temperature range of 25–65°C and inlet CO₂ concentration range of 10–30 mol% in He to determine the effects of the surface area, porosity and surface chemistry on adsorption capacity of the samples. Characterization of the micropore and mesopore texture was carried out using N₂ and CO₂ adsorption at 77 and 273 K, respectively. Central composite design was used to evaluate the combined effects of temperature and concentration of CO₂ on the adsorption behavior of the adsorbents. The KOH activated carbon with a total micropore volume of 0.62 cm³/g and surface area of 1400 m²/g had the highest CO₂ adsorption capacity of 1.8 mol/kg due to its microporous structure and high surface area under the optimized experimental conditions of 30 mol% CO₂ and 25°C. The performance of the adsorbents in multi-cyclic adsorption process was also assessed and the adsorption capacity of KOH and CO₂ activated carbons remained remarkably stable after 50 cycles with low temperature (160°C) regeneration.     

Phosphate adsorption performance of a novel filter substrate made from drinking water treatment residuals

Phosphate is one of the most predominant pollutants in natural waters. Laboratory experiments were conducted to investigate the phosphate adsorption performance of a(NFS) made from drinking water treatment residuals. The adsorption of phosphate on the NFS fitted well with the Freundlich isotherm and pseudo second-order kinetic models. At p H 7.0, the maximum adsorption capacity of 1.03 mg/g was achieved at 15°C corresponding to the wastewater temperature in cold months, and increased notably to 1.31 mg/g at 35°C.Under both acidic conditions(part of the adsorption sites was consumed) and basic conditions(negative charges formed on the surface of NFS, which led to a static repulsion of PO43-and HPO42-), the adsorption of phosphate was slightly inhibited. Further study showed that part of the adsorption sites could be recovered by 0.25 mol/L Na OH. The activation energy was calculated to be above 8.0 k J/mol, indicating that the adsorption of phosphate on NFS was probably a chemical process. Considering the strong phosphate adsorption capacity and recoverability, NFS showed great promise on enhancing phosphate removal from the secondary treated wastewater in the filtration process.     

紫外辐照改性生物炭对VOCs的动态吸附

采用365 nm紫外光辐照改性椰壳生物炭,以提升对挥发性有机污染物(VOCs)的吸附性能.选取苯和甲苯两种典型的VOCs为吸附质,考察了改性前后生物炭的吸附穿透曲线.结果表明,紫外辐照改性后的生物炭其吸附性能显著增加,对苯和甲苯的饱和吸附量分别由7.27 mg·g~(-1)和7.98 mg·g~(-1)提升至122.80 mg·g~(-1)和236.36 mg·g~(-1),吸附穿透时间也由1 min和2 min大大延长至390 min和620 min.生物炭表面理化特征分析表明,紫外辐照增大了生物炭表面含氧官能团的含量和外比表面积,这可能是改性生物炭吸附性能提升的关键因素.Yoon-Nelson、Thomas和BDST模型均能很好地模拟改性生物炭对不同浓度苯和甲苯的吸附过程,其相关系数大于0.992.热重分析结果表明,紫外辐射对生物炭的热稳定性影响甚微.改性生物炭吸附饱和后,可经热再生后重复利用,对甲苯的吸附重复利用5次后仍有较高的吸附能力.     

烧结金属催化材料净化印刷工艺中VOCs废气的试验研究

采用以烧结金属粉末微孔过滤材料为吸附材料和催化剂基体、CuMn／γ-Al2O3为催化剂的烧结金属催化净化装置,可实现对VOCs废气的有效去除。实验室试验表明：苯、甲苯和二甲苯的催化转化率均随温度的升高而增加。在250℃以上,甲苯和二甲苯的催化转化率高于99％;在280℃以上,苯的催化转化率高于99％。空速为2．0s^-1时催化荆的催化转化率要较空速为3．0s^-1时高。现场试验表明：在300℃左右,VOCs气体经过由烧结金属催化材料刺成的金属过滤器后,苯、甲苯、二甲苯的去除率均高于99％。经金属过滤器处理后,苯、甲苯、二甲苯的排放浓度可低于北京市《大气污染物综合排放标准》DB11／501—2007中的排放限值排放。     

Insight into the adsorption of tetracycline onto amino and amino–Fe functionalized mesoporous silica: Effect of functionalized groups

In order to study the influences of functionalized groups onto the adsorption of tetracycline (TC), we prepared a series of amino and amino–Fe^3 + complex mesoporous silica adsorbents with diverse content of amino and Fe^3 + groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction, Fourier transform infrared spectrometer and N₂ adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe^3 + groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe^3 + increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe^3 + content increased from 3.93% to 8.26%, the Q_max of the adsorbents increased from 102 to 188 mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications.     

Ultrasound-assistant preparation of Cu-SAPO-34 nanocatalyst for selective catalytic reduction of NO by NH3

The influence of the various preparation methods of Cu-SAPO-34 nanocatalysts on the selective catalytic reduction of NO with NH₃ under excess oxygen was studied. Cu-SAPO-34 nanocatalysts were prepared by using four techniques: conventional impregnation (IM), ultrasound-enhanced impregnation (UIM), conventional deposition precipitation (DP) using NaOH and homogeneous deposition precipitation (HDP) using urea. These catalysts were characterized in detail by various techniques such as N₂-sorption, XRD, TEM, H₂-TPR, NH₃-TPD and XPS to understand the catalyst structure, the nature and the dispersed state of the copper species, and the acid sites for NH₃ adsorption. All of the nanocatalysts showed high activities for NO removal. However, the activities were different and followed the sequence of Cu-SAPO-34 (UIM) > Cu-SAPO-34 (HDP) > Cu-SAPO-34 (IM) > Cu-SAPO-34 (DP). Based on the obtained results, it was concluded that the NO conversion on Cu-SAPO-34 nanocatalysts was mainly related to the high reducibility of the isolated Cu^2 + ions and CuO species, the number of the acid sites and the dispersion of CuO species on SAPO-34.     

Pollution characteristics of polycyclic aromatic hydrocarbons in common used mineral oils and their transformation during oil regeneration

The pollution characteristic of polycyclic aromatic hydrocarbons(PAHs) in common used mineral oils, semi-refined oils, refined oils and solid wastes produced during the used mineral oil regeneration process was analyzed. The results showed that total PAHs content in six common used mineral oils was as follows: used engine oil used quenching oil used casting oil used hydraulic oil used antirust oil used industrial lubricating oil. Furthermore, this order was dependent on the source of PAHs and oil working temperatures. Additionally, total PAHs content in regenerated oils was as follows: semi-refined oil refined oil crude oil, which was related to the catalytic cracking process of crude oil and adsorption refining process of semi-refined oil. The ranking of total PAHs content in regenerated wastes varied depending on the regeneration technology used as follows: waste adsorption sand acid sludge waste clay precipitation sludge cracked residue. In all types of used mineral oils and regenerated wastes, the maximum and minimum proportions of the total PAHs content were composed of 2–3 ring-PAHs and 5–6 ring-PAHs, respectively. The majority of PAHs in the used mineral oils entered into regenerated wastes during regeneration process, while a small number remained in the regenerated oil.     

生物炭降解苯和甲苯混合废气性能研究

该研究以生物炭为过滤介质 ,探讨过滤塔降解气流中苯、甲苯的生物降解性能 .实验表明 ,在总有机负荷低于 3 5 0 g/ (h·m3)、停留时间 1 5～ 90s的实验条件下 ,滤塔对苯和甲苯混合气体有较好的降解性能 ,苯、甲苯的最大削减能力分别为 1 2 0 g/ (h·m3)和 1 5 0 g/ (h·m3) ,甲苯比苯更易被微生物降解 .滤塔中CO2 生成量随苯、甲苯降解量的增加而增加 ,但实验增长速率小于理论增长速率 .菌落分析表明 ,滤塔中微生物主要有真菌、杆菌、芽孢杆菌 ,其中芽孢杆菌为优势菌种 .根据吸附 生物降解机理 ,建立了VOCs去除模型 ,并予以验证 .     

Removal of heavy metals and arsenic from a co-contaminated soil by sieving combined with washing process

Batch experiments were conducted with a heavy metals and arsenic co-contaminated soil from an abandoned mine to evaluate the feasibility of a remediation technology that combines sieving with soil washing.Leaching of the arsenic and heavy metals from the different particle size fractions was found to decrease in the order: 0.1,2–0.1,and 2 mm.With increased contact time,the concentration of heavy metals in the leachate was significantly decreased for small particles,probably because of adsorption by the clay soil component.For the different particle sizes,the removal efficiencies for Pb and Cd were75%–87%,and 61%–77% for Zn and Cu,although the extent of removal was decreased for As and Cr at 45%.The highest efficiency by washing for Pb,Cd,Zn,and As was from the soil particles 2 mm,although good metal removal efficiencies were also achieved in the small particle size fractions.Through SEM-EDS observations and correlation analysis,the leaching regularity of the heavy metals and arsenic was found to be closely related to Fe,Mn,and Ca contents of the soil fractions.The remediation of heavy metal-contaminated soil by sieving combined with soil washing was proven to be efficient,and practical remediation parameters were also recommended.     

Seasonal variations in the concentration and removal of nonylphenol ethoxylates from the wastewater of a sewage treatment plant

In this study, we investigated the occurrence and fate of nonylphenol (NP), nonylphenol monoethoxylate (NP1EO) and nonylphenol diethoxylate (NP2EO) in a full scale sewage treatment plant, which applied an Anaerobic/Oxic process. Concentrations of NP, NP1EO and NP2EO in the wastewater were measured during the period spanning a whole year. The results showed remarkable seasonal variation in the concentrations of the compounds. The NPnEO compounds were most abundant in winter, with the total concentrations of influent NP, NP1EO and NP2EO ranging from 3900 to 7000 ng/L, 4000 to 4800 ng/L and 5200 to 7200 ng/L, respectively. Regarding the total removal efficiencies of the three types of short-chain NPnEO compounds, different trends were exhibited according to different seasons. The average removal efficiency of NP for the different seasons ranked as follows: winter > summer > autumn > spring; NP2EO concentrations decreased as follows: summer > autumn > winter > spring, while NP1EO concentrations reduced according to: spring > summer > autumn > winter. We also investigated the contribution ratio of individual treatment units in the A/O process, with the findings suggesting that the anaerobic treatment unit plays an important role in the elimination of short-chain NPnEOs from the wastewater.     

Adsorption and desorption of SO2, NO and chlorobenzene on activated carbon

Activated carbon (AC) is very effective for multi-pollutant removal; however, the complicated components in flue gas can influence each other''s adsorption. A series of adsorption experiments for multicomponents, including SO₂, NO, chlorobenzene and H₂O, on AC were performed in a fixed-bed reactor. For single-component adsorption, the adsorption amount for chlorobenzene was larger than for SO₂ and NO on the AC. In the multi-component atmosphere, the adsorption amount decreased by 27.6% for chlorobenzene and decreased by 95.6% for NO, whereas it increased by a factor of two for SO₂, demonstrating that a complex atmosphere is unfavorable for chlorobenzene adsorption and inhibits NO adsorption. In contrast, it is very beneficial for SO₂ adsorption. The temperature-programmed desorption (TPD) results indicated that the binding strength between the gas adsorbates and the AC follows the order of SO₂ > chlorobenzene > NO. The adsorption amount is independent of the binding strength. The presence of H₂O enhanced the component effects, while it weakened the binding force between the gas adsorbates and the AC. AC oxygen functional groups were analyzed using TPD and X-ray photoelectron spectroscopy (XPS) measurements. The results reveal the reason why the chlorobenzene adsorption is less affected by the presence of other components. Lactone groups partly transform into carbonyl and quinone groups after chlorobenzene desorption. The chlorobenzene adsorption increases the number of C = O groups, which explains the positive effect of chlorobenzene on SO₂ adsorption and the strong NO adsorption.