柔性MOFs材料Cu(BDC)的氨气吸附及可逆转化性能

氨气（NH₃）作为氮肥合成的主要原料和PM_2.5的重要间接来源,在工业生产倡导绿色循环的大势之下,减排与回收是绿色发展的必行之路。基于吸附法具有氨气无相变,富集得到的氨气可以直接与二氧化碳反应合成氮肥（如尿素）的优势,研究了具有可逆转化性质的柔性MOFs材料Cu（BDC）的氨气吸附性能。实验中通过水热法制备了三维致密结构的Cu（BDC）（DMF）,高温加热脱除DMF后晶体结构发生改变,得到了具有一维孔道结构的Cu（BDC）材料,比表面积为535 m²·g^-1,纯氨气的吸附量在一个大气压下高达18.4 mmol·g^-1,高于传统吸附剂以及其他新型的多孔MOFs和COFs等材料,并且通过减压和加热,材料可以逐步实现再生,具有优良的“载氨”特性。直接制备的Cu（BDC）（DMF）也可以在氨气的环境中（DMF被NH₃替代）转变为Cu（BDC）（NH₃）₂,省去了制备Cu（BDC）的过程。     

氧化铝改性污泥生物炭粒制备及其对Pb(Ⅱ)的吸附特性

为拓展城市剩余污泥资源化利用途径,本文以剩余污泥球粒为原料在高温限氧条件下制备污泥生物炭粒（SBC）,同时以氢氧化铝溶胶为前体浸渍污泥球粒后在500℃下热解获得氧化铝改性污泥生物炭粒（SBC-Al）。使用BET、XRD、FTIR和SEM对生物炭粒进行了表征,并研究了生物炭粒改性前后对Pb(Ⅱ)的吸附特征及效果。结果表明：SBC-Al比表面积和总孔容分别达到83.266m²/g和0.158cm³/g,相比于SBC分别增大了142.42%和167.80%;XRD显示氢氧化铝溶胶浸渍使SBC-Al表面负载了γ-Al₂O₃粒子,FTIR红外谱图说明氧化铝改性可能会增加炭粒表面官能团数量,同时SEM显示出SBC-Al表面相较于SBC具有更多的层片状结构,从而增加生物炭粒的吸附性能。Pb(Ⅱ)的吸附动力学符合二级动力学方程和Elovich方程,同时用二阶段颗粒内扩散模型可以较好地拟合。吸附等温线以Freundlich模型为主,且SBC和SBC-Al对低浓度（＜50mg/L）Pb(Ⅱ)的去除率均较高,分别在95%和99%以上,实测最大吸附量可分别达626.73mg/g和663.97mg/g,但SBC-Al提高了对更高浓度（50～100mg/L）Pb(Ⅱ)的去除率。热力学计算数据表明吸附过程为吸热反应;脱附解吸试验说明,生物炭粒具有良好的循环再生利用性能。     

球磨时间对机械化学法NaBr改性飞灰脱汞性能的影响

采用全方位行星式球磨机对燃煤飞灰进行机械化学改性。在固定床反应装置上探究了球磨时间对改性飞灰脱汞性能的影响,并对飞灰改性前后的理化特性和脱汞机理进行了分析。结果表明,在单一机械球磨改性条件下,飞灰的脱汞效率随着球磨时间的增加出现先升高后降低的趋势。这是由于球磨过程中飞灰粒径变小,非晶相程度增加,Hg⁰与飞灰样品接触面积增加,有利于Hg⁰的脱除;但过长的球磨时间会造成飞灰孔隙结构的破坏并发生细微颗粒的团聚,使比表面积降低,不利于Hg⁰的脱除。机械球磨条件下添加改性剂NaBr后,飞灰的脱汞效率显著提升,并随着球磨时间的增加而单调增加,这是由于在机械球磨与NaBr的共同作用下,在飞灰表面产生了较多的羰基、羧基/酯基等活性官能团,同时生成C-Br共价基团,促进Hg⁰的吸附脱除。原始飞灰和单一机械化学改性飞灰对Hg⁰的脱除主要以吸附为主,氧化作用占比较少,约为吸附作用的1/3。机械化学NaBr改性飞灰对Hg⁰的吸附能力和氧化能力均显著提升,且吸附作用和氧化作用占比相当。     

直接空气捕集CO2吸附剂综述

综述直接空气捕集CO₂吸附剂的研究进展,对比碱/碱土金属基吸附剂、金属有机框架吸附剂、负载胺基吸附剂、变湿吸附剂的优缺点,从吸附容量与胺效率、动力学与载体选择、再生方式与能耗、热稳定性与抗降解等方面对吸附剂性能进行评估. 简要叙述相关工程示范项目和技术经济性;总结研究中存在的问题,展望未来的研究方向.     

Adsorption behavior of uranyl ions onto amino-type adsorbents prepared by radiation-induced graft copolymerization

Amino-type adsorbents(ATAs) were prepared by radiation-induced graft copolymerization of 4-hydroxybutyl acry late glycidyl ether(HB) onto a polyethylene-coated polypropylene(PE/PP) duplex fiber of a non-woven fabric,and modified with different amines of ethylenediamine(EDA),diethylenetriamine(DETA),triethylenetetramine(TETA) and diethylamine(DEA).The adsorption behavior of uranyl ions onto the ATAs was studied in batch experiments.The effects of the contact time,initial concentration of the ions,temperature,and pH value.The salinity were investigated along with the adsorption kinetics and the adsorption isotherms.The kinetic experimental data followed the pseudo second-order kinetic model,and the adsorption isotherms correlated well with the Langmuir model.The ATAs showed good efficiency in adsorbing uranyl ions,with the best saturation adsorption capacity being 64.26 mg g~(-1) for ATA-DETA within 120 min.The temperature dependence of ATADETA was quite abnormal and the quickest behavior was obtained at 25 ℃.ATAs showed good adsorption capacity over a wide pH range of 4.0-8.5,and HCl could be used in the elution process.Salinity of the solution had great effect on the adsorption capacity,3.5%salinity resulted in a 55%loss of capacity from ATA-DETA.The selectivity of ATA-DETA showed an order of:UO_2~(2+)≈Fe~(3+) Zn~(2+) VO_3~- Co~(2+) Ni~(2+).     

Removal of Lead Ions from Aqueous Solutions by Different Types of Industrial Waste Materials: Equilibrium and Kinetic Studies

Abstract

A comparative study of the adsorbents prepared from several industrial wastes for the removal of Pb²⁺ has been carried out. Fertilizer industry waste viz. carbon slurry and steel plant wastes viz. blast furnace (B.F.) slag, dust, and sludge were investigated as low‐cost adsorbents after proper treatment in the present study. The adsorption of Pb²⁺ on different adsorbents has been found in the order: B.F. sludge>B.F. dust>B.F. slag>carbonaceous adsorbent. The least adsorption of Pb²⁺ on carbonaceous adsorbent even having high porosity and consequently greater surface area as compared to other three adsorbents, indicates that surface area and porosity are not important factors for Pb²⁺ removal from aqueous solutions. The adsorption of Pb²⁺ has been studied as a function of contact time, concentration, and temperature. The adsorption has been found to be exothermic, and the data conform to the Langmuir equation. The kinetic results reveal that the present adsorption system follows Lagergren's first order rate equation. Since all three waste products from the steel industry show higher potential to remove lead from water, therefore, it is suggested that these metallurgical wastes can be fruitfully employed as low‐cost adsorbents for effluent treatment containing toxic metal ions.     

Synthesis,characterization, and amidoximation of diaminomaleodinitrile-functionalized polyethylene terephthalate grafts for collecting heavy metals from wastewater

Synthesis, characterization, and amidoximation of diaminomaleodinitrile-functionalized polyethylene terephthalate (PET) grafts were studied. Azobisisobutyronitrile (AIBN) was used as an initiator. Optimum conditions for grafting were as follows: monomer concentration [DAMN] = 0.5M, [AIBN] = 1.50 × 10⁻³ mol/L, T = 80°C and t = 3 h. Water uptake of the grafted-PET film increased with the increase of grafting yield. The imparted cyano group of the grafted polymer chains (with degree of grafting up to 83%) was converted into amidoxime group by reaction with hydroxylamine. The unique advantage of this polymer is that it contains double amidoxime groups per repeating unit and an additional diethylene spacer unit between neighboring amidoxime groups in each monomeric unit. The grafted-PET films were characterized by FTIR spectroscopy, differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA). The grafted-PET films are more thermally stable than the ungrafted-PET membrane, since the grafted membrane showed a single degradation pattern despite having two components. A decrease in T_g values is observed as the grafting yield of copolymers increases indicating the incorporation of polydiaminomaleodinitrile chains in amorphous copolymers with higher thermal stability. The prepared amidoximated DAMN83-g-PET was investigated for its properties in removing heavy toxic metals, such as Pb²⁺, Cd²⁺, Zn²⁺, Fe²⁺, Cu²⁺, Ni²⁺, Co²⁺, and Ag¹⁺ from waste water. The amidoximated-film is characterized by a considerably greater binding ability with respect to heavy metals. The nature of the metal ion also has great importance in the amount binding to the polymeric material. The kinetics of the sorption/desorption process for Co²⁺, Ni²⁺, and Zn²⁺ are investigated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of Grain Size of AgNO3 Loaded in Porous Material on Adsorption of CH3I

In the development of a new chemical decontamination method which provides a high decontamination effect, less corrosion of base metal, and less radioactive waste generation, we developed a decomposition method for oxalic acid coexisting with hydrazine to decrease the amount of radioactive waste.

Using a catalyst of 0.5 wt% Ru supported by activated carbon grains, we decomposed oxalic acid and hydrazine, simultaneously and efficiently, with a stoichiometric concentration of H₂O₂2. The decomposition ratios were decreased by the deposition of oxides. But even if the simulated reducing agent solution with high concentrations of coexisting Fe and K ions, which negatively effect decomposition ratio, was decomposed, the decomposition ratios of oxalic acid and hydrazine were kept high during decomposition of the amount of reducing agent used in actual chemical decontamination.

Additionally, we examined the deposition ratios of metal ions on the catalyst as metal oxides. These results indicated about 2% of the radioactive species which were removed by the chemical decontamination were deposited on the catalyst column. ⁵⁹Fe and ⁵¹Cr were estimated to be about 90% of the total deposited amount of radioactive species and about 60% of the dose equivalent in the model calculation. But this problem should be easily dealt with by using shielding.     

Removal of Tritiated Water Vapor by Adsorption

Abstract

Experiments were conducted on the dynamic adsorption of tritiated water vapor, using a column packed with either silica-gel, activated alumina, or molecular sieve 5A. The column was 4 mm I.D. and 5–30 cm long. The runs were performed at 30°–70°C. Tritiated water vapor (HTO) was loaded into the column with a concentration of 170 μμCi/ml, either in pulses of predetermined duration or continuously (breakthrough). The concentrations of H₂O and HTO at column outlet were measured. Particular interest was attached to observing the effect of differences in the pretreatment applied to the adsorbents (whether dried or saturated with water), and in the H₂O partial pressure of the carrier gas. It was found that the adsorption characteristics shown for HTO were not influenced to any appreciable extent by differences in the pretreatment applied to the adsorbents. On the other hand, adsorbent performance depended sensitively on the H₂O pressure in the carrier gas.

Adsorption models for a two-component mixture composed of H₂O and HTO were sought for describing the adsorption mechanism. For the particular case of the molecular sieve 5A, the Langmuir-type mixed adsorption model was found to give values agreeing fairly well with experiment. A model postulating chemisorption of H₂O into hydroxyl group on the adsorbent surface, to be subsequently replaced by tritium, was found suitable for explaining the adsorbent behavior in the case of silica-gel.     

Uranium Extraction from Sea Water with Composite Adsorbents, (II)

A composite hydrous oxide, prepared from the mixed solution of titanium tetrachloride and ferrous chloride by addition of sodium hydroxide solultion, was investigated because of its rather high uranium adsorption capacity and its magnetic property. Results obtained may lead to easier handling of adsorbent species in the extraction of uranium from sea water.

The uranium adsorption capacity of the composite hydrous oxide was measured using sea water to which a small amount of uranyl chloride was added. The initial uranium concentration was 10.1 μg/l. Physical and chemical properties, such as specific surface area, mean pore radius and amount of surface OH groups, were also measured. The composite hydrous oxide was found to be composed mainly of relatively small particles of anatase and large particles of magnetite. Uranium adsorption capacity reaches its maximum when the precipitation temperatures are 50–70°C. The capacity of the composite hydrous oxide was found to be closely related to the mean pore size and the amount of surface OH groups.