燃料油中硫化物的选择性吸附研究进展

综述了不同吸附剂脱硫和选择性吸附两方面的机理及研究进展。在燃料油选择性吸附脱硫研究的吸附剂中,使用最多的是金属阳离子改性的Y型分子筛,以Cu、Ni和Ce改性的Y型分子筛最为成熟。其吸附脱硫机理主要包括π-络合吸附和金属S—M键作用。燃料油（以汽油和柴油为主）组成复杂,含大量烯烃、芳烃、烷烃及少量的氮化物、氧化物、水及胶质,影响吸附剂的吸附脱硫效果,而烯烃和芳烃严重影响吸附剂的选择性吸附脱硫性能。各种吸附剂对富含烯烃或芳烃的燃料油中的硫化物选择性和硫容量不同,但都不高。研究吸附剂与燃料中的硫化物的选择性吸附机理,对研发具有高选择性和高吸附容量的吸附剂起推动作用。     

金属改性分子筛吸附脱硫研究新进展

从分子筛金属改性的方式、吸附脱硫机理、吸附剂再生等方面综述了近几年国内外关于金属改性的微、介孔分子筛在燃料油液相吸附脱硫中的应用,分析了微、介孔分子筛作为脱硫吸附剂的优势和存在的问题,指出如何提高吸附剂的硫容量和选择性仍是未来研究的主要方向。     

多级孔道5A分子筛的合成及其对正构烷烃的吸附性能研究

为了提高5A分子筛对正构烷烃吸附分离的速率,以二甲基十八烷基[3-(三甲氧基硅基)丙基]氯化铵(TPOAC)为软模板剂,采用水热合成方法合成出具有微孔和介孔结构的多级孔道5A分子筛。结果表明,合成的分子筛以0.5 nm左右的微孔为主,介孔孔道集中在7~13 nm。通过改变模板剂用量可以调控合成分子筛的介孔数量。合成的多级孔道5A分子筛在保持对正构烷烃具有较高平衡吸附量的同时,显著提高正构烷烃在分子筛内的扩散系数,从而提高吸附分离的速率。     

多孔炭吸附剂的乙烯-乙烷选择性反转机制

烯烃是重要的化工原料,吸附分离技术可在温和工况下实现烯烃纯化,而吸附剂的烷烃选择性是实现高效化工分离过程的关键。基于分子模拟,提出调节孔道尺寸以控制多孔炭优先吸附乙烯或乙烷的选择性反转机制;控制活化条件,实验制备出不同孔径的多孔炭材料并验证了乙烯-乙烷选择性反转规律。结果表明,多孔炭的石墨化表面优先吸附乙烷;随着孔径尺寸的增大,可出现优先吸附乙烯的孔道区间;若孔径进一步增大,多孔炭可回归到优先吸附乙烷的石墨化表面吸附特征。选择性反转机制适用于不同形状的孔道结构。因此,可利用微孔孔道的限域作用放大多孔炭表面的烷烃选择性,并得到高性能的烷烃选择性吸附剂。     

碳酸二甲酯-甲醇共沸物的吸附分离

分别采用疏水硅沸石Si-1和高硅HZSM-5分子筛吸附剂,对碳酸二甲酯(DMC)-甲醇(MeOH)气相共沸物进行动态吸附分离的实验研究。实验结果表明:疏水硅沸石Si-1及高硅HZSM-5分子筛均选择性吸附DMC,且表现良好的吸附分离性能。其中Si-1对DMC的吸附选择性达86%,100 g吸附剂对DMC的饱和吸附质量为3.48 g,分离因子α为14.77。此外,利用红外光谱分析了疏水硅沸石Si-1和高硅HZSM-5分子筛的特性基团,并采用热重分析对吸附饱和的吸附剂进行吸附机理研究。结果表明:HZSM-5分子筛含Si—OH和H+强吸附位,DMC在其上的吸附为强化学吸附;而DMC在硅沸石上的吸附是选择性物理吸附。     

间接模板剂法合成介孔SAPO-11分子筛及其加氢异构化性能

采用水热合成法,将未焙烧的介孔材料SBA-15作为硅源合成介孔SAPO-11分子筛。利用X射线衍射、N2吸附-脱附等温曲线,BET物理吸附,NH3-TPD以及扫描电子显微镜等对分子筛的形貌和孔结构性质进行表征。将正十二烷作为原料,考察负载量为0.5%的Pt/SAPO-11分子筛催化剂的加氢异构化反应催化性能。结果表明:以未焙烧的SBA-15作为硅源制备介孔SAPO-11分子筛,介孔比表面积为77.2 m2/g以及介孔孔容为0.261 m~3/g,有效降低孔道传质阻力,酸量显著增加,活性位增多,使长链烷烃加氢异构化的选择性达到65.21%。     

吸附材料吸附分离天然气中二氧化碳的研究进展

列举了目前分离天然气中的二氧化碳的3种典型研究方法,包括吸附法、吸收法和膜分离法,认为吸附分离法具有能耗低、稳定性强、再生性能好、操作弹性大、无腐蚀、不产生二次污染且分离效果好等优点,在脱除天然气中二氧化碳领域有着广泛应用。对几种不同类型的吸附材料进行了详细的介绍,综述了活性炭、硅胶、介孔材料、金属有机骨架材料(MOF)和沸石分子筛等几种常用吸附剂的国内外研究进展,并对其吸附二氧化碳的效果进行分析,同时指出开发高效廉价、物理化学性质稳定、吸附能力强、选择性好的吸附剂是今后研究的主要方向。     

PEI改性介孔分子筛KIT-6对CO_2吸附性能的研究

CO2的大量排放是造成温室效应的主要因素,对全球排放的CO2进行捕集非常重要。今采用浸渍法将PEI(聚乙烯亚胺)负载到KIT-6介孔分子筛孔道表面上,使孔的吸附作用和胺的吸收作用相结合,制备出吸附容量大和选择性高的CO2吸附剂,从穿透时间、吸附量、分离因子等方面研究了PEI负载率对CO2吸附性能的影响。结果表明:KIT-6介孔分子筛经PEI改性后对CO2的吸附量和选择性增强。随着PEI负载量的增大,吸附剂对CO2的吸附性能先增大后降低,当PEI负载率为0.6时,CO2的吸附量和分离因子分别达到最大值为2.09 mmol?g?1和30.56,为无负载时的6.0倍和7.2倍。随着温度的升高,PEI改性吸附剂对CO2的吸附量呈增长趋势。再生实验表明吸附饱和的PEI改性吸附剂在378 K条件下能够完全再生,且具有较好的循环再生稳定性。     

部分脱除模板剂对MCM-41修饰负载有机胺吸附CO_2的影响

介孔分子筛MCM-41具有单一的孔道结构和较大的比表面积。通过负载有机胺形成的介孔有机胺二氧化碳固体吸附剂比常见的固体吸附剂具有高选择性、高吸附量等特点。利用化学方法部分脱除模板剂,负载PEI制备固体吸附剂,研究了模板剂脱除率PEI负载和对二氧化碳吸附性能的影响。用XRD、FT-IR、TEM、BET等方法对吸附剂结构进行表征,利用TG/DTA方法测定了CO2吸附量。研究结果表明,使用MCM-41原粉负载50%PEI吸附量达到131.0 mg/g(即262.0 mg/gPEI),比相同负载量除去模板剂的分子筛提高了12.6%;比单一的PEI分子吸附量(80.3 mg/g)提高了3.26倍,这说明在MCM-41原粉孔道内部由于存在丝状胶束而形成的亚纳米空间结构提高了有机胺的分散和利用率,增加了对CO2的吸附量。     

低成本制备MCM-41介孔分子筛及其对镉离子的吸附性能

以廉价的硅铁行业的废弃物微硅粉为硅源,十六烷基三甲基溴化铵(CTAB)为模板剂,采用碱法提纯-水热法合成制备了纯硅的MCM-41介孔分子筛。用红外光谱(FTIR)、小角X射线衍射、液氮吸附脱附、场发射扫描电子显微镜和高分辨透射电子显微镜对分子筛进行了结构表征和表面积及孔径分析。结果表明:所制备的分子筛的比表面积是918 m2/g,孔容1.11 cm3/g和孔径2.9 nm。采用静态吸附方法,研究了所合成的分子筛对水溶液中Cd2+离子的吸附行为,分析了pH值、分子筛质量、吸附时间和Cd2+的初始浓度对吸附的影响,并探讨了该吸附剂对Cd2+的吸附热力学和动力学特性。结果表明:当溶液的pH值为2.0～7.0,吸附剂的量在30～130 mg范围内时,吸附率随着pH值和吸附剂用量的增加而增加,当吸附剂用量为130 mg时,有序介孔分子筛对Cd2+离子的去除率基本稳定。有序介孔分子筛对Cd2+离子的吸附量随吸附时间的增加而增加,在120 min时达到吸附平衡。有序介孔分子筛对Cd2+的等温吸附过程更符合Freundlich模型,吸附动力学较符合准二级吸附方程。     

AgNO3/MCM-41/NiFe2 O4的制备及吸附烯烃行为研究

基于长链烯烃/烷烃络合分离的目标,设计构造了AgNO3/MCM-41/NiFe2 O4磁性吸附剂。样品采用X射线衍射( XRD),N2吸附-脱附,红外线光谱分析( FTIR)和振动样品磁强计( VSM)等手段进行表征,结果表明磁性吸附剂中NiFe2 O4呈尖晶石结构,AgNO3最佳负载量为0.2 g/g AgNO3,且单层分散于MCM-41六方孔道内,其比表面积为717.89 m2/g,孔径为2.94 nm。利用磁性吸附剂对C11烯烃/C11烷烃混合物进行液相络合吸附分离研究,实验表明AgNO3/MCM-41/NiFe2 O4对长链烯烃分子具有选择性吸附功能,在100 min内达到吸附平衡,单级平衡吸附量为2.14 g/g。考察了吸附剂重复使用对吸附选择性和磁回收率的影响,使用10次后,吸附剂可保持较高的回收率(98.9%),烯烃吸附选择性略有降低,但仍能实现对烯烃的选择性吸附。     

Removal of Ammonium from Wastewater by Pure Form Low-Silica Zeolite Y Synthesized from Halloysite Mineral

Pure form, single phase, and highly crystalline low-silica zeolite Y was synthesized from natural nanotubular halloysite mineral by the hydrothermal method. In the synthesis process, the halloysite consisted of SiO₂ and Al₂O₃ was used as starting material with adding supplementary silica and alumina sources. Ammonium adsorption properties of the as-synthesized zeolite Y were studied using batch experiments and the results revealed that its adsorption properties were strongly dependent on contact time, adsorbent dosage, pH, ionic strength, temperature, and initial concentration. The equilibrium data fit well with the Langmuir isotherm compared with the Freundlich isotherm. Kinetic studies showed that the adsorption followed the pseudo-second-order model. Thermodynamic parameters such as change in free energy (ΔG ⁰), enthalpy (ΔH ⁰), and entropy (ΔS ⁰) were also determined, which indicated that the adsorption of ammonium on zeolite Y was a spontaneous and exothermic process at ambient conditions. Due to its low cost, high adsorption capacity and fast adsorption rate, the zeolite Y synthesized from halloysite has the potential to be utilized for the cost-effective removal of ammonium from wastewater.     

Selective online solid-phase extraction of copper using p-morpholino-methylcalix[4]arene appended silica-based column

ABSTRACT

This study deals with investigation of selectivity of p-morpholino-methylcalix[4]arene appended silica from a group of metal ions having similar charge and radii. The values of distribution ratio revealed that modified silica possess higher selectivity for Cu²⁺. In addition, relative selectivity coefficients of modified silica were found to be 24.1, 13.8, 8.6 and 4.01 for Cu²⁺/Ni²⁺, Cu²⁺/Co²⁺, Cu²⁺/Cd²⁺, Cu²⁺/Pb²⁺, respectively. The maximum adsorption capacity was 1.5 mmolg^?1. The reusability data suggested no any loss of adsorption capacity of this material up to 10 cycles. The developed material was also applied for determination of copper in lake water samples with satisfactory results.     

Adsorbent Evaluation Based on Experimental Breakthrough Curves: Separation of p‐Xylene from C8 Isomers

The search for new adsorbents with enhanced capacity and selectivity, suitable for application on large‐scale simulated moving‐bed units for separation of p‐xylene, requires efficient, reliable, and fast adsorbent characterization methods for this specific separation. Fixed‐bed experiments were carried out under the conditions of the Parex process to evaluate a faujasite‐type zeolite as adsorbent for the separation of p‐xylene from its isomers in the proportions of the real Parex feed stream. The experimental breakthrough curves were used to evaluate the selected adsorbent in terms of nonselective and selective volumes, adsorption capacity, selectivity, and productivity, which can be applied to identify the feasible separation region for different operating conditions.     

Selective removal of sulfur compounds in city-gas by adsorbents

Silver nitrate impregnated on beta zeolite (BEA), mesoporous silica MCM-41 and SBA-15 (AgNO₃/BEA, AgNO₃/MCM-41, AgNO₃/SBA-15) were prepared to remove sulfur compounds selectively in city-gas, which contains tetrahydrothiophene and tert-butylmercaptane. Sulfur adsorption capacity was determined when the sulfur concentration of effluent gas in breakthrough test reached 0.1 ppm, which is acceptable sulfur concentration for hydrogen production in a reformer for fuel cells. As the AgNO₃ concentration in AgNO₃/BEA, AgNO₃/MCM-41, and AgNO₃/SBA-15 increased, their sulfur adsorption capacities also increased. Although microporous zeolite BEA has smaller pore volume and lower surface area than those of mesoporous silica MCM-41 and SBA-15, the sulfur adsorption capacity of AgNO₃/BEA was higher than those of AgNO₃/MCM-41 and AgNO₃/SBA-15. Adsorbed sulfur molecules per impregnated silver nitrate and the shape change of breakthrough curves depending on the adsorption temperature showed that not only chemisorption but also physisorption was involved in sulfur compounds adsorption on AgNO₃ impregnated adsorbent. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

The skeletal isomerization of C4-C7 1-olefins over ferrierite and ZSM-5 zeolite catalysts

The skeletal isomerization of C₄-C₇ 1-olefins was studied on ferrierite (FER) and ZSM-5 (MFI) zeolites to elucidate the effect of the molecular distribution in zeolite pores on the selectivity foriso-olefin formation. Regardless of the difference in molecular length of 1-olefins, the FER zeolite showed high selectivity foriso-olefins, while the selectivity became slightly low at the skeletal isomerization of long olefin molecules. The drastic decrease in the selectivity of MFI zeolites by increasing the conversion is concurrently observed in the skeletal isomerization of C₄-C₇ 1-olefins. The high selectivity of FER zeolites is explained by their sparse distributions of olefin molecules in pores, which induces a high preference for monomolecular skeletal isomerization.     

Fractionated Vacuum Swing Adsorption Process for Air Separation

Abstract

A novel adsorptive process for air separation using a zeolitic adsorbent is described. The process essentially consists of three simple cyclic steps, and it can be used for simultaneous production of an 80—90% oxygen-enriched gas and a 98 + % nitrogen-enriched gas from ambient air. Successful operation of the process requires the use of a zeolite which exhibits high nitrogen adsorption capacity and selectivity from air. The role of nitrogen adsorption selectivity of the zeolite in the vacuum desorption process is examined, and experimental performance data for the air separation process are reported.     

Preparation of a surface molecular‐imprinted adsorbent for Ni2+ based on Penicillium chrysogenum

A new chitosan molecular‐imprinted adsorbent was prepared from the mycelium of waste biomass. The results showed that an adsorbent using Penicillium chrysogenum mycelium as the core material was better than one derived from peanut coat. The adsorption capacity of the surface‐imprinted adsorbent for Ni²⁺ was enhanced by increasing the chitosan concentration in the imprinting process. Epichlorohydrin was better than glutaraldehyde as a cross‐linking agent; the optimal imprinted Ni²⁺ concentration for preparing the surface‐imprinted adsorbent was 2 mg (Ni²⁺) g^?1 of mycelium. The adsorption capacity of the surface‐imprinted adsorbent was 42 mg g^?1 (at 200 mg dm^?3 initial metal ions concentration) and twice that of the mycelium adsorbent. The surface‐imprinted adsorbent can be reused for up to 15 cycles without loss of adsorption capacity. Copyright © 2005 Society of Chemical Industry     

Influence of synthesis conditions on the production of molecularly imprinted polymers for the selective recovery of isovaleric acid from anaerobic effluents

Two molecularly imprinted polymers (MIPs) – poly(methacrylic acid‐co‐TRIM) (TRIM, trimethylolpropanetrimethacrylate) and poly(acylamide‐co‐TRIM) – were synthesized in different solvents for the selective recovery of isovaleric acid (template) generated during the anaerobic digestion process. The chemical and structural characterizations of the synthetic adsorbent were carried out by Fourier transform infrared spectroscopy, TGA and porosimetry through N₂ adsorption–desorption isotherms. The selective and adsorptive performances of the imprinted polymers were evaluated by kinetic, isothermal, thermodynamic and selectivity studies and by adsorbent reuse experiments. The poly(methacrylic acid‐co‐TRIM) synthesized with dimethyl sulfoxide:chloroform presented higher selectivity and adsorption capacity for isovaleric acid in the presence of six volatile fatty acids. The kinetic results were well adjusted to the pseudo‐nth order and intraparticle diffusion models, leading to k values of 10^?4 and 6 × 10^?5 for the best synthesis of MIPs and not‐imprinted polymers, respectively. Moreover, the Sips model best described the adsorption isotherm and generated a maximum adsorption capacity of ca 209 mg g^?1 (at 25 °C). Cycles of MIP use–desorption–reuse indicated that the selective adsorbent performed better than commercial adsorbents, losing less than 3% of adsorption capacity after three cycles. © 2018 Society of Chemical Industry     

一种具有高CO吸附容量和高CO/N2及CO/CO2分离选择性的CuCl@β吸附剂

研制了一种新型的CuCl@β分子筛吸附剂材料,它不仅对CO有着高吸附容量,而且对CO/N₂和CO/CO₂的二元混合气有着高吸附选择性。利用自发单层分散的原理制备了一系列的CuCl@β分子筛材料,分别应用氮气吸附以及XRD进行表征。CO在CuCl@β分子筛上吸附等温线和动态透过曲线分别通过静态吸附和固定床实验获得。依据IAST理论模型计算了CuCl@β分子筛对CO/N₂二元混合物和CO/CO₂二元混合物的吸附选择性。研究结果表明:(1)氯化亚铜的负载增强了一氧化碳在CuCl@β分子筛上的吸附容量,其最佳负载量为0.4 g·g^-1。(2)CuCl@β分子筛吸附剂在增强CO的吸附量的同时,还降低了对二氧化碳和氮气的吸附。由于Cu⁺-CO π位络合键的存在,提高了CuCl@β分子筛对二元混合物CO/N₂和CO/CO₂的吸附选择性。(3)在低压下(0～10 kPa)下0.4CuCl@β分子筛对CO/N₂和CO/CO₂的吸附选择性分别高达1600～5200和120～370,远大于原始的β分子筛。CuCl@β分子筛对CO有着超高吸附容量以及吸附选择性,将会是一种很有潜力的CO分离提纯材料。