离子液体吸收CO2的研究进展

CO2的捕集、分离与利用已成为人类共同关心的重要课题。工业上,通常使用传统的有机胺水溶液或热钾碱溶液等脱除CO2。有机胺具有蒸气压,易产生挥发性有机物(VOCs)对环境造成污染;热钾碱溶液等脱除CO2需要较高操作温度因而能耗较高,生产过程经济性有待改善。离子液体具有几乎无蒸气压、热稳定性、结构可设计性等独特优点,在CO2分离领域的巨大应用潜力已成共识。本文结合课题组近期的研究工作,就国内外离子液体吸收CO2的主要研究成果进行综述。     

Absorption of NO by Aqueous Solutions of KMnO4/H2SO4

The absorption of NO in aqueous solutions of KMnO₄ and H₂SO₄ was carried out in a stirred tank reactor under atmosphere pressure. The results indicated that the absorption process was under a fast pseudo-m th reaction regime. The reaction between NO and aqueous solutions of KMnO₄/H₂SO₄ was found to be first-order with respect both to NO and to KMnO₄. The addition of H₂SO₄ to KMnO₄ solutions increased the absorption rate of NO and increasing reaction temperature was also favorable to the absorption of NO.     

SO2 absorption/desorption performance of renewable phenol-based deep eutectic solvents

Six renewable DESs prepared from choline chloride (CC) and phenols (guaiacol, GC; cardanol, CL) with molar ratios of phenols to CC of 3:1, 4:1 and 5:1 were investigated to absorb SO₂ at 293.15–323.15 K and 0–1.0 bar. Results showed that DESs demonstrated satisfactory SO₂ absorption performance, and GC–CC (3:1) exhibited the maximum absorption capacity of 0.528 g SO₂ per g DES. The SO₂ enriched DESs could be easily regenerated and recycled five times. Moreover, the DESs exhibited high selectivity of SO₂/CO₂. Present DESs seem to be promising absorbents for SO₂ due to good performance.     

SO2 SCRUBBING IN A TAPERED BUBBLE COLUMN SCRUBBER

SO₂ emissions from various sources are found to occur in various concentrations and quantities. Abatement of SO₂ emission, therefore, assumes significant importance over the decades. Wet scrubbers offer great advantage over other devices for gas cleaning. That is the reason that compliance with SO₂ standards will in many cases result in the installation of scrubbing devices. This article presents results of a study on the scrubbing of SO₂ (initial concentration ranging between 400 and 1780 ppm) in a tapered bubble column scrubber using water and dilute sodium alkali. Preliminary studies reveal that the tapered bubble column is capable of generating higher fractional gas holdup than a standard bubble column under similar situations. Moreover, the tapered bubble column has generated bubbles with less power consumption than the existing columns under comparable hydrodynamical conditions. Experimental results indicate that almost 100% SO₂ removal (i.e., zero penetration) can be achieved in the scrubber developed in alkali scrubbing at an optimum Q_L/Q_G ratio of 3.0 m³/1000 ACM. The selection of any gas-cleaning device is based on the performance of the system. In view of this, empirical and semi-empirical correlations are put forward for the prediction of the performance of the scrubber in terms of different pertinent variables of the system for water as well as alkali scrubbing. Experimental results fit extremely well with the correlations. The removal efficiency achievable in the present tapered bubble column scrubber has been found to be higher than that of a single-stage standard bubble column with some modification. The present tapered bubble column is, therefore, hydrodynamically, energetically, and efficiency-wise much better than a standard bubble column.     

First-principles DFT study of SO2 and SO3 adsorption on 2PANI: a model for polyaniline response

Interaction of SO_x (x?=?2,3) molecules on active sites of dianiline (as a model for polyaniline, denoted here as 2PANI) was studied using density functional theory at the BLYP-D/6-31+G(d) level of theory. Natural population analysis was used to find out the charge distribution as well as the net transferred charge of SO_x upon adsorption on 2PANI and the result has been compared with Mulliken charge analysis to evaluate the sensing ability of 2PANI. The computed density of states point to the remarkable orbital hybridization between SO_x and 2PANI during the adsorption process. As a consequence, the results of UV–VIS confirm the sensing ability of 2PANI toward SO₂ and SO₃. Based on our results, it can be found that at proper configuration the SO₂ and SO₃ molecules can be adsorbed on 2PANI with adsorption energies (E_ads) of ?18.2 and ?62.9?kJ/mol (BSSE), respectively.     

SIMULATION OF SO2 ABSORPTION IN A VENTURI SCRUBBER

In this study, a three-dimensional mathematical model, based on a nonuniform droplet concentration distribution, has been developed to simulate gas absorption in a venturi scrubber. The mass transfer process was illustrated by assuming the liquid phase as a combination of droplets and film. The flow, just as the annular two-phase flow, includes a flow of liquid film layer on the walls and a flow of gas and liquid drops in the core. Peclet number was determined using experimental data reported by Viswanathan et al. (1984 Viswanathan , S. , Gnyp , A. W. , and St. Pierre , C. C. ( 1984 ). Examination of gas-liquid flow in a venturi scrubber , Ind. Eng. Chem. Fundam. , 23 , 303 – 308 . [Google Scholar]) for distribution of droplets across the cross section of the scrubber. The mathematical model for gas absorption was justified by comparing the theoretical predictions with the experimental data reported by Johnstone et al. (1954 Johnstone , H. F. , Feild , R. B. , and Tassler , M. C. (1954). Gas absorption and aerosol collection in a venturi atomizer, Ind. Eng. Chem. , 46, 1601–1608.[Crossref] , [Google Scholar]) and the Office of Air Programs, U.S. Environmental Protection Agency (Wen and Fan, 1975 Wen , C. Y. , and Fan , L. T. ( 1975 ). Models for Flow Systems and Chemical Reactors , 390 – 420 , Marcel Dekker , New York . [Google Scholar]), for SO₂ removal by alkaline solution and H₂O.     

2种咪唑类离子液体的合成与表征

采用两步合成法,以[BMIM]Cl和717#氯型阴离子交换树脂为原料合成2种咪唑类离子液体[BMIM]-[HCOO]和[BMIM][CH3COO],分别通过核磁氢谱和红外谱图对合成物进行表征和分析,结果表明所合成的物质确为目标离子液体。     

SO2 oxidation over the V2O5/TiO2 SCR catalyst

The effects of V₂O₅ loading of the V₂O₅/TiO₂ SCR catalyst on SO₂ oxidation activity were examined by infrared spectroscopy (DRIFT) and SO₂ oxidation measurement. Vanadium oxide added to the catalyst was found to be well dispersed over the TiO₂ carrier until covered with monolayer V₂O₅. The rate of SO₂ oxidation increased almost linearly with V₂O₅ loading below the monolayer capacity and attained saturation with further increase. The hydroxyl groups bonded to vanadium atoms, V–OH, might be altered by SO₂ oxidation. Both V=O and V–OH groups are likely involved in the adsorption and desorption of SO₂ and SO₃.     

SO2-Assisted Simultaneous Reduction of SO2 and NO by CO on SnO2-TiO2 Solid Solution

Sn_0.5Ti_0.5O₂ shows excellent catalytic performance both for the CO-SO₂ reaction and the CO-SO₂-NO reaction. At 350 ° C, 525 ppm SO₂/520 ppm NO/2085 ppm CO, SV = 3000 h^-1, the conversion of SO₂ is nearly complete in the CO-SO₂ reaction and above 89% in the CO-SO₂-NO reaction; NO conversion is above 98% in the latter reaction. The selectivities of S and N₂ are both close to 100%. SO₂ shows a significant promoting effect on the activity of the Sn_0.5Ti_0.5O₂ catalyst for NO reduction by CO. Combining transient response experiments, catalytic tests and TPD results, we propose a SO₂-assisted NO-CO reaction concept. The existence of a surface sulfur species, which was formed during the CO-SO₂ or CO-SO₂-NO reaction, is proved by XPS analysis. It is the active site for NO reduction in the CO-SO₂-NO reaction, and through which SO₂ accomplishes its promoter role. On the basis of the results obtained, the SO₂-assisted redox mechanism of simultaneous reduction of SO₂ and NO by CO is proposed.     

Modeling of CO2 Solubility in Selected Imidazolium-Based Ionic Liquids

This study explores the use of COSMO-RS model and Peng-Robinson (PR) equation of state (EoS) to predict the solubility of carbon dioxide (CO₂) in specific ionic liquids (ILs). COSMO-RS was employed to estimate of CO₂ solubility at atmospheric pressure in eight imidazolium-based ILs resulting from the combination of ethyl, butyl, hexyl, and octyl-imidazolium cations with two anions: bis(trifluoromethylsulfonyl)imide ([Tf₂N]) and Trifluoromethanesulfonate ([TFO]). The results indicated relatively acceptable qualitative consistency between the experimental and predicted values. The PR EoS was employed at high pressure by tuning the interaction parameters to fit the experimental data reported in the literature. The model demonstrated excellent accuracy in predicting the solubility of CO₂ at pressure values less than the critical pressure of CO₂; however, at higher pressures, the calculated solubility diverged from the experimental values. Furthermore, the type of anion and cation used in the IL affected the performance of the PR EoS.     

用于CO_2吸收的离子液体的合成、表征及吸收性能

以N-甲基咪唑和3-溴丙胺氢溴酸盐为起始原料,合成了一种含氨基的离子液体(ionic liquid,IL)——1-(1-氨基丙基)-3-甲基咪唑溴盐(简写为[NH2p-mim]Br),总产率为90.1%,溴含量为0.980 mol Br/mol IL,胺含量为0.948 mol NH2/mol IL。探讨了合成工艺,并通过1HNMR、13CNMR、IR和MS对产物结构进行了表征。吸收实验结果表明,该离子液体能够有效地吸收CO2,在40℃和106 kPa下,质量分数为45%的离子液体水溶液吸收CO2至饱和时,溶液中CO2的摩尔分数可达0.444 mol CO2/mol IL,接近理论吸收量0.5 mol CO2/mol IL;在90℃的真空状态下,吸收的CO2能够完全解吸,重复吸收实验表明,该离子液体吸收CO2的能力无明显下降。     

离子液体吸收烟气中SO_2的研究

寻找新型高效的烟气SO2处理方法是当前环境保护的重点。离子液体作为一种环境友好溶剂在气体吸收方面有其独特的优势。本文研究了烟气中SO2的成因、危害,分析了常规处理方法优缺点,得出了离子液体可以应用于烟气中SO2的处理的结论,总结了离子液体对SO2的吸收行为,展望了离子液体回收SO2的前景及今后研究的方向。     

Extraction of Uranium and Thorium from Nitric Acid Solution by TODGA in Ionic Liquids

Extraction of uranium (UO₂²⁺) and thorium (Th⁴⁺) from a nitric acid solution into an imidazolium-type ionic liquids (ILs) of 1-alkyl-3-methylimidazolium hexafluorophosphate ([C_nmim][PF₆], n = 6 or 8) was carried out using N,N,N′,N′-tetraoctyl-3-oxapentanediamide (TODGA) as an extractant. It was found that the extraction efficiencies of UO₂²⁺ and Th⁴⁺ ions are higher in comparison with that done in n-dodecane. The extraction mechanism was deduced by the slope analysis and extraction experiment. Transfer of both ions is assumed to proceed predominantly through the neutral solvation mechanism from nitric acid solution into ILs. The UO₂²⁺ ion forms a 1:2 complex with TODGA in ILs at lower acidity, and a 1:1 complex in ILs and in n-dodecane at higher acidity. The Th⁴⁺ ion forms a 1:2 complex with TODGA in C₆mimPF₆ IL or a 1:1 complex in C₈mimPF₆ IL at lower acidity and a 1:1 complex in both ILs, and n-dodecane at higher acidity. Stripping studies were conducted using sodium salt of EDTA as a stripping ligand. The thermodynamics of extracting UO₂²⁺ ions and Th⁴⁺ ions from a 3 M HNO₃ solution was also studied. The results indicated that the extraction reactions are spontaneous and go through an exothermic process.     

Preparation and characterization of SO42-/TiO2 and S2O82-/TiO2 catalysts

Nanosized solid superacids SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂, as well as MCM-41-supported SO₄ ²⁻/ZrO₂, were prepared. Their structures, acidities, and catalytic activities were investigated and compared using XRD, N₂ adsorption-desorption, and in situ FTIR-pyridine adsorption, as well as an evaluation reaction with pseudoionone cyclization. The results showed that SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ possess not only nanosized particles with diameters < 7.0 nm, a BET surface greater than 140 cm²/g and relatively regular mesostructures with pores around 4.0 nm, but also a pure anatase phase and strong acidity. Different from the Lewis acid nature of SO₄ ²⁻/ZrO₂/MCM-41, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibit mainly Bronsted acidities. The strongest Bronsted acid sites were produced on SO₄ ²⁻/TiO₂ promoted with H₂SO₄, while Lewis acid sites on S₂O₈ ²⁻/TiO₂ even stronger than those on SO₄ ²⁻/ZrO₂/MCM-41 were generated when persulfate solution was used as sulfating agent. Because of their distinct acid natures, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO₄ ²⁻/ZrO₂/MCM-41. It can be concluded that the existence of more Br?nsted acid sites was favorable for proton participation in the cyclization reaction. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(2): 239–244 [译自: 高校化学工程学报]     

Reduction of lean NOx by ethanol over Ag/Al2O3 catalysts in the presence of H2O and SO2

The reduction of lean NOx using ethanol in simulated diesel engine exhaust was carried out over Ag/Al₂O₃ catalysts in the presence of H₂O and SO₂. The Ag/Al₂O₃ catalysts are highly active for the reduction of lean NOx by ethanol but the reaction is accompanied by side reactions to form CH₃CHO, CO along with small amounts of hydrocarbons (C₃H₆, C₂H₄, C₂H₂ and CH₄) and nitrogen compounds such as NH₃ and N₂O. The presence of H₂O enhances the NOx reduction while SO₂ suppresses the reduction. The presence of SO₂ along with H₂O suppresses the formation of acetaldehyde and NH₃. By infrared spectroscopy, it was revealed that the reactivity of NCO species formed in the course of the reaction was greatly enhanced in the presence of H₂O. The NCO species readily reacts with NO in the presence of O₂ and H₂O at room temperature, being converted to N₂ and CO₂ (CO). Addition of SO₂ suppresses the formation of NCO species and lowers the reactivity of the NCO species. However, the reduction of NOx is still kept at high conversion levels in the presence of H₂O and SO₂ over the present catalysts. About 80% of NOx in the simulated diesel engine exhaust was removed at 743 K. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Preparation and Characterization of High-Strength PMMA-Na2SO4 Composite Film

PMMA-Na₂SO₄ composite films were prepared by a solvent casting method and were characterized by SEM, EDX, DSC, UTM, TG/DTA and FTIR techniques. From the SEM it is clear that Na₂SO₄ were well dispersed, having sizes ranging from micrometer to nanometer. EDX results confirm the presence of Na₂SO₄ particles in a polymer matrix. UTM studies show that the tensile strength of PMMA-Na₂SO₄ composite is better than pure PMMA. FTIR spectra indicates the strong interaction between C=O of PMMA and Na₂SO₄. According to DSC, TG/DTA analysis the thermal stability and glass transition temperature of PMMA-Na₂SO₄ has increased as compared with that of pure PMMA.     

Characteristics of CO2 Absorption into Aqueous Ammonia

Abstract

Aqueous ammonia was investigated as a new absorbent of the chemical absorption process for CO₂ capture from combustion flue gas. The effects of the temperature and concentration of aqueous ammonia on CO₂ absorption in a semi‐batch reactor were studied by interpreting breakthrough curves. Raman spectroscopy analysis of CO₂ loaded aqueous ammonia provided concentration changes of bicarbonate, carbonate, and carbamate as well as CO₂ sorption capacity at given time during the absorption with 13 wt% aqueous ammonia at 25°C. It was observed that carbamate formation was dominating at the early stage of absorption. Then, the bicarbonate formation took over the domination at the later stage while the carbonate remained unchanged.     

离子液体催化2-氯噻吩氯甲基化反应研究

以2-氯噻吩、多聚甲醛为原料,以离子液体[C2mim]Br、[C3mim]Br、[C4mim]Br、[C5mim]Br、[C6mim]Br、[C7mim]Br、[C8mim]Br、[C12mim]Br、[Bmim]PF6、[Bmim]BF4、[Bmim]C4F9SO3和[Bmim]Cl为催化剂进行氯甲基化反应,得到产物2-氯-3-氯甲基噻吩。研究表明,离子液体可以促进2-氯噻吩的氯甲基化反应,具有相转移催化剂的效果,并且以[C4mim]Br和[C8mim]Br的催化效果为佳。反应最佳条件为:离子液体[C8mim]Br摩尔分数为5%(相对于2-氯噻吩),温度40℃,反应时间8h,产物产率可达92.1%。     

离子液体捕集二氧化碳的研究进展(英文)

Due to their negligible volatility,reasonable thermal stability,strong dissolubility,wide liquid range and tunability of structure and property,ionic liquids have been regarded as emerging candidate reagents for CO2 cap-ture from industries gases.In this review,the research progresses in CO2 capture using conventional ionic liquids,functionalized ionic liquids,supported ionic-liquids membranes,polymerized ionic liquids and mixtures of ionic liquids with some molecular solvents were investigated and reviewed.Discussion of relevant research fields was presented and the future developments were suggested.