变压吸附分离工业废气二氧化碳的研究进展

概述了未来人类对过量二氧化碳排放的处理办法,即碳的捕获和存储(CCS).简介了4种二氧化碳的分离工艺及特点和工业中二氧化碳的捕获系统.阐述了变压吸附工艺的基本原理和其在捕获工业废气中二氧化碳上的应用,以及变压吸附分离二氧化碳的工艺在循环结构设计、吸附剂材料和数值模拟等方面的研究进展和国内外的工业化应用.分析了目前该工艺仍存在的问题,指出该技术具有广阔的应用前景.     

A novel lead ion‐imprinted chelating nanofiber: Preparation,characterization, and performance evaluation

A novel Pb(II) ion‐imprinted chelating nanofibers (nIIP), synthesized by combining electrospinning with surface ion imprinting technique, was reported in this study. nIIP was characterized with Fourier transmission infrared spectrometry and scanning electron microscopy, respectively. The performance of nIIP for Pb(II) sorption was conducted through a batch adsorption experiments. Experimental data showed that adsorption capacity of nIIP was much higher than that of non‐ion imprinted chelating acrylic microfibers (mNIP) derived from commercial available acrylic microfibers, and adsorption behaviors agreed well with pseudo‐second‐order kinetic and Langmuir isotherm model. The values of Gibbs free energy change derived from experimental data suggested that the adsorption Pb(II) on nIIP is spontaneous and favorable at high temperature. In addition, nIIP had the highest selectivity among three tested fibrous adsorbents for Pb(II) from binary metal solution, the selectivity coefficients for Pb(II) from binary metal solution of Pb(II)/Cu(II), Pb(II)/Ni(II), and Pb(II)/Cd(II) onto nIIP were 47, 101, and 162, respectively. Besides, a forty adsorption/desorption cycles revealed that nIIP was a promising recyclable adsorbent. In conclusion, the novel nIIP is a highly effective adsorbent for enrichment and separation of Pb(II) in the presence of competitive ions in aqueous solution, and it is potential to be applied for recovering metals from heavy metal polluted industrial wastewater such as Pb(II)/Cd(II), Pb(II)/Ni(II), and Pb(II)/Cu(II) polluted wastewater. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41507.     

Preparation of metal ions impregnated polystyrene resins for adsorption of antibiotics contaminants in aquatic environment

In this study, the strong‐acid polystyrene resin D001 was modified by impregnation with metal ions Fe³⁺, Cu²⁺, and Zn²⁺ to prepare new kinds of sorbents. The modified D001 was characterized by N₂ sorption–desorption isotherms, X‐ray powder diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The sorption performance of the metal modified resins for removal of antibiotics tetracycline (TC) and doxycycline (DC) from aquatic environment was investigated and excellent sorption capability with more than 98% removal ratio was observed for these resins after modification. Although these modified resins also presented pH‐dependent sorption, they showed much better flexibility with pH fluctuation than those of the unmodified original D001, and extremely strong sorption capability was exhibited in a wide range of pH 2–8 for both TC and DC. Pseudo‐second‐order kinetic equation described the sorption process more reasonably than pseudo‐first‐order equation. Langmuir isotherm model provided the best match to the equilibrium data with monolayer maximum sorption capacity of 417–625 mg g^?1 under 288–318 K. The sorption capacity decreased with the increase of ionic strength of NaCl. The main sorption mechanism was proposed to be surface complexation, cation bridge interaction and electrostatic attraction/competition between antibiotics and metal modified resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41803.     

Preparation and adsorption behaviors of ethylene diamine tetraacetic acid modified zwitterionic hybrid materials

Novel ethylene diamine tetraacetic acid (EDTA)‐modified zwitterionic hybrid materials were prepared via a sol–gel process. Their adsorption performances for Pb²⁺ ions were examined. Fourier transform infrared spectroscopy confirmed the reaction products. Thermogravimetric analysis revealed that the thermal stability of these hybrid materials could reach 200°C. Differential scanning calorimetry measurement showed that the addition of titanium butoxide could impact the crystallization transformation of these materials. Field emission scanning electron microscopy images showed that EDTA modification induced a decrease in the particle size. Adsorption experiments demonstrated that the optimal initial pH was 5. Moreover, we observed that the adsorptions for Pb²⁺ ions followed the Lagergren pseudo‐second‐order kinetic model, intraparticle diffusion, and Langmuir isotherm model. In addition, we found that the maximal Langmuir constant was 0.86 mmol/g. The negative Gibbs free energy values suggested that Pb²⁺ adsorption onto these samples was spontaneous in nature. The desorption experiment indicated that these samples could be recovered with aqueous HCl solution as a desorbent. These results suggest that the synthesized EDTA‐modified zwitterionic hybrid materials are promising adsorbents that could be used to separate and recover heavy‐metal ions from polluted wastewater. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39801.     

以硅藻土为原料制备铯吸附剂及其吸附性能初探

铯是一种极为重要的稀有碱金属资源,在光纤通信、催化、医疗以及能源等领域有着广泛的应用。中国青海、西藏等地的盐湖卤水中蕴藏着储量可观的铯资源有待开发,因此开展溶液中铯离子分离提取技术的研究意义重大。以无毒且价廉的硅藻土为硅源,以三嵌段聚合物P-123为模板剂,采用一步法合成了磷钼酸铵负载量为27%（质量分数）的磷钼酸铵/二氧化硅（AMP/SiO₂）复合吸附材料用于吸附铯离子（Cs⁺）。通过扫描电镜（SEM）、X射线衍射（XRD）、傅里叶变换红外光谱仪（ICP-OES）等对合成的AMP/SiO₂进行了表征,并初步考察了AMP/SiO₂对水溶液中Cs⁺的吸附性能。研究结果表明,AMP较为均匀地分散在介孔二氧化硅的结构和孔道中,并且该复合材料有较大的比表面积（451.2 m²/g）和孔体积（0.95 cm³/g）。此外,该吸附剂对Cs⁺的吸附过程符合拟二级动力学模型和Freundlich等温吸附模型,Cs⁺平衡吸附容量可达63.45 mg/g。     

Synthesis and CO2 adsorption behavior of amine‐functionalized porous polystyrene adsorbent

A solid amine adsorbent was prepared by modifying a porous polystyrene resin (XAD‐4) with chloroacetyl chloride through a Friedel–Crafts acylation reaction, followed by aminating with tetraethylenepentamine (TEPA). The adsorption behavior of CO₂ from a simulated flue gas on the solid amine adsorbent was evaluated. Factors that could determine the CO₂ adsorption performance of the adsorbents such as amine species, adsorption temperature, and moisture were investigated. The experimental results showed that the solid amine adsorbent modified with TEPA (XAD‐4‐TEPA), which had a longer chain, showed an amine efficiency superior to the other two amine species with shorter chains. The CO₂ adsorption capacity decreased obviously as the temperature increased because the reaction between CO₂ and amine groups was an exothermic reaction, and its adsorption amount reached 1.7 mmol/g at 10 °C in dry conditions. The existence of water could significantly increase the CO₂ adsorption amount of the adsorbent by promoting the chemical adsorption of CO₂ on XAD‐4‐TEPA. The adsorbent kept almost the same adsorption amount after 10 cycles of adsorption–desorption. All of these results indicated that amine‐functionalized XAD‐4 resin was a promising CO₂ adsorbent. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45046.     

Structure characterization and adsorption properties of tetraethylenepentamine ion exchange fiber

A novel tetraethylenepentamine ion exchange fiber (TAIEF) was prepared using polypropylene grafted styrene (PP‐g‐ST) fiber as raw material. The chemical structure of TAIEF was characterized using infrared spectrum (IR) method. TAIEF had good appearance and shape after reaction in SEM images, the TGA curves revealed that both PP‐g‐ST fiber and acetyl PP‐g‐ST fiber had good thermal stability below 250 °C, and the weight loss rate of TAIEF is 9% from 50 °C to 200 °C obtained by TGA. TAIEF adsorption capacity to Fe(III) is larger than that of In(III) in the pH value 1.00 to 3.00, while the pH value is at 2.50 to 3.00, TAIEF adsorption capacity to Fe(II) and Zn(II) are smaller than that of In(III). The selective adsorption ability to Fe(III) is higher than In(III), and the selective absorptivity to In(III) is better than Fe(II) and Zn(II). The mechanism was explained of TAIEF favorable selective adsorption to In(III) and Fe(III) ions in mixed solutions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44513.     

多孔氢键金属-有机框架材料对乙炔和二氧化碳的吸附分离

以腺嘌呤和溴化铜（氯化铜）为原料,采用慢扩散合成法,合成多孔氢键金属-有机框架材料MPM-1-Br和MPM-1-Cl。采用SEM、PXRD、TGA及比表面积分析等技术对材料进行综合表征,并测定了此二种同构多孔氢键金属-有机框架材料对乙炔和二氧化碳单组分气体的吸附等温线。实验结果表明,MPM-1-Br和MPM-1-Cl的比表面积分别为373 m²·g^-1和417 m²·g^-1,且在<240℃的温度范围内有良好的稳定性;在298 K和总压100 kPa下,通过IAST理论计算得到其对C₂H₂/CO₂混合气体（体积比50：50）的吸附选择性分别达到了3.8和3.0,与HKUST-1（4.7）和UTSA-30（3.3）等金属-有机框架材料有相当的分离性能。     

AC/X-G吸附剂的制备及CH4/N2吸附分离性能

采用浓度为0.2g·ml^-1的葡萄糖溶液对13X沸石/活性炭复合材料(AC/X)进行碳沉积,研究沉积次数对复合吸附剂(AC/X-G)孔结构、表面性质和CH₄/N₂吸附分离性能的影响。通过X射线衍射,77K下的N₂吸附/脱附,扫描电镜,CO₂-TPD以及红外光谱表征样品的晶型、孔结构和表面性质,在298K、100kPa下对其CH₄和N₂吸附等温线进行测定,并将吸附结果与文献中碳材料和13X沸石的吸附性能进行比较。结果表明:随着沉积次数的增加,AC/X-G吸附剂中X型沸石的相对含量降低,微孔比表面积和微孔体积减少。AC/X-G的表面被碳膜覆盖,碱量降低,但出现强碱位和含氧基团C-O键。AC/X-G的CH₄和N₂吸附量下降,但吸附分离系数提高,沉积3次的样品AC/X-G-3的CH₄/N₂吸附分离系数达到3.0,表面的含氧基团有利于提高复合材料的CH₄/N₂吸附分离性能。     

Preparation of a heterogeneous hollow‐fiber affinity membrane having a mercapto chelating resin and its recovery of Hg2+ cations

A kind of heterogeneous hollow‐fiber affinity filter membrane with a high chelating capacity for Hg²⁺ was prepared by phase separation with blends of a mercapto chelating resin and polysulfone as the membrane materials, N,N‐dimethylacetamide as the solvent, and water as the extraction solvent. The adsorption isotherms of the hollow‐fiber affinity filter membrane for Hg²⁺ were determined. The heterogeneous hollow‐fiber affinity filter membrane was used for the adsorption of Hg²⁺ cations through the coordination of the mercapto group and Hg²⁺ cations, and the effects of the morphology and structure of the affinity membrane on the chelating properties were investigated. The chelating conditions, including the chelating resin grain size, pH value, concentration of the metallic ion solution, mobile phase conditions, and operating parameters, had significant effects on the chelating capacity of the hollow‐fiber affinity filter membrane. The results revealed that the greatest chelating capacity of the hollow‐fiber affinity filter membrane for Hg²⁺ was 1090 μg/cm² of membrane under appropriate conditions, and the adsorption isotherms of Hg²⁺ could be described by the Langmuir isotherm. The dynamic chelating experiments indicated that the hollow‐fiber affinity membrane could be operated at a high feed flow rate and that large‐scale removal of Hg²⁺ could be realized. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hierarchically porous graphitic carbon monoliths containing nickel nanoparticles as magnetically separable adsorbents for dyes

The hierarchically porous graphitic carbon monoliths containing nickel nanoparticles (HPGCM‐Ni) were fabricated via multi‐component co‐assembly in polyurethane (PU) foam scaffold associated with a direct carbonization process from triblock copolymer F127, diblock copolymer PDMS‐PEO, phenolic resol, and nickel nitrate and subsequent silicates removal with NaOH solution. The decomposable PU foam scaffold played important role in the process of multi‐component co‐assembly and macrostructure formation. The nickel salts were reduced to metallic Ni nanoparticles during the carbonization process. The obtained HPGCM‐Ni materials exhibited macropores of 100–450 μm, mesopore size of 7.2 nm, BET surface area of 725 m² g^?1, pore volume of 0.74 cm³ g^?1, and saturation magnetization of 2.3 emu g^?1. Using methyl orange as model dye pollutant in water, HPGCM‐Ni samples showed good adsorption capacity of 440 mg g^?1, exhibiting excellent adsorption characteristics desirable for the application in adsorption of dyes and separation under an external magnetic field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41322.     

铝基锂吸附剂制备及其吸附性能研究

以氯化锂、无水氯化铝为原料,通过正交实验优化反应合成条件,采用“一步法”制备LiCl·2Al（OH）₃·nH₂O型铝基锂吸附剂。分别探究了吸附时间、吸附温度、溶液初始pH、溶液初始Li⁺浓度对吸附性能的影响,对吸附前后的无机铝吸附材料做了表征,并考察了吸附剂的离子选择吸附性及稳定性能。结果表明：最佳吸附条件为在45 ℃下pH=7的锂溶液中吸附2 h,吸附容量高达到8.66 mg/g。XRD、FT-IR表征结果表明：所制吸附材料有良好的稳定性。且该吸附剂对Li⁺分配系数（K=10.06）远高于其他金属阳离子,吸附材料经5次循环使用后,吸附容量仍能保持原来的91.5%。在西藏龙木错盐湖卤水中,对锂的吸附量达到5.24 mg/g。吸附平衡数据拟合结果表明：铝基锂吸附剂符合Langmuir等温吸附模型,吸附是发生在吸附剂表面的单层吸附;吸附过程符合伪二级动力学,是典型的化学吸附过程。     

ZL50活性炭吸附脱除二氧化硫的吸附动力学模型(英文)

A semi-empirical adsorption kinetic model was proposed with the time compensation method to describe the chemisorption of SO2 in flue gas by carbon adsorbents for flue gas purification. The change in adsorption capacity and adsorption rate with time at different water vapor concentrations and different SO2 concentrations was studied. The model was in good agreement with experimental data. The surface reaction was probably the rate controlling step in the early stage for SO2 adsorption by ZL50 activated carbon. The parameters m and n in the nth order adsorption kinetic model were related to the magnitude of the time compensation and adsorption driving force, respectively. The change of parameter n with water vapor concentrations and sulfur dioxide concentrations was studied and some physical implications were given. The sum of square errors was less than 1.0 and the average absolute percentage deviations ranged from 0.5 to 3.2. The kinetic model was compared with other models in the literature.     

功能化离子液体在二氧化碳吸收分离中的应用

吸收及分离二氧化碳是降低碳排放和应对全球气候变化的主要策略之一,这就必然要求全球科技工作者注重开发具有选择性高效吸收分离二氧化碳的新材料和新路线。作为近20多年来发展的一类代表性的新材料,离子液体（尤其是功能化离子液体）具有独特的物理化学性质,例如几乎没有蒸气压、液态温度范围大、热稳定性和化学稳定性好、电化学窗口宽、不可燃、结构-性质可调控等。这些性质使离子液体在二氧化碳吸收及分离领域受到广泛关注。重点综述了近5年（2015~2019）来功能化离子液体吸收分离二氧化碳的研究进展, 主要内容包括单位点离子液体、多位点离子液体、基于功能化离子液体的混合物、功能化离子液体杂化材料对二氧化碳的吸收分离。同时, 对目前该领域的发展所面临的主要问题和进一步的研究工作进行了分析讨论。     

吸附制冷用复合吸附剂的吸附性能

固体吸附式制冷因具有环保和节能两大优势,成为国内外竞相开发的热点,尤其是将其用于新型空调系统和太阳能应用产品方面的开发研究备受关注．但从实用化研究成果来看,还远不满足工业化条件,其主要原因之一是受吸附制冷工质对（吸附剂-制冷剂）的性能制约．目前,国内外关于吸附制冷工质对的研究报道比较多,所采用的吸附（工）质仍然以水、甲醇、乙醇和氨为主,对于吸附剂的研究进展比较快,已从当初单一组分吸附剂的选用发展到目前多组分、复合吸附剂的研制．研制性能优良的吸附剂被认为是推动固体吸附式制冷工业化的关键之一．     

Preparation of Cr(VI)-imprinted polypropylene nonwoven fibers using plasma polymerization-assisted grafting

Polypropylene (PP) fibers were grafted with glycidyl methacrylate (GMA) using plasma polymerization and then aminated, imprinted, and crosslinked to prepare Cr(VI)-imprinted fibers. The plasma polymerization conditions were optimized by single factor experiment and response surface methodology, and various properties and adsorption mechanism of the fibers were analyzed. The results showed that at pH 3, the imprinted fibers had a maximum Cr(VI) adsorption capacity of 173.36 mg/g, and the adsorption equilibrium could be reached within 40 min. In the presence of competing ions (SO₄²⁻, NO₃⁻ and PO₄³⁻) each at a concentration of 5 times of that of Cr(VI), the Cr(VI) adsorption rate of the fibers could be maintained at around 50%, which indicates that the imprinted fibers have high selectivity towards Cr(VI). The results also showed that the imprinted fibers had good reusability and enrichment ability, thus can be a good candidate for treating actual Cr(VI)-contaminated water.     

燃烧后CO_2捕集技术研究

对燃烧前、燃烧后CO2捕集以及富氧燃烧3种CO2捕集技术的特点,以及适用于燃煤电厂的燃烧后CO2捕集技术进行了介绍,分析了吸收分离法、吸附分离法和膜分离法的原理及优缺点。其中,化学吸收法应用最广,但再生能耗大,运行成本高;吸附法虽再生能耗小,但对CO2选择性低,吸附能力有限;膜分离法目前仍处于实验室研究阶段,但应用前景巨大。对上述技术整合形成复合技术以及对新材料进行开发将有助于克服现有CCS技术面临的困难。     

Preparation of polysulfone hollow fiber affinity membrane modified with mercapto and its recovery properties. II. Preparation of PSF‐SH hollow fiber affinity membrane for recovery of Hg2+

A high qualified polysulfone hollow fiber affinity membrane modified with mercapto as chelating groups was prepared by phase inversion technology using chlormethyl polysulfone (CMPSF) as membrane matrix materials, through the reaction between thiourea and CMPSF hollow fiber matrix membrane to afford the methyl isothiourium polysulfone and was then alkaline hydrolyzed. The adsorption isotherms of the hollow fiber affinity membrane chromatography for Hg²⁺ were determined, and the effects of mobile phase conditions and the operating parameters on removal performance of the hollow fiber affinity membrane chromatography for Hg²⁺ were also investigated. The experimental results showed that adsorption isotherms of Hg²⁺ could be described by the Langmuir isotherm. Addition of NaCl into feed solution for the increase of ionic strength was harmful for the removal of Hg²⁺. The recovery of Hg²⁺ decreased at low pH and the optimum range of pH was from 5.0 to 7.0. The feed concentration had a remote effect on recovery of Hg²⁺ at the specified loading amount of Hg²⁺, and the Hg²⁺ could be removed from different concentration feed solution by the hollow fiber affinity membrane chromatography. The increase of feed flow rate led to slight decrease of recovery of Hg²⁺ at the specified loading amount of Hg²⁺. The hollow fiber affinity membrane chromatography could be operated at height feed flow rate and a large scale removal of Hg²⁺ could be realized. With the increase of load amount, Hg²⁺ recovery decreased, but the saturation degree of hollow fiber affinity membrane chromatography increased. According to required recovery of Hg²⁺ and the saturation degree of membrane chromatography, the optimum loading amount of Hg²⁺ should be selected in the actual removal of Hg²⁺. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4795–4803, 2006