利用粉状聚合物吸附剂脱除盐酸溶液中氯仿的研究

为了选择合适的吸附剂来脱除盐酸溶液中的氯仿,本文测定了几种聚合物吸附剂在298.15 K温度下对水溶液和20%盐酸溶液中氯仿的吸附等温线,考察了其吸附能力,并将其吸附能力与活性炭和固体石蜡进行了比较。所研究的吸附剂包括粉末状氯化橡胶,聚丙烯,氯化聚丙烯,聚氯乙烯,活性炭和固体石蜡。结果表明,这些吸附剂的吸附行为服从Langmuir 方程,其吸附能力的次序为活性炭>聚氯乙烯>氯化橡胶>聚丙烯 >氯化聚丙烯 >固体石蜡。该次序基本上与从聚氯乙烯到固体石蜡吸附剂中氯含量逐渐降低的次序相一致。聚氯乙烯与氯化橡胶的吸附能力与活性炭相当,其饱和吸附量大约为1.4g-CHCl3/g-吸附剂。所有吸附剂对氯仿的吸附能力均随着溶液中盐酸浓度的增加而降低。结果表明,工业级的粉状聚氯乙烯或氯化橡胶可以作为一种有效的吸附剂脱除水溶液中的氯仿,且具有成本低,吸附性好和易于通过热再生循环利用的特点。     

钙基类吸附剂脱除烟气中气态汞的试验研究

用恒温水浴中汞渗透管的汞蒸气发生装置和其他烟气主要气体成分模拟烟气条件，在小型固定床试验台上开展钙基类物质作为吸附剂脱除单质汞的试验研究。结果表明，无SO2时，两种钙基吸附剂以及飞灰和熟石灰混合物对单质汞的吸附效率不高；当SO2存在时，对单质汞的脱除效率可增加15％～20％，30min时吸附量可增加50％以上，且吸附在较高温度下更有利。其原因在于SO2同钙基吸附剂之间的化学反应，在钙基物质表面产生了活性区域，有利于提高对Hg0的捕捉效率，化学吸附起到了促进吸附的作用。     

活性炭的表面处理对二苯并噻吩催化氧化脱除的影响

将一种木质活性炭经过三种表面处理,即高锰酸钾稀硫酸溶液液相氧化、浓硝酸液相氧化和350℃低温气相氧化处理。实验所选活性炭及相应的表面改性炭使用氮气吸附和Boehm滴定分别进行了结构性质和表面化学表征。研究了所选活性炭和相应的表面改性炭催化过氧化氢氧化脱除二苯并噻吩（DBT）。实验结果表明,活性炭表面化学对二苯并噻吩的氧化脱除影响很大;炭表面化学对DBT吸附脱除的影响不同于对DBT氧化脱除的影响,表面酸性越强越有利于DBT的吸附;表面羰基能加速过氧化氢产生自由基,表面羰基量的增加明显有利于DBT的氧化脱除。活性炭经过热处理后,在二苯并噻吩的氧化脱除中催化活性明显增加,正辛烷溶液中硫的体积质量从0.556g·L-1降到0.009g·L-1。     

氨再生条件对V2O5/AC同时脱硫脱硝活性的影响

对烟气同时脱硫脱硝过程中吸附SO2后的活性炭载V2O5（V2O5/AC）催化 吸附剂在含NH3气氛下的再生条件进行了考察，发现3%～5%NH3/Ar气氛、300℃、60min再生可有效恢复V2O5/AC的脱硫活性，并明显提高其脱硝活性。基于对SO2和NO的脱除率、再生后V2O5/AC的硫质量分数以及FT IR谱图分析发现，NH3的存在对V2O5/AC所吸附硫的脱附行为没有明显影响，但可显著改变V2O5/AC的表面化学性质，有利于烟气脱硫；NH3还可在V2O5/AC表面储存，显著促进脱硝。     

甲烷在富纳米孔炭质吸附剂上的吸附

分析了以石油焦为原料采用复合活化工艺制备的吸附剂的孔结构特性。发现吸附剂微孔含量在90%以上并且主要集中于1 nm～2 nm之间，是富含纳米孔的吸附材料。甲烷在此吸附剂上的吸附研究表明，在25 ℃，3.5 MPa的条件下，甲烷质量吸附量超过14.0%；有效体积吸附量超过120?V/V(吸附甲烷的体积/容器的体积)。甲烷在富纳米孔炭质吸附剂上的等温吸附曲线表明，吸附类型属于Ⅰ类吸附，符合微孔填充理论；等压吸附曲线表明，低温有利于体积吸附量的增加；吸附剂中水分的增加对吸附有不利的影响。     

两种金属有机配合物的制备及其对多环芳烃吸附性能的考察

用水热合成和常温合成法分别制备了以锌离子和铜离子为主体、1,2,4-苯三甲酸和4,4’-联吡啶为配体的两种金属有机配合物材料,并考察了其对多环芳烃（PAHs）的吸附性能。用粉末衍射仪（XRD）、热重分析仪（TGA）、傅里叶红外光谱仪（FT-IR）、扫描电镜仪（SEM）和比表面积测试仪（BET）表征了材料的组成、形貌、热稳定性和吸附等性能。结果表明,两种配合物具有较好的热稳定性和吸附能力;PAHs在两种配合物材料上的吸附动力学均符合假二级动力学模型,吸附行为均符合Langmuir方程,且两种配合物对PAHs吸附量随着配合物用量的增加而增大。此外,两种配合物材料对10种PAHs均能有效富集吸附,且吸附具有选择性。通过对该金属有机配合物材料进一步优化有望作为色谱固定相使用。     

活性炭纤维的脱硫性能

活性炭纤维作为一种新型高效吸附剂，在环保领域尤其是在烟气脱硫方面显示了广阔的应用前景。本文在作者所做工作和分析别人实验结果的基础上，综述了包括前驱体材料、制备条件以及活性炭纤维表面物理化学性能等影响活性炭纤维脱除烟气中SO2的主要因素，阐述了活性炭纤维脱硫的反应机理。认为含有较多量氮元素的前驱体材料具有较高的脱硫性能，类似的结果也出现在用不同方法制备的活性炭纤维中；众多的研究结果表明，活性炭纤维表面化学性能的影响尤其是表面物理性能的影响，其中表面含氧官能团对活性炭纤维脱除SO2不利，但用热处理方法脱除掉以CO形式释出的含氧官能团后可显著增强活性炭纤维的脱硫活性；此外，含氮官能团引入到活性炭纤维表面后也可显著增强活性炭纤维的脱硫活性。     

微波辐照活性炭床烟气脱硝实验研究

微波诱导催化作用结合活性炭的吸附和还原能力可以实现烟气中氮氧化物的还原脱除. 利用微波反应器开展了微波辐照活性炭烟气脱硝实验, 研究了微波辐照功率(反应温度)、烟气流率、NO浓度以及烟气共存成分对脱硝效率的影响. 实验结果表明, 微波功率越高, 脱硝效率也越高, 在560 W可达80%左右的脱硝效率|活性炭质量越大脱硝反应越完全, 50 g活性炭可脱除83%的NO|烟气流率增加脱硝效率降低|烟气中氧的存在对脱硝有一定促进作用, 烟气含湿量过大对脱硝不利. 脱硝反应动力学研究表明, NO的反应级数近似为1, 速率常数为k＝1.33 min^－1. BET测试表明, 微波辐照活性炭后其表面积有少量下降.     

活性炭孔隙结构对催化氧化脱除单质汞的影响

研究活性炭在硫化氢存在条件下催化氧化脱除煤气中单质汞的吸附机理和探讨提高其吸附能力的方法,在模拟煤气气氛下对3种活性炭和一种活性焦进行汞的吸附性能实验,并进一步分析活性炭(焦)的孔隙结构。用BET方程处理N₂等温吸附数据,计算比表面积;用HK法进行微孔分析;用BJH法计算中孔孔径分布。结果表明,硫化氢被催化氧化后,生成吸附在活性炭孔壁上的活性硫促进了对汞的吸附;随着活性炭微孔和中孔体积的增大,活性炭对汞的吸附能力得到提高。     

活性炭的改性及对Pb2+的动力学吸附研究

论文以活性炭为主体吸附剂，进行氯化铁改性，制备出氯化铁改性活性炭吸附剂，并通过FT-IR、SEM、比表面积和孔体积进行表征。实验进一步探究改性活性炭对Pb²⁺的吸附能力，结果表明，当吸附时间为300 min,吸附剂投加量为0.4 g, pH为6时，吸附效果最佳。在此吸附条件下，改性活性炭对Pb²⁺的去除率达到91.2%。对改性活性炭吸附Pb²⁺进行动力学吸附研究，结果表明二级速率方程能够更好地描述其动力学吸附过程，吸附的机理可归结为氯化铁改性导致活性炭孔道结构中酸性官能团增加，使得金属阳离子与官能团上的H之间产生离子交换作用，有利于吸附的进行，这一实验结果为后期循环吸附研究提供了新依据。     

Sensitive determination of polycyclic aromatic hydrocarbons in water samples by HPLC coupled with SPE based on graphene functionalized with triethoxysilane

The graphene functionalized with (3‐aminopropyl) triethoxysilane was synthesized by a simple hydrothermal reaction and applied as SPE sorbents to extract trace polycyclic aromatic hydrocarbons (PAHs) from environmental water samples. These sorbents possess high adsorption capacity and extraction efficiency due to strong adsorption ability of carbon materials and large specific surface area of nanoparticles, and only 10 mg of sorbents are required to extract PAHs from 100 mL water samples. Several condition parameters, such as eluent and its volume, adsorbent amount, sample volume, sample pH, and sample flow rate, were optimized to achieve good sensitivity and precision. Under the optimized extraction conditions, the method showed good linearity in the range of 1–100 μg/L, repeatability of the extraction (the RSDs were between 1.8 and 2.9%, n = 6), and satisfactory detection limits of 0.029–0.1 μg/L. The recoveries of PAHs spiked in environmental water samples ranged from 84.6 to 109.5%. All these results demonstrated that this new SPE technique was a viable alternative to conventional enrichment techniques for the extraction and analysis of PAHs in complex samples.     

Microcolumn liquid chromatography on carbon sorbents

Summary The retention volume dependences on the molar volume were found for aromatic compounds using liquid microcolumn chromatography. The contributions of the functional groups in molecules of these compounds to the total retention value were calculated from the capacity factor values. The comparison of capacity factor values for carbon sorbents and octadecyl-silicagel has shown that for several microcolumn separations the carbon sorbent column has a better selectivity and resolution than the octadecyl-silicagel column.     

Methane preconcentration in a microtrap using multiwalled carbon nanotubes as sorbents

The GC monitoring of green house gases is a challenging task because the concentration of organic species such as methane are relatively low (ppm to ppb) and their analysis requires some level of preconcentration. Since methane is highly volatile, it is not easily retained on conventional sorbents. In this paper we present multiwalled carbon nanotubes (MWNTs) as an effective sorbent for a microtrap designed for methane preconcentration. Its performance was compared to other commercially available carbon based sorbents, and it was found to be the most effective sorbent in terms of breakthrough volume and enthalpy of adsorption.     

Preparation of carbon coated Fe3O4 nanoparticles and their application for solid-phase extraction of polycyclic aromatic hydrocarbons from environmental water samples

The carbon coated Fe₃O₄ nanoparticles (Fe₃O₄/C) were synthesized by a simple hydrothermal reaction and applied as solid-phase extraction (SPE) sorbents to extract trace polycyclic aromatic hydrocarbons (PAHs) from environmental water samples. The Fe₃O₄/C sorbents possess high adsorption capacity and extraction efficiency due to strong adsorption ability of carbon materials and large surface area of nanoparticles, and only 50 mg of sorbents are required to extract PAHs from 1000 mL water samples. The adsorption attains equilibrium rapidly and analytes are eluted with acetonitrile readily. Salinity and solution pH have no obvious effect on the recoveries of PAHs, which avoids fussy adjustment to water sample before extraction. Under optimized conditions, the detection limits of PAHs are in the range of 0.2–0.6 ng L⁻¹. The accuracy of the method was evaluated by the recoveries of spiked samples. Good recoveries (76–110%) with low relative standard deviations from 0.8% to 9.7% are achieved. This new SPE method provides several advantages, such as high extraction efficiency, high breakthrough volumes, convenient extraction procedure, and short analysis times. To our knowledge, this is the first time that Fe₃O₄/C nanoparticles are used for the pretreatment of environmental water samples.     

CARBONIZED FIBROUS RESIN AS A NEW SORBENT FOR SAMPLING POLYCYCLIC AROMATIC HYDROCARBONS （PAHS）IN AMBIENT AIR

A new sampling method of ambient air analysis using carbonized fibrous resin as a sorbent for polycyclic aromatic hydrocarbons(PAHs) was reported.The physical and chemical properties of the carbonized fibrous resins were measured.The sample pretreatment with ultrasonic extraction and subsequent clean-up elution through a silica gel column was optimized.The suitable ultrasonic extraction conditions were selected as follows:resin weight was 1.5g,ultrasonic extraction time 20min,volume of extraction solvent 100 ml and extraction operation times 2-3.The concentrated extractable organic matter was submitted to next step of clean-up procedure of adsorption chromatography on silica gel column/n-hexane and a mixture of dichloromethene:n-hexane solution 2:3(v/v).The PAHs fractions in the real samples from Changzhou,China were particularly analyzed using GC-MS data system and the data of mass spectra,retention times and scan numbers of the real samples were compared with that of the standards of 16 PAHs listed by the US EPA as “priority pollutants” of the environment. The pretreatment of samples of ambient air with carbonized fibrous resin as a sorbent for PAHs is proved to be reliable and might be used for the procedure of the determination of PAHs in atmospheric environment.     

Desulfurization of liquid fuels by adsorption on carbon-based sorbents and ultrasound-assisted sorbent regeneration

Several carbon-based adsorbents, CuCl/AC, PdCl2/AC, and Pd/AC (where AC denotes activated carbon), were studied for desulfurization of a model jet fuel by selective adsorption of thiophenic molecules. Comparisons with gamma-Al2O3 support and desulfurization of a commercial jet fuel were also studied. The results showed that the selective sulfur adsorption capacity of PdCl2 was higher than that of CuCl and Pd(0), in agreement with molecular orbital results. It was also found that the activated carbon is the best support for pi-complexation sorbents to remove sulfur-containing compounds, i.e., benzothiophene and methylbenzothiophene. Among all the adsorbents studied, PdCl2/AC had the highest capacity for desulfurization. A significant synergistic effect was observed between the carbon substrate and the supported pi-complexation sorbent, and this effect was explained by a geometric effect. The saturated sorbent was regenerated by desorption assisted by ultrasound with a solvent of 30 wt % benzene and 70 wt % n-octane. The results showed that the amount of sulfur desorbed was higher with ultrasound, 65 wt % desorption vs 45 wt % without ultrasound in a static system at 50 degrees C.     

Enrichment of polycyclic aromatic hydrocarbons in seawater with magnesium oxide microspheres as a solid-phase extraction sorbent

The enrichment of polycyclic aromatic hydrocarbons (PAHs) in water samples with magnesium oxide (MgO) microspheres was evaluated, and four 3-5-ring PAHs were used as probes to validate the adsorption capacity of the material. Factors affecting the recovery of PAHs were investigated in detail, including the type and concentration of organic modifiers, elution solvents, particle size of the adsorbent, volume and flow rate of the samples, and the lifetime of MgO cartridges. The recoveries of four PAHs extracted from 20 mL of seawater spiked with standard PAHs ranged from 85.8% to 102.0% under the optimised conditions. The limits of detection varied from 1.83 ng L⁻¹ to 16.03 ng L⁻¹, indicating that the analytical method was highly sensitive. Additionally, the proposed method was successfully used to enrich PAHs in seawater. Compared to conventional methods, the proposed method consumed less organic modifier (5% acetone), and cheaper sorbents with comparable extraction efficiency were employed.     

SPE for the simultaneous determination of various isothiocyanates

Several SPE sorbents were investigated for the extraction of a group of chemically diverse isothiocyanates (ITCs). They included bonded silica, carbon‐based, and polymer‐based sorbents with various functional groups. Results showed large differences in the ability of these sorbents to simultaneously extract ITCs from standard solutions. Recovery rates were on average the highest with divinylbenzene (DVB) based polymeric sorbents, especially with a DVB/N‐vinylpyrrolidone copolymer that had recovery rates ranging between 86.7 and 95.6%. These sorbents achieved the most balanced extraction efficiency between aliphatic and aromatic, polar, and nonpolar ITCs. With graphitized carbon, C₁₈‐bonded silica, and amide‐containing sorbent, recovery levels were higher for the two least polar aromatic ITCs (benzyl ITC and phenylethyl ITC), whereas for the polar aliphatic ITCs levels were the lowest. The least retained one, was methyl ITC that is the most polar with recoveries between 0 and 31.5%. The presence of amide groups, especially in a polyamide sorbent, appeared to be particularly unsuitable for the extraction of aliphatic ITCs. A copolymer made up of DVB and N‐vinylpyrrolidone was therefore shown to be the most suited for the extraction of both aliphatic and aromatic ITCs.     

黏结剂对铁酸锌脱硫剂在高温煤气中脱硫性能的影响

以硝酸铁、硝酸锌、氨水及黏结剂为主要原料,用共沉淀法制成六种铁酸锌脱硫剂。研究了各种黏结剂的加入对脱硫剂的尖晶石结构、硫容量和脱硫效果的影响,在固定床上对其进行脱硫试验。并用X射线衍射（XRD）、扫描电子显微镜(SEM)和气体吸附等测试手段,对脱硫剂的物相组成、结构、比表面积和孔容进行了表征。结果表明,用共沉淀法制备的铁酸锌,具有不受黏结剂影响的尖晶石结构,其颗粒属于微米级;添加高岭土黏结剂的脱硫剂的脱硫效果最好,添加硅藻土的脱硫剂的脱硫效果最差;不同黏结剂对脱硫剂的织构的影响不同;脱硫剂的反应活性和硫容量与其孔容的大小有关。     

葡萄糖还原法制备CuCl/NaY吸附剂及其CO吸附和CO/H2分离性能

以NaY分子筛为载体,CuCl2为铜源,加入还原剂葡萄糖,在温和条件下制备CuCl/NaY吸附剂,通过变压吸附考察了该吸附剂对CO的吸附性能及CO/H2的分离性能。运用X射线衍射（XRD）、X射线光电子能谱（XPS）及程序升温还原（TPR）对吸附剂进行表征,结果表明采用葡萄糖还原法制备CuCl/NaY吸附剂,其制备条件温和,吸附剂表面的亚铜含量高,对CO的吸附及CO/H2的分离性能优越且稳定性好。