活性炭催化氧化脱除单质汞的研究

模拟煤气的气氛,在硫化氢（H₂S）和氧气（O₂）存在条件下,对活性炭催化氧化吸附单质汞（Hg⁰）的性能进行了研究。结果表明,H₂S和O₂存在条件下,活性炭对Hg⁰的吸附能力明显提高。在180min内,H₂S和O₂共存气氛下,脱汞效率约为78%;只有H₂S存在下,脱汞效率约为69%;没有H₂S和O₂气氛下活性炭脱汞效率快速下降为28%。随着吸附温度的升高,入口汞浓度的提高和吸附剂粒径的增大,活性炭的脱汞效率会随着下降。通过XRD表征表明,Hg⁰的吸附反应机理是Hg⁰在活性炭催化氧化下与H₂S形成硫化汞（HgS）,从而实现了Hg⁰的稳定化脱除。     

聚丙烯腈活性炭纤维对硫化氢的常温吸附

聚丙烯腈活性炭纤维（PAN-ACF）对硫化氢（H2S）有比其他活性炭材料更强的吸附能力。H2S在PAN-ACF上的吸附是一个兼具物理吸附特征的化学吸附、催化转化过程。其化学吸附位主要位于微孔表面。吸附过程为：H2S分子首先被物理吸附进入微孔空间,而后在微孔表面的化学吸附位上进行包含电子转移的化学吸附、催化氧化,在炭表面产生相对稳定的化学结构。     

几种植物基活性炭材料的孔结构与吸附性能比较——(I)孔结构表征

测定了3种植物基活性炭材料:椰壳活性炭 (CAC4)、剑麻茎基活性炭 (SSAC) 和剑麻基活性碳纤维 (SACF) 的氮吸附等温线,并用不同的理论方法对其孔结构进行了分析和表征。结果表明:CAC4为微孔型,孔径分布集中且大部分是0.7nm以下的极微孔;在相同条件下制备的SSAC和SACF孔分布较为相似,都呈多分散性,结构中除微孔外,还含有丰富的中孔,中孔率均超过50%以上。两者相比,SACF的中孔量和平均孔径更大。3个样品的形态特征和孔结构虽然不同,但其吸附过程都可以用微孔多段填充机理来解析。     

无氧下低浓度硫化氢在浸渍活性炭上的吸附研究

为了考察常温、无氧下浸渍Na2CO3改性、原料气相对湿度对活性炭吸附硫化氢的促进作用，用动态吸附法分别测试了不同湿度下原活性炭和浸渍活性炭对低浓度硫化氢的吸附，同时考察了温度对该吸附过程的影响。结果表明，吸附平衡数据均符合Freundlich吸附等温方程。与原活性炭相比，浸渍活性炭的孔容和比表面积略有降低，但对硫化氢的吸附能力却显著提高，说明硫化氢与浸渍剂在活性炭表面上发生了化学反应。相对湿度增加，活性炭和浸渍活性炭对H2S的吸附能力均显著增强。温度升高，平衡吸附量均略有下降。     

几种植物基活性炭材料的孔结构与吸附性能比较--(Ⅰ)孔结构表征

测定了3种植物基活性炭材料：椰壳活性炭(CAC4)、剑麻茎基活性炭(SSAC)和剑麻基活性碳纤维(SACF)的氮吸附等温线，并用不同的理论方法对其孔结构进行了分析和表征．结果表明：CAC4为微孔型，孔径分布集中且大部分是0．7nm以下的板微孔：在相同条件下制备的SSAC和SACF孔分布较为相似，都呈多分散性，结构中除微孔外，还含有丰富的中孔，中孔率均超过50％以上．两者相比，SACF的中孔量和平均孔径更大，3个样品的形态特征和孔结构虽然不同，但其吸附过程都可以用微孔多段填充机理来解析。     

吸附树脂和活性炭对气体中苯的吸附研究

采用了动态吸附实验方法研究了吸附树脂NDA-201和椰壳型活性炭C1对苯蒸汽的吸附行为.对吸附平衡数据采用Dubinill-Astakov方程进行了拟合分析,并根据吸附剂孔结构特征探讨了吸附机理.实验结果表明,两种吸附剂的苯吸附等温线存在交叉现象,对高浓度苯蒸汽吸附治理可采用NDA-201树脂,低浓度则采用椰壳型活性炭C1;Dubinin-Astakov方程能用来对两种吸附剂的等温线进行拟合,表明吸附剂的微孔区域对吸附起着重要作用.微孔体积计算值的比较和特征曲线叠合的程度说明了.Polanyi吸附势理论更适合于描述椰壳型活性炭C1对苯的吸附,这可能是由于椰壳型活性炭C1的孔分布集中于微孔区,而NDA-201树脂除了微孔外还有一定量的中孔和大孔.     

Fe-K/AC催化氧化脱硫剂制备及反应机理研究

采用正交实验法制备了负载铁、钾的活性炭(Fe-K/AC)热煤气催化氧化脱硫剂,考察了活性组分铁、钾含量、二价铁和三价铁比例、煅烧温度对催化氧化脱硫反应活性的影响。由正交实验极差分析可知,各因素影响程度依次为:钾含量>铁含量>煅烧温度> Fe²⁺/Fe³⁺,最优制备条件为,铁含量0.5%、钾含量5.0%、煅烧温度600 ℃、Fe²⁺/Fe³⁺比0.5。通过对脱硫剂的孔隙结构和表面形貌分析可知,活性炭表面负载的铁金属氧化物具有催化氧化硫化氢生成单质硫的活性,碱金属氧化物具有协同作用,可以改变表面酸碱性,促进硫化氢的催化转化,但过高的金属氧化物负载量会阻塞孔道,减小反应比表面积,从而降低脱硫剂的反应活性。     

硫化氢对活性炭脱除单质汞的影响

H₂S是煤气中的含硫成分,活性炭能否催化氧化煤气中的H₂S形成活性硫,以促进H₂S和Hg⁰的协同脱除是值得研究的。 本文首先通过程序升温脱附和热力学分析了低温情况下H₂S对活性炭脱除Hg⁰的影响。 在较低吸附温度130 ℃下,H₂S不仅不能作为硫源,还使活性炭对Hg⁰的吸附显著减弱,这主要是由于H₂S对活性炭表面的吸附氧的消耗以及H₂S对含氧官能团的氧的取代反应造成的。 在此基础上,进一步研究了高温下H₂S对活性炭的影响,高温也不能使活性炭有效渗入单质硫。 所以无论低温还是高温情况下,利用H₂S作为硫源使Hg⁰以HgS的形式脱除并不是活性炭脱汞的可行手段。 本文揭示了较宽的温度范围内H₂S对单纯的活性炭脱除Hg⁰的影响机理,能为用于煤气脱汞的活性炭的设计以及作为负载时机理研究提供支持作用。     

硝酸改性活性炭上氧/氮官能团对脱汞性能的促进作用

采用硝酸氧化手段对活性炭进行了表面处理, 并在固定床反应器上测试了其脱除单质汞的性能. 研究表明, 在模拟烟气中硝酸改性活性炭能有效脱除单质汞. 采用元素分析、Brunauer-Emmett-Teller (BET)比表面积、扫描电子显微镜(SEM)、拉曼(Raman)光谱、Boehm滴定、程序升温脱附(TPD)和X射线光电子能谱(XPS)等手段研究了活性炭表面官能团对其脱汞性能的影响. 结果表明: 硝酸氧化处理能同时增加活性炭表面含氧官能团和含氮官能团的含量. 与改性活性炭的物理性质相比, 其化学性质对脱汞性能的影响更大, 单质汞主要被改性活性炭氧化为HgO而去除. 在脱汞反应中, 羰基、酯基和酸酐等含氧官能团可能是活性吸附位点, 反应后这些官能团被还原为羟基或者醚基; 而吡咯等含氮官能团可能是活性催化位点. 此外, 基于上述表征结果提出了硝酸改性活性炭表面官能团的脱汞机制.     

Preparation and mechanism of Fe-K/AC for catalytic oxidation of hydrogen sulfide

采用正交实验法制备了负载铁、钾的活性炭(Fe-K/AC)热煤气催化氧化脱硫剂,考察了活性组分铁、钾含量、二价铁和三价铁比例、煅烧温度对催化氧化脱硫反应活性的影响.由正交实验极差分析可知,各因素影响程度依次为:钾含量＞铁含量＞煅烧温度＞ Fe2+/Fe3+,最优制备条件为,铁含量0.5％、钾含量5.0％、煅烧温度600℃、Fe2+/Fe3+比0.5.通过对脱硫剂的孔隙结构和表面形貌分析可知,活性炭表面负载的铁金属氧化物具有催化氧化硫化氢生成单质硫的活性,碱金属氧化物具有协同作用,可以改变表面酸碱性,促进硫化氢的催化转化,但过高的金属氧化物负载量会阻塞孔道,减小反应比表面积,从而降低脱硫剂的反应活性.     

Adsorption of oxygen-containing aromatics used in petrochemical,pharmaceutical and food industries by means of lignin based active carbons

The adsorption processes of three aromatic chemicals onto activated carbons (ACs) from aqueous solutions have been studied. Eucalyptus kraft lignin obtained from cellulose industry as a residual biomass has been used to prepare activated carbons by physical activation with CO₂. The influences of the activation time on the surface areas and pore volumes of the ACs were analyzed. The physicochemical properties and the surface chemical structure of the adsorbents have been studied by means of N₂ and CO₂ adsorption, ultimate analysis, XPS, TPD and SEM. XPS and TPD spectra of the ACs have suggested the presence of aromatic rings and carbon-oxygen functional groups in the solid surfaces. The potential use of the ACs for the removal of acetaminophen (paracetamol), salicylic acid and benzoic acid has been investigated at different pH, temperature and contact time. The adsorption equilibrium data have been correlated to Langmuir isotherm model. The thermodynamic study has been developed, the values of ΔH, ΔG, and ΔS have been calculated and they indicated that the processes are endothermic for acetaminophen and exothermic for salicylic and benzoic acids. The analysis of the kinetic experiments showed that the effective diffusivities are low; 10⁻¹² to 10⁻¹¹ cm²/s, and they are the corresponding to intraparticle mass transfer, which appears as the controlling step for the net adsorption processes.     

Effect of pore characteristics on electrochemical capacitance of activated carbons

Activated carbons (ACs) for electric double layer capacitors (EDLCs) were fabricated from waste tea leaves, activated with the pore-forming substances ZnCl₂ then, carbonized at high-temperature in N₂ atmosphere. The surface texture and porosity of the ACs were determined using transmission electron micros-copy and N₂ adsorption/desorption studies. The surface area of the 20 wt % ZnCl₂ treated sample was found to be 1029 m²g^?1 and had a distribution of micropores and mesopores. The electrochemical properties of the ACs were evaluated by using cyclic voltammetry and galvanostatic charge-discharge studies. ACs from waste tea leaves exhibited excellent specific capacitance as high as 196 F g^?1 in the 0.1 M Na₂SO₄ neutral electrolyte, with rectangular-like cyclic voltammetry curves at a cell potential of 1.5 V and good cyclability with a capacitance retention of 95% at a high current density of 100 mA g^?1 for 2000 cycles. The results show that the pore texture properties and specific surface area of ACs are dominated by changing carbonization temperature and the amount of activating agent ZnCl₂. The electrochemical performance is influenced mainly by surface area, but the pore size distribution becomes a dominating factor for specific capacitance of a carbon electrode material when the pore structure is in range of micropores/mesopores.     

Adsorption of mercury from single and multicomponent metal systems on activated carbon developed from cherry stones

The adsorption of mercury from a single/multi-solute aqueous solution by activated carbon (AC) prepared from cherry stones (CS) by chemical activation with H₃PO₄, ZnCl₂ or KOH is studied. Three series of AC (i.e., P, H₃PO₄; Z, ZnCl₂; K, KOH) were prepared by controlling the impregnation ratio and carbonization temperature. The textural characterization of AC was carried out by gas adsorption, mercury porosimetry and density measurements. The surface chemistry was analyzed by the pH of the point of zero charge (pH_zpc), FT-IR spectroscopy and Boehm’s method. Experiments of mercury adsorption were conducted by the batch method, using aqueous solutions of mercury and of mercury, cadmium and zinc without pH adjustment. The ACs possess a wide range of pore volumes and sizes. Their microporosity is usually well developed. The meso- and macropore volumes are higher for the P carbons and K carbons, respectively. BET surface areas as a rule range between 1000 and 2000 m²?g^?1. The pH_zpc is much lower for the P carbons. The content of acidic oxygen surface groups is lower for the K carbons, whereas the content of basic groups is higher for these carbons. The kinetics of the adsorption process of mercury is faster for ACs with high volumes of large size pores. However, the surface groups have a marked unfavorable influence on the kinetics. The pseudo-second order rate constant (k₂×10^?3, g/mol?h) is higher by the order Z-4-800 (67.69)>K-3-800 (43.45)>P-3.44-400 (36.98). The incorporation of zinc and cadmium to the mercury solution usually decelerates the adsorption process for the P carbons and Z carbons and accelerates it for the K carbons. The amount adsorbed of mercury is much larger for the K carbons than for the other ACs. For the Z carbons, competition effects of zinc and cadmium on the adsorption of mercury are negligible, which indicates that mercury adsorbs specifically on surface active sites of these adsorbents.     

Preparation of active carbons from corn stalk for butanol vapor adsorption

Active carbons(ACs) were prepared through chemical activation of biochar from whole corn stalk(WCS)and corn stalk pith(CSP) at varying temperatures using potassium hydroxide as the activating agent. ACs were characterized via pore structural analysis and scanning electron microscopy(SEM). These adsorbents were then assessed for their adsorption capacity for butanol vapor. It was found that WCS activated at900 °C for 1 h(WCS-900) had optimal butanol adsorption characteristics. The BET surface area and total pore volume of the WCS-900 were 2330 m2/g and 1.29 cm3/g, respectively. The dynamic adsorption capacity of butanol vapor was 410.0 mg/g, a 185.1% increase compared to charcoal-based commercial AC(143.8 mg/g).     

One‐stage Template‐free KOH Activation for Mesopore‐enriched Carbons and Their Application in CO2 Capture

Activated carbons with a high mesoporous structure were prepared by a one‐stage KOH activation process without the assistance of templates and further used as adsorbents for CO₂ capture. The physical and chemical properties as well as the pore structures of the resulting mesoporous carbons were characterized by N₂ adsorption isotherms, scanning electron microscopy (SEM ), X‐ray diffraction (XRD ), Raman spectroscopy, and Fourier transform infrared (FTIR ) spectroscopy. The activated carbon showed greater specific surface area and mesopore volume as the activation temperature was increased up to 600°C, showing a uniform pore structure, great surface area (up to ~815 m²/g), and high mesopore ratio (~55%). The activated sample exhibited competitive CO₂ adsorption capacities at 1 atm pressure, reaching 2.29 and 3.4 mmol/g at 25 and 0°C, respectively. This study highlights the potential of well‐designed mesoporous carbon as an adsorbent for CO₂ removal and widespread gas adsorption applications.     

Hydrogen adsorption in transition metal carbon nano-structures

Templated microporous carbons were synthesized from metal impregnated zeolite Y templates. Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were employed to characterize morphology and structure of the generated carbon materials. The surface area, micro- and meso-pore volumes, as well as the pore size distribution of all the carbon materials were determined by N₂ adsorption at 77 K and correlated to their hydrogen storage capacity. All the hydrogen adsorption isotherms were Type 1 and reversible, indicating physisorption at 77 K. Most templated carbons show good hydrogen storage with the best sample Rh-C having surface area 1817 m²/g and micropore volume 1.04 cm³/g, achieving the highest as 8.8 mmol/g hydrogen storage capacity at 77 K, 1 bar. Comparison between activated carbons and synthesized templated carbons revealed that the hydrogen adsorption in the latter carbon samples occurs mainly by pore filling and smaller pores of sizes around 6 Å to 8 Å are filled initially, followed by larger micropores. Overall, hydrogen adsorption was found to be dependent on the micropore volume as well as the pore-size, larger micropore volumes showing higher hydrogen adsorption capacity.     

The effect of pre-carbonization of mesophase pitch-based activated carbons on their electrochemical performance for electric double-layer capacitors

The activated carbons (ACs) are prepared from mesophase pitch which is pre-carbonized by using potassium hydroxide as an activating agent. Nitrogen adsorption at 77 K is used to characterize the surface area and the porous structure of the ACs. By changing the pre-carbonization temperature from 560 to 750 °C, the arrangement of the ACs’ microcrystallines might be controllable, and the pore size could be adjusted between 1.5 and 2.4 nm. The electrochemical performance of the ACs in organic solvent (1 M Et₄NBF₄ in propylene carbonate) is investigated by voltage sweep cyclic voltammetry and constant current charge–discharge cycling tests. The results show that the ions can transfer rapidly and freely in the pore larger than or equal to 1.85 nm, even when the current density increases to 25 A g⁻¹.     

Adsorption of phenol by oil-palm-shell activated carbons

Steam activated carbons from oil-palm shells were prepared and used in the adsorption of phenol. The activated carbon had a well-developed mesopore structure which accounted for 45% of the total pore volume. The BET surface area of the activated carbon was 1183 m²/g and a total pore volume of 0.69 cm³/g using N₂ adsorption at 77 K. The adsorption capacity of the activated carbon for phenol was 319 mg/g of adsorbent at 298 K. The adsorption isotherms could be described by both the Langmuir-Freundlich and the Langmuir equations. The adsorption kinetics consisted of a rapid initial uptake phase, followed by a slow approach to equilibrium. A new multipore model is proposed that takes into account of a concentration dependent surface diffusion coefficient within the particle. This model is an improvement to the traditional branched pore model. The theoretical concentration versus time curve generated by the proposed model fitted the experimental data for phenol adsorption reasonably well. Phenol adsorption tests were also carried out on a commercial activated carbon known as Calgon OLC Plus 12×30 and the agreement between these adsorption data and the proposed model was equally good.     

Influence of KMnO4 oxidation on the electrochemical performance of pitch-based activated carbons

In this work, activated carbons (ACs) are obtained from petroleum pitch by the combination of a chemical treatment with different potassium permanganate (KMnO₄) amounts, i.e., 0, 0.5, 1.0, and 2.0 g, and a chemical activation with KOH at a constant KOH/pitch ratio of 3/1. The effects of the chemical activating agent on the surface morphology and porosity are evaluated with scanning electron microscopy and N₂ adsorption isotherms at 77 K, respectively. The specific surface area of the pitch-based ACs is increased with increasing the amount of KMnO₄ pre-treatment and showed the highest value of 2,334 m² g^?1 at 2 g of KMnO₄ amount. The electrochemical performance of AC electrodes is examined by cyclic voltammetry and galvanostatic charge/discharge characteristics in 6 M KOH electrolyte. Among the prepared ACs, 2.0 K-ACs possesses a specific capacitance as high as 237 F g^?1 and showed excellent electrochemical performance due to its suitable porous structure and low interface resistance.