Study of diesel fuel desulfurization by adsorption

Removal of sulfur from diesel fuel by adsorption on a commercial activated carbon and 13X type zeolite was studied in a batch adsorber. Kinetic characterization of the adsorption process was performed applying Lagergren's pseudo-first order, pseudo-second order and intraparticle diffusion models using data collected during experiments carried out to determine the sulfur adsorption dependency on time. The experiments investigating adsorption efficiency regarding initial sulfur concentration were also performed and the results were fitted to Langmuir and Freundlich isotherms, respectively. Activated carbon Norit SXRO PLUS was found to have much better adsorption characteristics. The process of sulfur adsorption on the fore mentioned activated carbon was further studied by statistically analyzing data collected during experiments which were carried out according to three-factor two-level factorial design. Statistical analysis involved the calculation of effects of individual parameters and their interactions on sulfur adsorption and the development of statistical models of the process.     

The role of activated carbon as a catalyst in GAC/iron oxide/H2O2 oxidation process

The catalytic properties of granular activated carbon (GAC) in GAC/iron oxide/hydrogen peroxide (H₂O₂) system was investigated in this research. Batch experiments were carried out in de-ionized water at the desired concentrations of ethylene glycol and phenol. Rate constants for the degradation of hydrogen peroxide and the formation rate of iron species were determined and correlated with mineralization of ethylene glycol at various GAC concentrations. The observed first order degradation rate of hydrogen peroxide in the absence of iron oxide and organic matter increases linearity with the increasing of the GAC concentration. The decomposition rate of hydrogen peroxide was suppressed significantly as the solution pH became acidic or by reducing the surface area of the GAC. The reduction of the surface area was obtained by loading an organic compound (such as phenol) on the GAC or by using the oxidizing agent (H₂O₂). The addition of both chemicals, phenol and H₂O₂, affects mainly the surface area of the small pores, resulting in reducing the catalytic activity inside the micropores.The catalytic properties of the GAC were used to accelerate the formation rate of the ferrous ions, which is known in the literature to be the limiting rate reaction in the classic Fenton like reagent. It was shown that the ethylene glycol mineralization rate was increased by more than 50%.Finally, optimization of the GAC consumption leading to the fastest mineralization of the ethylene glycol, resulting in decreasing of the decomposition rate of H₂O₂ while enhancing the generation rate of ferrous ions.     

Microporous activated carbon prepared from coconut shells using chemical activation with zinc chloride

Microporous activated carbon samples were prepared from coconut shells (low-cost lignocellulose waste), using chemical activation with zinc chloride followed by physical activation. Textural characterization was performed using nitrogen adsorption at 77 K. The sample that presented the best characterization results was then evaluated for methane adsorption at pressures between 0.1 MPa and 7 MPa and temperatures in the range 283–333 K. At 298 K and 40 bar, a capacity of ca. 122 mg of methane/g of carbon (80 v/v) was observed, just short of the target established in Brazil for ANG in remote sites transportation (100 v/v). These results suggest that activated carbons prepared from coconut shells, using chemical activation followed by physical activation, may be further developed as potential adsorbents for natural gas storage applications.     

Kinetics of removal of p-toluene sulphonic acid from concentrated solution by granular activated carbon

The removal of p-toluene sulphonic acid (p-TSA) from concentrated solution by granular activated carbon (GAC) was studied in batch experiments. The first order rate constant was found to be 5.5010 × 10^?5 s^?1 for a solution of 1000 mg dm^?3. In order to establish the rate limiting step the pore and film diffusion coefficients were calculated from the half time equations. Film diffusion was found to be rate limiting. The average value of the external mass transport rate constant was 2.91 × 10^?6 cm s^?1. The adsorption isotherm was adequately described by the Langmuir model and belongs to type ‘H’ of Giles' classification.     

Effluent organic matter removal from reverse osmosis feed by granular activated carbon and purolite A502PS fluidized beds

Applying pre-treatments to remove dissolved organic matter from reverse osmosis (RO) feed can help to reduce organic fouling of the RO membrane. In this study the performance of granular activated carbon (GAC), a popular adsorbent, and purolite A502PS, an anion exchange resin, in removing effluent organic matter (EfOM) from RO feed collected from a water reclamation plant located at Sydney Olympic Park, Australia were evaluated and compared through adsorption equilibrium, kinetics and fluidized bed experiments. The maximum adsorption capacity (Q_max) of GAC calculated from the Langmuir model with RO feed was 13.4 mg/g GAC. The operational conditions of fluidized bed columns packed with GAC and purolite A502PS strongly affected the removal of EfOM. GAC fluidized bed with a bed height of 10 cm and fluidization velocity of 5.7 m/h removed more than 80% of dissolved organic carbon (DOC) during a 7 h experiment. The average DOC removal was 60% when the bed height was reduced to 7 cm. When comparing GAC with purolite A502PS, more of the later was required to remove the same amount of DOC. The poorer performance of purolite A502PS can be explained by the competition provided by other inorganic anions present in RO feed. A plug flow model can be used to predict the impact of the amount of adsorbent and of the flow rate on removal of organic matter from the fluidized bed column.     

水蒸气催化活化半焦制活性炭和氢气的研究

以神府半焦为原料,通过水蒸气催化活化法制备了活性炭和氢气。考察了不同金属氧化物对活性炭吸附性能、活化过程中氢气产量的影响。结果表明,氧化物对活性炭吸附性能以及氢气产量影响很大。当氧化铁和氧化钙共同催化时,所制得的活性炭性能较好,氢气产量较大;活性炭碘吸附值为678 mg/g,亚甲基蓝值为55 mg/g,BET比表面积为775 m2/g,总孔容达0.414 8 cm3/g,平均孔径为3.902 nm,活化阶段氢气的产量为535 mmol/g半焦,约占活化过程释放气体总量的73.90%。     

Dual functions of activated carbon air-cathode: Nitrobenzene removal and electricity production in microbial fuel cells

The removal of nitrobenzene (NB) in microbial electrochemical systems generally requires electrical power to operate systems in the mode of microbial electrolysis cells (MECs). The present study demonstrates that single-chamber microbial fuel cells (S-MFCs) assembled with a bioanode and an activated carbon (AC) air cathode could simultaneously remove NB and generate electricity. S-MFCs with 1 mM NB exhibit long term NB tolerance and stable electricity production, with NB removal up to 98% in an operation cycle and a maximum power of 16.2 ± 1.3 W m⁻³. High NB loadings significantly inhibited the activity of anodic biofilms, but the inhibition was reversible. Investigating the removal of NB and its reduction product aniline (AN) in different operations supported the fact that the adsorption at the AC air cathode is the main pathway for the removal of NB and AN from solution, except for the partial conversion of NB to AN by anaerobic reduction in solution. In S-MFCs, the activated carbon in the cathode plays both functions: catalyzing the oxygen reduction reaction and adsorbing NB and AN, so that the S-MFC assembled with the AC air cathode, unlike most NB removing MECs, functions as a system with both NB removal and electricity production.     

Pyrolysis of cellulose, xylan and lignin with the K2CO3 and ZnCl2 addition for bio-oil production

The chemical structure of liquid products of the wood biopolymers, i.e. cellulose, xylan and lignin pyrolysis at 450 °C with and without the 10 wt.% addition of potassium carbonate or zinc chloride was investigated. The yield of liquid products of pyrolysis was in the range of 24-44 wt.% and their form was depending on the chemical structure of pyrolyzed material. The potassium carbonate and zinc chloride addition to biopolymers has also influenced the temperature range of samples decomposition as well as the structure of resulted bio-oils. All bio-oils from biopolymer were dark-brown water-oil emulsions. Contrarily, bio-oils obtained from biopolymer with K₂CO₃ or ZnCl₂ addition were orange liquids with well-separated water and oil phases. All analyses proved that the composition and the quality of bio-oil strongly depends on both the nature of the starting sample and the presence of the additive. The FT-IR analyses of oils showed that oxygen functionalities and hydrocarbons contents highly depend on the type of biopolymer. Results confirmed the significant removal and/or transformation of oxygen containing organic compounds due to the zinc chloride and potassium carbonate presence during pyrolysis process.     

表面改性活性炭吸附CS2及微波场中再生的研究

利用浸渍法探讨氧化物和含氮物质表面改性活性炭对CS2吸附性能的影响,通过boehm滴定和FT-IR分析结果证明:双氧水改性使活性炭表面碱性基团数增多,CS2动态吸附量增大;氨水和乙二胺改性活性炭,其表面碱性基团数增多,并引入含氮官能团,提高了CS2吸附容量。建立微波再生正交实验,确定微波再生最优实验条件:微波功率110 W、辐射时间2 min、载气流量250 mL/min时,活性炭再生综合率最大。对改性活性炭进行TG-DSC热分析,为活性炭微波热再生提供可靠参考依据。实验结果证明:双氧水、氨水、乙二胺改性可提高活性炭综合再生恢复率,硝酸改性对活性炭再生不利。     

Effects of oxidative modification of carbon surface on the adsorption of sulfur compounds in diesel fuel

This work examines the effects of modification of activated carbons (ACs) by HNO₃ oxidation and gas-phase O₂ oxidation, respectively, on the liquid-phase adsorption of sulfur compounds in diesel fuel. The adsorption characteristics of the oxidized and the original AC samples were evaluated in a fixed-bed flow system by using a model diesel fuel containing 400 parts per million by weight (ppmw) of sulfur as thiophenic compounds and 10 wt% of aromatics in a paraffinic solvent. The pore structure and surface properties of the AC samples were characterized by N₂ adsorption, SEM, FTIR, XPS and surface pH measurements. The adsorptive selectivity factor of the AC samples increases in the order of benzothiophene (BT) ≈ naphthalene (Nap) < 2-methyl naphthalene (2-MNap) < dibenzothiophene (DBT) < 4-methyldibenzothiophene (4-MDBT) < 4,6-dimethyldibenzothiophene (4,6-DMDBT). It was found that the HNO₃ oxidation was an efficient method in improvement of the adsorption performance of the AC for sulfur compounds. The improved adsorption performance upon the HNO₃ oxidation can be attributed mainly to an increase in the acidic oxygen-containing functional groups. However, the improved adsorption capacity upon oxidation is unlikely due to an increase in mesoporous or microporous surface/volume, although such attribution might have been inferred from the literature. An excellent correlation between the concentration of the surface oxygen-containing functional groups and the adsorption capacity per unit area as well as a good relationship between the adsorption capacity and the surface pH value were observed in this work, which suggest that the adsorption of the sulfur compounds over AC from the liquid hydrocarbon fuel may involve an interaction of the acidic oxygen-containing groups on AC with the sulfur compounds.     

活性炭吸附法脱硫实验研究和工业性应用

研究了周期性水洗涤脱附对活性炭脱硫性能的影响。经过 4次吸附、脱附循环后 ,活性炭的动态吸附性能和脱附性能达到平衡。活性炭颗粒越小 ,床层穿透时间越长 ,脱硫效率越高。当进口SO2 质量分数为 3× 1 0 - 3时 ,活性炭脱硫效率达到96 %以上。工业性实验表明 ,采用水洗涤脱附 ,活性炭脱硫效率稳定。燃煤烟气工业性实验排放烟气SO2 质量分数小于 9×1 0 - 5,脱硫效率达到 93 %。     

Hydrodesulfurization of model diesel using Pt/Al2O3 catalysts prepared by supercritical deposition

Pt/Al₂O₃ catalysts with Pt loadings ranging from 0.5 to 11 wt.% were synthesized by supercritical carbon dioxide (scCO₂) deposition method. Transmission electron microscopy (TEM) images showed that the synthesized catalysts contained small Pt nanoparticles (1–4 nm in diameter) with a narrow size distribution, no observable agglomeration, and uniformly dispersed on the alumina support. The catalysts were found to be active for hydrodesulfurization of dibenzothiophene (DBT) dissolved in n-hexadecane (n-HD) without sulfiding the metal phase. The reaction proceeded only via the direct hydrogenolysis route in the temperature range 310–400 °C and at atmospheric pressure. The activity increased with increasing the metal loading. Increasing [H₂]₀/[DBT]₀ by either increasing [H₂]₀ or decreasing [DBT]₀, increased the DBT conversion. At a fixed weight hourly space velocity and feed concentration, conversion did not increase with increasing temperature beyond 330 °C. The presence of toluene inhibited the catalyst activity presumably due to competitive adsorption between DBT and toluene. Under the operating conditions, the reaction was far from equilibrium.     

超声波强化活性炭颗粒吸附PFOA和PFOS

研究了20 kHz超声波强化活性炭颗粒吸附不同种类水溶液中全氟辛烷磺酸（PFOS）和全氟辛酸（PFOA）的动力学。结果表明：平衡吸附被证实符合BET多层等温吸附,最大单层吸附容量为qmPFOS>qmPFOA;在PFOS和PFOA初始浓度为50 mg/L时超声波辐照下活性炭颗粒吸附符合表观拟二级动力学关系,平衡吸附容量和起始吸附速率分别为qePFOS>qePFOA和 hPFOS> hPFOA;在去离子水（MQ）中的PFOS和PFOA 最大单层吸附平衡容量qm和平衡吸附容量qe及起始吸附速率h和吸附动力学常数K均大于预处理或未预处理后的垃圾渗滤地表水（Pre-GW和GW）中对PFOS和PFOA的平衡吸附量和吸附动力学常数;20 kHz超声波强化活性炭颗粒吸附PFOS和PFOA效果明显,其吸附动力学常数增强因子为7.7和4.4。     

活性炭催化氧化脱除汽油和柴油中噻吩类硫化物的选择性

研究了活性炭催化氧化脱除汽油和柴油中噻吩类硫化物的选择性。采用气相色谱-硫化学发光检测器（GC-SCD）分析了汽油和柴油中噻吩类硫化物的分布及浓度;以活性炭作为催化剂,以30％过氧化氢溶液为氧化剂,在甲酸存在条件下考察了汽油和柴油中噻吩类硫化物催化氧化脱除的选择性,讨论了硫化物中硫原子电子密度对硫化物氧化选择性的影响。结果表明：汽油中噻吩类硫化物主要有噻吩（T）及其烷基衍生物（T alkylated derivatives）和苯并噻吩（BT）;而柴油中噻吩类硫化物主要分布有苯并噻吩(BT)及其烷基衍生物(BT alkylated derivatives)和二苯并噻吩（DBT）及其烷基衍生物（DBT alkylated derivatives）;硫原子电子密度大于5.716的含3个C烷基噻吩（C3-T）、BT、BT alkylated derivatives、DBT 和DBT alkylated derivatives 能被催化氧化脱除,硫原子的电子密度越大,其被氧化的速率越快,被脱除的选择性也越大;被脱除选择性顺序为：DBT alkylated derivatives > DBT > BT alkylated derivatives> BT> C3-T;然而硫原子电子密度小于5.716的T,含1个烷基噻吩（C1-T）和含2个C烷基噻吩（C2-T）则不能被氧化脱除。采用此方法,能将初始硫浓度为1200 μg&#8226;g^-1的柴油降低至小于10 μg&#8226;g^-1,可将初始硫浓度为320 μg&#8226;g^-1的汽油降低至155 μg&#8226;g^-1。     

Removal of thiophenic compounds from liquid fuel by different modified activated carbon cloths

The adsorption behavior of benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (DMDBT) from n-heptane was investigated onto activated carbon cloth (ACC) and its modified forms at 30 °C in batch condition. ACC was modified by HNO₃, (NH₄)₂S₂O₈, H₂SO₄, HCl and NaOH at ambient temperature. The adsorbents were characterized using nitrogen adsorption/desorption. It was found that the adsorbents are mainly microporous but differ in their surface chemistry, which is related to the effect of oxidizing agent. The adsorption process was studied from both equilibrium and kinetics point of view. The equilibrium experimental data were fitted to the Langmuir, Freundlich and Langmuir-Freundlich by non-linear method. Among the tested adsorbents, the modified ACC with HNO₃ (ACC-HNO₃) had the highest capacity for adsorption of DBT. Kinetic characterization of the adsorption process indicated that the mixed-order and modified pseudo-n-order models can describe the kinetics of adsorption of thiophenic compounds onto ACCs. The ACC and ACC-HNO₃ were used to test the removal efficiency of total sulfur contents (BT, DBT and DMDBT, 150 ppmw for each of them), too. The effect of shaking and ultrasound methods and also temperature and time on the regeneration of saturated ACC-HNO₃ with DBT was studied.     

NH4Cl改性活性炭脱除气态Hg0的特性分析

制备了原始活性炭与NH₄Cl改性活性炭,对其进行了物化特性表征,在固定床汞吸附实验台上考察了N₂气氛下颗粒粒径、NH₄Cl溶液浓度、SO₂、CO₂等因素对活性炭脱除Hg⁰性能的影响。研究结果表明：NH₄Cl浸渍改性没有造成活性炭孔隙结构的明显变化,但使得Cl元素成功担载到活性炭表面;随着颗粒粒径增大,活性炭吸附Hg⁰的外部传质速率、内部扩散速率均降低,较小的颗粒粒径有利于活性炭脱汞;由NH₄Cl改性在活性炭表面所产生的卤素官能团（AC-Cl）能够有效地氧化烟气中的Hg⁰,增强了活性炭对于Hg⁰的氧化吸附作用;SO₂能有限地促进原始活性炭的脱汞性能,对NH₄Cl改性活性炭脱汞性能则表现出先促进后抑制并主要体现抑制作用的现象,并且抑制作用随SO₂浓度的增大而增加;CO₂由于能在活性炭表面极化,且能与氨基官能团反应生成有利于吸附汞的羰基,促进了活性炭的脱汞性能。     

Color removal from dye wastewaters by adsorption using powdered activated carbon: Mass transfer studies

Color removal from synthetic dye wastewater which typically emanates from the Taiwan textile industry has been studied using powdered activated carbon (PAC) as an adsorbent. The CIE colorimetric system has been used in the measurement of color for the treatment of disperse-red-60 dye wastewater. The effect of contact time, dye concentrations and PAC dosage on color and color removal has been investigated. A film-pore double resistance diffusion model for mass transfer has also been used in this study to determine the effective diffusivity, D_eff, for the adsorption of disperse-red-60 dye wastewater to PAC.     

Decomposition of H2O2 on activated carbon obtained from olive stones

Activated carbons were prepared from olive oil solid wastes by treatment in different schemes: impregnation with H₃PO₄ followed by pyrolysis at 300–700 °C, by steam pyrolysis at 600–700 °C, or by conventional steam activation at 850 °C. Porosity characteristics were determined by analysis of nitrogen adsorption isotherms, and carbons of widely different properties and surface pH values were obtained. Decomposition of H₂O₂ in dilute unbuffered solution was followed by measuring evolved oxygen volumetrically. First‐order kinetics was followed, and the catalytic rate coefficients were evaluated. The carbons tested showed appreciable activity where evolved oxygen attained ≈10% of the stoichiometric amount in 1 h. The degree of decomposition showed inverse dependence on surface area, pore volume and mean pore dimensions. The chemical nature of the surface, rather than the porosity characteristics, was the principal factor in enhancing the disproportionation of H₂O₂ on the activated carbon surface. © 2001 Society of Chemical Industry