STORAGE OF HYDROGEN ON CARBON MATERIALS: EXPERIMENTS AND ANALYSES

Superactivated carbon and carbon nanotubes are both considered potential hydrogen carriers. Adsorption isotherms of H₂ on activated carbon AX-21 and multi-wall carbon nanotubes were collected with a volumetric method for the temperature range of 77, 233–298 K and pressures up to 7 or 10 MPa. Based on the experimental data for 233–298 K, the limiting heats of adsorption of 7.6 and 1.8 kJ/mol were obtained for activated carbon and carbon nanotubes, respectively. The absolute adsorption was determined with a recently presented method, and the adsorption behavior of H₂ on carbon nanotubes was thus reasonably explained. A comparison was given for the storage capacities of compression alone and of filling powder or pellets of the two materials. It was concluded that adsorption of H₂ on carbon nanotubes is too weak to enhance storage, but activated carbon enhances storage capacity considerably. The weight percentage of hydrogen stored in carbon powder reaches 10.8% at 77 K and 6 MPa, including the quantity compressed in the void space, and 4.1 kg H₂ was stored in a 100-liter container filled with carbon pellets for the same condition.     

H2 uptake and synthesis of the fluorinated Li-dispersed nickel oxide nanotubes

Aligned Li-dispersed nickel oxide nanotubes were prepared using LiNO₃, Ni(NO₃)₂·6H₂O and an anodic aluminum oxide (AAO) template for potential applications in H₂ storage. The nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The nickel(II) oxide nanotubes obtained had a trigonal structure with a uniform length, 40–50 nm in wall thickness and 200 ± 10 nm in the outer diameter. The external surface of the nanotubes was modified by fluorination. The level of H₂ adsorption was determined using the gravimetric method. The fluorinated Li-dispersed nickel oxide nanotubes showed a 0.06 wt% and 1.65 wt% increase in weight due to H₂ adsorption under an equilibrium pressure of 47 atm at 298 K and 77 K, respectively.     

Hydrogen storage on chemically activated carbons and carbon nanomaterials at high pressures

Hydrogen adsorption measurements have been carried out at different temperatures (298 K and 77 K) and high pressure on a series of chemically activated carbons with a wide range of porosities and also on other types of carbon materials, such as activated carbon fibers, carbon nanotubes and carbon nanofibers. This paper provides a useful interpretation of hydrogen adsorption data according to the porosity of the materials and to the adsorption conditions, using the fundamentals of adsorption. At 298 K, the hydrogen adsorption capacity depends on both the micropore volume and the micropore size distribution. Values of hydrogen adsorption capacities at 298 K of 1.2 wt.% and 2.7 wt.% have been obtained at 20 MPa and 50 MPa, respectively, for a chemically activated carbon. At 77 K, hydrogen adsorption depends on the surface area and the total micropore volume of the activated carbon. Hydrogen adsorption capacity of 5.6 wt.% at 4 MPa and 77 K have been reached by a chemically activated carbon. The total hydrogen storage on the best activated carbon at 298 K is 16.7 g H₂/l and 37.2 g H₂/l at 20 MPa and 50 MPa, respectively (which correspond to 3.2 wt.% and 6.8 wt.%, excluding the tank weight) and 38.8 g H₂/l at 77 K and 4 MPa (8 wt.% excluding the tank weight).     

Adsorption of SO2 from flowing air by alkaline-oxide-containing activated carbons

Adsorption of SO₂ under dynamic conditions from an SO₂-air mixture at 298 and 573 K on alkaline-oxide-containing activated carbons has been studied. The adsorption capacity of these samples at 298 K was, in general, lower than that in the original activated carbons and mainly governed by their microporosity accessible to benzene. However, at 573 K, the alkaline-oxide-containing activated carbons adsorbed a greater amount of SO₂ than the original activated carbon, following the order Na ≥ K > Rb. At both adsorption temperatures, part of the SO₂ adsorbed formed H₂SO₄ and Me₂SO₄, where Me = Na, K or Rb. When the SO₂ adsorption was carried out at 573 K, this gas fixed additional oxygen complexes that evolved as CO₂ under heating up to 873 K in He flow, probably by reaction of SO₂ with carbon surface atoms of a basic nature that are not able to chemisorb oxygen from the air at the same conditions.     

低湿CO2/H2O混合气体吸附特性实验

CO₂捕集、封存及利用是实现“双碳”目标的重要途径,为将碳捕集后的低湿CO₂/H₂O进行CO₂提纯和资源化利用,采用动态吸附实验研究了不同温度（303K、313K）、H₂O含量（0.7%~3.0%）的CO₂/H₂O在活性炭、活性氧化铝、分子筛3A和13X四种吸附剂上的动态吸附穿透曲线、吸附床温度分布、吸附量,分析了CO₂/H₂O分离系数和吸附热。结果表明,在CO₂/H₂O动态吸附过程中,吸附床温度与各组分浓度随时间变化趋势相同。H₂O饱和时间随进气温度升高而缩短;H₂O含量增加,抑制CO₂吸附;活性炭和氧化铝中H₂O的饱和时间随H₂O含量增加而增长,但分子筛3A和13X饱和时间缩短。H₂O吸附量随H₂O含量增加而增加,吸附热随吸附量增加而减小,CO₂则相反。分子筛3A对CO₂吸附量最小且CO₂/H₂O分离系数最大。H₂O含量小于1%时,CO₂吸附量最大的分子筛13X分离系数大于活性氧化铝,分子筛3A和13X适合分离低湿CO₂/H₂O。     

CH4-N2在自支撑颗粒型Silicalite-1上的吸附分离及PSA模拟

纯硅分子筛Silicalite-1原粉（Si/Al>470）在6 MPa压力下制成自支撑颗粒状吸附剂,经XRD和77 K氮气吸脱附表征表明自支撑颗粒型的Silicalite-1保留了原粉的晶体结构和比表面。静态重量法测试了273/298/313 K下CH₄和N₂在其上的吸附等温线,利用理想吸附溶液理论（IAST）法计算了吸附剂对CH₄/N₂的选择性。动态气体穿透实验测试了颗粒型Silicalite-1吸附剂对不同浓度CH₄/N₂混合气的分离效果,结果表明该吸附剂更适合于低浓度甲烷（20%/80% CH₄/N₂）的富集脱氮。通过总传质模型利用数值模拟预测了颗粒型Silicalite-1吸附剂的变压吸附分离（PSA）富集低浓度煤层气中甲烷的效果。模拟结果显示20%/80%的CH₄/N₂混合气经一次提浓,CH₄浓度可以提升至37%~41%,回收率达到60%~92%;30%/70%的CH₄/N₂混合气经一次提浓,CH₄浓度可以提升至50%~53%,回收率达到58%~92%。     

GAS PERMEANCE BEHAVIOR AT ELEVATED TEMPERATURE IN MESOPOROUS ANODIC OXIDIZED ALUMINA SYNTHESIZED BY PULSE-SEQUENTIAL VOLTAGE METHOD

Mesoporous anodic oxidized alumina (MAOA) capillary tubes with and without a barrier layer have been synthesized by applying a pulse-sequential voltage. The single gas permeances at an elevated temperature and the thermal and hydrothermal stabilities of MAOA were investigated. A highly oriented radial mesopore channel with pore sizes from 40 to 4 nm was formed in the MAOA tubes. Micropores with sizes from 0.4 to 0.8 nm were formed in the barrier layer. The H₂ permeance of MAOA with a barrier layer (barrier type) was approximately 540 times lower than that of MAOA without a barrier layer (block type) at 773 K. The H₂/N₂ permselectivity of the barrier type in the temperature range from 333 to 673 K was 3.4; those of the barrier type at 773 and 823 K were 4.4 and 11, respectively. On the other hand, the H₂/N₂ permselectivities of the block type were from 3.1 to 3.6 in the temperature range from 333 to 773 K. The H₂ permeance and the H₂/N₂ permselectivity of the amorphous silica membrane on the block type were 1.1 × 10^-7 mol/m² · s · Pa and 40 at 773 K, respectively. MAOA synthesized by the pulse-sequential voltage method can be applied to the mesoporous support of the gas separation membrane at elevated temperatures.     

Natural gas storage in activated carbon pellets without a binder

Activated carbon pellets without a binder from cellulose microcrystals as a raw material were investigated. After compression of the raw materials, the thus obtained raw material pellets were slowly carbonized to 1073 K under nitrogen. To activate them, the carbon pellets were heated to 1173 K under carbon dioxide. The activated carbon pellet shape, after heat treatment, was columnar by using the previous employed compression of the raw material. The total surface area, pore volume, and average pore diameter for all the samples were evaluated from the analysis of N₂ adsorption isotherm data. The total surface area and the pore volume were decreased with an increase in compression pressure under the same heat treatment conditions. On the contrary, the bulk densities of the activated carbon pellets were increased. However, these properties can be easily controlled by changing the sintering temperature and time. The bulk density of sample pellet was 0.56 g/cm³. It is 2.3 times higher than activated carbon powder, which was made without the compression process. The total methane storage capacity at 298 K reached 164 cm³ in 1 cm³ volume of activated carbon pellets at 3.5 MPa.     

The improvement in oxidation resistance of carbon by a graded SiC/SiO2 coating

A dense functionally gradient SiC/SiO₂ coating has been developed to improve the oxidation resistance of carbon at elevated temperatures. SiC was coated on the surface of a graphite substrate by a reaction between thermally evaporated silicon and carbon at 1400 °C. The SiO₂ layer was deposited by exposing the SiC coated specimens next to a bed of Si powder in a flowing H₂–H₂O gas (P_H2O=2.6×10⁻² atm) at 1400 °C. The formed SiC/SiO₂ layers were dense and had gradient compositions with good adhesion to the carbon substrate. However, as the coating thickness increased, the coating layer became cracked and delaminated from the substrate due to thermal stress. The specimens with the continuous SiC/SiO₂ layer showed a remarkably improved oxidation resistance up to 1200 °C.     

Preparation and adsorption performances of mesopore-enriched bamboo activated carbon

Activated carbon with high specific surface area and considerable mesopores was prepared from bamboo scraps by phosphoric acid activation. The effect of activation conditions was studied. Under the conditions of impregnating bamboo with 80% H₃PO₄ at 80°C for 9 days and activation at 500°C for 4 h, the prepared activated carbon had the highest mesopore volume of 0.67 cm³/g, a specific surface area of 1567 m²/g, and the mesopore ratio reached 47.18%. The study on adsorption isotherms of CH₄, CO₂, N₂ and O₂ on the activated carbon were carried out at 298 K. The considerable difference in the adsorption capacity between CO₂ and the other gases was observed, which would be of interest for the adsorptive separation/purification of gaseous CO₂ from its mixtures, especially from mixtures with N₂ and/or O₂.     

Synthesis of graphene-like nanosheets and their hydrogen adsorption capacity

Graphene-like nanosheets have been synthesized by the reduction of a colloidal suspension of exfoliated graphite oxide. The morphology and structure of the graphene powder sample was studied using scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectroscopy. The graphene sheets are found to be in a highly agglomerated state, with many wrinkles. The sample has a BET surface area of 640 m²/g as measured by nitrogen adsorption at 77 K. Hydrogen adsorption-desorption isotherms were measured in the temperature range 77-298 K and at pressures of up to 10 bar. This gives hydrogen adsorption capacities of about 1.2 wt.% and 0.1 wt.% at 77 K and 298 K, respectively. The isosteric heat of adsorption is in the range of 5.9-4 kJ/mol, indicating a favourable interaction between hydrogen and surface of the graphene sheets. The estimated room temperature H₂ uptake capacity of 0.72 wt.% at 100 bar and the isosteric heat of adsorption of our sample are comparable to those of high surface area activated carbons, however significantly better than the recently reported values for graphene and a range of other carbon and nanoporous materials; single and multi walled carbon nanotubes, nanofibers, graphites and zeolites.     

Structural changes and activation treatment in a Co/SiO2 catalyst for Fischer–Tropsch synthesis

We examined the effect of the activation process on the structural and morphological characteristics of a cobalt-based catalyst for Fischer–Tropsch synthesis. A 10 wt.% Co/SiO₂ catalyst prepared by wet impregnation was separately activated under H₂, CO or a H₂/CO mixture. The structural changes during activation from 298 to 773 K were studied by in situ X-ray diffraction. Catalysts were examined by SEM, TEM, XPS and in situ DRIFT-MS. The H₂/CO activation produced redispersion of cobalt particles and simultaneous carbon nanostructures formation. The catalyst showed the highest performance in the Fischer–Tropsch synthesis after the H₂/CO activation.     

MODELLING OF THE INTERACTION OF NITROGEN DIOXIDE WITH ACTIVATED CARBON I. ADSORPTION DYNAMICS AT THE SINGLE PARTICLE SCALE

The adsorption dynamics of nitrogen dioxide on activated carbon are measured using a microbalance technique. A theoretical model, incorporating the mechanisms of micropore, macropore and concentration dependent sorbed phase (surface) diffusion, with nonlinear equilibrium (dual Langmuir isotherm), is fitted to the experimental NO₂ adsorption dynamics over a range of temperatures, concentrations and particles sizes. The data are well fitted by the model over the temperature range 298-373 K, with typical extracted values of the diffusivities at 298 K being: D/R²_μ=0.003 s^-11 (micropore), D_p = 0.038 cm²/s (macropore) and D_so=1.0 × 10^-6cm²/s (surface) with micropore and surface diffusion activation energies of 14.8 and 11.0 kJ/mole, respectively. The influence of the NO₂/N₂O₄ ratio on the adsorption dynamics is also discussed. At temperature higher than 373 K, significant reaction of NO₂ with activated carbon results in consumption of the carbon.     

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.     

多壁碳纳米管吸附处理柴油废水的动力学特性

通过静态吸附实验研究了多壁碳纳米管(MWCNTs)对柴油废水中油的吸附特性,并与活性炭进行了比较。表明MWCNTs和活性炭对柴油的吸附量均在前10 min上升迅速60 min左右可达到吸附平衡,但MWCNTs的吸附能力远大于活性炭。在动力学分析中发现准二级动力学模型能较好地符合研究体系,且随温度的升高,吸附速率增加。根据Arrhenius公式,算得MWCNTs吸附柴油2^#的活化能(E_a)的值为14.21 kJ·mol^-1,可推断吸附应是物理吸附。利用颗粒内扩散模型发现MWCNTs吸附分外表面吸附、碳管间大空隙的内扩散和管间小空隙内扩散3阶段,而活性炭对柴油2^#的吸附分为外表面吸附和颗粒内扩散两个阶段,且受边界层的影响较大。MWCNTs对柴油的吸附存在初始吸附行为。在298 K下MWCNTs对3种柴油的吸附及在288、298和308 K下对柴油2^#的吸附,都是中等起始吸附,柴油2^#的吸附,随温度的升高,起始吸附行为增强,在318 K时吸附过程具有较强烈的起始吸附行为。     

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。     

磷酸中添加剂对核桃壳活性炭性能的影响

采用磷酸活化法制备核桃壳颗粒活性炭,研究了在磷酸浸渍液中加入不同种类和含量添加剂对活性炭性能的影响。以亚甲基蓝和碘吸附值表征活性炭的吸附性能,并对活性炭的孔结构参数、机械强度和微晶结构进行了测试分析。结果表明：在磷酸中分别添加柠檬酸、柠檬酸钠、硼酸和糖精浸渍处理核桃壳原料,所得活性炭的亚甲基蓝吸附值都得到提高,而碘吸附值降低,说明添加剂促使活性炭中的微孔扩大为中孔。其中,添加0.5%的柠檬酸钠得到最佳的亚甲基蓝和碘吸附值,分别达到236.5和744.1 mg/g。此外,磷酸中添加1%硼酸后得到的活性炭结构中含坚固的炭微晶,起到了增强孔结构的作用,机械强度为85.8%;而添加1%糖精得到的活性炭中的炭微晶几乎全部发生了石墨化转变,生成质软的石墨,使强度下降,机械强度仅为80.1%;添加0.5%柠檬酸钠的活性炭由于发达的孔隙结构且没有炭微晶的加固而强度较低(82.5%)。     

BINARY AND MULTICOMPONENT VAPOR-LIQUID EQUILIBRIA OF SYNTHESIS GAS COMPONENTS, METHANOL AND WATER WITH TETRA ETHYLENE GLYCOL DIMETHYL ETHER (TETRAGLYME)

Binary and multicomponent vapor-liquid equilibria of synthesis gas components (H₂, CO, CH₄, and CO₂), methanol and water with tetraethylene glycol dimethyl ether (tetraglyme) were studied experimentally at temperatures (473-513 K) and pressures (5.3-10.4 MPa) typical of the conventional vapor phase methanol synthesis. Both vapor and liquid phases were sampled directly and analyzed by gas chromatography. Solubilities were expressed in terms of equilibrium K values. Optimal binary interaction coefficients for all components with tetraglyme were obtained for the Soave-Redlich-Kwong equation of state (SRKEOS [1] by minimizing the error in bubble point pressure prediction. K values predicted by the SRKEOS were in good agreement with those obtained experimentally.     

TEPA负载复合氧化活性炭吸附烟气中的CO2性能

以商业煤基活性炭为原料,经低浓度氧气焙烧、H₂O₂氧化改性,并以四乙烯五胺（TEPA）浸渍,得到胺负载复合氧化活性炭,用于模拟烟道气[(15%(体积)CO₂+85%(体积)N₂）+10%(体积)H₂O]中CO₂吸附。低浓度氧气焙烧后,活性炭的最大比表面积和孔体积分别为1421.82 m²/g、0.83 cm³/g。经复合氧化改性后,活性炭的介孔体积增大,表面含氧官能团增加,使得TEPA负载复合氧化活性炭的CO₂吸附性能提高。焙烧时间为4 h,H₂O₂氧化、负载40%TEPA的样品COAC-4-40TEPA,在60℃时CO₂饱和吸附量最高为2.45 mmol/g,是TEPA负载未改性活性炭AC-40TEPA的2.02倍。经过十次吸附循环后,COAC-4-40TEPA的 CO₂饱和吸附量可维持在92.24%,而TEPA的浸出量仅有0.67%。失活模型研究表明,COAC-4-40TEPA的初始吸附速率常数是AC-40TEPA的1.64倍,且失活速率常数低于AC-40TEPA。     

Investigation of CoNiMo/Al2O3 catalysts: Relationship between H2S adsorption and HDS activity

Sulfidation of trimetallic CoNiMo/Al₂O₃ catalysts was studied by thermogravimetry at 400 °C under flow and pressure conditions. Results were compared with those obtained on prepared and industrial CoMo/Al₂O₃ and NiMo/Al₂O₃ catalysts. The amount of sorbed H₂S on the sulfided solids was measured at 300 °C in the H₂S pressure range 0–3.5 MPa at constant H₂ pressure (3.8 MPa). The adsorption isotherms were simulated using a model featuring dissociated adsorption of H₂S on supported metal sulfides and bare alumina. The amount of sulfur-vacancy sites could thus be determined under conditions close to industrial practice. A relationship with activity results for thiophene HDS and benzene hydrogenation was sought for.