Influence of the gas pressure on single-wall carbon nanotube formation

Experiments and modeling are performed to predict the effect of gas pressure on species distributions and nanotube growth rate under specific conditions of synthesis of single-wall carbon nanotubes (SWCNTs) by arc discharge. Numerical results are compared with experiments in order to find a consistent correlation between the nanotube growth and the pressure. We use argon and helium as buffer gases with a total pressure varied between 0.1 and 1 bar. We experimentally observe that both the anode erosion rate and the Brunauer-Emmett-Teller (BET) surface area of the as-produced nanotube soot material are very sensitive to the total gas pressure in the reactor.     

Electrospun melamine-blended activated carbon nanofibers for enhanced control of indoor CO2

Electrospun carbon nanofibers were activated with melamine–polyacrylonitrile [melamine-blended carbon nanofibers (MACNFs)] for use as a fibrous adsorbent for indoor CO₂ removal. Although, melamine doping was intended solely to incorporate basic nitrogen functionalities on the nanofibers, it also shortened fabrication time, conserving time, and energy cost. The specific surface area and microporosity of the fibers were enhanced from 412 m² g⁻¹ and 0.1646 cm³ g⁻¹ to 547 m² g⁻¹ and 0.220 cm³ g⁻¹, respectively, upon final CO₂ activation of the nanofibers. With the chemical properties, we observed significant tethering of pyridine functionality. The sample, MACNF-7 (10 mL of polymer solution doped with 0.7 g of melamine), provided the optimum melamine doping condition to achieve the highest CO₂ adsorption capacity of 3.15 mmol g⁻¹. The adsorption performance was based on simultaneous improvement in microporosity (physical) and surface basicity (chemical) properties of the adsorbent. However, in a binary mixture with nitrogen, the selective adsorption of CO₂ showed the predominance of the improved surface basicity over microporosity. The highest CO₂ selective capture (1.22 mmol g⁻¹) was occurred for a CO₂:N₂ ratio of 0.15:0.85, with a selectivity of 58.19 at 273 K. In a regeneration test, stable and robust performance was achieved more than five cycles. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47747.     

Effect of LaB6 content on the gas evolution and structure of ZrC coating for carbon/carbon composites during ablation

ZrC coatings with different contents of LaB₆ for SiC-coated carbon/carbon composites were fabricated by supersonic atmosphere plasma spraying. The mechanism of gas evolution during oxidation at ultra-high temperatures and the oxide scale structure evolution of the coating after addition of LaB₆ with different contents were studied. Results showed that rare earth borate rather than rare earth oxide mainly reduced the melting resistance of the oxide scale. The oxide scale for ZrC coating with 10% LaB₆ was unfavorable to the gas escape. After addition of 20% LaB₆, the oxide scale was favorable to the gas escape but disadvantageous to the coating applied in the environment containing scouring because of the reduced melting resistance. High content of LaB₆ also could cause evident boiling of B₂O₃, leading to producing big pores in the oxide scale during ablation. Appropriate content of LaB₆ for ZrC coating was found to be 15%.     

Characterization of single-wall carbon nanotubes by N2 adsorption

N₂ adsorption isotherms at 77 K of single-wall carbon nanotubes (SWNTs), multi-wall carbon nanotubes (MWNTs), and mixtures of these carbon nanotubes (CNTs) were analyzed for differences in their pore size distributions (PSDs). The PSDs, calculated in the microporous region by the Horvath–Kawazoe method and in the mesoporous region by the BJH method, are in agreement with the structures of both types of CNTs deduced from high-resolution transmission electron microscopy. A characteristic peak in the microporous region in the PSD of SWNTs is not present in the PSDs of MWNTs and impurities such as amorphous carbon, metal residues of catalysts, etc. The evaluation of this peak is proposed as a convenient tool for the quantitative characterization of SWNT purity in carbon nanotube-containing samples.     

具有缺陷孔结构的炭膜分离CO2/CH4混合气的分子模拟

基于炭膜无缺陷Z字形孔模型研究结果,建立随机缺陷、均匀缺陷与局部缺陷3种不同缺陷方式的炭膜微孔模型,研究等摩尔CO₂/CH₄混合气在缺陷膜孔中的吸附和扩散过程,探讨缺陷对炭膜气体分离的影响。结果表明,在273~348 K的温度范围内,CO₂与CH₄在缺陷炭膜孔模型内的平衡吸附量与扩散系数均低于无缺陷炭膜孔模型;与无缺陷、均匀缺陷和随机缺陷孔模型相比,局部缺陷孔模型的CO₂/CH₄总分离系数最低;温度低于298 K时,随机缺陷和均匀缺陷孔模型的总分离系数均大于无缺陷孔模型;随机缺陷孔模型的总分离系数大于均匀缺陷孔模型,说明随机删除碳原子的方式比均匀删除和局部删除更加合理。研究结果可为炭膜气体渗透机理的深入研究提供依据。     

烟气CO2捕集热能梯级利用节能工艺耦合优化

醇胺法捕集CO₂技术是一种较成熟的CO₂捕集技术,具有吸收速度快、脱除效果好等显著优点,但其操作费用高、解吸能耗大。本文以降低醇胺法捕集烟气中CO₂系统再生能耗为出发点,对常规醇胺法捕集CO₂工艺统进行了节能优化研究。在常规工艺流程基础上引入压缩式热泵节能技术,并利用Aspen Plus软件建立了基于压缩式热泵技术的CO₂捕集工艺流程模型。研究了压缩式热泵与机械蒸汽压缩回收（MVR）热泵、分流解吸、分布式换热、级间冷却4种节能工艺耦合,通过模拟计算与优化,结果说明了最佳节能工艺组合为“解吸塔压缩式热泵+贫液MVR热泵+分流解吸+级间冷却”耦合的CO₂捕集工艺流程,当解吸塔顶气体分流比为0.25∶0.75、冷富液分流比为0.05∶0.95、级间冷却器位于吸收塔17块塔板位置、吸收塔输入冷量为-3.0GJ/h时,系统再生能耗最低,为2.533 GJ/tCO₂,相比常规有机胺工艺（再生能耗4.204GJ/tCO₂）节能率39.748%。     

Dynamic optimization for gas blending in pipeline networks with gas interchangeability control

The increasing penetration of unconventional gas and liquefied natural gas poses an operational challenge on existing regional gas networks for gas quality problems. A new dynamic model for natural gas pipeline network with multiple supplies is presented with a special emphasis on gas interchangeability control. Wobbe index serves as gas interchangeability indicator and is calculated by equations derived from rigorous composition-based partial differential equations. Disjunctive formulation is applied to represent different modes of gas blending due to gas reversal, and the disjunctive model is then reformulated as a nonsmooth model with min/max and absolute value functions, which is solved by a gradient-based nonlinear program solver after smooth approximation. Moreover, a heuristic algorithm is proposed to tune the penalty parameters in order to focus on different penalty terms while keeping the model well-conditioned. The developed model and strategy are first tested with a small pipeline network model and then extended to a large model. The results show that the model can effectively manage gas interchangeability issues in pipeline networks within reasonable CPU time.     

Wettability control on vertically-aligned multi-walled carbon nanotube surfaces with oxygen pulsed DC plasma and CO2 laser treatments

This work presents a method to obtain control on wettability of vertically-aligned multi-walled carbon nanotube surfaces, using oxygen pulsed directly current plasma and CO₂ laser irradiation. Superhydrophilic surfaces were obtained by the oxygen pulsed DC plasma treatment to incorporate polar groups on VACNT. The CO₂ laser was used to irradiate the functionalized samples, at different power levels, in order to restore the superhydrophobic characteristic. Evaluation of polar and dispersive components of superficial energy was performed by Owens and Wendt method.     

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。     

Influence of heating and laser irradiation on the Raman D band in single-wall carbon nanotubes

Fine structure of the Raman D band in single-wall carbon nanotubes (SWNTs) was investigated by heating and laser irradiation. It is shown that the D band is composed of three components at ～ 1313, 1340, and 1355 cm^? 1, denoted by D₁, D₂, and D₃, respectively. The D₁ and D₂ intensities significantly increase with laser irradiation in air and vacuum, respectively. The D₃ intensity drastically increases with heating in air. From these results, it is suggested that the fine structure of the D band is attributed to different kinds of defects introduced in SWNTs.     

Development of Fe-doped carbon electrode for mass-producing high-yield single-wall carbon nanotubes

High crystallinity single-wall carbon nanotubes (SWNTs) can be synthesized by arc discharge evaporation of Fe-doped carbon electrode in hydrogen mixed gas, but the purity of as-grown SWNTs is strongly affected by the kinds of Fe-doped carbon electrode. Various carbon materials (artificial graphite powder, carbon black, calcined coke, etc.) have been tried to prepare Fe-doped carbon electrodes. The calcined coke, a kind of graphitizing carbon, is suitable for preparing high-quality Fe-doped carbon electrode. Moreover, the heat-treatment of Fe-doped carbon electrode in vacuum at the temperature of 1600 °C also plays an important role. At present, the best carbon electrode containing 1 at.% Fe catalyst is capable of continuously generating SWNTs at a production rate of 8 mg/min, which can be easily purified to obtain high purity SWNTs.     

Preferential CO oxidation over activated carbon supported catalysts in H2-rich gas streams containing CO2 and H2O

Selective CO oxidation (PROX) was studied at 423 K over 1% Pt–0.25% SnO_x and 1% Pt–1% CeO_x catalysts supported on un-oxidized and oxidized activated carbon (AC) using feed mixtures simulating the reformate coming from fuel processors. Effects of the addition of 15% CO₂ or (15% CO₂ + 10% H₂O) into feed mixtures containing 1% CO, 1% O₂, 60% H₂ and He were determined for nine different AC-supported catalysts, and the results were compared with those obtained with pure H₂-rich feed. Unlike other PROX catalysts having oxide supports, introduction of CO₂ into pure feed drastically increased CO conversion on all nine catalysts supported on oxidized or un-oxidized AC regardless of impregnation strategy.1% Pt–0.25% SnO_x supported on HNO₃-oxidized AC stands out as a potential candidate for commercial use in PROX since it yields 100% CO conversion under realistic feed conditions. 1% Pt–1% CeO_x catalysts prepared by sequential or co-impregnation and supported on air-oxidized AC also give 100% CO conversion in H₂-rich feed containing (CO₂ + H₂O) during extended run times and hence hold promise as PROX catalysts.     

CO2 recovery from flue gas by PSA process using activated carbon

An experimental study was performed for the recovery of CO₂ from flue gas of the electric power plant by pressure swing adsorption process. Activated carbon was used as an adsorbent. The equilibrium adsorption isotherms of pure component and breakthrough curves of their mixture (CO₂ : N₂ : O₂=17 : 79 : 4 vol%) were measured. Pressure equalization step and product purge step were added to basic 4-step PSA for the recovery of strong adsorbates. Through investigation of the effects of each step and total feed rate, highly concentrated CO₂ could be obtained by increasing the adsorption time, product purge time, and evacuation time simultaneously with full pressure-equalization. Based on the basic results, the 3-bed, 8-step PSA cycle with the pressure equalization and product purge step was organized. Maximum product purity of CO₂ was 99.8% and recovery was 34%.     

Morphology,structure and density evolution of carbon nano-structures deposited by N-IR pulsed laser ablation of graphite

Carbon films were deposited by pulsed laser ablation on Si <100> substrates, heated at temperatures increasing from RT to 800 °C, from a pure graphite target, operating in vacuum (~ 10^− 4 Pa). The laser ablation was performed by an Nd:YAG laser, operating in the near IR wavelength (λ = 1064 nm).Micro-Raman and grazing incidence X-ray diffraction analysis (GI-XRD) established the progressive formation of ordered nano-sized graphitic structures, increasing substrate temperature. The surface morphology is characterised by macroscopic roughness (SEM, AFM) while the low temperature samples are characterised by very smooth surface. The film density, evaluated by X-ray reflectivity measurements, is also affected by the substrate temperature. This structural property modification induces relevant variation on the emission properties of carbon films, as evidenced by Field Emission measurements. The film structure and texturing is also strongly related to laser wavelength: the low energy associated to the IR laser radiation (1.17 eV) causes an early aromatic cluster formation at T = 400 °C associated to a sensible increase in the aromatic plane stacking distance (d₀₀₂ ~ 0.39 nm), compared to graphite. These density decrease shows a direct correlation with the electron emission properties. Roughness and presence of voids play a negative role both on the threshold electric field E_th and enhancement factor (β) The density decreasing and graphitic layer widening are notably to be ascribed to the very fast out-of-equilibrium growth and to the presence of large activated carbon species in the “plume”.     

Effect of the porous structure in carbon materials for CO2 capture at atmospheric and high-pressure

Activated carbons prepared from petroleum pitch and using KOH as activating agent exhibit an excellent behavior in CO₂ capture both at atmospheric (∼168 mg CO₂/g at 298 K) and high pressure (∼1500 mg CO₂/g at 298 K and 4.5 MPa). However, an exhaustive evaluation of the adsorption process shows that the optimum carbon structure, in terms of adsorption capacity, depends on the final application. Whereas narrow micropores (pores below 0.6 nm) govern the sorption behavior at 0.1 MPa, large micropores/small mesopores (pores below 2.0–3.0 nm) govern the sorption behavior at high pressure (4.5 MPa). Consequently, an optimum sorbent exhibiting a high working capacity for high pressure applications, e.g., pressure-swing adsorption units, will require a poorly-developed narrow microporous structure together with a highly-developed wide microporous and small mesoporous network. The appropriate design of the preparation conditions gives rise to carbon materials with an extremely high delivery capacity ∼1388 mg CO₂/g between 4.5 MPa and 0.1 MPa. Consequently, this study provides guidelines for the design of carbon materials with an improved ability to remove carbon dioxide from the environment at atmospheric and high pressure.     

CO2 laser welding of polymers

Deep penetration welding of polymers can be carried out at high speed with relatively low laser power. This results from an efficient coupling CO₂ laser radiation to polymers that leads to volume heating. A brief review of energy coupling and heat transfer effects in polymers under CO₂ laser welding conditions is given. Some examples of low power (10 to 100 watt) CO₂ welding of polypropylene and polyethylene at depths of up to 1.5 cm are discussed.