Synthesis of nanoporous carbons from mixtures of coal tar pitch and furfural and their application as electrode materials

Synthetic nanoporous carbons are prepared by polymerization of mixtures containing coal tar pitch and furfural in different proportions, followed by carbonization of obtained solid product and steam activation of the carbonizate. The chemical composition of the initial mixture significantly affects the physicochemical properties (surface area, pore structure, electro resistance and amount of oxygen-containing groups on the surface) of the obtained materials. The incorporation of oxygen in the precursor mixture by means of furfural, has a strong influence in the synthetic step; increasing the furfural content facilitates the formation of a solid product characterized by a large oxygen content. Moreover, the solid product is more reactive towards activation as the furfural content increases, giving rise to nanoporous carbons with large surface areas and unique chemical features (high density of oxygen functionalities of basic nature). These nanoporous carbons have been investigated as electrodes in electrochemical applications.     

Influence of oxidative stabilization on the electrochemical behaviour of coal tar pitch derived carbons in lithium batteries

A commercial coal tar pitch was thermally treated at 430 °C for 4 h and then submitted to hot filtration in order to separate the isotropic phase from the mesophase developed during the treatment. Each phase was then oxidatively stabilized in order to preserve its structure during carbonization and then carbonized at temperatures ranging from 700 to 1000 °C. The effect of the microstructure, particle morphology and chemical composition of the carbons and also the influence of their carbonization temperature on the electrochemical behaviour as electrode materials in lithium cells were studied.Galvanostatic cycling of lithium test cells using the carbon materials as positive electrodes showed the improvement of the electrochemical performance in both isotropic and anisotropic phases by stabilization with air previous to carbonization. More subtle differences between isotropic and anisotropic samples were evidenced and interpreted in terms of their textural properties. Moreover, the electrochemical impedance spectroscopy (EIS) has been demonstrated to be an interesting technique to elucidate the changes occurred in the electrode interfaces when these coal tar pitch based carbons are cycled.     

煤沥青的最新研究进展

综述了最近几十年国内外对煤沥青的主要分析方法和以它为原料在制备沥青基中间相、中间相炭微球、针状焦、活性炭、泡沫炭和高性能炭/炭复合材料基体方面的研究和进展,展望了其在材料领域潜在的应用前景和未来发展的趋势.     

Modified characteristics of mesophase pitch prepared from coal tar pitch by adding waste polystyrene

The toluene soluble of coal tar pitch was carbonized with waste polystyrene. The properties of mesophase pitches were characterized using polarized light optical microscope, apparent viscometer, FT-IR, ¹H NMR and X-ray diffractometer. After adding the waste polystyrene into the toluene soluble of coal tar pitch, the soluble mesophase were was increased from about 9% to 52% and the mesophase pitches were changed from 74% with coarse mosaic texture to 100% with flow domain texture. The mesophase pitches were transformed from thixotropy to unthixotropy. By waste polystyrene added into the toluene soluble of coal tar pitch, the methylene group was increased a lot. The presence of more alkyl groups modified the characteristics of mesophase pitches and improved the assembly of mesophase pitch molecules.     

A study of the properties of carbon foam reinforced by clay

A novel carbon foam with high strength and very low thermal conductivity was prepared by thermal treating of coal tar based mesophase pitch mixed with montmorillonite clay. SEM observation showed that less micro-cracking appeared on the cell wall of foam by adding of clay-montmorillonite. Foam mechanical properties were improved and its thermal conductivity was markedly decreased. The compressive strengths were increased by 64%, 96% and 100% when the additive amounts of clay were 2%, 5% and 10% (wt%), respectively. Due to the high thermal insulation and lamellar structure of clay, the thermal conductivity of carbon foam decreases from 2 W/m K to 0.25 W/m K.     

贫煤与煤沥青共炭化研究

进行了不同配比的煤沥青和贫煤的共炭化研究,研究表明,煤沥青与贫煤共炭化时的相互作用是物理融合和化学相互作用的共同作用。其中物理融合表现在使焦炭界面结合状态改善,化学相互作用表现在煤沥青使贫煤的炭化性能发生变化。随煤沥青配比的增加,配煤黏结性有较大改善,焦炭OTI值增大,ISO值减小。煤沥青通过增大焦炭光学组织各向异性程度,使焦炭的反应性降低,反应后强度提高。     

煤沥青制备针状焦的研究

通过溶剂-离心法净化原料沥青,应用延迟焦化工艺制备针状焦,考察了在聚合过程中QI含量、温度、压力以及时间对成焦的影响.结果表明,原料中QI含量的减少有利于针状结构的生成,当QI含量小于0.1％时能形成大面积的针状结构;适当的温度和压力能使体系的黏度降低,促进气流拉焦作用,在470℃、0.35 MPa条件下得到的针状焦较为理想;充足的反应时间保证小球的充分融并,反应24h体系能融并、重排,形成良好的针状结构.     

煤沥青热聚合研究

以煤沥青为原料,采用直接热聚合工艺制备出优质中间相沥青。研究了热聚合温度及保温时间对中间相沥青族组成及光学组织结构等性能的影响,并对反应机理进行了深入研究,得到了制备中间相沥青的最佳工艺条件。研究表明,在一定条件下,通过热聚合,在低温、长时间或高温、短时间都能制备优质中间相沥青。在360℃、5 h条件下制备的中间相球晶较小,分布较分散;而在380℃、4 h条件下制备的球晶较大,分布较集中。制备的中间相可作为高级炭材料的优质前躯体,为制取高质量的新型炭材料提供了一条新的途径,对煤炭资源的综合利用具有十分重要的意义。     

Characterization of the surface properties of nitrogen-enriched carbons by inverse gas chromatography methods

The characterization of the surface properties of carbonaceous materials by inverse gas chromatography (IGC) techniques is described. The cokes investigated were produced by the co-pyrolysis of a coal-tar pitch (CTP) with different amounts of polyacrylonitrile (PAN) as a possible method to synthesize carbonaceous materials enriched in nitrogen. IGC at infinite dilution and LSER (linear solvation energy relationship) techniques were used to determine the physical and chemical surface properties of the cokes. In general, the surface free energy of adsorption is due to both dispersive and specific interactions. The dispersive component of the surface free energy was determined using n-alkane probes. For the specific component, which is primarily due to acid-base interactions, different polar probes were used. The LSER method was applied to improve our understanding of the adsorption process in terms of molecular interactions. We show that, to characterize dispersive interactions using n-alkanes, the LSER and IGC methods are equivalent. On the other hand, with both methods we find that all the samples present acidic and basic characteristics. However, the sensitivity of the LSER method does not allow us to discriminate between the three samples in terms of specific interactions.     

芳香族硝基化合物改性煤沥青研究

以煤沥青为原料,通过添加不同含量的芳香族硝基化合物对煤沥青进行改性处理,采用TG、CO2反应性、XRD和SEM对改性沥青焦进行表征。结果表明,芳香族硝基化合物有效地促进了煤沥青在炭化过程中的焦化缩聚,使产物沥青焦结构更加致密,并在一定程度上改变了沥青焦的氧化行为,从而显著提高了沥青黏结焦的抗氧化性能。     

改性煤沥青在炭素生产中的应用

概述了沥青的分类和性质以及沥青改性、改性方法,讲述了在改性煤沥青生产应用中的要求,改性沥青的应用过程、效果和缺点。根据实验数据阐述了在改性煤沥青生产应用中的温度选择。结果表明,改性煤沥青特有的高软化点和粘度决定了在熔化、输送和混捏过程对温度的要求较高。数据分析表明软化点不能够准确指导下料温度,而粘度与下料温度呈正比例关系。因此,粘度可以作为下料温度的一个可靠的参考指标。     

Electrochemical capacitors based on highly porous carbons prepared by KOH activation

Various coal and pitch-derived carbonaceous materials were activated for 5 h at 800 °C using potassium hydroxide and 1:4 component ratio. Porosity development of the resultant activated carbons (ACs) was assessed by N₂ sorption at 77 K and their capability of the charge accumulation in electric double layer was determined using galvanostatic, voltammetric and impedance spectroscopy techniques. ACs produced from different precursors are all microporous in character but differ in terms of the total pore volume (from 1.05 to 1.61 cm³ g⁻¹), BET surface area (from 1900 to 3200 m² g⁻¹) and pore size distribution. Very promising capacitance values, ranging from 200 to 320 F g⁻¹, have been found for these materials operating in acidic 1 mol l⁻¹ H₂SO₄ electrolytic solution. The variations in the electrochemical behavior (charge propagation, self-discharge, frequency response) are considered in relation to the porous texture characteristics, elemental composition but also possible effect of structural ordering due to various precursor materials used. Cycling investigation of all the capacitors has been also performed to compare ability of the charge accumulation for different carbon materials during subsequent cycles.     

聚乙二醇改性脱除煤沥青中3,4-苯并芘

以聚乙二醇为改性剂,研究在溶剂条件下降低煤沥青中3,4-苯并芘的工艺。研究表明,当混合溶剂V环己烷∶V甲苯=2∶1为反应溶剂、硫酸用量为煤沥青质量的6.67%、聚乙二醇600用量为煤沥青质量的10%、反应温度为80℃、反应时间为5h时,3,4-苯并芘降低率为85.59%。     

Synthesis of boron/nitrogen substituted carbons for aqueous asymmetric capacitors

Boron/nitrogen substituted carbons were synthesized by co-pyrolysis of polyborazylene/coal tar pitch blends to yield a carbon with a boron and nitrogen content of 14 at% and 10 at%, respectively. The presence of heteroatoms in these carbons shifted the hydrogen evolution overpotential to −1.4 V vs Ag/AgCl in aqueous electrolytes, providing a large electrochemical potential window (∼2.4 V) as well as a specific capacitance of 0.6 F/m². An asymmetric capacitor was fabricated using the as-prepared low surface area carbon as the negative electrode along with a redox active manganese dioxide as the positive electrode. The energy density of the capacitor exceeded 10 Wh/kg at a power density of 1 kW/kg and had a cycle life greater than 1000 cycles.     

煤焦油沥青纤维的不熔化过程研究

以硫化法制得的高软化点（２５５ ℃） 煤焦油沥青为原料,通过熔融纺丝、氧化不熔化及炭化处理制备煤焦油基沥青纤维。探讨了不熔化终温对产品炭纤维抗拉强度的影响,借助于元素分析、气相色谱分析（ＧＡ）、ＤＴＡ、ＴＧ 和红外光谱分析等表征手段,对沥青纤维的不熔化过程进行了研究。结果表明：氧化终温强烈影响着炭纤维的抗拉强度;煤焦油沥青纤维在空气中的不熔化过程在低于３４０ ℃时表观上表现为恒重恒热,氧化反应主要发生于２００～３４０ ℃之间。     

煤焦油沥青树脂黏结剂的制备研究

采用交联合成法,以煤焦油为原料,多聚甲醛为交联剂,在酸性催化剂对甲苯磺酸的作用下制备煤焦油沥青树脂。采用正交试验法研究了交联剂量、催化剂量、反应温度和反应时间对合成煤焦油沥青树脂的影响。结果表明,增加交联剂量和催化剂量可以起到降低反应温度和缩短反应时间的效果;煤焦油沥青树脂的软化点、结焦值和黏结强度等指标均随反应温度升高和反应时间延长而明显增加。     

Activation of coal tar pitch carbon fibres: Physical activation vs. chemical activation

Activated carbon fibres (ACF) are obtained mainly by physical activation with steam or carbon dioxide. Additionally, there are many papers dealing with chemical activation of carbon fibres, or a polymeric raw material, with several chemical agents like for example, phosphoric acid, zinc chloride, aluminium chloride,… Nevertheless, although it is well known that hydroxides are good activating agents, there are few papers about the activation of carbon fibres with KOH or NaOH. In the present work, ACF with high surface area are obtained by chemical activation with KOH and NaOH. Both chemical agents present different behaviour; thus, NaOH developed the highest value of porosity and KOH developed samples with narrower micropore size distribution. In order to compare the results with those obtained by physical activation, some ACF have been prepared using CO₂ activation. The main conclusion of this work is that by using chemical activation it is possible to obtain similar, or even higher, porosity (∼1 ml/g, ∼3000 m²/g) than by physical activation. However, chemical activation presents two important advantages: (1) a much higher yield (27-47% for chemical activation and 6% physical activation for ∼2500 m²/g activated carbon fibres) and (2) the surface of the fibres prepared by chemical activation is less damaged than by physical activation.     

Carbon-ceramic composites from coal tar pitch and clays: application as electrocatalyst support

Carbon-ceramic composites have been prepared and characterised by different techniques (electron microscopy, X-ray microanalysis, X-ray diffraction and cyclic voltammetry). The effect on the conductivity of the thermal treatment temperature of the composites and the structure of the starting ceramic has been analysed. The results demonstrate that the layered structure of the clay determines their conductivity. The composites prepared are conductors and the conductivity goes through a maximum with increasing thermal treatment. Platinum has been successfully deposited on the carbon-ceramic composite by chemical and electrochemical methods. A better distribution of platinum and smaller particle sizes are obtained by the electrochemical method. The direct electrooxidation of methanol in acid medium has been studied on platinum-modified carbon-ceramic electrodes.     

Sulfur removal in coal tar pitch by oxidation with hydrogen peroxide catalyzed by trichloroacetic acid and ultrasonic waves

A procedure for the desulfurization of coal tar pitch (CTP) by oxidation with hydrogen peroxide (H₂O₂) was developed, in which trichloroacetic acid (TCA) was used as a catalyst combined with ultrasonic waves. For comparison, the effects of H₂O₂ combined with different catalysts on sulfur removal were also investigated. The oxidative system composed of H₂O₂ and TCA is highly effective for sulfur removal from CTP. The reaction conditions such as type of solvent used, temperature, and CTP-to-TCA ratio considerably influence sulfur removal when the same oxidant is used. The desulfurization efficiency for CTP with 0.9 wt.% sulfur content reaches 91.1 wt.% at a xylene-to-CTP volume ratio of 2.5, a CTP-to-TCA mass ratio of 0.5, an ultrasonic treatment duration of 60 min, a reaction temperature of 70 °C, and with an extraction liquid containing methanol and sodium hydroxyl. The experiment confirms that the addition of surface active agent has no beneficial effect on sulfur removal.