Stabilisation of low softening point petroleum pitch fibres by HNO3

This paper deals with the stabilisation of low softening point pitch fibres obtained from petroleum pitches using HNO3 as oxidising agent. This method presents some advantages compared with conventional methods: pitches with low softening point (SP) can be used to prepare carbon fibres (CF), the stabilisation time has been reduced, the CF yields are similar to those obtained after general methods of stabilisation, and the initial treatments to increase SP when low SP pitches are used to prepare CF, are avoided. The parent pitches were characterised by different techniques such as diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), elemental analysis and solvent extraction with toluene and quinoline. The interaction between HNO3 and the pitch fibres, as well as the changes occurring during the heat treatment, have been followed by DRIFTS.

Isotropic petroleum pitch as a carbon precursor for the preparation of activated carbons by KOH activation

Results show that it is possible to activate a low softening point isotropic petroleum pitch, without intermediate pre-treatments, by chemical activation with KOH. The chemical activation is carried out by direct heat treatment of a mixture of the isotropic pitch and KOH. It produces activated carbons (ACs) with micropore volumes as high as 1.12 cm3/g, and BET surface areas around 3000 m2/g. The activating agent/precursor ratios studied (from 1/1 to 4/1; wt./wt.) show, as expected, that increasing the ratio enhances the adsorption characteristics of the resulting AC.

Stabilisation of low softening point petroleum pitch fibres by iodine treatment

A method using iodine has been developed for the stabilisation of low softening point (SP) pitch fibres that avoids air stabilisation in the production of carbon fibres (CF). The interaction between iodine and petroleum pitches has been studied by following the changes in the hydrogen content, aromatic or aliphatic, during the heat treatment of iodine-treated pitch fibres. Two low SP petroleum pitches were used and the iodine-treated pitch fibres were analysed by TGA, DSC, DRIFT, XPS and SEM. The results confirm that using this novel method pitches with low SP can be used to prepare CF with two advantages, compared with conventional methods. The stabilisation time is considerably reduced and treatments to increase the SP, usually required when low SP pitches are used to prepare CF, can be avoided.

New insights on the direct activation of isotropic petroleum pitch by alkaline hydroxides

The paper provides interesting evidences that a low softening point isotropic petroleum pitch can be used as a good carbon precursor for the preparation of activated carbons. The activation is carried out by KOH and/or NaOH and the resulting activated carbons present well developed porosity. Such hydroxide activations can be done directly on the pristine petroleum pitch (P) or on the pitch that has been submitted to an air stabilisation followed by a N2 heat treatment (TAN). In general, KOH activation produces better results than NaOH, both in terms of porosity and yield, the results obtained for the activation of TAN being impressive because of the good porosity developments and high yields reached. The different treatments carried out over the petroleum pitch precursor clearly show that they significantly influence the extent of microporosity development. This is due to different changes occurring in the porous structure of the precursor as a function of the treatment carried out. The efficiency of the activation process increases as the mesophase content of the precursor decreases, as well as the mesophase formation during the activation process is avoided.

Effect of the stabilisation time of pitch fibres on the molecular sieve properties of carbon fibres

The stabilisation of pitch fibres (PFs) is the most important step for their subsequent use in the preparation of carbon fibres (CFs) and their resulting characteristics. The present work studies the influence that the stabilisation time has on the porosity of the CFs, and on the subsequent properties as carbon molecular sieve (CMS). The increase of the stabilisation time carried out at 573 K, from 2 to 8 h favours their CMS properties producing a decrease in the microposity accessible to N2, which gets completely blocked after 6 and 8 h, while the narrow microporosity (V-DR CO2) remains accessible. Adsorption kinetic studies with CH4 and CO2 were performed to assess the possibility of using these CFs as CMS by comparing them with Takeda 3A CMS. The results suggest that there is an optimal stabilisation time which allows the preparation of CFs from an abundant raw precursor with properties similar to Takeda 3A CMS.

Very high methane uptake on activated carbons prepared from mesophase pitch: A compromise between microporosity and bulk density

Two petroleum residues were pyrolyzed under two different conditions to obtain pitches with low or high mesophase content. The effect of the KOH: precursor ratio and the activation temperature on the packing density and porous texture of the carbons have been studied and optimized. Activated carbons combining high micropore volume (>1 cm3/g) and high packing density (0.7 g/cm3) have been successfully prepared. Regarding excess methane adsorption capacities, the best results (160 cm3 (STP)/cm3 at 25 °C and 3.5 MPa) were obtained using the pitch with the higher content of the more organized mesophase, activated at relatively low temperature (700 °C), with a medium KOH: precursor ratio (3:1). Some of the activated carbons exhibit enhanced adsorption capacity at high pressure, giving values as high as 175 cm3 (STP)/cm3 at 25 °C and 5 MPa and 200 cm3 (STP)/cm3 at 25 °C and 10 MPa (the same amount as in an empty cylinder but at half of the pressure), indicating a contribution of large micropores and narrow mesopores to adsorption at high pressure. The density of methane in pores between 1 and 2.5 nm at pressure up to 10 MPa was estimated to understand their contribution to the total adsorption capacity.

Activated carbon fibre monoliths

Activated carbon fibre monoliths were prepared by physical activation of carbon fibre monoliths derived from two kinds of pitch-based carbon fibre (CF) (carbon fibres from a coal tar pitch and carbon fibres derived from a petroleum pitch). The monoliths were conformed using a coal tar pitch binder. The carbon fibre monoliths and the activated carbon fibre monoliths were studied by scanning electron microscopy (SEM) and gas adsorption (i.e. N2 at 77 K and CO2 at 273 K). The results obtained reveal that monoliths perform a good activation process that produce a quite high development of microporosity (BET surface areas around 2600 m2/g and N2 micropore volume of 1.23 cm3/g). On the other hand, it is remarkable that the activation process used allow to easily control the degree of activation and hence to select the adsorption capacities of the activated carbon fibre monoliths.

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.

KOH activation of carbon materials obtained from the pyrolysis of ethylene tar at different temperatures

A complete study of the importance of the pyrolysis temperature (up to 1500 °C) of a petroleum residue (ethylene tar) in the activation with KOH of the resultant pyrolysis products (covering from the own ethylene tar to pitches and well developed cokes) has been carried out. The trend in the porosity found for activated carbons is as follows: the pore volume increases with the pyrolysis temperature reaching a maximum value (1.39 cm3/g) at about 460 °C, just at the transition temperature between a fluid pitch and a solid coke. It is the pitch with highest mesophase content that develops the maximum porosity when activated with KOH. The amount of H2, CO and CO2 produced during the reaction of the mesophase pitch and coke with KOH has been quantified, and a trend as described for the pore volume was found with the pyrolysis temperature. Therefore, there is a relationship between the reactivity of the precursor with KOH and the porosity developed by the activated carbon. Since the reactions that produce H2 initiate at temperatures as low as 300 °C, it seems that KOH is modifying the conditions under which the pyrolysis occurs, and this fact is critical in the development of porosity.

Preparation of high metal content nanoporous carbon

Activated carbons with high metal content have been prepared by the pyrolysis of ethylene tar with dissolved metal acetylacetonates (Ti, V, Fe, Co, Ni and Cu) and subsequent activation with KOH of the pitch obtained in pyrolysis. These metal compounds decompose during the pyrolysis of ethylene tar yielding metal nanoparticles formed by metal and/or oxide which are homogeneously distributed in the pitch and remain in the activated carbon, so that the concentration of metal is, in most cases, 4–5 times higher than in the pristine ethylene tar. Since KOH is an effective activating agent, all activated carbons combine a high porosity development with a high metal content. In some of the carbons, such as P2FeA (3.3% Fe, pore volume 1.84 cm3/g, BET surface area 3270 m2/g), there is even an increase in the pore volume when compared to the activated carbon prepared in the same way without metal, in spite of the fact that the metal increases the weight of carbon without contributing to the adsorptive capacity. It seems that iron, on the one hand modifies the pyrolysis to give a pitch with larger mesophase content and on the other hand it locally catalyzes carbon gasification with the CO2 produced along the synthesis of the carbon. In addition to its influence on activation, iron promotes the formation of graphitic carbon fibers.

Production of nanoTiC–graphite composites using Ti-doped self-sintering carbon mesophase powder

This work reports the synthesis of nanoTiC–graphite composites using mesophase pitch containing titanium as TiC or TiO2 nanoparticles. NanoTiC–graphite composites have been prepared using Ti-doped self-sintering mesophase powders as starting materials without using any binders or a metal carbide-carbon mixing stage. The effect of manufacture variables on the graphite compacts properties was studied. Graphites were characterised using XRD and Raman spectroscopy, SEM and TEM, as well as by their mechanical, electrical and thermal properties. The presence of TiC promotes graphitisation producing materials with larger crystal sizes. The kind of titanium source and mesophase content of the starting pitch affects to the final properties. Mesophase pitch with higher amount of mesophase content produces graphites with higher degree of graphitisation. The incorporation of TiC nanoparticles to the graphites composites improved thermal conductivity more than four times, and mechanical properties are not significantly modified by the presence of TiC.

Electrochemical Performance of Hierarchical Porous Carbon Materials Obtained from the Infiltration of Lignin into Zeolite Templates

Hierarchical porous carbon materials prepared by the direct carbonization of lignin/zeolite mixtures and the subsequent basic etching of the inorganic template have been electrochemically characterized in acidic media. These lignin-based templated carbons have interesting surface chemistry features, such as a variety of surface oxygen groups and also pyridone and pyridinic groups, which results in a high capacitance enhancement compared to petroleum-pitch-based carbons obtained by the same procedure. Furthermore, they are easily electro-oxidized in a sulfuric acid electrolyte under positive polarization to produce a large amount of surface oxygen groups that boosts the pseudocapacitance. The lignin-based templated carbons showed a specific capacitance as high as 250 F g−1 at 50 mA g−1, with a capacitance retention of 50 % and volumetric capacitance of 75 F cm−3 at current densities higher than 20 A g−1 thanks to their suitable porous texture. These results indicate the potential use of inexpensive biomass byproducts, such as lignin, as carbon precursors in the production of hierarchical carbon materials for electrodes in electrochemical capacitors.