The Utilization of Douglas-Fir Bark for the Production of Oxalic Acid and High Density Carbon Pellets

The production of oxalic acid by the catalytic oxidation of Douglas-fir (Psedotsuga menfiesii (Mirb) Franco) bark and subsequent pyrolysis of the residue to produce high density carbon pellets is discussed. Kinetic rate data are presented for oxalic acid production from Douglasfir bark. A maximum yield of 38 wt% oxalic acid has been obtained in 8 h at 80°C with 62.5 vol% HNO₃ and 0.5 mg V₂O₅/g of bark. Additional oxalic acid can be produced by the conversion of pyrolytic oils and tars (obtained during carbonization of the residue) to increase the total yield to 45 wt%. An economic analysis based on the current cost of oxalic acid indicates the viability of the proposed process.     

Chemicals from forest products by supercritical fluid extraction

Supercritical acetone or methanol extraction of wood gave liquid products with a maximum yield of 74%. Approximately 5% of these complex products was identified as substituted guaiacols and levoglucosan. Acetone extract could substitute for 30% of the phenol in phenolic resins.

Resin and fatty acids were extracted from southern pine and waxes from Douglas-fir bark using supercritical carbon dioxide, nitrous oxide, propane or ethylene. Of these, propane and nitrous oxide gave the best yields.     

Preparation and characterization of templated porous carbons from sucrose by one-pot method and application as a CO2 adsorbent

The templated porous carbons were prepared from sucrose by one-pot method. In this method in which the pre-synthesis of the hard template is eliminated, the porous carbons were produced by organic-inorganic self-assembly of sucrose, tetraethyl ortosilicate (TEOS), Pluronic P123 and n-butanol in an acidic medium, and subsequent carbonization. The synthesis parameters such as sucrose amount, TEOS molar ratio and carbonization temperature were evaluated for describing their effects on the pore structures of the synthesized carbons. The prepared porous carbons were characterized by N₂ adsorption, thermogravimetric analysis (TGA), Raman spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) techniques. The carbon dioxide adsorption uptakes of the obtained porous carbons were determined at 1 bar and 273 K. The templated carbon obtained with the lowest TEOS molar ratio exhibited the highest BET surface area of 1289 m²/g and micropore volume of 0.467 cm³/g, and showed the highest CO₂ uptake of 2.28 mmol/g.     

Catalytic activity of gold nanoparticles deposited on N-doped carbon-based supports in oxidation of glucose and arabinose mixtures

Oxidation of a mixture of glucose and arabinose over Au particles deposited on porous carbons, N-doped carbons and carbon nitrides was investigated at 70 °C, under constant pH of 8, and oxygen partial pressure 0.125 atm. In particular, Au deposited on nitrogen-containing carbon-based mesoporous structures demonstrated activity in the oxidation of the sugars to the corresponding aldonic acids higher than gold deposited on undoped carbon supports (conversion of glucose up to ca. 60%, arabinose–ca. 30% after 200 min). The results can be explained by the basic nature of the supports leading to an increase in the polarity of the carbon surface and the oxygen activation. Glucuronic acid (with selectivity ca. 10–93.5%) together with gluconic acid was formed as a result of glucose oxidation, while arabinose was selectively oxidized to arabinonic acid.

     

Physical and electrochemical characterization of activated carbons with high mesoporous ratio for supercapacitors based on ionic liquid as the electrolyte

A series of activated carbons with high mesoporous ratio were prepared by KOH reactivation based on activated carbon as the precursor. As the KOH/AC mass ratio was increased to 4:1, the mesoporous ratio increases from 60% to 76%, and the average pore size from 2.23 to 3.14?nm. Moreover, the specific capacitance for the activated carbon in ionic liquid 1-ethyl-3-methylmidazolium tetrafluoroborate ([EMIm]BF₄) can reach the maximum value of 189?F?g^?1 (8.0???F?cm^?2). In addition, the decrease of specific capacitance for activated carbons by KOH reactivation with current density increase shows two regimes, suggesting that activated carbons with high mesoporous ratio are much fit for charge?Cdischarge at larger current density.     

Isolation and comparative characterization of a Björkman lignin from the saponified cork of Douglas-fir bark

Cork from Douglas-fir bark (Pseudotsuga menziesii) was separated, extracted and submitted to suberin depolymerization by transesterification with sodium methoxide in methanol. As a result a saponified cork fraction (cork_sap) with a yield of 19% was obtained. From cork_sap a milled cork lignin (MCL_sap) was isolated using the Björkman procedure with a yield of 0.75% (based on cork_sap, corresponding to 0.14% based on original cork). The isolated Douglas-fir MCL_sap was characterized by elemental analysis and OMe determination, FT-IR spectroscopy and analytical pyrolysis (Py-GC/FID). Data are presented in comparison with those of MCL_sap isolated from cork-oak (Quercus suber) and milled wood lignins (MWL) of spruce. All data revealed that the Douglas-fir cork lignin has a guaiacyl-type structure (G-lignin). Results of Py-GC/FID demonstrate that this polymer consists of approximately 97% guaiacyl, 2% p-hydroxyphenyl and 1% syringyl units.     

Rapid Multielement Analysis of Tree Bark by EDXRF

A rapid and simple method for multielement analysis of tree bark using energy dispersive X-ray fluorescence (EDXRF) spectrometry has been developed. Sample preparation consisted of crushing tree bark into a fine powder prior to the production of pressed pellets. Limits of detection for elements of interest (Pb, Hg, Zn, Cu, Ni, Al, Sn, Fe, Cr, Mn, Ti, As, Cd, Sb, and Ag) were at or below the µg/g level. Analysis of environmental certified reference materials (fly-ash, soil and tea-leaves) was used to check accuracy and precision. Survey analysis was performed at industrial, urban and rural sites in diverse locations throughout the world. The potential for source apportionation was demonstrated as reflected in elevated levels of Pb (up to 12,300 µg/g) and Sb (up to 86 µg/g) near a lead smelter site (UK) and high concentrations of Hg (up to 4.2 µg/g) in gold extraction regions of Brazil.     

Oxidation of Polyisoprene Popcorn Polymer. II. Gravimetric Analysis

Water, carbon dioxide, and condensable condensate produced during the oxidation of polyisoprene popcorn polymer were determined gravimetrically. For pure polyisoprene popcorn polymer from which 4.6% soluble polymer and volatiles were removed, the rates of water and carbon dioxide production during the early stages of the autoxidation were linear and amounted to approximately 2 moles of water and 0.2 moles of carbon dioxide for every 10 moles of oxygen reacted.

The generally accepted scheme for polyisoprene oxidation must be modified to account for the water production. Two possible routes for its synthesis are:

ROOH + ROOH → RO· + ROO· + H₂O

ROOH → RO· + ·OH

HO· + R → R· + H₂O     

Pilot production of activated carbon from cotton stalks using H3PO4

Cotton stalks, an agricultural waste, were chemically activated in a batch process using H₃PO₄ in a locally designed carbonizer at 420 °C in the absence of any purging gases. Mechanically cut short sticks were soaked in diluted H₃PO₄ for a short duration (Batch 1) and an extended period (Batch 2) prior to thermal treatment. The derived carbons contained both coarse and fine grains with acidic effect. Porosity was characterized by N₂ adsorption at −196 °C and the isotherms analyzed by the α-method to estimate total and microporous surface areas in addition to total and microporous volumes. The produced carbons exhibited well-developed porosity that was essentially microporous in composition. Several key performance parameters were altered considerably as a result of impregnation with H₃PO₄ and the extended chemical activation period (Batch 2). Most of the internal porosity of both carbons was accessible to adsorption of iodine, whereas the uptake of methylene blue dye was proportional to the average size of micropores which were larger for the batch with a longer acid soaking time. SEM and FTIR investigations revealed the presence of a developed honeycomb structure and different oxygen functionalities on surfaces of the activated products which are advantageous in liquid-phase applications. Preliminary laboratory-scale experiments with Pb(II) indicate that adsorption capacity of target heavy metals compares favorably with commercially available activated carbons. The raw material, pre-processing, and activation process prove feasible for the production of activated carbon on a large scale, thereby providing a sustainable strategy for treatment of toxic waste streams.     

High field carbon 13 relaxation of 5CB. Chemical shift anisotropy as a probe of nematic dynamics

Abstract

The carbon 13 spin-lattice relaxation times of the ring carbons at 22·6 MHz in the nematic phase and at 20·0 MHz in the isotropic phase of 5CB have been published previously. An analysis of the results in the nematic phase based on diffusion constants obtained from deuteron relaxation was presented. In this paper measurements of the carbon 13 spin-lattice relaxation times of the ring carbons of 5CB at 125·6 MHz are given along with an analysis which makes use of the wide variation in the field to interpret the relatively simple relaxation of the protonated aromatic carbons. An effort to interpret the more complicated relaxation behaviour of the unprotonated carbons using the simplification in relaxation behaviour at high fields where chemical shift anisotropy dominates the relaxation is less successful. However, the conclusion that order director fluctuations account for almost 50 per cent of the relaxation rate in the nematic phase at high fields suggests that study of high field rotating frame relaxation for these carbons might be a rich source of information on critical fluctuations.     

Tannin-based hard carbons as high-performance anode materials for sodium-ion batteries

The demand for efficient and cheap electrochemical storage devices is very high today. Na-ion batteries are emerging as a promising alternative to Li-ion batteries for large-scale applications because of the much larger abundance of sodium. Among the different negative electrode materials allowing Na insertion at low potentials, hard carbons are the materials with the best electrochemical performances reported so far. Here we investigate the synthesis of hard carbons from tannins, an abundant and cheap bio-sourced carbon precursor made of polyphenolic molecules. We show that by a well-controlled synthesis method and high-temperature pyrolysis (1600°C), a hard carbon with developed ultra-microporosity is obtained. This hard carbon delivers a reversible capacity of 306 mAh g^?1 at C/20 with a first-cycle coulombic efficiency of 87%. To our knowledge, these electrochemical performances are among the best ever reported in the literature for biomass-derived hard carbons.     

Ordered porous carbon with tailored pore size for electrochemical hydrogen storage application

Ordered porous carbon with tailored pore size represents an innovative concept in electrochemical hydrogen storage. This work deals with physical characteristics and electrochemical hydrogen storage behavior of the ordered porous carbons with well-tailored pore size, synthesized by a replica technique using hexagonal mesoporous silica as templates. By using a mixture of two surfactants (HTAB and C16EO8) at different ratios, it is possible to control the wall thickness of silica and, consequently, the pore diameter of carbons within a narrow range of 2.1-2.8 nm. In addition, highly developed ultramicroporosity (pore size smaller than 0.7 nm), which plays a predominant role in hydrogen storage, can be produced in the ordered porous carbons. A discharge capacity of up to 527 mAh/g (corresponding to 1.95 wt % hydrogen storage) has been achieved in 6 M KOH for the ordered porous carbon. Furthermore, the ordered porous carbons also possess excellent capacity retainability after charge-discharge cycles and rate capability.     

The effect of the physical and chemical characteristics of activated carbons on the adsorption energy and affinity coefficient of Dubinin equation

The dependency of adsorption energy (E) and affinity coefficient (beta) of Dubinin equations (Dubinin-Radushkevich (DR) or Dubinin-Astakhov (DA)) on surface chemistry and porosity of activated carbons was investigated by analyzing adsorption of nitrogen, benzene, trichloroethylene (TCE), and water vapor by several surface-modified activated carbons and carbon fibers. For all studied nonpolar adsorbates, carbons with smaller average micropores showed higher adsorption energies independent of their surface chemistry. For water vapor, carbons with higher surface polarities showed higher adsorption energies due to specific adsorbate-adsorbent interactions. Adsorption energies increased with decreasing average micropore widths. betaN2,DR for different carbons were observed to vary in the 0.292-0.539 range. Carbons with higher degrees of mesoporosity had higher betaN2,DR values, while no dependency was observed between betaN2,DR and surface chemistry. A comparison of DR and DA cases indicates that: (1) the average value of betaN2,DA is considerably above the classical value of this parameter; and (2) the range of betaN2,DA values were smaller compared to betaN2,DR, despite a wide range of mesoporosity of carbons examined. Obtained beta(TCE,DR) values varied in the 0.952-1.243 range, with an average value of 1.085+/-0.083, independent of surface chemistry or porosity of activated carbons. A similar result was observed for beta(TCE,DA). betaH2O,DR values of different granular and fibrous activated carbons changed in the range of 0.081-0.271. They depended more on the carbon surface chemistry and less on the porosity. A similar result was obtained when DA equation was considered.     

Liquid-phase adsorption of multi-ring thiophenic sulfur compounds on carbon materials with different surface properties

This work examines the effects of structural and surface properties of carbon materials on the adsorption of benzothiophene (BT), dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) in the presence of 10 wt % of aromatics in liquid alkanes that simulate sulfur compounds in diesel fuels. The equilibrium-adsorption capacity varies significantly, from 1.7 to 7.0 mg-S/g-A. The results show that different carbon materials have significantly different sulfur-adsorption capacities and selectivities that depend not only on textural structure but also on surface functional groups. The adsorption of multi-ring sulfur compounds on carbon materials was found to obey the Langmuir isotherm. On the basis of adsorption tests and the characterization of carbon materials by BET and XPS, the oxygen-containing functional groups on the surface appear to play an important role in increasing sulfur-adsorption capacity. The adsorption-selectivity trend of the carbon materials for various compounds increases in the order of BT < naphthalene < 2-methylnaphthalene < DBT < 4-MDBT < 4,6-DMDBT, regardless of carbon material types. This selectivity trend for sulfur compounds is dramatically different and almost opposite from that previously observed for adsorption over nickel-based adsorbents. The regeneration of spent activated carbons was also conducted by solvent washing. The high-adsorption capacity and selectivity for methyl DBTs indicate that certain activated carbons are promising adsorbents for selective adsorption for removing sulfur (SARS) as a new approach to ultra deep desulfurization of diesel fuels.     

Activated carbons obtained from agro-industrial waste: textural analysis and adsorption environmental pollutants

In this study, we aimed to use as a new lignocellulosic precursor in the production of activated carbon. The physicochemical characteristics of the activated carbons obtained under optimum conditions were determined by using some techniques such as thermo-gravimetric (TG/DTG) analysis, nitrogen adsorption–desorption, scanning electron microscopy (SEM) and surface functional group analysis by Fourier transform infrared spectroscopy (FT-IR), Boehm titration method and point of zero charge (pHpzc). In addition, the activated carbons were tested to remove phenols from aqueous solutions. The results indicated that activated carbon the orange peel, pine cone and yerba mate, could be employed as an alternative low-cost activated carbon for the removal the phenolic contaminants from wastewater.     

Ozonation of naphthalenesulphonic acid in the aqueous phase in the presence of basic activated carbons

The present study aimed to explore the possibility of increasing the purification efficacy of ozone in the removal of high-toxicity contaminants by using carbons of basic character and to analyze the mechanism involved in this process. These carbons were prepared by treating a commercial activated carbon (Witco, W) with ammonia (W-A), ammonium carbonate (W-C), or urea (W-U), under high pressure and temperature. The ammonia and carbonate treatments slightly increased the mesoporosity and, to a greater degree, the macroporosity of carbon W, whereas the urea treatment produced an increase in the porosity across the whole range of pore sizes. In addition, treatment of the activated carbon with these nitrogenating agents produced a marked change in the chemical nature of its surface. Thus, according to the pH of the point of zero charge (pHPZC) values obtained for each sample, carbon W was neutral (pHPZC = 7.12), but the treated carbons were basic, especially carbon W-U (pHPZC = 8.85). This basicity results from an increased concentration of basic oxygenated and nitrogenated surface functional groups, as confirmed by the results of elemental and XPS analyses. An increase in the degradation of 1,3,6-naphthalenetrisulfonic acid was observed when the activated carbon samples were added to the system. This degradation was especially enhanced in the presence of carbon W-U. The increased NTS degradation rate in the presence of the activated carbon is due to an increased concentration of highly reactive radicals in the system. When the catalytic activity of the activated carbon samples was related to their chemical and textural characteristics, it was found that: (i) The catalytic activity increased with an increase in the surface basicity. Interestingly, in the sample with greatest catalytic activity in NTS ozonation, carbon W-U, most of the nitrogenated surface groups introduced were pyrrol groups. These groups increase the electronic density of the basal plane of the activated carbon, thereby enhancing the reduction of ozone on the surface and the generation of highly reactive radicals in the system. (ii) The greater catalytic activity of carbon W-U may also be partly related to its greater surface area and higher volume of mesopores and macropores; these large pores facilitate access of the ozone to the surface active centers of the carbon, increasing its catalytic activity. The presence of the activated carbon samples during NTS ozonation also favored the removal of total organic carbon present in the solution, due to (a) transformation of organic matter into CO2 through the generation of highly reactive species catalyzed by the presence of the activated carbons (catalytic contribution) and (b) adsorption of NTS oxidation byproducts on the activated carbon (adsorptive contribution). The results obtained show that activated carbons treated with nitrogenating agents are very promising catalysts for application in the ozonation of aromatic compounds.     

Highly N/O co-doped ultramicroporous carbons derived from nonporous metal-organic framework for high performance supercapacitors

A new nonporous Zn-based metal-organic framework (NPMOF) synthesized from a high nitrogen-containing rigid ligand was converted into porous carbon materials by direct carbonization without adding additional carbon sources. A series of NPMOF-derived porous carbons with very high N/O contents (24.1% for NPMOF-700, 20.2% for NPMOF-800, 15.1% for NPMOF-900) were prepared by adjusting the pyrolysis temperatures. The NPMOF-800 fabricated electrode exhibits a high capacitance of 220 F/g and extremely large surface area normalized capacitance of 57.7 μF/cm² compared to other reported MOF-derived porous carbon electrodes, which could be attributed to the abundant ultramicroporosity and high N/O co-doping. More importantly, symmetric supercapacitor assembled with the MOF-derived carbon manifests prominent stability, i.e., 99.1% capacitance retention after 10,000 cycles at 1.0 A/g. This simple preparation of MOF-derived porous carbon materials not only finds an application direction for a variety of porous or even nonporous MOFs, but also opens a way for the production of porous carbon materials for superior energy storage.     

A study on adsorption of metals by activated carbon in a large-scale (municipal) process of surface water purification

Elements that enter the aquatic environment may pose a health risk to wildlife and humans. The aims of this study were: to determine how the introduction of activated carbon for a water purification system will improve the quality of the water produced; and to investigate the sorption of metals on activated carbons, including determination of the accumulation, as well as changes in concentrations of elements in carbons. The tests were carried out on three types of activated carbons with different granular structure. All samples were collected from Water Treatment Plant Goczalkowice, Poland. Concentrations of elements were measured using an optical emission spectrometer with inductively coupled plasma. The experiment showed that metals accumulating in the activated carbons during the operation included: Ca, Mn, Zn, and Cu. In each of the three types of carbons, it can distinguish such elements as Ba, Al, Cr, Ni, Ti, which are characterized by irregular accumulation during the operation of the filter. The introduction of carbon sorbent for water treatment largely contributed to improvement in the quality of raw material supplied to customers, mainly with regard to taste and smell, as well as to reduction of basic parameters: color, absorbance in the UV range and oxidability.      

The Analysis of Pore Development and Formation of Surface Functional Groups in Bamboo-Based Activated Carbon during CO2 Activation

Pore development and the formation of oxygen functional groups were studied for activated carbon prepared from bamboo (Bambusa bambos) using a two-step activation with CO₂, as functions of carbonization temperature and activation conditions (time and temperature). Results show that activated carbon produced from bamboo contains mostly micropores in the pore size range of 0.65 to 1.4 nm. All porous properties of activated carbons increased with the increase in the activation temperature over the range from 850 to 950 °C, but decreased in the temperature range of 950 to 1000 °C, due principally to the merging of neighboring pores. The increase in the activation time also increased the porous properties linearly from 60 to 90 min, which then dropped from 90 to 120 min. It was found that the carbonization temperature played an important role in determining the number and distribution of active sites for CO₂ gasification during the activation process. Empirical equations were proposed to conveniently predict all important porous properties of the prepared activated carbons in terms of carbonization temperature and activation conditions. Oxygen functional groups formed during the carbonization and activation steps of activated carbon synthesis and their contents were dependent on the preparation conditions employed. Using Boehm’s titration technique, only phenolic and carboxylic groups were detected for the acid functional groups in both the chars and activated carbons in varying amounts. Empirical correlations were also developed to estimate the total contents of the acid and basic groups in activated carbons in terms of the carbonization temperature, activation time and temperature.     

Preparation and characterization of bimodal porous carbons derived from a styrene-divinylbenzene copolymer

A styrene/divinylbenzene copolymer has been used as precursor for making porous carbons with bimodal pore size distributions (i.e., with both microporosity and mesoporosity). Pretreatment of the as-received copolymer by mild oxidation in air, significantly increased the carbon yield after carbonization. Reactivity studies of the polymer-based chars to CO₂ clearly show the influences of some important factors such as carbonization temperature, heating rate, soak time on char reactivities. Bimodal porous carbons were prepared by carbonization of the preoxidized styrene/divinylbenzene copolymer in N₂, followed by activation in CO₂ at different temperatures to different levels of burnoff. The pore structures of the porous carbons produced have been characterized by various techniques such as gas adsorption and mercury porosimetry. The surfaces of the porous carbons produced, and a commercial carbon adsorbent, have been modified with HNO₃ and H₂O₂ treatment at various conditions. Characterization of the surface oxygen functionality, both quantitatively and qualitatively, has been achieved using techniques such as Linear Temperature Programed Desorption (LTPD) and selective neutralization of bases.