Study and Characterisation of Activated Carbon Treated with H2SO4 Solutions

Several samples of activated carbon (AC), previously outgassed and treated with H₂SO₄ solutions of varying concentration, were prepared. The contact between the phases and the outgassing of AC were carried out under controlled conditions. The chemical composition and the thermal behaviour as well as the texture of the samples were studied. Techniques used were chemical analysis, FT-IR spectroscopy, thermogravimetric analysis, gas adsorption, mercury porosimetry and density measurements. After the contact of H₂SO₄ solutions with AC, the mass of samples increased greatly. It was associated with the uptake by AC of components of the solution, especially H₂SO₄. The presence in the samples of HSO₄⁻ and SO₄²⁻ ions was shown by the FT-IR spectra. The mass increase was strongly dependent on the method of preparation of the samples. In the heat treatment of the samples between 30 and 800°C a great mass loss occurred below 400°C. However, it was small at higher temperatures and when the samples were outgassed at 120°C for 12 h, at 133×10⁻³ Pa. The introduction of H₂SO₄ solution in AC pores produced a drastic reduction in the surface area and in the microporosity of the material. It also affected the pore-size distribution in the mesopore and macropore ranges. © 1997 SCI.     

Direct oxidation of hydrogen sulphide to sulphur using impregnated activated carbon catalysts

Low concentrations of H₂S were directly oxidized to sulphur and small quantities of SO₂, over seven different activated carbons with or without impregnation. The effectiveness of virgin activated carbon was tested at 175°C, 700 kPa, and O₂/H₂S ratio with 5% greater than stoichiometry. The conversion of H₂S was 99.9 mol% with SO₂ production of 3–6%, for 360 min runtime for Fisher coconut shell activated carbon and 648 min for Envirotrol bituminous (EB) activated carbon. Then the activated carbons became deactivated due to deposition of sulphur on the surface. Under these conditions mesoporous activated carbons such as EB and Hydrodarco had the longest breakthrough time. The addition of 5.5 wt% ammonium iodide, potassium iodide and potassium carbonate individually to EB decreased the production of SO₂ while having minimal effect on the overall H₂S conversion. The addition of 5.5 wt% NH₄I decreased the average SO₂ production from 2.5% to 0.9%. The activation energy for the H₂S oxidation on the 5.5 wt% NH₄I on EB activated carbon was determined to be 40 kJ/mol.     

Heterogeneous Reactions of Chlorine Nitrate and Dinitrogen Pentoxide on Sulfuric Acid Surfaces Representative of Global Stratospheric Aerosol Particles

Increasing evidence from field measurements, modeling studies, and laboratory experiments suggests that heterogeneous reactions on stratospheric sulfate aerosol particles can change the partitioning in the nitrogen and chlorine families and thereby affect global ozone levels. In this study, a Knudsen cell flow reactor was used to measure the uptake of ClONO₂ and N₂O₅ by sulfuric acid solutions representative of background and volcanic stratospheric aerosol particles. The uptake coefficient (γ) of chlorine nitrate on 50–75 wt% H₂SO₄ at 223 K was found to be markedly dependent on the acid concentration, with γ ranging from about 1 × 10⁻² to 1 × 10⁻⁴. These results are in good agreement with literature reports and the data fit the expression log γ= 1.87 – 0.074 × (wt% H₂SO₄). This reaction will thus have its largest impact when stratospheric temperatures are low and sulfuric acid aerosols are most dilute. Uptake of N₂O₅ was studied on solutions with compositions in the range 58–96 wt% H₂SO₄ at temperatures from 193 to 303 K. N₂O₅ reacted readily on sulfuric acid surfaces with uptake coefficients of about 0.06. The uptake coefficient was found to be independent of the sulfuric acid concentration and the solution temperature over the ranges studied. These results suggest that the reaction of N₂O₅ with H₂O will occur readily on sulfuric acid aerosol particles for most stratospheric conditions.     

Ion exchange resins from phenol/formaldehyde resin‐modified lignin

Phenol/formaldehyde resin, commonly sulfonated, is used as ion exchanger. Lignin, which is the phenolic polymer matrix in wood, was isolated from olive stone biomass by alkaline hydrolysis of weak ether bonds (Kraft lignin, KRL). It was then hydroxymethylated (KRLH) with an aqueous solution of formaldehyde. Novolac resin (N) was synthesized from phenol and formaldehyde under acidic conditions. KRL or KRLH was incorporated into phenol/formaldehyde during polymerization (N‐KRL, N‐KRLH). The products of polymerization (N, N‐KRL and N‐KRLH) were sulfonated with concentrated H₂SO₄ (1:3 w/w as typical proportion according to literature or 1:6 w/w as an excess of H₂SO₄) and then cross‐linked with formaldehyde. The different products were characterized by IR spectroscopy, swelling in ethanol, acetone and in an aqueous solution of 1 N NaOH. The ion‐exchange capacity, the moisture retention capacity and the titration curves of the sulfonated and cured products were determined. The ion‐exchange capacity and the uptake of metal ions (mainly Co²⁺ and Cu²⁺) detected by atomic absorption spectroscopy, on the sulfonated materials, prepared in an excess of H₂SO₄, is higher for N‐KRL and N‐KRLH than for N and it takes place at the same rate or faster. The latter shows a medium acidic behaviour according to the titration curves, in contrast with the sulfonated N‐KRLH and N‐KRL which show a strongly acidic behaviour. © 2001 Society of Chemical Industry     

Towards waste minimisation in WWTP: activated carbon from biological sludge and its application in liquid phase adsorption

Surplus sludge produced during the biological treatment of wastewater requires costly disposal procedures. With increasing environmental and legislative constraints, increasing sludge production and more limited disposal options, new recycling alternatives have to be found. The possibility of obtaining activated carbons from surplus biological sludge by chemical activation with H₂SO₄ has been investigated. Operational parameters such as the amount of H₂SO₄ added, the temperature, and activation time were modified to ascertain their influence on the quality of the activated carbon obtained. The quality of the sludge‐based activated carbons was evaluated by established characterisation parameters for adsorption from solution such as phenol value, iodine number, methylene blue number and tannin value and compared with commercial activated carbons. Activation at 700 °C for 30 min in the presence of 0.5 cm³ H₂SO₄ g^?1 dry solids in the sludge led to an activated carbon with a good capacity for iodine and tannic acid. The sludge‐derived activated carbon obtained is mesoporous in nature with a high presence of large macropores. Weak and moderate acidic surface functional groups were detected on the surface, which impart a hydrophilic nature to the solid. When compared with a commercial activated carbon, the sludge‐derived activated carbon performed better when removing dyes with a high presence of anionic solubilising groups and heavy metals. The results indicate that COD adsorption from a biologically‐treated effluent may also be an area for application. © 2002 Society of Chemical Industry     

Conversion of Poly(Ethylene Terephthalate) Waste into Activated Carbon: Chemical Activation and Characterization

Due to its high carbon content, low impurities, low cost and easy availability, poly(ethylene terephthalate) (PET) waste is considered as a suitable precursor for the production of activated carbon. The chemical activation of PET wastes using different chemical agents such as H₃PO₄, H₂SO₄, ZnCl₂, and KOH was investigated. KOH‐ and ZnCl₂‐activated PET were found to be the best choices for the adsorption of small and large molecules. The capacities of the adsorbents towards I₂, methylene blue, N₂, CH₄, and CO₂ followed the order KOH‐PET >H₃PO₄‐PET > ZnCl₂‐PET > H₂SO₄‐PET; however, in the molasses uptake and selective adsorption of CO₂ compared to CH₄, ZnCl₂‐PET performed better than the other adsorbents.     

Selective Production of C4 Hydrocarbons from Syngas Using Fe‐Co/ZrO2 and SO42—/ZrO2 Catalysts

Modified Fischer‐Tropsch (MFT) syntheses were carried out to convert synthesis gas to C₄ hydrocarbons over Fe‐Co/ZrO₂ (FT) and SO₄^2—/ZrO₂ (SZ) catalysts in a dual reactor system, keeping the FT to SZ catalysts ratio at 1:1.5. Five Fe‐Co/ZrO₂ catalysts with different Fe and Co loading, and SZ with 15 wt% SO₄^2— were prepared and extensively characterized using various physico‐chemical methods. The FT synthesis process was initially performed using a Fe‐Co/ZrO₂ catalyst in a single reactor and the effects of Fe and Co mass ratio, reaction temperature, space velocity on the production of C₄ hydrocarbons and C₂‐C₄ olefins were investigated. Results indicated that a 3.71% Fe—8.76% Co/ZrO₂ mixed oxide catalyst alone at 260°C and 5 h^—1 gave high selectivities of C₂‐C₄ olefins (～26.1 wt%) and total C₄ hydrocarbon product (～16.2 wt%). The MFT process 150°C gave higher C₄ (～31.6 wt%), isobutane (～22.9 wt%) and C₂‐C₄ (31.1 wt%) selectivities.     

Preparation and characterization of polymer/multiwall carbon nanotube/nanoparticle nanocomposites and preparation of their metal complexes

Carbon nanotube‐polymer nanocomposites were synthesized and characterized successfully. In this work, multiwall carbon nanotubes (MWCNT) were opened using HNO₃/H₂SO₄ mixture and filled by metal nanoparticles such as silver nanoparticles through wet‐chemistry method. The oxidized MWCNT were reacted subsequently with thionyl chloride, 1,6‐diaminohexane, producing MWNT‐amine functionalized. Then the MWCNT containing metal nanoparticles were used as a monomer with different weight percentages in melt polymerization with An and CNCl separately. Furthermore, the polyamide and polytriazine modified MWCNT were used for the preparation of metal ion complexes such as Fe⁺² and La⁺³. The structures and properties of nanocomposites were evaluated by TEM, DSC, TGA, and FT‐IR methods. The chelating behavior and sorption capacities of prepared nanocomposites were carried out by using some metal ions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of borate–modified expandable graphite and its flame retardancy on acrylonitrile‐butadiene‐styrene resin

A borate‐modified expandable graphite (written as MEG) was prepared through one step intercalating reaction of natural graphite, using KMnO₄ as oxidant, H₂SO₄ and sodium tetraborate as intercalator and assistant intercalator, respectively. The dilatability, structure, element contents, thermal stability, and flame retardancy on acrylonitrile‐butadiene‐styrene (ABS) were investigated. Compared with the normal expandable graphite (written as EG, which was prepared with only H₂SO₄ as intercalator), the results show that MEG exhibits higher expandable property, thermal stability and flame retardancy on ABS. The EDS, FT‐IR, and XRD results reveal that borate has been inserted into graphite layers. With the addition of MEG or EG at a 30 wt%, LOI of 70ABS/30MEG composite improved to 27.9%, 2.2% higher than that of 70ABS/30EG. Moreover, the synergistic effect between MEG and traditional intumescent flame retardant (IFR, consists of ammonium polyphosphate (APP), pentaerythritol (PER), and melamine (MEL) with a mass ratio of 7.5:4.5:3.0) improves the LOI of 70ABS/15MEG/15IFR composite to 32.6%, and the UL‐94 level reaches V‐0. This synergistic efficiency is attributed to the formation of continuous and compact residual char. Addition of MEG together with IFR changes the ABS pyrolysis behavior, and there is not only physical synergy, but also chemical reaction. POLYM. COMPOS., 37:2673–2683, 2016. © 2015 Society of Plastics Engineers     

Infrared studies of SO2 on carbons—II. the SO2 species adsorbed on carbon films

IR spectroscopic studies were carried out on the character of interactions between adsorbed molecules of SO₂ and O₂, H₂O or H₂S on the surface of carbons. The character of bonding between adsorbed molecules and the carbon films depends on the chemical structure of the surface functional groups. Weakly adsorbed SO₂ gives rise to the bands at 1330 and 1140 cm⁻¹. Strongly held SO₂ is indicated by the band around 1045 cm⁻¹. Catalytic activity of carbon films in the oxidation of aqueous sulfur dioxide solution has been studied. The results suggest that Superoxide ions take part in the adsortion of acids on the surface of carbon as well as in the catalytic oxidation of aqueous SO₂ solution by O₂.     

The solubilities of Fe,Ni, V and Na salts in concentrated aqueous H2SO4 solutions at temperatures between 400 and 460 K

When residual fuel oil, which contains up to 4 wt% S, is burned in boiler plant, H₂SO₄ is formed which condenses as aqueous solutions (65–90 wt% H₂SO₄) on surfaces in the cool back-end. The oil contains traces of other elements, in particular Na, V, Fe and Ni, which also deposit on these surfaces as either sulphates (Na, Fe, Ni,) or oxides (V). When designing techniques to control acid deposition and the corrosion which it subsequently causes, account must be taken of the degree to which the acid properties can be modified by taking these compounds into solution. A series of measurements of the solubilities of relevant compounds in acid solutions within the appropriate ranges of concentration and temperature (400–460 K) have been made. Sodium sulphate has by far the highest solubility (55 wt% in a solution originally containing 85 wt% H₂SO₄ at 423 K). Of the other compounds considered, only V₂O₅ exhibits a solubility of more than 2 wt%; for example, at 463 K, in 75 wt% H₂SO₄, solutions containing up to 16 wt% V₂O₅ can be formed. Solutions with up to 23 wt% V₂O₅ can be stabilised by the presence in solution of small amounts (～0.5 wt%) of Fe³⁺ ions. The structure of these solutions is discussed.     

Melt processing of poly(vinyl alcohol) through adding magnesium chloride hexahydrate and ethylene glycol as a complex plasticizer

The melt processing of poly(vinyl alcohol) (PVA) was achieved using magnesium chloride hexahydrate (MgCl₂·6H₂O) and ethylene glycol as a complex plasticizer. The interaction between the complex plasticizer and PVA was studied by Fourier transform infrared spectroscopy (FT‐IR). The PVA films were characterized using X‐ray diffraction (XRD), differential scanning calorimetry, thermogravimetric analysis (TGA), scanning electron microscope, and dynamic thermomechanical analysis (DMA) techniques. The band shift of the observed peak around 3335 cm^?1 in the FT‐IR spectra indicates that the complex plasticizer MgCl₂·6H₂O and ethylene glycol could form strong interactions with PVA and thus interrupt the intermolecular and intramolecular hydrogen bonding in PVA. The XRD results show that the addition of the complex plasticizer would significantly destroy the crystallites of PVA and result to the decrease of the degree of crystallinity of PVA. The melting point was reduced from 229°C of pure PVA to around 170°C after the plasticization. The TGA studies show that with the complex plasticizer, the thermal stability of PVA is improved. PVA plasticized by 30 wt% MgCl₂·6H₂O and 10 wt% ethylene glycol shows the tensile strength of 33 MPa and the elongation at break of 362%. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Preparation of porous Al2O3 ceramics by starch consolidation casting method

Porous alumina ceramics were fabricated by starch consolidation casting using corn starch as a curing agent while their microstructure, mechanical properties, pore size distribution, and corrosion resistance were examined. Results showed that the porous alumina ceramics with the flexural strength of about 44.31MPa, apparent porosity of about 47.67% and pore size distribution in the range of 1‐4 μm could be obtained with 3wt% SiO₂ and 3wt% MgO additives. Corrosion resistance results showed mass losses: hot H₂SO₄ solution and NaOH solution for 10 hours were 0.77% and 2.19%, which showed that these porous alumina ceramics may offer better corrosion resistance in acidic conditions.     

Nanoporous rice husk derived carbon for gas storage and high performance electrochemical energy storage

We report on the gas storage behaviour and electrochemical charge storage properties of high surface area activated nanoporous carbon obtained from rice husk through low temperature chemical activation approach. Rice husk derived porous carbon (RHDPC) exhibits varying porous characteristics upon activation at different temperatures and we observed high gas uptake and efficient energy storage properties for nanoporous carbon materials activated even at a moderate activation temperature of 500 °C. Various experimental techniques including Fourier transform-infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy and pore size analyser are employed to characterise the samples. Detailed studies on gas adsorption behaviour of CO₂, H₂ and CH₄ on RHDPCs have been performed at different temperatures using a volumetric gas analyser. High adsorption capacities of ~9.4 mmol g^?1 (298 K, 20 bar), 1.8 wt% (77 K, 10 bar) and ~5 mmol g^?1 (298 K, 40 bar) were obtained respectively for CO₂, H₂ and CH₄, superior to many other carbon based physical adsorbents reported so far. In addition, these nanoporous carbon materials exhibit good electrochemical performance as supercapacitor electrodes and a maximum specific capacitance of 112 F g^?1 has been obtained using aqueous 1 M Na₂SO₄ as electrolyte. Our studies thus demonstrate that nanoporous carbon with high porosity and surface area, obtained through an efficient approach, can act as effective materials for gas storage and electrochemical energy storage applications.     

Effect of H2SO4 concentration in washing solution on regeneration of commercial selective catalytic reduction catalyst

Commercial SCR catalysts used in a coal-fired power plant were regenerated by H₂SO₄ solution. The characterization study of the catalysts was carried out by using various analytical techniques. Major deactivating elements for the SCR catalyst were determined and the optimal condition for regeneration of the catalyst was investigated. The catalyst regenerated with 0.5 wt% H₂SO₄ solution showed a high catalytic activity due to an increase in the polymeric vanadates and acid sites by surface sulfates. A higher H₂SO₄ concentration than 2.5 wt% in the washing solution leads to a loss of active components out of the catalyst by dissolution and a dramatic decrease in the surface area.     

Indoor formaldehyde removal over CMK-3

The removal of formaldehyde at low concentrations is important in indoor air pollution research. In this study, mesoporous carbon with a large specific surface area was used for the adsorption of low-concentration indoor formaldehyde. A mesoporous carbon material, CMK-3, was synthesized using the nano-replication method. SBA-15 was used as a mesoporous template. The surface of CMK-3 was activated using a 2N H₂SO₄ solution and NH₃ gas to prepare CMK-3-H₂SO₄ and CMK-3-NH₃, respectively. The activated samples were characterized by N₂ adsorption-desorption, X-ray diffraction, and X-ray photoelectron spectroscopy. The formaldehyde adsorption performance of the mesoporous carbons was in the order of CMK-3-NH₃ > CMK-3-H₂SO₄ > CMK-3. The difference in the adsorption performance was explained by oxygen and nitrogen functional groups formed during the activation process and by the specific surface area and pore structure of mesoporous carbon.     

Study of vanadium(IV) species and corresponding electrochemical performance in concentrated sulfuric acid media

The vanadium(IV) ion is found to form the [VO(SO₄)(H₂O)₄]·H₂O complex, as well as the dimer, [VO(H₂O)₃]₂(μ-SO₄)₂, in concentrated H₂SO₄ media. Their formation mechanisms were investigated by UV–Visible spectroscopy (UV–Vis), Raman spectroscopy, X-ray diffraction (XRD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). UV–Vis spectroscopy study showed that [VO(SO₄)(H₂O)₄]·H₂O concentration in H₂SO₄ solution was proportional to concentrations of VO²⁺ and SO₄²⁻. The increased deviation from the near centrosymmetry of the octahedral complexes is due to the replacement of an equatorial water oxygen in [VO(H₂O)₅]SO₄ by a sulfate oxygen in [VO(SO₄)(H₂O)₄]·H₂O. The dimer shows symmetrical structure, which correlates very well with non-activity in UV–Vis spectroscopic analysis. Structural information on both vanadium(IV) species can be confirmed by Raman and XRD measurements of crystals from the supersaturated solution of VOSO₄ in 1 M, 6 M and 12 M sulfuric acid. A solution of vanadium(IV) (0.05 M) in 12 M H₂SO₄, in which the vanadium(IV) species is [VO(H₂O)₃]₂(μ-SO₄)₂, exhibits a reversible redox behavior near 1.14 V (vs. SCE) on the carbon paper electrode.     

Adsorption of SO2 on Activated Carbon for Low Gas Concentrations

Adsorption experiments of SO₂ on activated carbon has been carried out for low concentrations (about 100 ppm) at room temperature (15 to 33 °C) with varying humidity in the air. The breakthrough curves show that at high relative humidity or relative higher SO₂ concentration, the load capacity increases with respect to temperature. The humidity of the air is also of benefit to the load capacity of SO₂. When an adsorption process is interrupted and the activated carbon is kept closed for a while, the SO₂ concentration at the exit of a fixed‐bed adsorber is similar to that of the fresh activated carbon and begins at a very low value. It appears that the sorption potential has been refreshed after the storage period. Analysis of desorption experiments by simultaneous thermal analysis combined with mass spectrometry (MS) after loading, shows that the physisorbed SO₂ and H₂O are desorbed at low temperatures. At higher temperatures, the MS peak of SO₂ and H₂O occur at the same time. Compared with desorption immediately after loading, after one day, the desorption peak due to the physisorbed SO₂ disappears. From this, it can be concluded that the refreshment of the loading capacity of the activated carbon after storage is mainly due to a change in the nature of the SO₂ from a physisorbed state to a chemisorbed form. The same mechanism leads to a continuous refreshment of the sorption potential by means of a chemical reaction during the adsorption process.     

Removal of ampicillin sodium in solution using activated carbon adsorption integrated with H2O2 oxidation

BACKGROUND: The removal of antibiotic ampicillin sodium using H₂O₂ and modified granular activated carbon (GAC) is discussed. Two types of modified activated carbons were used in experiment to catalyze ·OH production from H₂O₂. One was modified with base (NaOH; called B‐GAC), the other was modified with Fe(NO₃)₃ (Fe‐GAC) and the nominal Fe metal loading was 5 wt%. In the experiment, pH, contact time, dosage of activated carbon and H₂O₂ and initial concentration of ampicillin sodium were investigated to determine their influence on the removal efficiency. The stability of Fe‐GAC was also evaluated. RESULTS: With an initial ampicillin sodium concentration of 200 mg L^?1, 85.2% of chemical oxygen demand (COD) and 76.4% of total organic carbon (TOC) can be removed with 8.0 g L^?1 of B‐GAC and 80 mg L^?1 of H₂O₂ (at pH 5.0). For the Fe‐GAC/H₂O₂ process, with 5.0 g L^?1 of activated carbon and 80 mg L^?1 of H₂O₂, COD and TOC removal can be elevated to 91.2% and 79.5% (at pH 3.0), respectively. CONCLUSION: The integration of activated carbon and H₂O₂ treatment was more effective for the removal of ampicillin from aqueous solution than using activated carbon alone. In the process, adsorption played a dominant role and the addition of a small amount of H₂O₂ accelerated the reaction rate and improved the removal efficiency. pH also greatly affected removal efficiency. Copyright © 2011 Society of Chemical Industry     

Thermal Decomposition Study of HNIW by Synchrotron Photoionization Mass Spectrometry

Thermal decomposition of hexanitrohexaazaisowurtzitane (HNIW) was investigated through tuneable vacuum ultraviolet photoionization with molecular‐beam sampling mass spectrometry (MBMS). According to photoionization efficiency (PIE) spectroscopic results, the initial decomposition products of HNIW were identified including HCN, CO, NO, HNCO, N₂O, CO₂ (a little), NO₂, C₂H₂N₂, C₃H₃N₃, C₄H₃N₃, C₃H₄N₄, C₅H₄N₄, C₅H₅N₅ and C₆H₆N₆. The possible ionization energies of C₂H₂N₂, C₄H₃N₃, C₃H₄N₄ and C₆H₆N₆ were analyzed on basis of the PIE spectra. The data were compared with those of thermogravimetry‐mass spectrometry (TG‐MS) and thermogravimetry‐Fourier transform‐infrared spectroscopy (TG‐FT‐IR). The kinetic parameters for the formation of HNCO, HCN and CO₂ were calculated from the current curves of species by TG‐FT‐IR spectroscopy, typically the apparent activation energy (E_a) and prefactor (A) for HNCO were E_a=161.3 ± 2.5 kJ mol⁻¹ and A=38.9 ± 0.6 s⁻¹ with an optimal mechanism function f(α)=(1−α). Global thermal decomposition reaction and Arrhenius equation of HNIW were suggested at the end.