Modified bentonites as adsorbents of hydrogen sulfide gases

Carbonate-rich bentonite was modified by iron and copper chlorides in order to synthesize effective and cheap adsorbents for neutralization of H₂S in low-concentrated exhaust gases. Bentonite and modified bentonite were analysed using atomic absorption spectroscopy (AAS), X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and BET surface area analysis. In addition, bentonite and modified bentonite were tested as hydrogen sulfide adsorbents. Iron-containing material showed a significant improvement in the capacity for H₂S removal. The longest time of effective protective action (before H₂S appears on the outlet of the column) was obtained for the bentonite modified with copper hydroxide. The results indicated that on the surface of modified samples hydrogen sulfide reacts with metal hydroxide forming sulfides. Sulfided iron-containing sample could be regenerated by exposing it to the air.     

Dynamic adsorption on activated carbons of SO2 traces in air: I. Adsorption capacities

Sulphur dioxide is an atmospheric pollutant which, among numerous others, has to be eliminated by habitacle filters. Breakthrough curves of low concentration SO₂ streams through beds of activated carbons have been obtained. Two carbons were studied, an activated PAN fiber (CF) and a granulated activated carbon (CN) under SO₂ concentrations lower than 100 ppm. Carbon CN used ‘as received’ is able to trap SO₂ in air at concentrations as low as 2.5 ppm. At this concentration, the adsorption of SO₂ is essentially irreversible. The fraction of reversibly adsorbed SO₂ rapidly increases when SO₂ content in air increases from 2.5 to 100 ppm. As expected, the amounts of SO₂ adsorbed per gram of carbon are much smaller than in the case of high SO₂ contents in air (>1000 ppm). The presence of water in carbon micropores enhances both reversible and irreversible adsorption of SO₂. The reversibly adsorbed part is physisorbed while the irreversibly adsorbed part results in oxidation of SO₂ at the carbon surface. This oxidation was evidenced by TPD from carbon samples after adsorption. The mechanism of SO₂ adsorption is discussed in relation to the mechanisms proposed in literature for high SO₂ contents (>1000 ppm).     

Adsorption and reaction behavior for the simultaneous adsorption of NO-NO2 and SO2 on activated carbon impregnated with KOH

This study examined the individual and simultaneous adsorption of NO_x (NO-NO₂) and SO₂ on activated carbon impregnated with KOH (KOH-IAC). For individual component adsorption, KOH-IAC showed a higher adsorption capacity in NO-NO₂ rich air than in SO₂-air. In the simultaneous adsorption of NO-NO₂-SO₂, SO₂ showed a greater adsorption affinity than NO-NO₂. The smaller the amount of NO-NO₂ adsorbed, the more SO₂ was adsorbed. XPS analysis of the adsorption of NO-NO₂ rich SO₂-air on KOH-IAC revealed that the adsorbed SO₂ was predominantly found on the external surface, producing mainly K₂SO₄ and, additionally, H₂SO₄ and K₂SO₃. Depth profile analysis showed that the amount of SO₂ adsorbed decreased regularly away from the surface, while the amount of adsorbed NO-NO₂ increased irregularly. We confirmed that the presence of the impregnant in KOH-IAC is a determining factor in the adsorption of NO-NO₂ and SO₂ by chemical reaction, clarifying the surface chemical behavior.     

Catalytic removal of SO2, NO and HCl from incineration flue gas over activated carbon-supported metal oxides

Activated carbon-supported copper, iron, or vanadium oxide catalysts were exposed to incineration flue gas to investigate the simultaneous catalytic oxidation of sulfur dioxide/hydrogen chloride and selective catalytic reduction of nitrogen oxide by carbon monoxide. The results show that AC-supported catalysts exhibit higher activities for SO₂ and HCl oxidation than traditional γ-Al₂O₃-supported catalysts and the iron and vanadium catalysts act as catalysts instead of sorbents, and can decompose sulfate with evolution of SO₃ and then regenerate for more SO₂ adsorption to take place. The AC-supported catalysts also display a high activity for NO reduction with CO generated from a flue gas incineration process and the presence of SO₂ in the incineration flue gas can significantly promote catalytic activity. Using CO as the reducing agent for NO reduction is more effective than using NH₃, because NH₃ may be partially oxidized in the presence of excess O₂ (12 vol%. in the incineration flue gas used) to form N₂, which can decrease the overall extent of NO reduction.     

Influence of surface properties and iron addition on the SO2 adsorption capacity of activated carbons

When iron derivatives are added to low ash activated carbons having basic surface characteristics (obtained by suitable oxidation at 800°C with 2% of O₂ in N₂), certain materials are obtained showing high SO₂ sorbent properties from gaseous mixtures having a composition close to that of the flue gases. This behaviour seems to be related to the simultaneous presence of both basic surface sites promoting the initial adsorption of SO₂ and iron promoting the transformation of the adsorbed SO₂ into other, more stable forms. The sorbent properties of these activated carbons are more stable, following consecutive cycles, in the processes of adsorption and desorption of SO₂, than those shown by similar carbons with different surface characteristics.     

Flue gas desulphurization by activated carbon fibers obtained from polyacrylonitrile by-product

By pyrolysis of a polyacrylonitrile textile by-product, subsequent activation by CO₂ and treatment (at high temperature) with a N₂ flow containing a low percentage of O₂ or of NH₃, three carbonaceous matrices are obtained having a high surface area and surface sites with basic characteristics. The SO₂ sorption properties of these carbon samples (in the temperature range between 100 and 160 °C) from gaseous mixtures having a similar composition to flue gases, seems to be promoted by nitrogen bonded to carbon. The SO₂ adsorbed by the carbons can be divided, by suitable extraction with distilled water, into: (i) desorbable, such as SO₂ or H₂SO₃, (ii) desorbable, such as SO₃ or H₂SO₄, (iii) non-desorbable. Following 10 SO₂ adsorption and desorption cycles, the surface area values of the activated carbons remain practically constant, while both the content of the acidic surface sites and the amount of non-desorbable SO₂ increase; this results in the decrease in the SO₂ carbon sorption property seeming to be even more marked for the carbon sample containing nitrogen.     

Adsorption Behaviour of Ethylene Vinyl Acetate and Polycaprolactone-Bentonite Composites for Pb2+ Uptake

The results presented in this work show that the hydrophobic thermoplastics, namely ethylene vinyl acetate (EVA) and polycaprolactone (PCL), could be good matrices for the synthesis of polymer/bentonite composites via the melt-blending method for the removal of heavy metals from water. The hydrophobic nature of the polymers was countered by using dry Na₂SO₄ to form large free-volume pores. These pores, formed after the removal of the Na₂SO₄ by washing, improved the contact ratio between bentonite particles and Pb²⁺ ions. The composites were able to achieve up to 78% Pb²⁺ removal at an initial concentration of 200 mg/L in 10 h with a clay loading of 3% (w/w). The results confirmed that the PCL/bentonite composite was more effective and efficient in the adsorption of Pb²⁺ than the EVA/bentonite composite. The experimental data for both composites followed Langmuir and Freundlich models. The uptake of Pb²⁺ was found to be a result of a chemical interaction between the heavy metal, silanol (Si–OH) and aluminol (Al–OH) groups. The adsorption of Pb²⁺ onto the composites was found to follow pseudo-first-order kinetics and the results supported a monomolecular reaction mechanism.     

Sorptive and activity behavior of iron minerals for hydrocarbon synthesis

The sorptive behavior of hydrogen and of carbon monoxide and of their mixtures on a low grade iron ore, magnetite, hematite and a commercial synthetic NH₃—iron catalyst was studied in an attempt to describe their catalytic properties for Fischer-Tropsch hydrocarbon synthesis.In comparison to hydrogen and carbon monoxide adsorbed individually, the adsorption of both the gases is enhanced invariably when adsorbed simultaneously from the mixture. Sorption of hydrogen is enhanced by the presorption of carbon monoxide on the catalyst surface while a small amount of presorbed hydrogen hardly enhances the carbon monoxide adsorption.Initial rates of carbon monoxide hydrogenation, which are most representative of clean surfaces, measured over the temperature range 250–360°C, are in the order hematite > magnetite > synthetic-NH₃-iron > iron ore. From the initial rates, the selectivity for methane formation at 250°C for all the four catalysts is about 20 percent.     

On adsorption and electro-oxidation of some compounds on tungsten carbide; their effect on hydrogen electro-oxidation

Adsorption and electro-oxidation of carbon monoxide, ethylene, acetylene, and hydrogen sulphide on tungsten carbide, in solutions of these compounds in 1 N H₂SO₄, have been investigated. It was found that CO, C₂H₄, and C₂H₂ do not undergo adsorption and oxidation and do not affect adsorption and electro-oxidation of hydrogen. H₂S does not oxidise as well, and it does not displace adsorbed hydrogen in any measurable amounts, though it does inhibit electro-oxidation of molecular hydrogen. Methanol is inert on tungsten carbide like carbon monoxide and hydrocarbons. Electro-oxidation of formaldehyde and formic acid proceeds without apparent WC-surface coverage by the adsorbed compound.     

Study of SO2 adsorption and thermal regeneration over activated carbon-supported copper oxide catalysts

The mechanisms of SO₂ adsorption and regeneration over activated carbon-supported copper oxide sorbent/catalysts were analyzed. Studies were carried out in a fixed-bed reactor equipped with a non-dispersive infrared gas analyzer to detect the reaction products and by using X-ray powder diffraction (XRPD) and temperature-programmed desorption (TPD) experiments to characterize the nature of the sulfate species and surface oxygen complexes. The results indicate that SO₂ was catalytically oxidized to SO₃ over a copper phase in the presence of gaseous oxygen, and then reacted with a copper site to form a sulfate linked to copper without desorption into the gas phase. The activated carbon support did not participate in this sulfation reaction. After the adsorption of SO₂, the exhausted sorbent/catalysts could be regenerated by direct heat treatment in inert gas at temperatures between 260 and 480 °C, while the neighboring surface oxygen complexes on the carbon surface were acting as the reducing agents to reduce CuSO₄ to Cu. During the subsequent adsorption process, the copper is rapidly oxidized by oxygen in the flue gas.     

Removal of ethoxylated aliphatic amines from zinc containing effluents by adsorption on macroporous resins

The separation of ethoxylated aliphatic amines from zinc containing effluents with macroporous polymeric adsorbents Wofatit EP 61, EP 62, Y 59, Y 77 and active carbons has been examined. The adsorption behaviour has been investigated as a function of temperature, time and concentration of Na₂SO₄, ZnSO₄ and H₂SO₄. The macroporous polymers EP 61, Y 77 and Y 59 are capable of separating ethoxylated aliphatic amines from effluents of viscose fibre industry at higher temperatures and under weakly acidic conditions. In contrast to active carbon, inorganic components are not adsorbed on the investigated macroporous resins. Data obtained in a concentration range of 0 to 10 g of adsorbate per litre produced a Langmuir profile for adsorption of ethoxylated aliphatic amines by polymeric adsorbents.     

H2S adsorption/oxidation on unmodified activated carbons: importance of prehumidification

Three microporous activated carbons supplied by Norit^® (of peat and bituminous coal origin) were used in this study as hydrogen sulfide adsorbents. Their surface properties were evaluated by means of nitrogen adsorption, Boehm titration, potentiometric titration, and thermal analysis. The results show that the carbons significantly differ in their pore structure and surface chemistry. This is reflected in their hydrogen sulfide breakthrough capacity. The breakthrough capacity is underestimated when not enough water is adsorbed on the carbon surface. The performance follows the expectations after extensive humidification of the sorbents’ surfaces. Moderately low pH in the acidic range of coal-based carbon, Vapure 612, promotes the oxidation of H₂S to sulfur oxides which is important from the point of view of water regeneration. The high pH of peat-based carbon, RB 4, results in H₂S oxidation to elemental sulfur.     

A new strategy for hydrogen sulfide removal by amido-functionalized reduced graphene oxide as a novel metal-free and highly efficient nanoadsorbent

In this research, hydrogen sulfide is adsorbed on amido-functionalized reduced graphene oxide (AFRGO) as a nanoadsorbent. By the use of n-propylamine and allylamine, reduced graphene oxide (RGO) was amidated for the adsorption of hydrogen sulfide. The materials were characterized by adsorption of H₂S, potentiometric titration, scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD) analysis. The effect of the operational conditions of 4000–6000 h^?1 space velocities and 60,000?ppm H₂S feed concentrations were examined on adsorption capacity. The results show that H₂S feed concentration, space velocity, and functional groups of adsorbents have a major effect on H₂S adsorption. It was also found that the temperature in the range of 30–70°C had a significant effect on H₂S adsorption. The concentration of H₂S adsorbed in 3?h by AFRGO containing allyl substituent, AFRGO containing propyl substituent, graphene oxide (GO), and reduced graphene oxide (RGO) were reported as 59,710, 59,650, 59,600, and 59,500?ppm, respectively. Hydrogen sulfide adsorption analysis showed that nanoadsorbents increase adsorption capacity of H₂S.     

Electrochemical remediation of acid mine drainage

Acid mine drainage (AMD), which has long been a significant environmental problem, results from the microbial oxidation of iron pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Electrochemical treatment of AMD offers possible advantages in terms of operating costs and the opportunity to recover metals, along with cathodic reduction of protons to elemental hydrogen. This work describes the electrolysis of synthetic AMD solutions containing iron, copper and nickel and mixtures of these metals using a flow-through cell divided with an ion exchange membrane. Iron was successfully removed from a synthetic AMD solution composed of FeSO₄/H₂SO₄ via Fe(OH)₃ precipitation outside the electrochemical cell by sparging the electrolysed catholyte with air. The work was extended to acidic solutions of Fe²⁺, Cu²⁺, and Ni²⁺, both singly and in combination, and to an authentic AMD sample containing principally iron and nickel.     

SO2 and NO selective adsorption properties of coal-based activated carbons

The aim of this paper is to study binary gas adsorption on the activated carbon in the fixed-bed reactor. Coal-based granular activated carbons can selectively adsorb SO₂ and NO. Physically adsorbed NO is replaced and desorbed by SO_2. Chemically adsorbed NO can promote the absorption of SO₂. The presence of SO₂ and NO can enhance the chemical adsorption of NO and SO₂, respectively. When the diameter of granular activated carbon decreases and the specific surface area increases, both the penetration time of the activated carbon bed and SO₂ removal efficiency increase. The whole removal efficiency of SO₂ is more than 99% in the penetration time, but the whole removal efficiency of NO is only 55% in the coexistence of SO₂ and NO. SO₂ adsorption capacity of HNO₃ dipped granular activated carbon is higher than that of non-treated one. The two experimental results are agree with each other.     

Mass spectrometric investigation of the electrochemical behavior of adsorbed carbon monoxide at platinum in 0.2 M sulphuric acid

The technique of Electrochemical Mass Spectrometry is applied to the cathodic adsorption of CO at platinum in 0.2 M H₂SO₄ and the anodic desorption of the reaction product CO₂. From the data obtained by CO shielding during the adsorption reaction and by CO₂ collection during the desorption process, one site adsorption of the principal CO adsorbate at the electrode surface is determined to occur over the whole range of CO coverage. A two electron transfer is involved in the oxidation of this adsorbed CO species to CO₂. CO adsorbed in the hydrogen adsorption region produces a small amount of adsorbate requiring a three electron transfer to produce CO₂.     

Sulfur dioxide adsorption by activated carbons having different textural and chemical properties

Activated carbons from Turkish lignite were prepared with different methods to investigate the influence of physico-chemical characteristics of the carbon materials on the sulfur dioxide (SO₂) adsorption. The effects of SO₂ concentration, adsorption temperature, and sample particle size on adsorption were investigated using a thermogravimetric analysis system. An intraparticle diffusion model based on Knudsen diffusion and Freundlich isotherm (or Henry isotherm) was applied for predicting the amount of SO₂ adsorbed. The textural and chemical properties of the activated carbon samples, resulted from the effects of activation conditions and demineralization of the carbon precursor, on the SO₂ adsorption were also analyzed.     

Effect of electrolyte environment and Pt crystallite size on hydrogen adsorption—V

The role of Pt crystallite surface morphology on hydrogen adsorption isotherms in H₂SO₄ and alkaline electrolytes was examined by a potentiodynamic sweep technique. By varying the crystallite size (40–280Å) of highly dispersed Pt electrocatalysts, the relative concentrations of edges, vertices and crystallite faces which contribute to the surface morphology are changed. The potentiodynamic i-V profiles for adsorbed hydrogen oxidation on highly dispersed Pt electrocatalysts in 0.05 and 1 M H₂SO₄ showed similar changes with Pt crystallite size. Only two states of adsorbed hydrogen on highly dispersed Pt were observed in 0.05 M H₂SO₄, compared to four states reported by Angerstein-Kozlowska et al on smooth polycrystalline Pt electrodes.In 1 M NaOH and 35 wt % KOH, less than a monolayer of adsorbed hydrogen was present on highly dispersed Pt electrocatalysts at the reversible hydrogen potential. Two states of chemisorbed hydrogen were observed at 23–91°, while at low temperature (?47°) in 35 wt % KOH, an additional adsorbed hydrogen species was evident in the potentiodynamic i-V curves. A Pt crystallite size effect on the adsorption of hydrogen on highly dispersed Pt in alkaline electrolytes was not deduced.     

A study of the interaction of nitric oxide with nickel and oxidized nickel surfaces by X-Ray photoelectron spectroscopy

The adsorption of nitric oxide by nickel and also nickel surfaces preexposed to oxygen has been studied by X-ray photoelectron spectroscopy in the temperature range 80 to 290 °K. The surface reactivity to NO interaction has been controlled by varying the temperature and conditions of preexposure to oxygen. This has enabled three distinct states of NO adsorption to be delineated, a dissociative state and two molecular states. One of the molecular states is weakly adsorbed while the other, more strongly chemisorbed, is the precursor to dissociation. We suggest the latter is adsorbed in the “bent” form while the former is linearly bonded to the surface. N₂O is also observed within the adlayer at 80 °K particularly with nickel surfaces preoxidized at 290 °K. The N₂O is weakly adsorbed. There are strong analogies between the present data and previous studies with copper, iron, and aluminum, metals with very different electronic structures. It should be noted, however, that although in all cases a new surface phase is generated, the inherent reactivities of the clean metals differ only in degree rather than in kind.     

Water purification of removal aqueous copper (II) by as-grown and modified multi-walled carbon nanotubes

This study compares aqueous copper (II) adsorbed onto as-grown and modified carbon nanotubes (CNTs), using H₂SO₄ and H₂SO₄/KMnO₄ processes. H₂SO₄ and H₂SO₄/KMnO₄ modifications reduced pH_iep and Fourier Transform Infrared Spectroscopy (FTIR) analysis revealed that some functional groups were formed on modified CNTs. The adsorption capacity of copper (II) onto modified CNTs was greater than that of as-grown CNTs, especially at pH 6. The results demonstrate that the modified processes increased the adsorption capacity because the functional groups were generated on the modified surfaces of the CNTs. Additionally, the adsorption capacity of copper (II) onto as-grown and modified CNTs both increased with temperature, and the results indicated that the Langmuir isotherm fitted the experimental data well. Simulation results indicated that the ΔH⁰ values of as-grown, H₂SO₄-modified CNTs and H₂SO₄/KMnO₄-modified CNTs were 4.83, 14.37 and 29.92 kJ/mol, respectively. Based on ΔH⁰, the adsorption of Cu²⁺ onto H₂SO₄/KMnO₄-modified CNTs is suggested to proceed simultaneously by physisorption and chemisorption but that onto as-grown and H₂SO₄-modified CNTs may proceed only by physisorption.