Bituminous coal-based activated carbons modified with nitrogen as adsorbents of hydrogen sulfide

Bituminous coal-based activated carbon was modified by impregnation with melamine and heat treatment at 850 °C. Another sample was impregnated with melamine and urea and heat treated at 650 and 850 °C. Chemical and physical properties of the materials were determined using Boehm titration, thermal analysis, sorption of nitrogen and SEM with EDX. Then the H₂S breakthrough capacity tests were carried out and the sorption capacity was calculated. The results revealed that carbons modified with nitrogen-containing species and heat-treated at 850 °C have a hydrogen sulfide removal capacity exceeding more then 10 times the capacity of unmodified sample. H₂S on the surface of these materials is oxidized to sulfuric acid and elemental sulfur and stored in the pore system. New carbons are hypothesized to act as catalytic reactors promoting two different pathways of hydrogen sulfide oxidation in two different locations. In small micropores, where water is present, hydrogen sulfide dissociate to HS⁻ ions and those ions are oxidized to sulfur radicals and sulfur dioxide leading to the formation of sulfuric acid. In larger pores with incorporated nitrogen, basic sites promote dissociation and formation of sulfur polymers, which are resistant to further oxidation.     

Activated carbon catalyst for selective oxidation of hydrogen sulphide: On the influence of pore structure, surface characteristics, and catalytically-active nitrogen

The catalytic oxidation of hydrogen sulphide (H₂S) on various activated carbon materials was studied. The effects of pore structure, surface characteristics, and nitrogen content on the activity and selectivity of the carbons towards oxidation of H₂S were investigated. It was found that a high volume of both micropores and small mesopores, in combination with a relatively narrow pore size distribution, were crucial for the retention of sulphur dioxide (SO₂), a by-product of H₂S oxidation. For the retention of carbonyl sulphide (COS), another H₂S oxidation by-product, high surface reactivity with a significant amount of basic groups were found to be important. The only carbon with all these characteristics, and consequently the carbon that was able to retain both H₂S and COS for an extended period of time, was an experimental product, “WSC”. This carbon was found to be superior to the other carbons studied, exhibiting high activity and selectivity for oxidation of H₂S to sulphur. H₂S breakthrough capacities and selectivity values of the carbons were found to be dependent on the nitrogen content of the carbons. In a hydrogen stream, carbons possessing the highest nitrogen contents exhibited the greatest H₂S breakthrough capacities but, at the same time, the lowest selectivity with respect to sulphur formation. In reformate streams, the maximum breakthrough capacity and greatest selectivity were exhibited by carbons with a nitrogen content of about 1-1.5 wt%.     

活性炭的改性条件及其对硫化氢吸附性能的影响

以工业活性炭为载体制备改性活性炭,对比研究了未改性活性炭,NaOH、Na2CO3、Fe(NO3)3、Cu(Ac)2改性活性炭及挂膜硫氧化细菌后活性炭在相同条件下对硫化氢穿透时间及吸附容量的影响。结果表明：在相同控制条件下,NaOH改性活性炭明显优于其它改性剂;不同梯度改性剂条件下,20% NaOH改性活性炭对硫化氢的吸附效果最好,吸附穿透容量为78.25 mg/g,穿透时间可以达到2000 min以上;不同改性剂挂膜硫氧化细菌后对硫化氢均有一定的处理效果,其中对已达到饱和吸附的NaOH改性活性炭挂膜后的再生效果可以达到100%以上,说明挂膜硫氧化细菌活性炭对硫化氢的处理具有很好的效果。     

The effect of H2 treatment on the activity of activated carbon for the oxidation of organic contaminants in water and the H2O2 decomposition

In this work, hydrogen peroxide reactions, i.e. H₂O₂ decomposition and oxidation of organics in aqueous medium, were studied in the presence of activated carbon. It was observed that the carbon pre-treatment with H₂ at 300, 500, 700 and 800 °C resulted in an increase in activity for both reactions. The carbons were characterized by BET nitrogen adsorption, thermogravimetric analyses (TG), temperature programmed reduction (TPR), electron paramagnetic resonance (EPR), iodometric titration and determination of the acid/basic sites. TPR experiments showed that activated carbon reacts with H₂ at temperatures higher than 400 °C. The treatment produces a slight increase in the surface area. EPR analyses indicate the absence of unpaired electrons in the carbon. Iodometric titrations and TG analyses suggested that the treatment with H₂ generates reduction sites in the carbon structure, with concentration of approximately 0.33, 0.53, 0.59, 0.65 and 0.60 mmol/g for carbons treated at 25, 300, 500, 700 and 800 °C, respectively. It was also observed the appearance of basic sites which might be related to the reduction sites. It is proposed that these reducing sites in the carbon can activate H₂O₂ to generate HO^* radicals which can lead to two competitive reactions, i.e. the hydrogen peroxide decomposition or the oxidation of organics in water.     

Activated carbons with metal containing bentonite binders as adsorbents of hydrogen sulfide

Wood-based activated carbon was ground and mixed with 10% bentonite binders containing either iron, zinc or copper cations adsorbed within the interlayer space and/or on the external surface of bentonite flakes. To better understand the role of transition metals, carbon was also impregnated with iron, zinc and copper salts. The structure of materials after modification was determined using nitrogen adsorption. The modification resulted in a decrease in porosity, especially in micropore volume, as a result of combined mass dilution effect and adsorption/re-adsorption of metals in small pores. Introduction of bentonite binders containing adsorbed metal increased the capacity of carbon for hydrogen sulfide only in the case of material containing copper. Copper also significantly increases the performance of carbon as an H₂S adsorbent when impregnation is applied whereas the effects of other metals used in this study are much less pronounced. It is likely that copper present in the small pores acts as a catalyst for oxygen activation causing hydrogen sulfide oxidation. As a result of this process, elemental sulfur is formed which, when present in small pores, is oxidized to weakly adsorbed SO₂. The SO₂ is removed from the surface when continuous reaction with hydrogen sulfide occurs. Thus, even though binding carbon with spent bentonites after copper adsorption increases the capacity of carbon toward H₂S removal, the formation of SO₂, another undesirable pollutant, does detract somewhat from the procedure.     

Adsorption of hydrogen sulphide (H2S) by activated carbons derived from oil-palm shell

Adsorption of hydrogen sulphide (H₂S) onto activated carbons derived from oil palm shell, an abundant solid waste from palm oil processing mills, by thermal or chemical activation method was investigated in this paper. Dynamic adsorption in a fixed bed configuration showed that the palm-shell activated carbons prepared by chemical activation (KOH or H₂SO₄ impregnation) performed better than the palm-shell activated carbon by thermal activation and a coconut-shell-based commercial activated carbon. Static equilibrium adsorption studies confirmed this experimental result. An intra-particle Knudsen diffusion model based on a Freundlich isotherm was developed for predicting the amount of H₂S adsorbed. Desorption tests at the same temperature as adsorption (298 K) and at an elevated temperature (473 K) were carried out to confirm the occurrence of chemisorption and oxidation of H₂S on the activated carbon. Surface chemistries of the palm-shell activated carbons were characterized by Fourier transform infrared spectroscopy and Boehm titration. It was found that uptaking H₂S onto the palm-shell activated carbons was due to different mechanisms, e.g. physisorption, chemisorption and/or H₂S oxidation, depending on the activation agent and activation method.     

Removal of sulfur compounds from utility pipelined synthetic natural gas using modified activated carbons

Synthetic natural gas (SNG), which is produced from petroleum and distributed via pipeline in Honolulu by The Gas Company, was analyzed using a gas chromatograph equipped with a sulfur chemiluminescence detector (GC/SCD). Hydrogen sulfide (H₂S), methyl mercaptan (MM), ethyl mercaptan (EM), dimethylsulfide (DMS), dimethyl disulfide (DMDS), tetrahydrothiophene (THT), ethyl disulfide (EDS), and one unidentified compound (UN1) were detected. Among these sulfur compounds, THT is added as an odorant and was present in the highest concentration.A commercial activated carbon (Calgon OLC plus 12X30) was modified by oxidation and impregnation methods and the resulting materials were evaluated for their ability to adsorb sulfur compounds present in SNG. The evaluation results indicate that all of the modification methods can improve the retention of individual sulfur compounds or the total sulfur capacity compared with the untreated virgin carbon. It is also found that activated carbons impregnated with metal impurities have different selectivity for sulfur compounds. Cu and Zn loaded carbons had the highest capacity for H₂S removal, Fe loaded carbon was more efficient for DMS removal (the most difficult S compound to remove), and carbon oxidized by HNO₃ was the best for THT removal.Based on these findings, a composite sorbent consisting of Cu loaded and Fe loaded carbons was designed and tested. The test results indicate that the composite sorbent had improved performance in the removal of individual sulfur compound. A linear programming model was used to design a composite sorbent optimized to minimize the required sorbent mass based on a 1-kW scale fuel cell system service target. Validation tests showed that the optimized sorbent required less of the individual modified carbon components than when they were individually used for the same sulfur removal target.     

Oxidation of low concentrations of hydrogen sulfide over activated carbon

The oxidation of low concentrations of hydrogen sulfide with air over activated carbon was studied over the temperature range 24-200°C using both fixed and fluid bed reactors. The predominant reaction, H₂S + ½ O_a → H₂O + S, was found to have an order of 0.5 with respect of H₂S concentration. Activity of the catalyst decreased as the amount of sulfur deposited on it increased. Indirect evidence suggests that adsorption of water by the carbon also decreases its activity as a catalyst at lower temperatures. Values of the activation energy and the frequency factor were determined for various sulfur loadings using the fixed bed reaction system. Regeneration of the carbon loaded with sulfur was studied at temperatures between 150 and 500°C using steam as a carrier gas. Bright yellow sulfur was recovered. The regenerated carbon was shown to have its original activity.     

Sulfurization of carbon surface for vapor phase mercury removal - I: Effect of temperature and sulfurization protocol

The uptake of hydrogen sulfide by carbon materials (ACFs and BPL) under dry and anoxic conditions was tested using a fixed bed reactor system to determine the effects of sorbent properties, temperature (200-800 °C) and sulfurization protocols on the sulfur content, sulfur stability, sulfur distribution, and to elucidate possible reaction mechanisms for the formation of sulfur species. Sorbents with higher surface areas showed higher uptake capacity, indicating that active sites for sulfur bonding are formed during the formation of the pore structure. The sulfur content and stability generally increased with the increase in temperature due to a shift in the reaction mechanism. The sulfurization process is associated with the decomposition of surface functionalities, which creates active sites for sulfur bonding. The presence of H₂S during the cooling process increased the sulfur content by increasing the presence of less stable sulfur forms. Sulfurized sorbents produced at high temperatures have pore structure similar to that of the virgin carbons.     

The phenomenology and the mathematical modeling of the silicone‐supported chemical oxidation of aqueous sulfide to elemental sulfur by ferric sulphate

When pumping a sulfide solution through a silicone cylinder immersed in a solution of ferric sulfate, a cloud of elemental sulfur is formed in the ferric sulfate if the pH of the sulfide solution is below about 8.5. The elemental sulfur subsequently sediments as orthorhombic α‐sulfur particles. H₂S(aq) diffuses through the pores of the hydrophobic silicone membrane and simultaneously reacts to become sulfur. This was confirmed by a mass balance between the amount of sulfide removed from the sulfide solution and the amount of solid product formed in the ferric solution. During the experiment, the pH of the non‐buffered sulfide solution rises up to a maximum of 8.5; this is explained by the continuous protonation of HS caused by the removal of H₂S(aq). The pH of the strongly acidic (pH 1.5) ferric sulfate solution hardly decreased. A mathematical model has been developed to quantify the phenomena related to the removal of H₂S(aq). The model has been succesfully validated with the data of batch experiments. An Arrhenius‐like relationship was found between the process temperature and the overall mass transfer coefficient K. A sulfide oxidation rate of 2.5 g S dm⁻³ day⁻¹ was predicted for a plug flow reactor. The integration of the novel process with biological sulfate reduction was studied. © 1999 Society of Chemical Industry     

Etude de la reaction du carbone avec le sulfure d'hydrogene H2S a hautes temperatures et sous basses pressions

Reaction of carbon with hydrogen sulfide at high temperature (1000–2000°C) and low pressure (10^?4–10^?2 Torr) exhibits the following features:—carbon disulfide CS₂ is the only carbonaceous reaction product. There is no indication that CS₂ would originate from a secondary reaction of the unstable carbon monosulfide CS. Some decomposition of H₂S into its elements is also observed (Figs. 1–3).—as already observed in other high temperature carbon gasification reactions, the intrinsic reactivity of the sample surface is temperature and pressure dependent. Consequently, transitory or stationary rates are observed, depending respectively upon a changing or a stationary surface state of the carbon sample (Fig. 4). The changes in the surface state are more marked for amorphous than for graphitized samples (Fig. 5).—below 1700°C, the true reaction order is smaller than one, as a consequence of the high stability of the carbon-sulfur surface complexes.—for ungraphitized samples, the carbon surface loses slowly and irreversibly its ability to change with changes in pressure and temperature.All these features were previously observed in the reaction of carbon with sulfur vapor: consequently hydrogen sulfide appears to behave simply as a gaseous sulfur carrier. The kinetic behaviour is in agreement with former interpretations assuming presence of peculiar reactive sites, which originate from chemical attack of the solid but disappear due to a surface thermal heating process.Confirming also previous assumptions, sulfur chemisorption strongly affects the reaction kinetics, as shown by the influence of H₂S traces on the kinetics of the C-O₂ reaction (Fig. 10):—at lower temperatures (< 1300°C) there is an important inhibiting effect on the CO production: H₂S is adsorbed strongly on the reactive sites which become inaccessible to O₂ molecules.—in the intermediate temperature range an enhancing effect is observed which is attributed to a hindrance of thermal healing (caused by chemisorption still present).Finally, the kinetic features as a whole are tentatively summarized in a comprehensive diagram where the consistency of experimental results appears clearly.     

Molten salt synthesis of nitrogen-doped porous carbons for hydrogen sulfide adsorptive removal

Nitrogen-doped porous carbons (NPCs) with high hydrogen sulfide (H₂S) adsorption capacity have been prepared through the molten-salt approach, using d-glucose as carbon source, melamine as nitrogen source and eutectic salt (LiCl/KCl) as porogen. The NPCs possess tunable nitrogen content (3.07–24.31 wt.%) and specific surface area (451–1190 m²/g) with the changing of the weight ratio of nitrogen source to carbon source and synthesis temperature. The H₂S adsorptive performance of NPCs is highly superior to that of non-doped porous carbon. X-rays photoelectron spectroscopy analyses combined with quantum chemical calculations demonstrate that the adsorption performance of the as-prepared NPCs depends on their nitrogen content and N-bonding configurations in the carbon materials, as well as their porosity. Pyridinic nitrogen doped carbon in NPCs have stronger interaction with H₂S compared to pyrrolic and graphitic nitrogen doped carbon. Based on the advantages of the developed porosity and abundant nitrogen functional groups, the saturated sorption capacities of 0.97–1.25 mmol H₂S/g can be achieved over NPCs at 25 °C under dry and anaerobic conditions.     

Chemoadsorption for Separation of Hydrogen Sulfide from Biogas with Iron Hydroxide and Sulfur Recovery

Hydrogen sulfide (H₂S) removal from biogas is essential to allow biogas storage in the natural gas grid. Several established methods exist, most of them making use of non-reusable substrates such as iron sponge or active carbon. Coated metallic foams provide a reusable sustainable alternative. Several iron oxides and hydroxides were tested to validate the H₂S adsorption properties before and after thermal regeneration, i.e., sulfur removal. Amorphous iron hydroxide proved to efficiently clean biogas after maximum four sulfur removal cycles and showed an almost ten times larger capacity for sulfur adsorption than crystalline hematite Fe₂O₃. Very low H₂S contents could be realized until breakthrough.     

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.     

Electrochemical improvement of low-temperature petroleum cokes by chemical oxidation with H2O2 for their use as anodes in lithium ion batteries

The electrochemical performance of non-graphitized petroleum cokes has been improved by mild oxidation using hydrogen peroxide, a procedure used for the first time in these materials. For this purpose, various carbonisation temperatures and H₂O₂ treatments were tested. For low sulfur content cokes, the aqueous oxidative treatment significantly increases the capacity values above 372 mAh/g during the first cycles. In contrast, cokes with a sulfur content of ca. 5%, did not shown a real improvement. The former results have been interpreted in terms of an effective oxidation of the particles surface, which removes unorganized carbon, where lithium can be irreversibly trapped. Moreover, a stable and less resistive passivating layer grows during the first discharge of lithium, as revealed by impedance spectroscopy. Therefore, chemical procedures, as mild oxidation, open an interesting field of research for the improvement of disordered carbons as anode materials in lithium ion batteries.     

Diesel fuel desulfurization with hydrogen peroxide promoted by formic acid and catalyzed by activated carbon

Desulfurization of diesel fuels with hydrogen peroxide was studied using activated carbons as the catalysts. Adsorption and catalytic properties of activated carbons for dibenzothiophene (DBT) were investigated. The higher the adsorption capacity of the carbons is, the better the catalytic performance in the oxidation of DBT is. The effect of aqueous pH on the catalytic activities of the activated carbons was also investigated. Oxidation of DBT is enhanced when the aqueous pH is less than 2, and addition of formic acid can promote the oxidation. The effect of carbon surface chemistry on DBT adsorption and catalytic activity was also investigated. Adsorption of DBT shows a strong dependence on carboxylic group content. The oxidative removal of DBT increases as the surface carbonyl group content increases. Oxidative desulfurization of a commercial diesel fuel (sulfur content, 800 wt. ppm) with hydrogen peroxide was investigated in the presence of activated carbon and formic acid. Much lower residual sulfur content (142 wt. ppm) was found in the oxidized oil after the oxidation by using the hydrogen peroxide-activated carbon-formic acid system, compared with a hydrogen peroxide-formic acid system. The resulting oil contained 16 wt. ppm of sulfur after activated carbon adsorption without any negative effects in the fuel quality, and 98% of sulfur could be removed from the diesel oil with 96.5% of oil recovery. Activated carbon has high catalytic activity and can be repeatedly used following simple water washing, with little change in catalytic performance after three regeneration cycles.     

Kinetics and reaction mechanism of hydrogen sulfide oxidation over activated carbon in the temperature range of 125–200°c

The kinetics and reaction mechanism of the oxidation of hydrogen sulfide over activated carbon were studied in the temperature range 125–200°C. The heats of adsorption of oxygen and H₂S were found to be 73.8 and 16.0 kJ/mol, respectively, in the above temperature range. The sorption constants and the reaction constant have been expressed as a function of temperature. The role of water in the oxidation reaction has been clarified. No evidence was found to show that sulfur catalyzes the oxidation reaction.     

Comparison of a single grain activated carbon and column adsorption system

Results from a single grain activated carbon adsorption study indicate that the effective diffusion coefficient was from 0.65×10⁻⁶ to 7.4×10⁻⁶ cm²/s for H₂S in the concentration range of 20–300 ppmv at 23 °C for both virgin activated carbon (FAC) and impregnated-regenerative activated carbon (IRAC). The effective diffusivity of the IRAC was nearly two times the FAC for H₂S adsorption. The surface reaction of H₂S-impregnated regenerative activated carbon was faster than that of H₂S and virgin activated carbon. The single grain activated carbon kinetic curve and a time scale conversion method were used to predict the breakthrough curve and the adsorption capacity of the column adsorption system. The single grain activated carbon adsorption system measured the breakthrough curve more efficiently than column adsorption. The prediction error was between 10 and 30%. Improvement can be further achieved by enhanced experimental approaches. It has a great potential for scale-up.     

Oxidation of H2S on activated carbon KAU and influence of the surface state

Properties of the oxidized activated carbon KAU treated at different temperatures in inert atmosphere were studied by means of DTA, Boehm titration, XPS and AFM methods and their catalytic activity in H₂S oxidation by air was determined. XPS analysis has shown the existence of three types of oxygen species on carbon catalysts surface. The content of oxygen containing groups determined by Boehm titration is correlated with their amount obtained by XPS. Catalytic activity of the KAU catalysts in selective oxidation of hydrogen sulfide is connected with chemisorbed charged oxygen species (O_3.1 oxygen type with BE 536.8–537.7 eV) present on the carbons surface.

Formation of dense sulfur layer (islands of sulfur) on the carbons surface and removal of active oxygen species are the reason of the catalysts deactivation in H₂S selective oxidation. The treatment of deactivated catalyst in inert atmosphere at 300 °C gives full regeneration of the catalyst activity at low temperature reaction but only its partial reducing at high reaction temperature. The last case is connected with transformation of chemisorbed charged oxygen species into CO groups.

The KAU samples treated in flow of inert gas at 900–1000 °C were very active in H₂S oxidation to elemental sulfur transforming up to 51–57 mmol H₂S/g catalyst at 180 °C with formation of 1.7–1.9 g S_x/g catalyst.     

Molecular hydrogen and spiltover hydrogen storage on high surface area carbon sorbents

A series of templated carbons with various high surface areas (2033–3798 m²/g) have been prepared using various microporous zeolites as hard templates. Molecular hydrogen storage and spiltover hydrogen storage on these templated carbons were investigated and compared with superactivated carbon AX-21 and other reported porous carbon sorbents at 298 K and 100 atm. Two relationships between the surface areas of these carbons and their hydrogen capacities were obtained. The relationship between molecular hydrogen capacity and surface area showed a 0.23 wt.% H₂/1000 m²/g of carbon sorbent at 298 K and 100 atm, indicating that merely increasing surface areas of the carbon sorbents cannot achieve a significant molecular hydrogen capacity at ambient temperature. Spiltover hydrogen storage was achieved by doping Pt nanoparticles (as dissociative hydrogen source) on these carbons (spiltover hydrogen receptor). Our first result on the relationship between the spiltover hydrogen capacity and surface area showed 0.4 wt.% H₂/1000 m²/g of carbon sorbent at 298 K and 100 atm, which indicated that storage via spillover can lead to an average of 70% enhancement compared to molecular hydrogen storage.