The effects of pressure and temperature on the catalytic oxidation of hydrogen sulfide in natural gas and regeneration of the catalyst to recover the sulfur produced

The influence of pressure up to 5600 kPa and temperature up to 175 °C on the oxidation of low concentrations of H₂S in natural gas was studied in a fixed bed reactor over an activated carbon catalyst. Operation of this system at 5600 kPa provides higher catalyst activity (virtually 100% H₂S conversion) over a longer period of time and with lower selectivity to SO₂ than when operated at atmospheric pressure. The desorption of sulfur from a loaded catalyst occurs first from the macropores (> 100 nm) of the catalyst which contain a substantial portion of the sulfur load and then from the micropores (< 100 nm). This study also indicated that the sulfur recovery process is both rapid and effective at 327°C.     

Catalytic Reduction of Nitric Oxide by Hydrogen Sulfide Over γ-alumina

The ability of H₂S to reduce NO in a fixed bed reactor using a γ-alumina catalyst was studied with the objective of generating new methods for conversion of NO to N₂. Compared to the homogenous reaction of NO with H₂S, the catalyzed reaction showed improved conversions of NO to N₂. Using a gas space velocity of 1000 h⁻¹ and a feed of 1% NO and 1% H₂S in argon, it was found that the conversion of NO to N₂ was complete at 800 °C. This result compared to a 38% conversion of NO to N₂ for the homogeneous gas phase reaction at 800 °C. At temperatures below 800 °C, a short fall in the nitrogen balance was discovered when the γ-alumina was employed as a catalyst. This discrepancy was explained by conversion of NO to NH₃ and subsequent reaction of the NH₃ with any SO₂ in the system to form ammonium sulfur oxy-anion salts. This suggestion is supported by the finding that when larger amounts of H₂S were used relative to NO, more NH₃ was formed together in tandem with lower N₂ mass balances. Several reaction pathways have been proposed for the catalytic reduction of NO by H₂S.     

Effect of Temperature and Water on the Selective Oxidation of H<Subscript>2</Subscript>S to Elemental Sulfur on a Macroscopic Carbon Nanofiber Based Catalyst

Abstract  

Carbon nanofibers were synthesized on graphite felt substrate by catalytic decomposition of ethane. The preshaped material was efficiently used as catalyst support for the active phase NiS₂ in the direct oxidation of H₂S into elemental sulfur. The catalyst was extremely active, selective, and stable at 60 °C in a fixed bed reactor due to the high resistance of carbon nanofiber based catalyst to the solid sulfur loading. This is explained by the specific mode of sulfur deposition, involving the role of water in the sulfur transport and the hydrophobic nature of the support.     

Characteristics of the mercury vapor removal from coal combustion flue gas by activated carbon using H2S

Removal of Hg⁰ vapor from the simulated coal combustion flue gases with a commercial activated carbon was investigated using H₂S. This method is based on the reaction of H₂S and Hg over the adsorbents. The Hg⁰ removal experiments were carried out in a conventional flow type packed bed reactor system in the temperature range of 80–150 °C using simulated flue gases having the composition of Hg⁰ (4.9 ppb), H₂S (0–20 ppm), SO₂ (0–487 ppm), CO₂ (10%), H₂O (0–15%), O₂ (0–5%), N₂ (balance gas). The following results were obtained: in the presence of both H₂S and SO₂, Hg removal was favored at lower temperatures (80–100 °C). At 150 °C, presence of O₂ was indispensable for Hg⁰ removal from H₂S–SO₂ flue gas system. It is suggested that the partial oxidation of H₂S with O₂ to elemental sulfur (H₂S+1/2O₂=S_ad+H₂O) and the Clause reaction (SO₂+2H₂S=3S_ad+2H₂O) may contribute to the Hg⁰ removal over activated carbon by the following reaction: S_ad+Hg=HgS. The formation of elemental sulfur on the activated carbon was confirmed by a visual observation.     

Production of H2 and medium heating value gas via steam gasification of lignins in fixed‐bed reactors

In this work, steam gasification of Alcell and Kraft lignins were carried out in a fixed‐bed reactor in order to produce H₂ and medium heating value gas. The conversion of lignins increased from a low of 64 wt% for Alceil lignin to a high of 88 wt% for Kraft lignin with increasing steam flow rate and temperature. Maximum H₂ production of 60.7 mol% was obtained at 800°C and at a steam flow rate of 15 g/h/g of Kraft lignin, whereas maximum heating value of 18000 kl/m³ of the product gas was obtained at 650°C and at 5 g/h/g of Alcell lignin. Also, the performance of a Ni‐based steam reforming catalyst for the production of H₂ was studied for both types of lignin in a dual fixed‐bed reaction system. A maximum H₂ production of 63 mol% was obtained at a catalyst bed temperature of 750°C and at a catalyst loading of 0.3 g for Alcell lignin. The sulfur present in Kraft lignin had detrimental effect on the catalyst performance.     

Effect of carbon deposition over carbonaceous catalysts on CH4 decomposition and CH4-CO2 reforming

An investigation was made using a continuous fixed bed reactor to understand the influence of carbon deposition obtained under different conditions on CH₄-CO₂ reforming. Thermogravimetry (TG) and X-ray diffraction (XRD) were employed to study the characteristics of carbon deposition. It was found that the carbonaceous catalyst is an efficient catalyst in methane decomposition and CH₄-CO₂ reforming. The trend of methane decomposition at lower temperatures is similar to that at higher temperatures. The methane conversion is high during the initial of stage of the reaction, and then decays to a relatively fixed value after about 30 min. With temperature increase, the methane decomposition rate increases quickly. The reaction temperature has significant influence on methane decomposition, whereas the carbon deposition does not affect methane decomposition significantly. Different types of carbon deposition were formed at different methane decomposition reaction temperatures. The carbon deposition Type I generated at 900°C has a minor effect on CH₄-CO₂ reforming and it easily reacts with carbon dioxide, but the carbon deposition Type II generated at 1000°C and 1100°C clearly inhibits CH₄-CO₂ reforming and it is difficult to react with carbon dioxide. The results of XRD showed that some graphite structures were found in carbon deposition Type II.     

Effect of carbon deposition over carbonaceous catalysts on CH<Subscript>4</Subscript> decomposition and CH<Subscript>4</Subscript>-CO<Subscript>2</Subscript> reforming

An investigation was made using a continuous fixed bed reactor to understand the influence of carbon deposition obtained under different conditions on CH₄-CO₂ reforming. Thermogravimetry (TG) and X-ray diffraction (XRD) were employed to study the characteristics of carbon deposition. It was found that the carbonaceous catalyst is an efficient catalyst in methane decomposition and CH₄-CO₂ reforming. The trend of methane decomposition at lower temperatures is similar to that at higher temperatures. The methane conversion is high during the initial of stage of the reaction, and then decays to a relatively fixed value after about 30 min. With temperature increase, the methane decomposition rate increases quickly. The reaction temperature has significant influence on methane decomposition, whereas the carbon deposition does not affect methane decomposition significantly. Different types of carbon deposition were formed at different methane decomposition reaction temperatures. The carbon deposition Type I generated at 900°C has a minor effect on CH₄-CO₂ reforming and it easily reacts with carbon dioxide, but the carbon deposition Type II generated at 1000°C and 1100°C clearly inhibits CH₄-CO₂ reforming and it is difficult to react with carbon dioxide. The results of XRD showed that some graphite structures were found in carbon deposition Type II.     

Activation studies with an iron fischer-tropsch catalyst in fixed bed and stirred tank slurry reactors

A precipitated iron catalyst (100 Fe/5 Cu/4.2 K/25 SiO₂ on a mass basis) was tested in a fixed bed reactor and a stirred tank slurry reactor under the same process conditions (250°C, 1.48 MPa, 2 L (STP)/gcat · h, H₂ : CO = 2:3). Two different pretreatment procedures were employed (hydrogen reduction at 220°C and carbon monoxide activation at 280°C) in each of the two reactor types. In the stirred tank slurry reactor tests the activity (based on an apparent first order reaction rate constant) of the carbon monoxide pretreated catalyst was about 25% higher than that of hydrogen reduced catalyst, due to incomplete reduction of the latter. In all tests the catalyst selectivity changed slowly with time on stream. Hydrocarbon distribution shifted toward lower molar mass products, and secondary reactions (l-olefin hydrogenation, isomerization and readsorption) increased with time. The secondary reactions were the most pronounced on the hydrogen reduced catalyst in the fixed bed reactor.     

Catalytic activity of carbon supported potassium in the carbon monoxide shift reaction

The catalytic activity of carbon supported potassium was studied in a fixed bed flow reactor at 0.1 M Pa by using synthesis gas (CO + H₂) of various compositions and various water vapour contents. In the temperature range between 400 and 550 °C the carbon monoxide shift reaction: CO + H₂O ⇌ CO₂ + H₂, may be described by the following rate equation: r_CO2 = 2.10³exp(−82 500/RT)p_CO^0.6p_H2O^0.4. At 550 °C carbon supported potassium (28.3 mass parts K per 100 mass parts activated carbon) exhibits the same catalytic activity like an industrial high temperature catalyst (type K_6–10 of BASF).     

Catalytic Steam Reforming of Fast Pyrolysis Bio‐Oil in Fixed Bed and Fluidized Bed Reactors

Catalytic steam reforming of bio‐oil is an economically‐feasible route which produces renewable hydrogen. The Ni/MgO‐La₂O₃‐Al₂O₃ catalyst was prepared with Ni as active agent, Al₂O₃ as support, and MgO and La₂O₃ as promoters. The experiments were conducted in fixed bed and fluidized bed reactors, respectively. Temperature, steam‐to‐carbon mole ratio (S/C), and liquid hourly space velocity (LHSV) were investigated with hydrogen yield as index. For the fluidized bed reactor, maximum hydrogen yield was obtained under temperatures 700–800 °C, S/C 15–20, LHSV 0.5–1.0 h^–1, and the maximum H₂ yield was 75.88 %. The carbon deposition content obtained from the fluidized bed was lower than that from the fixed bed. The maximum H₂ yield obtained in the fluidized bed was 7 % higher than that of the fixed bed. The carbon deposition contents obtained from the fluidized bed was lower than that of the fixed bed at the same reaction temperature.     

Effects of preparation methods on the properties of cobalt/carbon catalyst for methane reforming with carbon dioxide to syngas

The effect of different preparation methods on the physicochemical property, reforming reactivity, stability and carbon deposition resistance of cobalt/carbon catalyst was investigated through fixed bed flow reaction. The catalysts were prepared by the impregnation and characterized by the XRD and scanning electron microscopy (SEM). The result indicated that the active components of cobalt/carbon catalyst prepared by using ultrasonic wave distributed evenly, activity was high and the loading time was short. The Co/Carbon catalyst prepared by incipient-wetness impregnation, 10 wt% loading and 300 °C calcination, achieved the best activity. Furthermore, the effect of reaction temperature, air speed and CH₄/CO₂ ratio on the catalyst activity and CO/H₂ ratio in products was investigated. It was found that the conversion of CO₂ and CH₄ increased with the increasing of reaction temperature. However, the conversion of CO₂ and CH₄ increased first and then decreased with the increasing of air speed. With the increasing of CH₄/CO₂ in feed gas, both the catalyst activity and the CO/H₂ ratio in products decreased.     

Oxidation of hydrogen sulfide over microporous carbons

Microporous carbon of high purity was produced by the carbonization of Saran at 900° followed by activation in either CO₂ at 900°, O₂ at 300°, or air at 425°. The activated carbons were characterized using N₂ adsorption at ?195° CO₂ adsorption at 25°, and mercury and helium displacements. Hydrogen sulfide oxidation (at H₂S pressures between 0.4–3.8 Torr) by O₂ (in excess of stoichiometric amount) was studied between 100–160° using a microbalance, that is by weighing the build-up of sulfur on the carbon. The predominant reaction, $\text{H}{}_2\text{S +}\text{1}\text{2}\text{O}{}_2\text{→}\text{1}\text{2}\text{S}{}_2\text{+ H}{}_2\text{O}$ was first order in H₂S concentration and independent of O₂ concentration. The rate was only slightly reduced by sulfur build-up to at least 36%, by weight, on the carbon. The oxidation rate was significantly higher over the O₂-activated carbon than over the CO₂-activated carbon. Throughout the studies, oxidation rates could be correlated with area active to O₂ chemisorption. It is concluded that H₂S oxidation proceeds via rapid dissociative chemisorption of oxygen on carbon sites followed by reaction with H₂S. Rates of H₂S oxidation were also studies over commercial, granular activated carbons of significant ash contents.     

Correlation of H<Subscript>2</Subscript>S and COS in the hot coal gas stream and its importance for high temperature desulfurization

Thermodynamic analysis of the correlation of H₂S and COS has been carried out at the temperature range of 400–650 °C at which high temperature desulfurization of coal gas is usually performed. The correlation of the two sulfur species is mainly through the reaction H₂S+CO→COS+H₂. Simulated coal gas with the following composition CO 32.69%, H₂ 39.58%, CO₂ 18.27%, N₂ 8.92% and H₂S 0.47% was used in this study, and the equilibrium concentrations of the two species at different temperatures were calculated. The results of Fe-based sorbents during sulfidation were compared with calculations. It is concluded that the above reaction may reach equilibrium concentration in the presence of the Fe-based sorbents, which means the Fe-based sorbents may effectively catalyze the reaction between H₂S and CO. Because of the correlation of the two sulfur species, both can be effectively removed at high temperatures simultaneously, offering high temperature desulfurization some advantages over low temperature desulfurization processes.     

COS Hydrolysis Using Zinc-promoted Alumina Catalysts

The effect of doping alumina catalysts with zinc oxide is investigated for the COS hydrolysis reaction (COS + H₂O=CO₂ + H₂S) at 150 °C. The effect of the catalyst preparation method is described and discussed, and two methods are compared, namely: impregnation by incipient wetness of zinc nitrate followed by calcination to form the oxide and coprecipitation to form a hydroxide followed by calcination. The most effective zinc-promoted catalysts are prepared using the incipient wetness impregnation method. The promotional effect of zinc oxide on alumina is only observed on the basis of intrinsic activity and is not particularly significant at the initial time on stream, but becomes more marked with increased reaction time. The addition of the zinc oxide therefore decreases the deactivation and experiments using catalysts pretreated with H₂S and H₂O show that the alumina is deactivated by adsorption of these reactants. However, the effect is related to ZnO acting as a sulfur scavenger at 150 °C and we conclude that any promotional effect is likely to be relatively short lived.     

Vanadium oxide catalysts on structured microfiber supports for the selective oxidation of hydrogen sulfide

Vanadium(V) oxide catalysts for the selective oxidation of hydrogen sulfide to sulfur on a nonporous glass-fiber support with a surface layer of a porous secondary support (SiO₂) are studied. The catalysts are obtained by means of pulsed surface thermosynthesis. Such catalysts are shown to have high activity and acceptable selectivity in the industrially important region of temperatures below 200°C. A glass-fiber catalyst containing vanadium oxide (10.3 wt % of vanadium) in particular ensures the complete conversion of H₂S at a temperature of 175°C and a reaction mixture hourly space velocity (RMHSV) of 1 cm³/(g_cat s) with a sulfur yield of 67%; this is at least 1.35 times higher than for the traditional iron oxide catalyst. Using a structured glass-fiber woven support effectively minimizes diffusion resistance and greatly simplifies the scaleup of processes based on such catalysts. Such catalysts can be used for the cleansing of tail gases from Claus units and in other processes based on the selective oxidation of H₂S.     

Kinetics of sulfur transfer from H2S to Fe1-xS

The rate of sulfur transfer across the gas/solid interface involving H₂S(g) and Fe_1-xS surface has been investigated using resistance relaxation measurements at 600°C. The rate of the oxidation reaction incorporating sulfur into Fe_1-xS has been found to decrease with sulfur activity (a_S) in the sample as (a_S)^-2/3, while the rate of the reduction reaction corresponding to sulfur loss is found to increase with the sulfur activity as (a_S)^1/3. The kinetic finding has been combined with the appropriate defect models for FeS to identify the rate limiting step for the sulfur transfer reaction from H₂S to FeS. Accordingly, the rate limiting step has been identified to be: H₂S(g) + 2e^-\rightleftharpoons S^2-(ad) + H₂(g). This revised version was published online in July 2006 with corrections to the Cover Date.     

Potassium‐catalyzed steam gasification of ash‐free lignite coal with CO2 capture

The purpose of this research was to study steam gasification of ash‐free coal integrated with CO₂ capture in the presence of a K₂O catalyst for enhancement of the key water‐gas shift reaction and promotion of hydrogen production. To achieve this goal, gasification experiments on ash‐free coal (AFC) were carried out at varying temperatures (600, 650, 675, 700, and 750 °C) with a sorbent‐to‐carbon (CaO/C) ratio of 2 and a catalyst (K₂O) loading of 0.2 g/g (20 weight percent (wt%)) in a fixed‐bed reactor equipped with a gas chromatography analyzer. The sorbent‐to‐carbon (CaO/C) ratio of 2 is based on dry and ash‐free basis. The CaO/C ratio and K₂O wt% were chosen to maximize hydrogen production based on our previously determined optimal values. The AFC was originally extracted from raw lignite coal using organic solvents, which allowed the sorption‐enhanced gasification to be conducted with minimal ash‐catalyst interactions. The effect of temperature on the yield and the initial reaction rate were investigated. The optimal reaction temperature of 675 °C was determined. Carbon balance and final carbon conversions were calculated based on the residue analysis. Activation energy was also calculated using intrinsic kinetics of the reaction. In this study, using AFC offered the potential advantage of operating the gasification process with catalyst recycle.     

Catalyst modification and process design considerations for the oxidation of low concentrations of hydrogen sulfide in natural gas

Low concentrations of hydrogen sulfide (H₂S) in natural gas can be selectively oxidized over an activated carbon catalyst to elemental sulfur, water and a small fraction of sulfur dioxide (SO₂). Efforts to improve catalyst performance and product sulfur quality have been made by a) modification of the catalyst composition b) removal of the heavy hydrocarbons from the feed and c) choice of reaction conditions. The use of a guard bed to absorb heavy hydrocarbons and operation at elevated pressures show positive results. A preliminary flow diagram incorporating these findings has been prepared for a small commercial unit capable of processing sour natural gas containing 1.0% H₂S.     

A Novel Process for Renewable Methane Production: Combining Direct Air Capture by K<Subscript>2</Subscript>CO<Subscript>3</Subscript>/Alumina Sorbent with CO<Subscript>2</Subscript> Methanation over Ru/Alumina Catalyst

CO₂ methanation over supported ruthenium catalysts is considered to be a promising process for carbon capture and utilization and power-to-gas technologies. In this work 4% Ru/Al₂O₃ catalyst was synthesized by impregnation of the support with an aqueous solution of Ru(OH)Cl₃, followed by liquid phase reduction using NaBH₄ and gas phase activation using the stoichiometric mixture of CO₂ and H₂ (1:4). Kinetics of CO₂ methanation reaction over the Ru/Al₂O₃ catalyst was studied in a perfectly mixed reactor at temperatures from 200 to 300 °C. The results showed that dependence of the specific activity of the catalyst on temperature followed the Arrhenius law. CO₂ conversion to methane was shown to depend on temperature, water vapor pressure and CO₂:H₂ ratio in the gas mixture. The Ru/Al₂O₃ catalyst was later tested together with the K₂CO₃/Al₂O₃ composite sorbent in the novel direct air capture/methanation process, which combined in one reactor consecutive steps of CO₂ adsorption from the air at room temperature and CO₂ desorption/methanation in H₂ flow at 300 or 350 °C. It was demonstrated that the amount of desorbed CO₂ was practically the same for both temperatures used, while the total conversion of carbon dioxide to methane was 94.2–94.6% at 300 °C and 96.1–96.5% at 350 °C.     

Oxidation of hydrogen sulfide to elementary sulfur on an activated carbon bed in the presence of iron (III) chloride aerosol

Oxidation of H₂S to elemental sulfur in a gas stream at room temperature was examined in a bed of activated carbon. The reaction was observed in the presence and absence of a ferric chloride aerosol.The H₂S concentration was in the range 500 – 2000 p.p.m., gas velocities from 4.2 – 22.5 cm/sec and aerosol concentration in the range 0.001 – 1 mg/l air.The activity of carbon as an adsorbent catalyst dropped to a relatively low value within a short time in the absence of the aerosol. The ferric chloride aerosol, which acted as another catalyst, improved the removal of H₂S to a great extent. This improvement depended on the concentration of the aerosol. Up to 98% removal was obtainable and was maintained indefinitely. These results suggest that iron chloride aerosols may be used to remove H₂S from gas streams in a dry particle bed of adsorptive material.