Dry SO2 Removal Process Using Calcium/Siliceous‐Based Sorbents: Deactivation Kinetics Based on Breakthrough Curves

The removal of sulfur dioxide (SO₂) from simulated flue gas was investigated in a laboratory‐scale stainless steel fixed‐bed reactor using sorbents prepared from various siliceous materials, i.e., coal fly ash (CFA), oil palm ash (OPA) and rice husk ash (RHA) mixed with lime (CaO) by means of the water hydration method. Experiments were carried out with a flue gas flow rate of 150 mL/min, reaction temperature of 100 °C, and SO₂ concentration of 1000 ppm. It was found that sorbents prepared from RHA have high BET surface areas and high SO₂ sorption capacities, based on breakthrough curve analysis. In addition, the SO₂ breakthrough curves were also described in terms of a simple first‐order deactivation model containing only two rate constants, one of which, k_s, describes the surface reaction rate constant while the other, k_d, describes the deactivation rate constant. The values of k_s and k_d obtained from the deactivation kinetics model were in good agreement with the experimental breakthrough curves and were also compared with those available in the literature.     

Dynamic CO2 adsorption performance of internally cooled silica‐supported poly(ethylenimine) hollow fiber sorbents

The dynamic adsorption behavior of CO₂ under both nonisothermal and nearly isothermal conditions in silica supported poly(ethylenimine) (PEI) hollow fiber sorbents (Torlon®‐S‐PEI) is investigated in a rapid temperature swing adsorption (RTSA) process. A maximum CO₂ breakthrough capacity of 1.33 mmol/g‐fiber (2.66 mmol/g‐silica) is observed when the fibers are actively cooled by flowing cooling water in the fiber bores. Under dry CO₂ adsorption conditions, heat released from the CO₂‐amine interaction increases the CO₂ breakthrough capacity by reducing the severity of the diffusion resistance in the supported PEI. This internal resistance can also be alleviated by prehydrating the fiber sorbent with a humid N₂ feed. The CO₂ breakthrough capacity of prehydrated fibers is adversely affected by the release of the adsorption enthalpy (unlike the dry fibers); however, active cooling of the fiber results in a constant CO₂ breakthrough capacity even at high CO₂ delivery rates (i.e., high adsorption enthalpy delivery rates). In full RTSA cycles, a purity of 50% CO₂ is achieved and the adsorption enthalpy recovery rate can reach ～72%. Studies on the cyclic stability of uncooled fiber sorbents in the presence of SO₂ and NO contaminants indicate that exposure to NO at 200 ppm over 120 cycles does not lead to a significant degradation of the sorbents, but SO₂ exposure at a similar high concentration of 200 ppm causes 60% loss in CO₂ breakthrough capacity after 120 cycles. A simple amine reinfusion technique is successfully demonstrated to recover the adsorption capacity in poisoned fiber sorbents after deactivation by exposure to impurities such SO₂. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3878–3887, 2014     

Hydration products of FBC wastes as SO2 sorbents: comparison between ettringite and calcium hydroxide

Fluidized bed combustion (FBC) enables the in situ capture of SO₂, but generates large amounts of wastes whose composition and physico-chemical properties make both landfilling and reuse in traditional fields of application (e.g., cement and concrete industries) problematic. Reactivation by water hydration of the desulphurizing ability of these residues is considered a viable mean for their recycling: besides Ca(OH)₂, this process can generate other hydration products, such as ettringite. This paper is devoted to a comparison between the behaviour of Ca(OH)₂ and ettringite as SO₂ sorbents. To this end, synthetic preparations (in the particle size range 0.4–0.6 mm) of the two materials were dehydrated and then sulphated in a lab-scale fluidized bed reactor. Sulphation tests were carried out at 850 °C by fluidizing the bed with an SO₂–N₂–O₂ mixture (1800 ppm SO₂) at 0.8 m/s. Calcium conversion degree and fines elutriation rate were evaluated as a function of sulphation time. The propensity of the sorbents to undergo fragmentation was also estimated by particle sizing of in-bed exhausted sorbent particles, with the aid of laser granulometry. Mercury intrusion porosimetry of samples was directed to the assessment of the influence of sorbent dehydration and subsequent sulphation on pore size distribution and porosimetric texture. X-ray diffraction and differential thermal analysis on the synthetic sorbents complemented the characterization. Results showed that dehydration/thermal decomposition brought about a significant increase of the overall porosity for both sorbents, more extensive than it is commonly observed with calcined commercial limestones. Upon sulphation, the two sorbents showed satisfactory degrees of calcium conversion, larger than those usually observed with limestones. Sulphation resulted into a decrease of particle voidage (that of the Ca(OH)₂-based sorbent was negligible after the process). Ettringite was more prone to attrition/fragmentation than calcium hydroxide. Results are discussed with a focus on differences between calcium hydroxide and ettringite and on key-parameters affecting the performance of the two materials as sorbents.     

Development of a Scalable Method for Manufacturing High‐Temperature CO2 Capture Sorbents

An engineered process for scalable manufacture of a calcium aluminum carbonate CO₂ sorbent with production amounts of about 1000 g per hour has been developed. The process includes mixing and heating, solid‐liquid separation, drying and extrusion, crushing and conveying, and calcined molding steps. The sorbent preparation involves the coprecipitation of Ca²⁺, Al³⁺, and CO₃^2– under alkaline conditions. By adjusting the Ca:Al molar ratio, a series of Ca‐rich materials could be synthesized for use as CO₂ sorbents at 750 °C. A calcium acetate‐derived sorbent exhibited better cyclic stability than sorbents originating from CaCl₂ and Ca(NO₃)₂. The initial sorption capacity increased with CaO concentration. High stability of more than 90 % was maintained by the Ca:Al sorbents after 40 looping tests.     

Calcium-based sorbents behaviour during sulphation at oxy-fuel fluidised bed combustion conditions

Sulphur capture by calcium-based sorbents is a process highly dependent on the temperature and CO₂ concentration. In oxy-fuel combustion in fluidised beds (FB), CO₂ concentration in the flue gas may be enriched up to 95%. Under so high CO₂ concentration, different from that in conventional coal combustion with air, the calcination and sulphation behaviour of the sorbent must be defined to determine the optimum operating temperature in the FB combustors.In this work, the SO₂ retention capacity of two different limestones was tested by thermogravimetric analysis at typical oxy-fuel conditions in FB combustors. The effect of the main operating variables affecting calcination and sulphation reactions, like CO₂ and SO₂ concentrations, temperature, and sorbent particle size, was analysed.It was observed a clear difference in the sulphation conversion reached by the sorbent whether the sulphation takes place under indirect or direct sulphation, being much higher under indirect sulphation. But, in spite of this difference, for a given condition and temperature, the CO₂ concentration did not affect to the sulphation conversion, being its major effect to delay the CaCO₃ decomposition to a higher temperature.For the typical operating conditions and sorbent particle sizes used in oxy-fuel FB combustors, the maximum sorbent sulphation conversions were reached at temperatures of about 900 °C. At these conditions, limestone sulphation took place in two steps. The first one was controlled by diffusion through porous system of the particles until pore plugging, and the second controlled by the diffusion through product layer. As a consequence, the maximum sulphation conversion increased with decreasing the particle size and increasing the SO₂ concentration.     

Steam reforming of ethanol on a Ni/Al2O3 catalyst coupled with a hydrotalcite‐like sorbent in a multilayer pattern for co2 uptake

Steam reforming of ethanol (SRE) on a Ni/Al₂O₃ catalyst was studied. The effects of the operating conditions and catalyst nature on the course of reaction were evaluated. Hydrogen was generated in the temperature range between 100 and 600°C. A mechanism was used to explain the reaction pathways. A commercial hydrotalcite‐like sorbent arranged in a multilayer pattern of catalyst and sorbent was used for CO₂‐uptake to enhance hydrogen production. The concept of sorption enhanced reaction process on SRE is illustrated by the operation of catalyst and CO₂‐sorbent at 400°C. A lower flow rate regime and multilayer pattern system enhances hydrogen production in the initial breakthrough periods. CO appears in traces in the product gas stream. © 2011 Canadian Society for Chemical Engineering     

Mesoporous-molecular-sieve-supported Polymer Sorbents for Removing H2S from Hydrogen Gas Streams

A series of sorbents with a linear polyethylenimine (PEI) supported on the mesoporous molecular sieves, including MCM-41, MCM-48 and SBA-15, have been prepared and used to remove H₂S from a model gas containing 0.40 v% of H₂S and 20 v% H₂ in N₂ gas. The sorption was conducted in a fixed-bed system at a temperature range of 22–75 °C, a GHSV range of 337–1,011 h^?1 and atmospheric pressure. The effects of the operating temperature, GHSV, the amount of PEI loading and the different molecular sieve supports were studied. A reduction in the temperature and GHSV improves the sorption performance of the supported PEI sorbents. A synergetic effect of the SBA?15 support and PEI on the H₂S sorption performance was observed. Loading 50 wt% PEI on SBA-15 gave the best breakthrough capacity, while loading 65 wt% PEI on SBA-15 had the highest saturation capacity. The mesoporous molecular sieve with large pore size and three-dimensional channel structure favors increasing the kinetic capacity of the supported PEI sorbent. In addition, the developed sorbents can be regenerated easily at mild conditions (temperature range of 75–100 °C) and have excellent regenerability and stability. The results indicate that the mesoporous-molecular-sieve-supported polymer sorbents are promising for removing H₂S from hydrogen gas streams.     

Sorption-enhanced water gas shift reaction by sodium-promoted calcium oxides

The water gas shift reaction was evaluated in the presence of novel carbon dioxide (CO₂) capture sorbents, both alone and with catalyst, at moderate reaction conditions (i.e., 300-600 °C and 1-11.2 atm). Experimental results showed significant improvements to carbon monoxide (CO) conversions and production of hydrogen (H₂) when CO₂ sorbents are incorporated into the water gas shift reaction. Results suggested that the performance of the sorbent is linked to the presence of a Ca(OH)₂ phase within the sorbent. Promoting calcium oxide (CaO) sorbents with sodium hydroxide (NaOH) as well as pre-treating the CaO sorbent with steam appeared to lead to formation of Ca(OH)₂, which improved CO₂ sorption capacity and WGS performance. Results suggest that an optimum amount of NaOH exists as too much leads to a lower capture capacity of the resultant sorbent. During capture, the NaOH-promoted sorbents displayed a high capture efficiency (nearly 100%) at temperatures of 300-600 °C. Results also suggest that the CaO sorbents possess catalytic properties which may augment the WGS reactivity even post-breakthrough. Furthermore, promotion of CaO by NaOH significantly reduces the regeneration temperature of the former.     

Low Temperature Liquid State Synthesis of Lithium Zirconate and its Characteristics as a CO2 Sorbent

Abstract

In this study, a new preparation method providing greatly improved CO₂ sorption is introduced. Li₂ZrO₃ sorbent was prepared by low temperature co‐precipitation and compared in CO₂ sorption performance with a sorbent prepared by the conventional high temperature solid‐state reaction method. The two sorbents were characterized using scanning electron microscopy, X‐ray diffraction and thermo‐gravimetric analysis. The Li₂ZrO₃ powder prepared by the relatively simple co‐precipitation method showed significantly better performance than the one prepared by solid‐state reaction with respect to both kinetics and CO₂ sorption capacity. Extensive study of the powder prepared by co‐precipitation has been performed at various conditions.     

Kinetics of the reaction of iron blast furance slag/hydrated lime sorbents with SO2 at low temperatures: effects of sorbent preparation conditions

Sorbents highly reactive towards SO₂ have been prepared from iron blast furnace slag and hydrated lime under different hydration conditions. The reaction of the dry sorbents with SO₂ has been studied under the conditions similar to those in the bag filters in the spray-drying flue gas desulfurization system. The reaction was well described by a modified surface coverage model which assumes the reaction rate being controlled by chemical reaction on sorbent grain surface and takes into account the effect of sorbent Ca molar content and the surface coverage by product. The effects of sorbent preparation conditions on sorbent reactivity were entirely represented by the effects of the initial specific surface area (S_g0) and the Ca molar content (M⁻¹) of sorbent. The initial conversion rate of sorbent increased linearly with increasing S_g0, and the ultimate conversion increased linearly with increasing S_g0M⁻¹. The initial conversion rate and ultimate conversion of sorbent increased significantly with increasing relative humidity of the gas. Temperature and SO₂ concentration had mild effects on the initial conversion rate and negligible effects on the ultimate conversion.     

Kinetic study of domestic limestone (Daesung)

Sulfidation and sulfation reactions of Daesung limestone, which is a calcium-based sorbent chosen out of domestic limestone for the removal of H₂S and SO₂, were investigated by using TGA (thermal gravimetric analyzer) Effects of H and H₂S on the sulfidation were also investigated The conversion rate of CaS to CaSO₄ in oxidation was low since the concentration of SO₂ used for this study was low and CaO was not completely converted into CaS It was observed that the effects of H₂ concentration on the sulfidation were relatively small and the maximum conversion rate and reaction rate increased with increase of H₂S concentration In the sulfation reaction, conversion rate could be raised with the injection of air at a sulfation reaction temperature above 800 °C However, the conversion rate decreased without the injection of air due to the blockage of sorbent pores.     

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 SO2 in Semi‐Dry Flue Gas Desulfurization Process with a Powder‐Particle Spouted Bed

Semi‐dry flue gas desulfurization was investigated with several kinds of SO₂ sorbents, such as slaked lime, limestone, Mg(OH)₂ and concrete pile sludge, in a powder‐particle spouted bed. Slurry droplets including sorbent fine particles were fed to a spouted bed of coarse inert particles spouted with hot gas containing SO₂. SO₂ removal efficiency was strongly affected by the approach to saturation temperature, Ca/S molar ratio and particle size of sorbent. Slaked lime showed the highest desulfurization efficiency. In this process, despite very short gas residence time, more than 90% SO₂ removal was easily achieved by choosing appropriate conditions.     

Effects of alkali-metal carbonates and nitrates on the CO<Subscript>2</Subscript> sorption and regeneration of MgO-based sorbents at intermediate temperatures

The effects of alkali-metal carbonates and nitrates on the CO₂ sorption and regeneration of MgO-based sorbents were investigated in the presence of 10 vol% CO₂ and 10 vol% H₂O in an intermediate temperature range, 300 to 450 °C. The CO₂ capture capacities of the MgO-based sorbents promoted with Na₂CO₃ and K₂CO₃ were 9.7 and 45.0 mg CO₂/g sorbent, respectively. On the other hand, a MgO-based sorbent promoted with both Na₂CO₃ and NaNO₃ exhibited the highest CO₂ capture capacity of 97.4mg CO₂/g sorbent at 200 °C in 10 vol% CO₂, which was almost ten-times greater than that of the MgO-based sorbent promoted with Na₂CO₃. The CO₂ sorption rate of these sorbents was higher than that of the MgO-based sorbents promoted with alkali-metal nitrates due to the formation of Na₂Mg(CO₃)₂ or K₂Mg(CO₃)₂ by the alkali-metal carbonate and the eutectic reaction of the alkali-metal nitrates. In addition, the reproducibility problem of double-salt sorbents obtained by the precipitation method was completely resolved by impregnating MgO with alkali-metal carbonates and nitrates. Furthermore, we found that their desorption temperatures are lower than those of the MgO-based sorbents promoted with alkali-metal carbonates due to the eutectic reaction during the regeneration process.     

Competitive adsorption of NO,SO2 and H2O onto mordenite synthesized from perlite

A new material, mordenite synthesized from volcanic ash (perlite) in the presence of sodium salts, has been shown to be a weak sorbent for NO and a strong and reversible sorbent for SO₂. The mordenite's capacity to adsorb SO₂ was found to be related to the amount of sodium present in the material. Capacities as high as 8 wt% were achieved at 1250 ppm of SO₂ in helium at 25°C. In multicycle tests the mordenite maintained its capacity after more than 40 cycles when desorbing the SO₂ at 300°C. The adsorption rate of SO₂ in the absence of water was modelled and the adsorption activation energy was found to be 3.2 kcal mol⁻¹. Water significantly decreased the mordenite's capacity to adsorb SO₂ and also caused the SO₂ to be chromatographically desorbed in a roll-up peak. In these water-SO₂ adsorption experiments a peculiar breakthrough was observed for water, where the water concentration exiting the bed first decreased and then increased. This peculiar water breakthrough could not be explained by assuming independent adsorption of the two species, but was qualitatively predicted by assuming that water adsorption is enhanced by the presence of adsorbed SO₂.     

Regeneration of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-based high-temperature coal gas desulfurization sorbent in atmosphere with sulfur dioxide

Regeneration of a high-temperature coal gas desulfurization sorbent is a key technology in its industrial applications. A Fe₂O₃-based high-temperature coal gas desulfurizer was prepared using red mud from steel factory. The influences of regeneration temperature, space velocity and regeneration gas concentration in SO₂ atmosphere on regeneration performances of the desulfurization sorbent were tested in a fixed bed reactor. The changes of phase and the composition of the Fe₂O₃-based high-temperature coal gas desulfurization sorbent before and after regeneration were examined by X-ray diffraction (XRD) and X-ray Photoelectron spectroscopy(XPS), and the changes of pore structure were characterized by the mercury intrusion method. The results show that the major products are Fe₃O₄ and elemental sulfur; the influences of regeneration temperature, space velocity and SO₂ concentration in inlet on regeneration performances and the changes of pore structure of the desulfurization sorbent before and after regeneration are visible. The desulfurization sorbent cannot be regenerated at 500°C in SO₂ atmosphere. Within the range of 600°C–800°C, the time of regeneration becomes shorter, and the regeneration conversion increases as the temperature rises. The time of regeneration also becomes shorter, and the elemental sulfur content of tail gas increases as the SO₂ concentration in inlet is increased. The increase in space velocity enhances the reactive course; the best VSP is 6000 h^?1 for regeneration conversion. At 800°C, 20 vol-% SO₂ and 6000 h^?1, the regeneration conversion can reach nearly to 90%.     

Regeneration of Fe2O3-based high-temperature coal gas desulfurization sorbent in atmosphere with sulfur dioxide

Regeneration of a high-temperature coal gas desulfurization sorbent is a key technology in its industrial applications. A Fe₂O₃-based high-temperature coal gas desulfurizer was prepared using red mud from steel factory. The influences of regeneration temperature, space velocity and regeneration gas concentration in SO₂ atmosphere on regeneration performances of the desulfurization sorbent were tested in a fixed bed reactor. The changes of phase and the composition of the Fe₂O₃-based high-temperature coal gas desulfurization sorbent before and after regeneration were examined by X-ray diffraction (XRD) and X-ray Photoelectron spectroscopy(XPS), and the changes of pore structure were characterized by the mercury intrusion method. The results show that the major products are Fe₃O₄ and elemental sulfur; the influences of regeneration temperature, space velocity and SO₂ concentration in inlet on regeneration performances and the changes of pore structure of the desulfurization sorbent before and after regeneration are visible. The desulfurization sorbent cannot be regenerated at 500°C in SO₂ atmosphere. Within the range of 600°C–800°C, the time of regeneration becomes shorter, and the regeneration conversion increases as the temperature rises. The time of regeneration also becomes shorter, and the elemental sulfur content of tail gas increases as the SO₂ concentration in inlet is increased. The increase in space velocity enhances the reactive course; the best VSP is 6000 h⁻¹ for regeneration conversion. At 800°C, 20 vol-% SO₂ and 6000 h⁻¹, the regeneration conversion can reach nearly to 90%.     

The effect of HCl and H<Subscript>2</Subscript>O on the H<Subscript>2</Subscript>S removing capacities of Zn-Ti-based desulfurization sorbents promoted by cobalt and nickel oxide

The sulfur removing capacities of various Zn-Ti-based sorbents were investigated in the presence of H₂O and HCl at high-(sulfidation, 650 °C; regeneration, 800 °C) and medium-(sulfidation, 480 °C; regeneration, 580 °C) temperature conditions. The H₂O effect of all sorbents was not observed at high-temperature conditions. At mediumtemperature conditions, the reaction rate of ZT (Zn/Ti : 1.5) sorbent decreased with the level of H₂O concentration, while modified (ZTC, ZTN) sorbents were not affected by the water vapor. HCl vapor resulted in the deactivation of ZT sorbent with a cycle number at high-temperature due to the production of ZnCl₂ while the sulfur removing capacities of ZTC and ZTN sorbents were maintained during 4–5 cyclic tests. In the case of medium-temperature conditions, ZT sorbent was poisoned by HCl vapor while cobalt and nickel added to ZT sorbent played an important catalytic role to prevent from being poisoned by HCl due to providing heat, emitted when these additives quickly react with H₂S even at medium-temperature conditions, to the sorbents     

Sulphur dioxide removal using South African limestone/siliceous materials

This study presents an investigation into the desulfurization effect of sorbent derived from South African calcined limestone conditioned with fly ash. The main aim was to examine the effect of chemical composition and structural properties of the sorbent with regard to SO₂ removal in dry-type flue gas desulfurization (FGD) process. South African fly ash and CaO obtained from calcination of limestone in a laboratory kiln at a temperature of 900 °C were used to synthesize CaO/ash sorbent by atmospheric hydration process. The sorbent was prepared under different hydration conditions: CaO/fly ash weight ratio, hydration temperature (55-75 °C) and hydration period (4-10 h). Desulfurization experiments were done in the fixed bed reactor at 87 °C and relative humidity of 50%. The chemical composition of both the fly ash and calcined limestone had relatively high Fe₂O₃ and oxides of other transitional elements which provided catalytic ability during the sorbent sorption process. Generally the sorbents had higher SO₂ absorption capacity in terms of mol of SO₂ per mol of sorbent (0.1403-0.3336) compared to hydrated lime alone (maximum 0.1823). The sorbents were also found to consist of mesoporous structure with larger pore volume and BET specific surface area than both CaO and fly ash. X-ray diffraction (XRD) analysis showed the presence of complex compounds containing calcium silicate hydrate in the sorbents.