Key factor in rice husk Ash/CaO sorbent for high flue gas desulfurization activity

Siliceous materials such as rice husk ash (RHA) have potential to be utilized as high performance sorbents for the flue gas desulfurization process in small-scale industrial boilers. This study presents findings on identifying the key factorfor high desulfurization activity in sorbents prepared from RHA. Initially, a systematic approach using central composite rotatable design was used to develop a mathematical model that correlates the sorbent preparation variables to the desulfurization activity of the sorbent. The sorbent preparation variables studied are hydration period, x1 (6-16 h), amount of RHA, x2 (5-15 g), amount of CaO, x3 (2-6 g), amount of water, x4 (90-110 mL), and hydration temperature, x5 (150-250 degrees C). The mathematical model developed was subjected to statistical tests and the model is adequate for predicting the SO2 desulfurization activity of the sorbent within the range of the sorbent preparation variables studied. Based on the model, the amount of RHA, amount of CaO, and hydration period used in the preparation step significantly influenced the desulfurization activity of the sorbent. The ratio of RHA and CaO used in the preparation mixture was also a significant factor that influenced the desulfurization activity of the sorbent. A RHA to CaO ratio of 2.5 leads to the formation of specific reactive species in the sorbent that are believed to be the key factor responsible for high desulfurization activity in the sorbent. Other physical properties of the sorbent such as pore size distribution and surface morphology were found to have insignificant influence on the desulfurization activity of the sorbent.     

Iron blast furnace slag/hydrated lime sorbents for flue gas desulfurization

Sorbents prepared from iron blast furnace slag (BFS) and hydrated lime (HL) through the hydration process have been studied with the aim to evaluate their reactivities toward SO2 under the conditions prevailing in dry or semidry flue gas desulfurization processes. The BFS/HL sorbents, having large surface areas and pore volumes due to the formation of products of hydration, were highly reactive toward SO2, as compared with hydrated lime alone (0.24 in Ca utilization). The sorbent reactivity increased as the slurrying temperature and time increased and as the particle size of BFS decreased; the effects of the liquid/solid ratio and the sorbent drying conditions were negligible. The structural properties and the reactivity of sorbent were markedly affected by the BFS/HL ratio; the sorbent with 30/70 ratio had the highest 1 h utilization of Ca, 0.70, and SO2 capture, 0.45 g SO2/g sorbent. The reactivity of a sorbent was related to its initial specific surface area (Sg0) and molar content of Ca (M(-1)); the 1 h utilization of Ca increased almost linearly with increasing Sg0/M. The results of this study are useful to the preparation of BFS/HL sorbents with high reactivity for use in the dry and semidry processes to remove SO2 from the flue gas.     

Improvement of the desulfurization and regeneration properties through the control of pore structures of the Zn-Ti-based H2S removal sorbents

To improve the sulfur removing capacity of the conventional Zn-Ti-based H2S removal sorbents, a new Zn-Ti based sorbent (ZT-cp) was prepared by the coprecipitation method and tested in a packed bed reactor at middle temperature conditions (H2S absorption at 480 degrees C, regeneration at 580 degrees C). The new Zn-Ti-based sorbent showed excellent sulfur removing capacity without deactivation, even after 10 cycles of absorption and regeneration. The conventional Zn-Ti-based sorbents (ZT-700, ZT-1000), however, that were prepared by physical mixing, were continuously deactivated. In particular, the initial sulfur removing capacity of the ZT-cp sorbent showed a very high absorption value (0.22 g S/g sorbent), which corresponded to 91.6% of theoretical absorption amount. These results can be explained by the difference in physical properties such as pore volume, surface area, and particle size. It was also found that the sulfides formed from the ZT-cp and ZT-1000 sorbents with spinel structure were easily regenerated even at 580 degrees C. Those from the ZT-700 sorbent, with separated ZnO and TiO2 structures, needed a temperature higher than 610 degrees C for regeneration.     

Hydration of natural organic matter: effect on sorption of organic compounds by humin and humic acid fractions vs original peat material

Natural organic matter (NOM) hydration is found to change activity-based sorption of test organic compounds by as much as 2-3 orders of magnitude, depending on the compound and the specific NOM sorbent. This is demonstrated for sorption on humin, humic acid, and the NOM source material. Hydration assistance in organic compound sorption correlates with the ability of the sorbate to interact strongly with hydrated sorbents, demonstrating the important role of noncovalent polar links in organizing the sorbent structure. Differences in hydration effect between the sorbents are caused mainly by differences in compound-sorbent interactions in the dry state. For a given compound, hydration of the sorbent tends to equalize the sorption capability of the three sorbents. No correlation was found between the strength of sorbate-sorbent interactions or the type of sorbate functional groups and the extent of sorption nonlinearity. Sorption nonlinearity compared over the same sorbed concentration range is greater on the original NOM than on either of the two extracted fractions. In elucidating sorption mechanisms on hydrated NOM, it is important to explicitly consider the participation of water molecules in organic compound interactions in the NOM phase.     

SO2 retention by reactivated CaO-based sorbent from multiple CO2 capture cycles

This paper examines the reactivation of spent sorbent, produced from multiple CO2 capture cycles, for use in SO2 capture. CaO-based sorbent samples were obtained from Kelly Rock limestone using three particle size ranges, each containing different impurities levels. Using a thermogravimetric analyzer (TGA), the sulfation behavior of partially sulfated and unsulfated samples obtained after multiple calcination-carbonation cycles in a tube furnace (TF), following steam reactivation in a pressurized reactor, is examined. In addition, samples calcined/sintered under different conditions after hydration are also examined. The results show that suitably treated spent sorbent has better sulfation characteristics than that of the original sorbent. Thus for example, after 2 h sulfation, > 80% of the CaO was sulfated. In addition, the sorbent showed significant activity even after 4 h when > 95% CaO was sulfated. The results were confirmed by X-ray diffraction (XRD) analysis, which showed that, by the end of the sulfation process, samples contained CaSO4 with only traces of unreacted CaO. The superior behavior of spent reactivated sorbent appears to be due to swelling of the sorbent particles during steam hydration. This enables the development of a more suitable pore surface area and pore volume distribution for sulfation, and this has been confirmed by N2 adsorption-desorption isotherms and the Barrett-Joyner-Halenda (BJH) method. The surface area morphology of sorbent after reactivation was examined by scanning electron microscopy (SEM). Ca(OH)2 crystals were seen, which displayed their regular shape, and their elemental composition was confirmed by energy-dispersive X-ray (EDX) analysis. The improved characteristics of spent reactivated sorbent in comparison to the original and to the sorbent calcined under different conditions and hydrated indicate the beneficial effect of CO2 cycles on sorbent reactivation and subsequent sulfation. These results allow us to propose a new process for the use of CaO-based sorbent in fluidized bed combustion (FBC) systems, which incorporates CO2 capture, sorbent reactivation, and SO2 retention.     

Novel CaO-SiO2 sorbent and bifunctional Ni/Co-CaO/SiO2 complex for selective H2 synthesis from cellulose

Catalysis- and sorption-enhanced biomass gasification is a promising route to high-purity hydrogen (H(2)); however, most CaO-based sorbents for CO(2) capture have poor surface area and mechanical properties, lose carrying capacity over multiple uses, and have insufficient porosity to accommodate extra catalyst sites. We aimed to develop a high-surface-area CaO-SiO(2) framework onto which catalysts could be grafted. The best CaO-SiO(2) sorbent (n(Ca)/n(Si) = 2:1) maintained a CaO conversion of 65% even after 50 carbonation-decarbonation cycles, better than commercial micrometer-sized CaO or tailored CaO, because of stabilization via Ca-O-Si interactions and an ordered porous structure. Bimetallic catalyst grains (Ni/Co alloy, <20 nm) could be evenly loaded onto this structure by impregnation. The resulting bifunctional complex produced H(2) at nearly the same rate as a mixture of catalyst and commercial CaO while using less total sorbent/catalyst. Furthermore, this complex was much more durable due to its higher coking resistance and stable structure. After 25 carbonation-decarbonation cycles, the new catalyst-sorbent complex enhanced the H(2) yield from cellulose far more than a mixture of catalyst and commercial CaO did following the same treatment.     

Development of regenerable MgO-based sorbent promoted with K2CO3 for CO2 capture at low temperatures

To improve their CO2 absorption capacity, alkali-based sorbents prepared by impregnation and wet mixing method of potassium carbonate on supports such as activated carbon and MgO (KACI30, KACP30, KMgI30, and KMgP30), were investigated in a fixed bed reactor (C02 absorption at 50-100 degrees C and regeneration at 150-400 degrees C). Total CO2 capture capacities of KMgI30-500 and KMgP30-500 were 178.6 and 197.6 mg CO2/g sorbent, respectively, in the presence of 11 vol % H2O even at 50 degrees C. The large amount of CO2 capture capacity of KMgP30-500 and KMgI30-500 could be explained by the fact that MgO itself, as well as K2CO3, could absorb CO2 in the presence of water vapor even at low temperatures. In particular, water vapor plays an important role in the CO2 absorption of MgO and KMgI30-500 even at low temperatures below 60 degrees C, in marked contrast to MgO and CaO which can absorb CO2 at high temperatures. The CO2 capture capacity of the KMgI30-300 sorbent, however, was less than that of KMgI30-500 due to the formation of Mg(OH)2 which did not absorb CO2. MgO based-sorbents promoted with K2CO3 after CO2 absorption formed new structures such as K2Mg(CO3)2 and K2Mg(CO3)2 x 4(H2O), unlike KACI30 which showed only the KHCO3 crystal structure. The new Mg-based sorbents promoted with K2CO3 showed excellent characteristics in that it could satisfy a large amount of CO2 absorption at low temperatures, a high CO2 absorption rate, and fast and complete regeneration.     

Fluidized bed combustion systems integrating CO2 capture with CaO

Capturing CO2 from large-scale power generation combustion systems such as fluidized bed combustors (FBCs) may become important in a CO2-constrained world. Using previous experience in capturing pollutants such as SO2 in these systems, we discuss a range of options that incorporate capture of CO2 with CaO in FBC systems. Natural limestones emerge from this study as suitable high-temperature sorbents for these systems because of their low price and availability. This is despite their limited performance as regenerable sorbents. We have found a range of process options that allow the sorbent utilization to maintain a given level of CO2 separation efficiency, appropriate operating conditions, and sufficiently high power generation efficiencies. A set of reference case examples has been chosen to discuss the critical scientific and technical issues of sorbent performance and reactor design for these novel CO2 capture concepts.     

Influence of high-temperature steam on the reactivity of CaO sorbent for CO₂ capture

Calcium looping is a high-temperature CO(2) capture technology applicable to the postcombustion capture of CO(2) from power station flue gas, or integrated with fuel conversion in precombustion CO(2) capture schemes. The capture technology uses solid CaO sorbent derived from natural limestone and takes advantage of the reversible reaction between CaO and CO(2) to form CaCO(3); that is, to achieve the separation of CO(2) from flue or fuel gas, and produce a pure stream of CO(2) suitable for geological storage. An important characteristic of the sorbent, affecting the cost-efficiency of this technology, is the decay in reactivity of the sorbent over multiple CO(2) capture-and-release cycles. This work reports on the influence of high-temperature steam, which will be present in flue (about 5-10%) and fuel (～20%) gases, on the reactivity of CaO sorbent derived from four natural limestones. A significant increase in the reactivity of these sorbents was found for 30 cycles in the presence of steam (from 1-20%). Steam influences the sorbent reactivity in two ways. Steam present during calcination promotes sintering that produces a sorbent morphology with most of the pore volume associated with larger pores of ～50 nm in diameter, and which appears to be relatively more stable than the pore structure that evolves when no steam is present. The presence of steam during carbonation reduces the diffusion resistance during carbonation. We observed a synergistic effect, i.e., the highest reactivity was observed when steam was present for both calcination and carbonation.     

Fabrication of CaO-based sorbents for CO₂ capture by a mixing method

Three types of sorbent were fabricated using various calcium and support precursors via a simple mixing method, in order to develop highly effective, durable, and cheap CaO-based sorbents suitable for CO(2) capture. The sorption performance and morphology of the sorbents were measured in a thermogravimetric analyzer and a scanning electron microscopy, respectively. The experimental results indicate that cement is a promising low-cost support precursor for contributing to the enhancement of cyclic CO(2) sorption capacity, especially when organometallic calcium precursors were used. A sorbent (with 75% CaO content) made from calcium l-lactate hydrate and cement showed the highest CO(2) sorption capacity of 0.36 g of CO(2)/g of sorbent and its capacity decreased only slightly after 70 cycles of carbonation and calcination.     

Capture of gas-phase arsenic oxide by lime: kinetic and mechanistic studies

Trace metal emission from coal combustion is a major concern for coal-burning utilities. Toxic compounds such as arsenic species are difficult to control because of their high volatility. Mineral sorbents such as lime and hydrated lime have been shown to be effective in capturing arsenic from the gas phase over a wide temperature range. In this study, the mechanism of interaction between arsenic oxide (As2O3) and lime (CaO) is studied over the range of 300-1000 degrees C. The interaction between these two components is found to depend on the temperature; tricalcium orthoarsenate (Ca3As2O8) is found to be the product of the reaction below 600 degrees C, whereas dicalcium pyroarsenate (Ca2As2O7) is found to be the reaction product in the range of 700-900 degrees C. Maximum capture of arsenic oxide is found to occur in the range of 500-600 degrees C. At 500 degrees C, a high reactivity calcium carbonate is found to capture arsenic oxide by a combination of physical and chemical adsorption. Intrinsic kinetics of the reaction between calcium oxide and arsenic oxide in the medium-temperature range of 300-500 degrees C is studied in a differential bed flow-through reactor. Using the shrinking core model, the order of reaction with respect to arsenic oxide concentration is found to be about 1, and the activation energy is calculated to be 5.1 kcal/mol. The effect of initial surface area of CaO sorbent is studied over a range of 2.7-45 m2/g using the grain model. The effect of other major acidic flue gas species (SO2 and HCl) on arsenic capture is found to be minimal under the conditions of the experiment.     

Steam reactivation of spent CaO-based sorbent for multiple CO2 capture cycles

This study examines steam reactivation of sorbent to improve the reversibility of multiple CaO-CO2 capture cycles. Experiments to obtain spent sorbent were performed in a tube furnace, and reactivation was achieved using steam in a pressurized reactor. Sorbent activity for CO2 capture was then tested in a thermogravimetric analyzer (TGA), in multi-cycle carbonation tests. After reactivation the sorbent had even better characteristics for CO2 capture than that of the natural sorbent. The average carbonation degree over 10 cycles for the reactivated sorbent approached 70%, significantly higher than for the original sorbent (35-40%). This means that the same sorbent may achieve effective CO2 capture over a large number of cycles, in the absence of other phenomena such as attrition. Partially sulfated sorbents may also be reactivated, but hydration itself is also hindered by sulfation.     

Lowering Phytic Phosphorus by Hydration of Soybeans

Response surface methodology (RSM) was used to study the effects of three independent variables at three levels of variation (ratio of liquid/solid, temperature and time of hydration) on the phytic and inorganic phosphorus concentration of hydrated soybeans; Temperature of hydration was the most important factor in lowering phytic phosphorus. Average reduced amount of phytic phosphorus was 26% and maximum reduction was 36.1% for cotvledons soaked at 50°C. Inorganic phosphorus, both in cotyledons and soak water, increased up to 225.8% at 50°C.     

Novel regenerable sorbent for mercury capture from flue gases of coal-fired power plant

A natural chabazite-based silver nanocomposite (AgMC) was synthesized to capture mercury from flue gases of coal-fired power plants. Silver nanoparticles were engineered on zeolite through ion-exchange of sodium ions with silver ions, followed by thermal annealing. Mercury sorption test using AgMC was performed at various temperatures by exposing it to either pulse injection of mercury or continuous mercury flow. A complete capture of mercury by AgMC was achieved up to a capture temperature of 250 degrees C. Nano silver particles were shown to be the main active component for mercury capture by amalgamation mechanism. Compared with activated carbon-based sorbents, the sorbent prepared in this study showed a much higher mercury capture capacity and upper temperature limit for mercury capture. More importantly, the mercury captured by the spent AgMC could be easily released for safe disposal and the sorbent regenerated by simple heating at 400 degrees C. Mercury capture tests performed in real flue gas environment showed a much higher level of mercury capture by AgMC than by other potential mercury sorbents tested. In our mercury capture tests, the AgMC exposed to real flue gases showed an increased mercury capture efficiency than the fresh AgMC.     

半干法制备阳离子淀粉的工艺优化

以玉米淀粉为原料,3-氯-2-羟丙基三甲基氯化铵(CTA)为醚化剂,在碱性条件下,采用半干法制备低取代度阳离子淀粉。采用Box-Behnken中心组合响应面设计,对半干法工艺进行优化,并分析反应温度、反应时间、碱的用量、体系含水量对阳离子淀粉取代度的影响。结果表明:回归方程能较好地预测取代度随工艺条件变化的规律,半干法制备低取代度阳离子淀粉工艺条件为:反应温度64.40℃,反应时间6.58 h,NaOH与醚化剂摩尔比2.12,体系含水量25.28%,在此条件下制得的阳离子淀粉取代度为0.051 9。     

Solid Phase Extraction of Pb(II) and Cd(II) in Food,Soil, and Water Samples Based on 1-(2-Pyridylazo)-2-Naphthol-Functionalized Organic–Inorganic Mesoporous Material with the aid of Experimental Design Methodology

An effective sorbent of 1-(2-Pyridylazo)-2-naphthol-functionalized mesoporous silica has been prepared to simultaneous separation and preconcentration of lead and cadmium ions in aqueous solution. Structural characterization of 1-(2-Pyridylazo)-2-naphthol-functionalized organic–inorganic hybrid mesoporous materials was conducted by Fourier transform infrared spectroscopy, transmission electron microscopy, N₂ adsorption–desorption measurement, X-ray diffraction, and elemental and thermal analysis, which confirmed the successful grafting of organic moiety on mesoporous silica. The affecting parameters on adsorption and desorption steps were optimized by Box-Behnken design through response surface methodology. Three variables (pH value, sorption time, and amount of the sorbent) were selected as the main factors affecting sorption step, while four variables (type of eluent, eluent volume, eluent concentration, and elution time) were selected for desorption step in the optimization study. The optimized values by this optimization method were 10 mg, 8 min, 6.3, HCl, 1.6 mL, 1.2 mol L^?l HCl, and 10 min, for amount of sorbent, sorption time, pH of solution, type, volume, and concentration of the eluent, and elution time, respectively. Under the optimized conditions, the detection limits of the proposed method for lead and cadmium ions were found to be 0.9 and 0.04 μg L^?1, respectively, while the relative standard deviation (RSD) for five replicate measurements was calculated to be <3 % for both ions. For proving that the proposed method is reliable, a wide range of food, soil, and water samples with different and complex matrixes was used.     

The effect of water-soluble sorbents on the exocrine function of the liver]

The effect of water-soluble sorbents on exocrine function of the liver was studied in chronic experiments on 2 dogs with a brought out bile duct. It is shown that choline and digitonin sorbents exhibit choleretic properties similar to those of cholestyramine. Choline sorbent causes a drop in the concentration of (2-4-fold) cholic acid in the bile unlike digitonin sorbent. No prolonging action was seen upon cholestyramine administration, while choline sorbent do demonstrate it. Cholesterol and bilirubin levels do not respond noticeably to the above sorbents.     

Effect of surfactants on the survival and sorption of viruses

There is an increasing concern about the protection of groundwater from contamination by enteric viruses and the prevention of outbreaks of waterborne diseases. Knowledge of survivability and transport of viruses from their point of origin is necessary to determine their potential effects on the neighboring groundwater systems. The distribution of virus is, in turn, dependent on the physical and chemical compositions of the surrounding soil and subsurface systems. For the present study, we have determined the effects of different surfactants (cationic, anionic, nonionic, and biological) and natural organic matter (NOM) on bacteriophages. Results indicated that surfactants and NOM adversely affect phage survival in binary systems, with surfactants being the most harmful. Studies with ternary systems also showed that the presence of surfactants reduced sorption of phages on sorbents either by occupying available sorption sites on the sorbent material or by displacing the sorbed phages from the sorbent surface. Water contact angles of the selected phages and different sorbent surfaces have been measured. Experimental data demonstrated that the sorption of hydrophobic viruses was favored by hydrophobic sorbents, while the sorption of hydrophilic viruses was favored by hydrophilic sorbents.     

Actinide sequestration using self-assembled monolayers on mesoporous supports

Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometalate anions, and radionuclides. Details addressing the design, synthesis, and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental cleanup necessary after 40 years of weapons-grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented.     

金属螯合亲和层析分离纯化谷胱甘肽(GSH)初探

从啤酒废酵母中分离纯化谷胱甘肽，通过对啤酒废酵母的预处理及细胞的破碎，得到富含谷胱甘肽的酵母抽提液，用自行制备的以壳聚糖为载体，Cu^2 为配基的螯合亲和吸附剂分离纯化谷胱甘肽。试验结果表明，上柱谷胱甘肽抽提液浓度为1．659mg／100mL，上柱pH为3．0时谷胱甘肽回收率可达61．39％。氢氧化钠洗脱浓度为0．25mol／L时，谷胱甘肽洗脱回收率达到65．59％。初步显示出较好的分离纯化效果。