磷石膏热分解制备二氧化硫和氧化钙研究

在氮气氛下研究了碳还原分解磷石膏制备二氧化硫和氧化钙的反应特性,用烟气分析仪分析析出的气体成分,用X射线衍射仪（XRD）分析热分解固体样品。考察了煤颗粒尺寸、原料配比和反应温度对磷石膏热分解的影响。得到磷石膏热分解制备二氧化硫和氧化钙的最佳条件：煤粒径小于150 μm,碳与硫酸钙物质的量比为0.8,反应温度为1 000 ℃。在此条件下,可以得到二氧化硫最大体积分数为12.5%的分解炉气,分解固体样品中氧化钙质量分数达到65.32%,可以用作水泥原料或二氧化碳吸收剂。     

Flue gas desulfurization by citrate process and optimization of working parameters

In this study, model flue gas was bubbled into 0.25 L tribasic sodium citrate (TSC) solution being in 0.5 L glass absorber to remove its SO₂ content. Size of gas bubbles, absorption temperature, gas flow rate, solution concentration and stirring rate were taken as working parameters to investigate their effect on SO₂ removal from flue gas. The Taguchi's experimental design method was used to obtain optimum values of working parameters for SO₂ saturation time of the TSC solution selected as a quality characteristic. The optimum levels of parameters to maximize the SO₂ saturation time of TSC solution were coarse bubbles for gas delivery, 35 °C for absorption temperature, 1.5 slm for gas flow rate, 0.5 M for TSC solution concentration and 500 rpm for stirring rate. Under these conditions, the SO₂ saturation time of the TSC solution was achieved as 511 min in average. The most effective parameters on the absorption of SO₂ in TSC solutions were ranked to the least as solution concentration, gas flow rate, size of gas bubbles, absorption temperature and stirring rate.     

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.     

The effect of water on the sulphation of limestone

A series of tests was conducted in a thermogravimetric analyzer (TGA) to study the sulphation behaviour of limestone in the presence of water over the temperature range of 800-850 °C. Four different Canadian limestones, all with a particle size range of 75-425 μm, were sulphated using a synthetic flue gas with a composition of 15% CO₂, 3% O₂, 0% or 10% H₂O, 1750 ppm SO₂ and the balance N₂. Water was shown to have a significant promotional effect on sulphation, especially in the diffusion-controlled stage. However, the effect of water during the kinetic-controlled stage appeared to be much less pronounced. Based on these results, it is proposed that the presence of water leads to the transient formation of Ca(OH)₂ as an intermediate, which in turn reacts with SO₂ at a faster rate than CaO does. Alternatively stated, it appears that H₂O acts as catalyst for the sulphation reaction of CaO.     

Experimental study on CO2 capture conditions of a fluidized bed limestone decomposition reactor

In this study, the decomposition conditions of limestone particles (0.25-0.50 mm) for CO₂ capture in a steam dilution atmosphere (20-100% steam in CO₂) were investigated by using a continuously operating fluidized bed reactor. The results show that the decomposition conversion of limestone increased with the steam dilution percentage in the CO₂ supply gas. At a bed temperature of 920 °C, the conversions were 72% without steam dilution and 98% with 60% steam dilution. The conversion was 99% with 100% steam dilution at 850 °C of the bed temperature. Steam dilution can decrease not only the decomposition temperature of limestone, but also the residence time required for nearly complete decomposition of CaCO₃. The hydration and carbonation reactivities of the CaO produced were also tested and the results show that both the reactivities increased with the steam dilution percentage for decomposing limestone.     

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.     

SO2 retention on CaO/activated carbon sorbents. Part II: Effect of the activated carbon support

The present paper analyses the role of the activated carbon (AC) properties on the SO₂ uptake capacity of CaO/AC sorbents prepared by AC impregnation or ionic exchange with calcium acetate water solutions. Gas adsorption and mercury porosimetry have been used for textural characterization of the AC and surface oxygen groups have been characterized by temperature programmed desorption (TPD). Thermogravimetry has been used for SO₂ retention tests and CO₂ chemisorption at 300 °C for CaO dispersion (d) determinations. The results show that the surface calcium on CaO/AC samples, determined as “Ca loading · CaO dispersion” (parameter Ca(%) · d), governs the SO₂ uptake. The surface oxygen content is the AC property that mainly controls both the calcium loading and surface calcium on CaO/AC samples, which could be explained by the fact that the surface oxygen lowers the hydrophobic character of the AC supports therefore favouring the interaction with the calcium acetate water solutions. The combination of high calcium loading and dispersion leads to SO₂ uptakes up to 123 mg SO₂/g. The textural properties of the supports have some influence in the calcium loading. However, the effect is masked by the blockage of AC porosity by the calcium loaded.     

Low cost coal-based carbons for combined SO2 and NO removal from exhaust gas

The aim of this paper is to show how a cheap carbonaceous material such as low rank coal-based carbon (or char) can be used in the combined SO₂/NO removal from exhaust gas at the linear gas velocity used in commercial systems (0.12 m s⁻¹). Char is produced from carbonization and optionally activated with steam. This char is used in a first step to abate the SO₂ concentration at the following conditions: 100 °C, space velocity of 3600 h⁻¹, 6% O₂, 10% H₂O, 1000 ppmv SO₂, 1000 ppmv NO and N₂ as remainder. In a second step, when the SO₂ concentration in the flue gas is low, NO is reduced to N₂ and steam at the following experimental conditions: 150 °C, space velocity of 900 h⁻¹, 6% O₂, 10% H₂O, 0-500 ppmv SO₂, 1000 ppmv NO, 1000 ppmv NH₃ and N₂ as remainder.It has been shown that the presence of NO has no effect on SO₂ abatement during the first step of combined SO₂/NO removal system and that low SO₂ inlet concentration has a negligible effect on NO reduction in the second step. Moreover, this char can be thermally regenerated after use for various cycles without loss of activity. On the other hand, this regenerated char shows the highest NO removal activity (compared to parent chars, either carbonized or steam activated) which can be attributed to the activating effect of the sulfuric acid formed during the first step of the combined SO₂/NO removal system.     

SO2 removal from flue gas by activated semi-cokes: 1. The preparation of catalysts and determination of operating conditions

The objective of this work was to use waste semi-coke as the raw material to prepare catalysts of industrial-scale size for SO₂ removal from flue gas and to find the optimal preparation methods. Results showed that lignite semi-coke was a suitable raw material, and that the catalyst, prepared by pre-activating in an autoclave, oxidizing with HNO₃, loading with CuSO₄ and finally calcining at 700 °C, exhibited the best desulfurizing property with a sulfur retention of about 9.6% SO₂/100 gC at a reaction temperature of 90 °C. Also, the effects of H₂O content in the flue gas, reaction temperature and space velocity on the desulfurizing property were investigated to determine optimum operating conditions. An H₂O content of 7% was appropriate for catalysts in this work. In the temperature range 80-120 °C, the catalyst showed good performance for SO₂ removal and was gradually deactivated at temperatures above 120 °C. Space velocity exhibited an optimal value of 830 h⁻¹. The kinetic behavior varied with space velocity and the desulfurizing property was controlled by diffusion at space velocities below 830 h⁻¹, and controlled by adsorption or catalytic reaction at space velocities above 830 h⁻¹.     

Experimental study of wet flue gas desulphurization with a novel type PCF device

Scrubbers are being widely used to remove the dust, sulphur dioxide and other harmful gases from coal-fired boilers. In this paper, a novel ‘wet-type’ desulphurization absorber, the PCF device (Chinese LOGO), was developed and studied through an experimental method. The mixture of air and SO₂ was used as simulated flue gas and CaCO₃-in-water suspension was used as absorbent. The results show that the PCF device has a good overall performance for FGD. Under moderate conditions employed, the content of SO₂ in outlet flue gas can achieve a level much lower than that permitted, while the pressure drop is very small due to co-flows in preliminarily treating chamber and no venturi structure in inlet tube. Guide plates and self-excitation chamber can improve the SO₂ removal efficiency by intensifying the mass-transfer and second purification. Some feasible process parameters are as follows: slurry pH value = 5.6-6.0, liquid-gas ratio = 8.7-10.4 L/m³, superficial gas velocity in inner cylinder = 3.5-4.5 m/s, and addition of Cl⁻ (in the form of CaCl₂) to the slurry (25 g/L) decreased the degree of SO₂ removal about 13.12%.     

Electrosynthesis of poly(aniline-co-p-aminophenol) having electrochemical properties in a wide pH range

Copolymerization of aniline and p-aminophenol in aqueous sulfuric acid solutions was electrochemically performed using cyclic voltammetry on platinum electrodes. The monomer concentration ratio can strongly affect the copolymerization rate and electrochemical property of the copolymer. The optimum conditions for the copolymerization are that the potential sweep covers the −0.20 to 0.95 V (vs. SCE) potential range, and that a solution contains 0.18 M aniline, 0.02 M p-aminophenol and 0.50 M H₂SO₄. A resulting copolymer synthesized under the optimum conditions has a good electrochemical activity in 0.50 M solutions of Na₂SO₄ with pH ≤ 10.0. IR and XPS spectra indicate that -OH groups and SO₄²⁻ ions are contained in the resulting copolymer. The SEM images reveal that the microstructure of the copolymer depends on the monomer concentration ratio during the electrolysis.     

Effect of fermentation conditions on yeast growth and volatile composition of wine produced from mango (Mangifera indica L.) fruit juice

In this study mango juice fermentation at laboratory scale with controlled inoculation using selected yeast strain was performed (Saccharomyces cerevisiae 101). Effect of fermentation conditions (temperature, pH, SO₂ and aeration) on wine fermentation was evaluated based on yeast growth, duration, fermentation rate and volatile composition. The composition of the major volatile compounds with low boiling points was determined by gas chromatography under the different operating conditions of fermentation temperature (15-35 °C), pH (3.5-6.0), SO₂ (100-300 ppm) and aeration (initial dissolved O₂ and shaking at 30 rpm). Temperature had important effect on yeast growth and on the levels of volatile compounds. It was observed that the final concentrations of ethyl acetate and some of the higher alcohols decreased when fermentation temperature increased to 25 °C (35 mg/l at 15 °C and 27 mg/l at 25 °C). SO₂ stimulated the yeast growth up to certain level and in excess it inhibited the yeast metabolism. Ethanol concentration slightly increased with the addition of 100 ppm SO₂ (8.2 g/l) and decreased with increase in concentration of SO₂ (6.2 g/l in 300 ppm SO₂). Aeration by shaking increased the viable cell count (from 52 × 10⁶ in the absence of oxygen to 98 × 10⁶ in shaking at 30 rpm) but decreased the ethanol productivity (from 7.2 in initial dissolved O₂ to 6.5 g/l shaking at 30 rpm). With the results obtained it was concluded that the temperature (25 °C), pH (5), SO₂ (100 ppm) and must with initial oxygen were optimum for better quality of wine from mango fruits. The results of the present study considering the traditionally recognized preference for low alcoholic fermentation temperatures in wine making.     

Acid base catalyzed transesterification kinetics of waste cooking oil

The present study reports the results of kinetics study of acid base catalyzed two step transesterification process of waste cooking oil, carried out at pre-determined optimum temperature of 65 °C and 50 °C for esterification and transesterification process respectively under the optimum condition of methanol to oil ratio of 3:7 (v/v), catalyst concentration 1%(w/w) for H₂SO₄ and NaOH and 400 rpm of stirring. The optimum temperature was determined based on the yield of ME at different temperature. Simply, the optimum concentration of H₂SO₄ and NaOH was determined with respect to ME Yield. The results indicated that both esterification and transesterification reaction are of first order rate reaction with reaction rate constant of 0.0031 min^− 1 and 0.0078 min^− 1 respectively showing that the former is a slower process than the later. The maximum yield of 21.50% of ME during esterification and 90.6% from transesterification of pretreated WCO has been obtained. This is the first study of its kind which deals with simplified kinetics of two step acid-base catalyzed transesterification process carried under the above optimum conditions and took about 6 h for complete conversion of TG to ME with least amount of activation energy. Also various parameters related to experiments are optimized with respect to ME yield.     

Advanced experimental analysis of the reaction of Ca(OH)2 with HCl and SO2 during the spray dry scrubbing process

This work evaluates both the removal efficiencies of HCl and SO₂ at different points in a spray dryer using Ca(OH)₂ as the absorbent. The operating conditions were specified in terms of the temperature of the flue gas (200-300 °C), the HCl concentration (120-1000 ppm), the SO₂ concentration (150-500 ppm) and the amount of CaCl₂ added (10-30 wt.%).The experimental results showed that the SO₂ removal efficiencies were higher in the presence of HCl (120-500 ppm) than in the absence of HCl at 250 °C and 20% relative humidity (RH). However, the removal efficiency of SO₂ decreased as the HCl concentration increased. The removal efficiency of SO₂ also increased with the amount of CaCl₂ in the spray dryer.     

Investigation of co-combustion of coal and olive cake in a bubbling fluidized bed with secondary air injection

In this study, a bubbling fluidized bed of 102 mm inside diameter and 900 mm height was used to burn olive cake and coal mixtures. Tunçbilek lignite coal was used together with olive cake for the co-combustion tests. Combustion performances and emission characteristics of olive cake and coal mixtures were investigated. Various co-combustion tests of coal with olive cake were conducted with mixing ratios of 25%, 50%, and 75% of olive cake by weight in the mixture. Operational parameters (excess air ratio, secondary air injection) were changed and variation of pollutant concentrations and combustion efficiency with these operational parameters were studied. The results were compared with that of the combustion of olive cake and coal. Flue gas concentrations of O₂, CO, SO₂, NO_x, and total hydrocarbons (C_mH_n) were measured during combustion tests.For the setup used in this study, the optimum operating conditions with respect to NO_x and SO₂ emissions were found to be 1.35 for excess air ratio, and 30 L/min for secondary air flowrate for the combustion of 75 wt% olive cake and 25 wt% coal mixture. The highest combustion efficiency of 99.8% was obtained with an excess air ratio of 1.7, secondary air flow rate of 40 L/min for the combustion of 25 wt% olive cake and 75 wt% coal mixture.     

高硫煤还原磷石膏制SO_2

在N2气氛下研究了高硫煤还原磷石膏的热分解反应特性,利用烟气分析仪分析析出的气体成分。研究了不同颗粒尺寸的高硫煤对磷石膏分解的影响,结果表明,高硫煤颗粒尺寸在97—147μm有利于磷石膏分解制SO2的反应。研究还发现原料摩尔比对磷石膏的反应历程有显著的影响,当摩尔比为1∶1.96时,磷石膏还原分解的固体产物有CaS和CaO;当摩尔比降为1∶1.18时,固体产物中CaO大量增加,而仅有少量CaS存在;当摩尔比降到1∶0.98时,固体产物中除了CaO和CaS外,还发现了未反应完的CaSO4。所以摩尔比在1∶1.18时有利于高硫煤还原磷石膏制SO2。     

Calcination and sintering characteristics of limestone under O2/CO2 combustion atmosphere

The O₂/CO₂ coal combustion technology is an innovative combustion technology that can control CO₂, SO₂ and NO_x emissions simultaneously. Calcination and sintering characteristics of limestone under O₂/CO₂ atmosphere were investigated in this paper. The pore size, the specific pore volume and the specific surface area of CaO calcined were measured by N₂ adsorption method. The grain size of CaO calcined was determined by XRD analysis. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere are less than that of CaO calcined in air at the same temperature. And the pore diameter of CaO calcined in O₂/CO₂ atmosphere is larger than that in air. The specific pore volume and the specific surface area of CaO calcined in O₂/CO₂ atmosphere increase initially with temperature, and then decline as temperature exceeds 1000 °C. The peaks of the specific pore volume and the specific surface area appear at 1000 °C. The specific surface area decreases with increase in the grain size of CaO calcined. The correlations of the grain size with the specific surface area and the specific pore volume can be expressed as L = 744.67 + 464.64 lg(1 / S) and L = − 608.5 + 1342.42 lg(1 / ε), respectively. Sintering has influence on the pore structure of CaO calcined by means of influencing the grain size of CaO.     

Full-scale measurements of SO2 gas phase concentrations and slurry compositions in a wet flue gas desulphurisation spray absorber

Two measurement campaigns were carried out at ENERGI E2's Asnæs Power plant, unit 5. The unit has a capacity of 620 MW_e and is equipped with a wet flue gas desulphurisation (FGD) plant employing a counter-current spray absorber with five spray levels. In the first campaign, the power plant was firing Orimulsion^® with 2.85 wt% S resulting in a flue gas concentration of SO₂ exceeding 2000 ppmv. In the second campaign, the fuel applied was a low-S blended coal and the SO₂ concentration in the raw gas was around 400 ppmv. A novel probe for in situ sampling of gas phase concentrations in wet FGD spray absorbers was developed and applied for measuring axial profiles of the SO₂ gas phase concentrations in the absorber. The expected decrease in SO₂ concentrations along the height of the absorber was found in the spray section (from height 26.5 to 36.2 m) whereas the SO₂ concentration above the holding tank and below the gas inlet was quite low probably due to long local residence times in the region. Horizontal variations, due to somewhat different flow conditions near the column wall were investigated and the SO₂ concentrations were found to be higher near the wall. Measurements at different gross loads showed that the SO₂ gas phase concentration at a given position inside the absorber was roughly linearly related to the L/G ratio in the measuring interval. Turning off one of the lower spray levels, while burning coal with low S content, did not lower the overall removal efficiency of the absorber. However, the SO₂ gas phase concentration inside the lower part of the absorber was increased by a factor of 2-3. Measurements of slurry pH at different positions showed a decrease of approximately 0.5 units from the upper to the lower part of the absorber. The full-scale measurements provide a detailed set of experimental data for validation of mathematical models of a wet FGD spray absorber.     

Carbonation of fly ash in oxy-fuel CFB combustion

Oxy-fuel combustion of fossil fuel is one of the most promising methods to produce a stream of concentrated CO₂ ready for sequestration. Oxy-fuel FBC (fluidized bed combustion) can use limestone as a sorbent for in situ capture of sulphur dioxide. Limestone will not calcine to CaO under typical oxy-fuel circulating FBC (CFBC) operating temperatures because of the high CO₂ partial pressures. However, for some fuels, such as anthracites and petroleum cokes, the typical combustion temperature is above 900 °C. At CO₂ concentrations of 80-85% (typical of oxy-fuel CFBC conditions with flue gas recycle) limestone still calcines, but when the ash cools to the calcination temperature, carbonation of fly ash deposited on cool surfaces may occur. This phenomenon has the potential to cause fouling of the heat transfer surfaces in the back end of the boiler, and to create serious operational difficulties. In this study, fly ash generated in a utility CFBC boiler was carbonated in a thermogravimetric analyzer (TGA) under conditions expected in an oxy-fuel CFBC. The temperature range investigated was from 250 to 800 °C with CO₂ concentration set at 80% and H₂O concentrations at 0%, 8% and 15%, and the rate and the extent of the carbonation reaction were determined. Both temperature and H₂O concentrations played important roles in determining the reaction rate and extent of carbonation. The results also showed that, in different temperature ranges, the carbonation of fly ash displayed different characteristics: in the range 400 °C < T ? 800 °C, the higher the temperature the higher the CaO-to-carbonate conversion ratio. The presence of H₂O in the gas phase always resulted in higher CaO conversion ratio than that obtainable without H₂O. For T ? 400 °C, no fly ash carbonation occurred without the presence of H₂O in the gas phase. However, on water vapour addition, carbonation was observed, even at 250 °C. For T ? 300 °C, small amounts of Ca(OH)₂ were found in the final product alongside CaCO₃. Here, the carbonation mechanism is discussed and the apparent activation energy for the overall reaction determined.     

Cobenefit of SO3 reduction on mercury capture with activated carbon in coal flue gas

Parametric experiments were carried out to study the interactions of mercury, SO₃, and injected activated carbon (AC) in a coal flue gas stream. The levels of SO₃ vapor in flue gas were altered by individually varying flue gas temperature, moisture, or sodium fume injection in the flue gas. Meanwhile, mercury emissions with AC injection (ACI) upstream of an electrostatic precipitator (ESP) were evaluated under varied SO₃ concentrations. SO₃ measurements using a condensation method indicated that low temperature, high moisture content, and sodium fume injection in flue gas shifted SO₃ partitioning from the vapor to particulate phase, subsequently improving mercury capture with ACI. 0.08 g/m³ of DARCO^® Hg-LH injection only provided approximately 20% mercury reduction across the ESP in a bituminous coal flue gas containing 28 ppm SO₃, but mercury capture was increased to 80% when the SO₃ vapor concentration was lowered less than 2 ppm. Experimental data clearly demonstrate that elevated SO₃ vapor is the key factor that impedes mercury adsorption on AC, mainly because SO₃ directly competes against mercury for the same binding sites and overwhelmingly consumes all binding sites.