Role of active sites in the steam activation of high unburned carbon fly ashes

Previous studies on carbon gasification have not included high unburned carbon content fly ashes, and therefore it remains unclear why not all fly ash carbon samples are equally suitable for activation. The concentration of active sites is well known to influence carbon gasification reactions. Therefore, the objective of this work was to investigate the effect of the concentration of active sites on the behavior of fly ash carbon samples upon steam activation. Six fly ash carbons were selected to produce activated carbons using steam at 850 °C. The concentration of active sites was determined by non-dispersive infrared analysis (NDIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). XRD analyses were also conducted to determine the crystallite size. It was observed that the concentration of active sites played a more significant effect on the surface areas of activated carbons in the carbon burn-off zone of >60%. Statistical analysis was used to relate the surface areas of activated carbon variances with carbon burn-off levels.     

Separation of unburned carbon from fly ash using a concurrent flotation column

In this study, a new concurrent flotation column that simulates the plug flow reactor was designed with the use of a static mixer, a froth separator column and an optional additional bubble generator for fly ash beneficiation. The objective was to improve the efficiency and effectiveness of unburned carbon removal from fly ash by minimizing energy costs. Cleaning tests were performed with and without the additional bubble genarator. Without the additional bubble generator unburned carbon in the ash product could be reduced to only 2.53%. Incidental loss of carbon particles and insufficient bubble generation were the main causes of poor carbon separation performance. By turning on the additional bubble generator it was aimed to assist bubble generation, to compensate bubble rupture and to recapture the detached or free carbon particles leaving the froth phase. With the additional bubble generator and under optimized conditions a froth product with 95% carbon recovery and a cleaned ash product with less than 1% unburned carbon was obtained. The separation process through the static mixer (feeder) and the separator column and the energy consumption of the unit were analyzed. It was seen that around 80% energy could be saved with the concurrent flotation column compared to conventional flotation.     

不同活化法制备的焦化除尘灰基活性炭的性能比较

采用焦化除尘灰为原料,分别用水蒸气和KOH为活化剂制备焦化除尘灰基活性炭,并对所制的活性炭进行碘吸附值、BET比表面积、孔径分布、孔容以及表面形貌测试。实验结果表明,采用KOH活化法制备的活性炭吸附性能强于采用水蒸气活化法制备的活性炭。氢氧化钾活化法制备的活性炭为中孔孔型,BET比表面积达275.51 m2/g。     

Effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample

The effect of porous structure and surface functionality on the mercury capacity of a fly ash carbon and its activated sample has been investigated. The samples were tested for mercury adsorption using a fixed‐bed with a simulated flue gas. The activated fly ash carbon sample has lower mercury capacity than its precursor fly ash carbon (0.23 vs. 1.85 mg/g), although its surface area is around 15 times larger, 863 vs. 53 m²/g. It was found that oxygen functionality and the presence of halogen species on the surface of fly ash carbons may promote mercury adsorption, while the surface area does not seem to have a significant effect on their mercury capacity.     

Size distribution of unburned carbon in coal fly ash and its implications

A set of nine coal fly ashes, obtained from various US utilities, were fractionated by standard dry-sieving techniques. The carbon contents of the different size fractions were measured, and the nature of the carbon particles was microscopically examined. Significant differences were found in the distribution of carbon in class F and class C ashes. The ‘foam index’ test is commonly used for quick evaluation of the suitability, with respect to air entrainment, of pozzolanic additives for concrete. This test measures adsorption of air entraining admixtures (AEAs) by the carbon in the fly ash. Application of this test to the different ash fractions confirmed that the smallest particle size fractions of ash make the major contribution to AEA adsorption. The carbon from class F ash has a comparable capacity for AEA adsorption as carbon from class C ash, when compared on a surface area basis. What makes the class C carbons apparently ‘worse’ is the fact that they have much higher surface areas than class F carbons (and it is only by virtue of the low carbon mass in most class C ashes that problems with these ashes are not more common). The importance of accessibility of the surface is also clearly seen from these results.     

Simultaneous Removal of Heavy Metals and PCDD/Fs from Hospital Waste Incinerator Fly Ash by Flotation Assisted with Hydrochloric Acid

Hospital solid waste (HSW) incinerator fly ash was designated as a special controlled waste because of its high concentrations of toxic heavy metals, polychlorinated dibenzo-p-dioxins, and dibenzofurans (PCDD/Fs). Most of the PCDD/Fs along with carbon constituents including powder activated carbon and unburned carbon in fly ash could be removed by column flotation on the basis of their hydrophobicity. The feasibility of extracting heavy metals from fly ash by adding a little of hydrochloric acid to the slurry during the flotation process was examined in this paper. The results showed that the acidic pulp could contribute to the high extraction ratio of the heavy metals, but the performance of decarburization and removal of PCDD/Fs was inhibited at very low pH value. Given consideration to the removal of two toxic matter including PCDD/Fs and heavy metals in HSW incinerator fly ash, the appropriate pulp pH value should be controlled at about 5. After flotation, both PCDD/Fs and heavy metals in the tailings could simultaneously meet the permitted limits of a landfill site of municipal solid waste in China. It was suggested that flotation with the assistance of an appropriate amount of acid might be a potential technology for the treatment of HSW incinerator fly ash.     

回收粉煤灰中未燃炭和降低碳含量的浮选研究

针对粉煤灰中未燃炭含量过高不利于大规模综合利用的问题,从理论上分析了浮选回收粉煤灰中未燃炭的基本原理,采用全浮选流程对粉煤灰中未燃炭进行了浮选回收试验,探讨了影响粉煤灰中未燃炭浮选效果的主要因素,确定了适宜的工艺条件。试验结果表明,采用全浮选流程可以使粉煤灰中可燃物降至4.1%左右。     

回收粉煤灰中未燃炭和降低碳含量的选研究

针对粉煤灰中未燃炭含量过高不利于大规模综合利用的问题,从理论上分析了浮选回收粉煤灰中未燃炭的基本原理,采用全浮选流程对粉煤灰中未燃炭进行了浮选回收试验,探讨了影响粉煤灰中未燃炭浮选效果的主要因素,确定了适宜的工艺条件.试验结果表明,采用全浮选流程可以使粉煤灰中可燃物降至4.1%左右.     

粉煤灰脱炭研究进展及展望

为了提高粉煤灰质量,实现粉煤灰的高效脱炭技术发展,促进粉煤灰资源可回收利用,介绍了粉煤灰脱炭的3种方法,即浮选法、重选法和电选法,其中,浮选法主要依据矿物的表面性质对粉煤灰进行脱炭;重选法依据矿物密度性质的差异对粉煤灰进行脱炭分离;电选法则依据矿物摩擦带电性质的不同进行分选。同时,对粉煤灰脱炭方法的发展趋势进行了展望,建议未来应深入研究粉煤灰性质,将脱炭方法与新型选矿设备相结合进行工业化生产,创新结合方式,如采取活性油泡与旋流静态微泡浮选柱结合的方式对粉煤灰进行脱炭处理。     

KOH预处理除尘灰制备颗粒活性炭的实验研究

用除尘灰分离炭粉为原料，采用KOH预处理，水蒸汽活化的方法制备颗粒活性炭。实验证明，KOH预处理制备的活性炭有较高的比表面积，并且KOH预处理对活性炭的微晶结构和表面形貌产生影响。当KOH含量为10％时，所制备的活性炭比表面积和收率较高，灰分较低。同时本文对KOH影响机理进行了探讨，在炭化阶段KOH有利于促进生成难石墨化的炭素前驱体；在活化阶段，KOH对碳的气化有催化作用。     

Utilization of bagasse fly ash for carbon–zeolite composite preparation

Bagasse fly ash (BFA), a solid waste from sugar cane industries, contains significant amount of carbon as well as silica. The coarse particles with high carbon content can be separated and further activated to produce BFA-based activated carbon, while silica content can be extracted from fine BFA particles to be used for zeolite crystallization. The zeolite crystal may be grown on a suitable solid surface to create a zeolitic composite. In this study, silicate extract from fine BFA particles were combined with pretreated carbon rich coarse BFA particles in a hydrothermal crystallization process to produce particular carbon–zeolite composites. The carbon rich particles could be subjected to any necessary activation or surface treatment before being used in the composite preparation. Meanwhile, a simple method based on thermogravimetry is proposed to evaluate the zeolite particles distribution on the carbon surface. Furthermore, the composite ability for treating mixed organic and inorganic pollutants in aqueous solution has been investigated.     

Catalytic reduction of NOx by biomass-derived activated carbon supported metals

In this study, to prepare a series of activated carbon-supported metals for the catalytic reduction of NO_x to N₂ in excess O₂, activated carbons derived from lignocellulosic and herbaceous biomasses were selected as the reducing agents, and alkali and transition metals were used as the catalytic active phases. The effects of the type of biomass, carbonization temperature and catalyst composition on NO_x reduction efficiency were analyzed in a fixed-bed flow reactor. The results showed that two temperature regimes are present for the NO_x-carbon reaction:at temperatures below 250℃, the NO_x adsorption process on the carbon surface was predominant, whereas true NO_x reduction by carbon occurred at temperatures above 250℃, producing N₂, CO₂ and CO. The influence of the carbonization temperature on carbon reactivity depended on the effect of the carbonization temperature on the carbon surface area and the reduction of the metal species on carbon. All studied metals catalyzed both NO_x and O₂ reduction by carbon, and potassium could strongly enhance the C-NO_x reaction without substantial carbon consumption by O₂. Moreover, the potassium supported by sawdust-derived activated carbon exhibited higher selectivity and capacity towards NO_x reduction than did its previously reported coal-derived counterparts. These properties were ascribed to the high dispersion of the active potassium species on the carbon surface, as observed through the comparison of X-ray photoelectron spectroscopy and powder X-ray diffraction results for the carbons made from biomass and coal-based precursors.     

Detoxification of medical waste incinerator fly ash through successive flotation

Medical waste incinerator (MWI) fly ash is considered hazardous waste because it contains hypertoxic polychlorinated dibenzo-p-dioxins and dibenzofurans as well as heavy metals. To detoxify both substances, successive flotations of MWI fly ash were performed. The first step involved decarburization flotation, whereby 91.0% of the dioxins in MWI fly ash were transformed into a froth product. In the second step (ion flotation), the influence of ionic strength on heavy metals recovered from both raw and stimulated filtrates was explored. The results revealed that the optimal conditions were sodium dodecyl sulfate at 480 ppm, methyl isobutyl carbonyl at 150 ppm, impeller speed at 2000 rpm, and flotation time of 18 min for raw leachate, through which Zn (47.0%), Pb (56.5%), Cu (57.5%), and Cd (49.1%) were recovered. For the simulated filtrate, higher removal efficiencies were noted: 60.5%, 80.6%, 69.1%, and 64.1% for Zn, Pb, Cu, and Cd, respectively. The harmful effects of the coexisting ions in the raw filtrate on heavy metal recovery were observed.     

炭吸附剂吸附水中残余浮选捕收剂煤油研究

以粉煤灰中的未燃炭粒(UC)和粉状活性炭(PAC)为吸附剂,研究对水体中残余煤油吸附性能。结果表明,UC和PAC的吸附过程符合Freundlich等温式和准2级反应动力方程,在吸附初期主要由边界层扩散为主,后期主要以微孔内扩散为主,并最终达到平衡状态。在搅拌转速190 r/min、吸附剂的质量浓度0.5 g/L时适宜吸附,且升温有利于吸附。对于初始煤油的质量浓度250 mg/L的水体,PAC在任何pH下,去除率都在70%以上;UC在pH=2时,吸附能力为佳,去除率为74.24%。AC能直接用于浮选废水处理,而UC需要进一步活化处理,提高吸附能力和适应性。     

Modifications to the surface chemistry of low-rank coal-based carbon catalysts to improve flue gas nitric oxide removal

The effectiveness of carbons as low-temperature selective catalytic reduction (SCR) catalysts will depend upon their physical and chemical properties. Surface functional groups containing oxygen are closely related to the catalytic activity of carbons. These groups are expected to change the interaction between the carbon surface and the reactants through a variation in adsorption and reaction characteristics. This paper presents a more detailed study of the effects of either gas-phase sulfuric acid or oxygen oxidation treatments on the catalytic NO reduction by low-rank coal-based carbon catalysts. Raw and treated carbons were characterized by N₂ and CO₂ surface areas, TPD and ash content. NO removal capacity of carbons was determined by passing a flow containing NO, H₂O, O₂, NH₃ and N₂ through a fixed bed of carbon at 150°C and 4 s of residence time, the effluent concentration being monitored continuously during the reaction. The effects of varying the type and conditions of the treatment on the physicochemical features of carbons were studied. The gas-phase sulfuric acid treatment (corresponding to a first step SO₂ removal) markedly enhanced carbon activities for NO removal. On the contrary, oxygen oxidation enhanced NO removal capacity of chars to a lower extent. Therefore, the carbons studied could be used in a combined SO₂/NO removal process, because the use and regeneration of the carbon in the first step is beneficial for the performance in the second one.     

污泥粉煤灰混合制备活性炭及其性能研究

为提高以污泥制备的活性炭的吸附性能,采用化学活化方法将污泥、粉煤灰混合制备活性炭并研究其吸附性能。研究表明,在污泥、粉煤灰和ZnCl2质量比为10∶3∶4、活化温度为500℃、活化时间为80 min条件下,制备的活性炭吸附性能最佳,其比表面积为459.56 m2/g,总孔面积为0.32 mL/g,碘值为376.17 mg/g。以污泥和粉煤灰制备活性炭技术在废水治理领域具有良好的工业应用前景。     

利用除尘灰制备颗粒活性炭的实验研究

以除尘灰分离炭粉为原料,煤焦油为粘结剂,通过物理活化法制备颗粒活性炭;用正交试验方法得到除尘灰制备颗粒活性炭的最佳工艺条件和工艺参数,确定了4种影响因素的作用程度大小顺序:活化温度>活化时间>炭化温度>水蒸气流量。按最佳工艺条件制备出的活性炭的碘吸附值达977.9mg/g,比表面积达911.1m2/g。     

The influence of carbon particle type in fly ashes on mercury adsorption

Recent research has shown that certain fly ash materials produced in coal combustion for power generation have an affinity for the mercury compounds present in flue gases. However, the exact nature of Hg-fly ash interactions is still unknown and the different variables that influence mercury adsorption need to be identified. In this work the microscopic components of fly ashes derived from the combustion of different types of feed blends of different coal rank and mercury adsorption were investigated. The aim of this research was to establish relationships between Hg retention and the type of unburned carbons present in various fly ashes. The fly ashes and fly ash fractions studied were used as sorbent beds for high mercury concentrations, conditions in which mercury retention is highly favored. From the results obtained it was confirmed that the role of the unburned carbon components in mercury capture may depend, among other factors, on the type of unburned carbon. Fly ashes capture different species of mercury depending on their nature and the type of anisotropic particles.     

Ozonation of 1,3,6-naphthalenetrisulphonic acid catalysed by activated carbon in aqueous phase

This paper presents experimental results of the ozonation of a model aromatic sulphonic compound, 1,3,6-naphthalenetrisulphonic acid (NTS), in the presence of different activated carbons with different physical and chemical surface properties. Carbons used were commercial activated carbons (Ceca AC40, Norit, Merck, Witco, Ceca GAC, Filtrasorb 400, Sorbo) with or without demineralisation pre-treatment. Carbon samples were texturally and chemically characterised using N₂ adsorption isotherms, mercury porosimetry, pH_PZC, selective neutralisation and elemental analysis. Results show that NTS was degraded by ozone at a faster rate in the presence of activated carbon, especially in the case of Sorbo, Ceca GAC and Norit carbons, which display catalytic activity, probably by enhancing ozone decomposition in aqueous phase in highly oxidative species. These catalytic properties seem to be favoured by both the basicity of the carbon surface and the higher macropore volume. Dissolved total organic carbon from the NTS degradation compounds was removed in the presence of activated carbon through both the catalytic activity of activated carbon to mineralise organic matter and the adsorption of these organic compounds on activated carbon.     

Effect of flotation on the dioxin distribution in size-fractioned fly ash of hospital solid waste incineration

After the flotation of hospital solid waste incinerator (HSWI) fly ash, two types of solid products, froths and tailings, are produced. This paper reports the effect of flotation on the dioxins distribution patterns in different particle size fractions (?25, ?38, +25, ?75, +38, ?106, +75 and +106 µm) of fly ash. The results showed that the froths had a higher small-size particle distribution than that of the raw fly ash. The dioxin content with particle size in the flotation products depended on the partition behavior of powder-activated carbon (PAC). The dioxin content in the fine particles of the froths was higher than that in the coarse particles, and the highest content was in the finest particles (?25 µm). The dominant dibenzo-p-dioxins and dibenzofurans (PCDD/F) congeners in the froths and tailings were similar to those in the raw fly ash. A positive correlation between carbon removal and PCDD/F removal with different size fractions was observed. The carbon removal efficiencies of the fractions of ?25 and ?38, +25 µm were evidently higher than those of the other particle size fractions. Similarly, the PCDD/F removal efficiencies in fractions of ?25 and ?38, +25 µm could reach 156.9% and 115.0%, respectively.