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Differential behaviour of combustion and gasification fly ash from Puertollano Power Plants (Spain) for the synthesis of zeolites and silica extraction

Coal gasification (IGCC) and pulverised coal combustion (PCC) fly ashes (FAs), obtained from two power plants fed with the carboniferous bituminous coal from Puertollano (Spain), were characterised and used as raw materials for zeolite synthesis by direct conversion (DC) and by alkaline fusion (Fu), and SiO2 extraction (Si-Ex) at laboratory scale. The Puertollano FAs are characterised by a high SiO2 content (59%) with respect to EU coal FAs. High zeolite synthesis yields were obtained from both FAs by using conventional alkaline activation. However, the Si extraction yields were very different. The results of the zeolite synthesis from the Si-bearing extracts from both FAs demonstrated that high purity zeolites with high cation exchange capacity (CEC, between 4.3 and 5.3meq/g) can be produced. The solid residue arising from Si-Ex is also a relatively high NaP1 zeolite product (CEC 2.4-2.7 meq/g) equivalent to the DC products. The zeolitic materials synthesised from both FAs by Fu showed an intermediate (between the high purity zeolites and the DC products) zeolite content with CEC values from 3.4 to 3.7 meq/g. Low leachable metal contents were obtained from high purity A and X zeolites and zeolite material synthesised by Fu for PCC FA.

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg2+ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive.

Germanium recovery from gasification fly ash: evaluation of end-products obtained by precipitation methods.

In this study the purity of the germanium end-products obtained by two different precipitation methods carried out on germanium-bearing solutions was evaluated as a last step of a hydrometallurgy process for the recovery of this valuable element from the Puertollano Integrated Gasification Combined Cycle (IGCC) fly ash. Since H(2)S is produced as a by-product in the gas cleaning system of the Puertollano IGCC plant, precipitation of germanium as GeS(2) was tested by sulfiding the Ge-bearing solutions. The technological and hazardous issues that surround H(2)S handling conducted to investigate a novel precipitation procedure: precipitation as an organic complex by adding 1,2-dihydroxy benzene pyrocatechol (CAT) and cetyltrimethylammonium bromide (CTAB) to the Ge-bearing solutions. Relatively high purity Ge end-products (90 and 93% hexagonal-GeO(2) purity, respectively) were obtained by precipitating Ge from enriched solutions, as GeS(2) sulfiding the solutions with H(2)S, or as organic complex with CAT/CTAB mixtures and subsequent roasting of the precipitates. Both methods showed high efficiency (>99%) to precipitate selectively Ge using a single precipitation stage from germanium-bearing solutions.

Synthesis of merlinoite from Chinese coal fly ashes and its potential utilization as slow release K-fertilizer

This study focuses on the synthesis of merlinoite from Chinese coal fly ashes by KOH direct conversion method, with special emphasis on the application of synthetic merlinoite as fertilizer. These fly ashes were collected from two pulverized-coal combustion (PCC) power plants in Xinjiang, Northwest China. The synthesis results are influenced by fly ash characteristics and different synthesis conditions (KOH solution concentrations, activation temperature, time, and KOH/fly ash ratios). A high quality merlinoite-rich product was synthesized under optimal activation conditions (KOH concentration of 5M, activation temperature of 150°C, activation time of 8h and KOH/fly ash ratio of 2l/kg), with a cation exchange capacity (CEC) of 160cmolkg(-1). The synthetic merlinoite is proved to be an efficient slow release K-fertilizer for plant growth, indicating that it can be widely used for high-nutrient demanding crops growing in nutrient-limited soils and for large-area poor soil amendment in opencast coal mine areas around the power plants that will substantially grow with the increasing coal combustion in Xinjiang in the near future.

Distribution of trace elements in particle size fractions for contaminated soils by a copper smelting from different zones of the Puchuncaví Valley (Chile).

Metal contents in soil samples are commonly used to evaluate contamination levels. However, the distribution of metals is dependent on particle size. We investigated the distribution of metals in various particle size fractions of the soil from four sites of the Puchuncaví Valley (Central Chile). The soil samples were segregated into size fractions ranging from 0.3 to 20μm and analyzed using inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The results of the statistical analysis of the total metal concentrations indicated that the soil samples from Greda and Maitenes, the sites nearest the industrial sources, are the most contaminated. For these sites, the size-fractionated samples containing higher concentrations of Cu, Zn, As, and Pb were found in the finer fractions, suggesting anthropogenic depositions from smelter facilities. In addition, a high Ca concentration was observed in the finer fractions, which could be attributed to the technological approaches used to reduce the SO2 emissions from the roasting process of copper sulfide. The mineral composition of fine particles permitted the identification of Tenorite and Calcium oxide, which are most likely associated with smelting activities, confirming emission of enriched particulate matter from the copper smelter.

Element behaviour during combustion in coal-fired Orhaneli power plant, Bursa-Turkey

This study focuses on element behaviour during combustion in the Orhaneli thermal power plant (a 210 MW unit, Bursa-Turkey). A total of 51 samples, feed coals (FCs), fly ashes (FAs) and bottom ashes (BAs), which were systematically collected over an eight-week period, have been analysed for major, minor and trace elements (Al, Ca, Fe, K, Mg, Na, S, As, B, Ba, Be, Bi, Cd, Co, Cr, Cs, Cu, Ga, Ge, Hf, Hg, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Se, Sn, Sr, Ta, Th, Ti, Tl, U, V, W, Y, Zn, Zr and REEs). This study shows that FCs on an airdried basis have high moisture (av. 9%), high volatile matter (av. 33%), very high ash yield (av. 53%), relatively high sulfur content (av. 2.14%) and low gross calorific value (av. 1775 kcal/kg). Proximate analyses of combustion residues imply that BAs have higher contents of unburned carbonaceous matter than FAs. Mean values of trace element concentrations in FCs fall within the ranges of most world coals, except for Cr, Cs, Ni and U which occur in concentrations slightly higher than those determined for most of world coals. Some elements such as S, Hg, As, B, Bi, Cd, Cs, Ge, K, Pb, Rb, Sb, Se, Sn, Tl, and Zn are indicating enrichments in FAs. The remaining elements investigated in this study have no clear segregation between FAs and BAs. The mass balance calculations point to Ca content of feed coal controlling the partitioning of elements in this power plant, producing a high removal efficiency for highly volatile elements such as Hg, B and Se, and a high retention of As, Bi, Cd, Cs, Ge, Pb, Rb, Sb, Sn, Tl and Zn in FAs. However, the high enrichment in trace elements of FAs can increase the hazardous potential of this coal by-product.

Speciation, behaviour, and fate of mercury under oxy-fuel combustion conditions.

The work presented here reports the first study in which the speciation, behaviour and fate of mercury (Hg) have been evaluated under oxy-fuel combustion at the largest oxy-Pulverised Coal Combustion (oxy-PCC) demonstration plant to date during routine operating conditions and partial exhaust flue gas re-circulation to the boiler. The effect of the CO2-rich flue gas re-circulation on Hg has also been evaluated. Results reveal that oxy-PCC operational conditions play a significant role on Hg partitioning and fate because of the continuous CO2-rich flue gas re-circulations to the boiler. Mercury escapes from the cyclone in a gaseous form as Hg(2+) (68%) and it is the prevalent form in the CO2-rich exhaust flue gas (99%) with lower proportions of Hg(0) (1.3%). The overall retention rate for gaseous Hg is around 12%; Hg(0) is more prone to be retained (95%) while Hg(2+) shows a negative efficiency capture for the whole installation. The negative Hg(2+) capture efficiencies are due to the continuous CO2-rich exhaust flue gas recirculation to the boiler with enhanced Hg contents. Calculations revealed that 44mg of Hg were re-circulated to the boiler as a result of 2183 re-circulations of CO2-rich flue gas. Especial attention must be paid to the role of the CO2-rich exhaust flue gas re-circulation to the boiler on the Hg enrichment in Fly Ashes (FAs).

Unusual speciation and retention of Hg at a coal-fired power plant.

An unusual and different speciation of Hg in the outgoing gaseous stream of the flue gas desulfurization (OUT-FGD) system was revealed at two Spanish power plants (PP1 and PP2) equipped with a forced oxidation wet FGD system with water recirculation to the scrubber. At PP1 and PP2, a high proportion of Hg escapes from the electrostatic precipitator in gaseous form, Hg(2+) (75-86%) being the species that enters the FGD. At PP1 Hg(0) (71%) was the prevalent Hg OUT-FGD species, whereas at PP2 Hg(2+) was the prevalent Hg OUT-FGD species in 2007 (66%) and 2008 (87%). The unusual speciation of gaseous Hg OUT-FGD and the different Hg retentions between 2007 and 2008 at PP2 were attributable to the evaporation of HgCl(2) particles from the aqueous phase of gypsum slurry in the OUT-FGD gas and the Al additive used at PP2, respectively. The Al additive induced the retention of Hg as HgS in the 2007 FGD gypsum, thus reducing gaseous emissions of Hg in the OUT-FGD gas.

Potential of Hazardous Waste Encapsulation in Concrete Compound Combination with Coal Ash and Quarry Fine Additives.

Coal power plants are producing huge amounts of coal ash that may be applied to a variety of secondary uses. Class F fly ash may act as an excellent scrubber and fixation reagent for highly acidic wastes, which might also contain several toxic trace elements. This paper evaluates the potential of using Class F fly ashes (<20% CaO), in combination with excessive fines from the limestone quarry industry as a fixation reagent. The analysis included leaching experiments (EN12457-2) and several analytical techniques (ICP, SEM, XRD, etc.), which were used in order to investigate the fixation procedure. The fine sludge is used as a partial substitute in concrete that can be used in civil engineering projects, as it an environmentally safe product.

Study of boron behaviour in two spanish coal combustion power plants

A full-scale field study was carried out at two Spanish coal-fired power plants equipped with electrostatic precipitator (ESP) and wet flue gas desulfurisation (FGD) systems to investigate the distribution of boron in coals, solid by-products, wastewater streams and flue gases. The results were obtained from the simultaneous sampling of solid, liquid and gaseous streams and their subsequent analysis in two different laboratories for purposes of comparison. Although the final aim of this study was to evaluate the partitioning of boron in a (co-)combustion power plant, special attention was paid to the analytical procedure for boron determination. A sample preparation procedure was optimised for coal and combustion by-products to overcome some specific shortcomings of the currently used acid digestion methods. In addition boron mass balances and removal efficiencies in ESP and FGD devices were calculated. Mass balance closures between 83 and 149% were obtained. During coal combustion, 95% of the incoming boron was collected in the fly ashes. The use of petroleum coke as co-combustible produced a decrease in the removal efficiency of the ESP (87%). Nevertheless, more than 90% of the remaining gaseous boron was eliminated via the FGD in the wastewater discharged from the scrubber, thereby causing environmental problems.