Synthesis of zeolite from Italian coal fly ash: Differences in crystallization temperature using seawater instead of distilled water

In this study Italian coal fly ash was converted into several types of zeolite in laboratory experiments with temperatures of crystallization ranging from 35 up to 90 °C. Distilled and seawater were used during the hydrothermal synthesis process in separate experiments, after a pre-treatment fusion with NaOH.The results indicate that zeolites could be formed from different kind of Italian coal fly ash at low temperature of crystallization using both distilled and seawater. SEM data and the powder patterns of X-ray diffraction analysis show that faujasite, zeolite ZK-5 and sodalite were synthesized when using both distilled and seawater; zeolite A crystallized only using distilled water. In particular the experiments indicate that the synthesis of zeolite X and zeolite ZK-5 takes place at lower temperatures when using seawater (35 and 45 °C, respectively). The formation of sodalite is always competitive with zeolite X which shows a metastable behaviour at higher temperatures (70–90 °C).The chemical composition of the fly ash source could be responsible of the differences on the starting time of synthesized zeolite with distilled water, in any case our data show that the formation of specific zeolites takes place always at lower temperatures when using seawater.     

Preparation of zeolitic material with simultaneous removal of NH4 + and PO4 3− from paper sludge ash via acid leaching

This study investigates the preparation of zeolitic material with removal of both NH₄ ⁺ and PO₄ ^3? from paper sludge ash (PSA) via acid leaching. PSA typically has a low Si and high Ca content, owing to the presence of calcite fillers. Acid leaching with 3 M HCl was used firstly to reduce the Ca content of the PSA, whereafter a zeolite-P (Na-P) product with high cation exchange capacity (CEC) was synthesized through reaction with 2.5 M NaOH solution at 80 °C. Ca-P zeolitic products were prepared by Ca-treatment with the leachant that had been in contact with the PSA. The product with high CEC capacity including Na-P could be synthesized from the acid-leached ash, and the high Ca content in the ash could be reduced by extraction of the Ca into the leachant via the acid leaching. The Ca-P zeolitic product could be prepared by Ca-treatment with the solution obtained from neutralization of the leachant with NaOH. This product was capable of removing NH₄ ⁺ and PO₄ ^3? from aqueous solution, simultaneously.     

Fabrication of bulk materials with zeolite from coal fly ash

After packing a compact of coal fly ash mixed with 3.5?M (mol/L) sodium hydroxide solution into a cylindrical plastic mold at 80?°C and 50?% relative humidity for 24?h, the plastic mold was released and the compact was immersed in 3.5?M sodium hydroxide solution at 80?°C for 48?h. When the resultant compact was removed from the solution and cured at 80?°C and 50?% relative humidity for 7?days, a bulk material with zeolite was formed. The strength of the resultant bulk material was a result of the formation of geopolymer (alkali-activated cement). The specific surface area and the compressive strength of the bulk body sample were 21.4?m²/g and 29.0?MPa, respectively. According to a quantitative analysis conducted using the X-ray diffraction (XRD) technique, the content of the formed Na-P type zeolite was estimated to be approximately 28.2?% in mass ratio. The pore size of the resultant bulk materials with zeolite ranges from sub-nanometer to several tens of nanometers, so the resultant bulk material with zeolite exhibited excellent water vapor retention characteristics.     

粉煤灰及其制备沸石对高浓度氨氮的去除比较

以粉煤灰为原料,采用改进的水热合成法制备了粉煤灰沸石,并将粉煤灰和粉煤灰沸石用于高浓度氨氮的吸附去除。实验结果表明:在粉煤灰和粉煤灰沸石的投加量分别为0.10 g/m L和0.04 g/m L、反应体系p H为5~7、初始氨氮质量浓度为500 mg/L的条件下,分别吸附660 min和60 min,粉煤灰和粉煤灰沸石对氨氮的去除率分别约为20.1%和50.7%左右,粉煤灰沸石对高浓度氨氮的去除效果明显优于粉煤灰;粉煤灰和粉煤灰沸石对氨氮的吸附动力学行为符合准二级动力学方程;Langmuir和Freundlich等温吸附模型能较好地描述粉煤灰对氨氮的等温吸附过程,而粉煤灰沸石对氨氮的等温吸附过程则更适宜用线性模型和Freundlich模型描述。     

粉煤灰两步水热法制备人工沸石

以粉煤灰为原料,采用两步水热法制备人工沸石。SEM、XRD、X射线荧光光谱分析结果表明:制得的人工沸石纯度较高,主要为Na-A型沸石和少量13X型沸石,主要化学成分为SiO2和Al2O3。说明采用两步法制备人工沸石克服了传统水热法杂质含量高的缺陷。采用人工沸石处理初始Mn2+质量浓度为50.00mg/L的模拟含锰废水,吸附125min后,Mn2+去除率达98.19%,模拟废水中剩余Mn2+质量浓度为0.90mg/L。     

The development of low cost adsorbents from clay and waste materials: a review

Increased energy consumption due to industrial growth has increased the levels of carbon dioxide (CO₂) emission being released into the atmosphere. CO₂ emission is a type of greenhouse gas which is a major cause of global warming. Since the issue of CO₂ emissions has drawn much attention in recent years, the development of CO₂ capture technology has become a necessity. Although CO₂ adsorbents are still at the early development stage, it has been suggested that CO₂ adsorbents are the most effective technology in controlling CO₂ emissions. Solid adsorbents have great potential as an alternative method to conventional adsorbents in adsorbing CO₂. In this paper, low cost adsorbents including activated carbon, zeolites, mesoporous silica and clays are discussed in terms of adsorbent preparation methods and CO₂ adsorption capacity. The low cost adsorbents are mainly derived from waste materials such as fly ash, steel slag, red mud, bagasses wastes and wood wastes. Besides that, natural resources such as clays have also been applied as low cost CO₂ adsorbents. Surface modifications have also been applied to the low cost adsorbents, including metal ion exchange and amine impregnation to enhance CO₂ adsorption capacity. In the last section, the current status of CO₂ adsorbents is summarized and future trends are discussed briefly to predict the potential materials which can be applied as CO₂ adsorbents.     

复合改性粉煤灰对磷的吸附性能

将粉煤灰（FA）与Na₂CO₃混合焙烧后浸渍负载Fe²⁺,制备了复合改性粉煤灰（CMFA）。通过多种手段对CMFA进行了表征,并将其用于含磷废水的吸附处理。表征结果显示：改性后的粉煤灰表面疏松多孔,比表面积增大了21倍,产生了金属盐类熔出物及羟基氧化铁和羟基官能团。实验结果表明：当初始磷质量浓度为50 mg/L、吸附温度为20 ℃、溶液pH为4.3、CMFA投加量为5 g/L、吸附时间为30 min时,磷去除率可达98.01%,较FA的50.10%大幅提升;20 ℃时,CMFA对磷的饱和吸附量可达22.15 mg/g;用拟二级动力学模型可较准确地描述CMFA对磷的吸附过程,该过程为自发的吸热过程,符合Langmuir等温吸附模型,为以离子交换为主的化学吸附。     

Preparation and characterization of sorbents prepared from ash (waste material) for sulfur dioxide (SO2) removal

Sorbents synthesized from various types of ash (coal fly ash, coal bottom ash, oil palm ash, and incinerator ash) for flue gas desulfurization were investigated. The sorbents were prepared by mixing the ashes with calcium oxide and calcium sulfate using the water hydration method. The effects of various sorbent preparation variables, such as the hydration period, the ratio of calcium oxide to ash, and the amount of calcium sulfate, on the Brunauer-Emmett-Teller (BET)-specific surface area of the resulting sorbent were studied using a two-level full factorial design. The surface area of the sorbents obtained range from 15.4 to 122.1m²/g. Regression models were developed to correlate the significant variables to the surface area of the sorbents. An analysis of variance (ANOVA) showed that the model was significant at a confidence level of 95%. It was found that apart from all the individual variables studied, interactions between variables also exerted a significant influence on the surface area of the sorbent. From the activity test results, it was found that sorbents prepared from coal fly ash and oil palm ash have the highest SO₂ absorption capacity. Scanning electron microscope (SEM) analysis showed that the sorbent was composed of a compound with a high structural porosity, while an X-ray diffraction spectrum showed that calcium aluminum silicate hydrate compounds are the main products of the hydration reaction.     

钛硅分子筛催化双氧水氧化水中间甲酚

探索催化双氧水氧化去除间甲酚对开发炼油厂碱渣废水处理新技术意义重大。采用钛硅分子筛催化双氧水氧化水中间甲酚,考察了反应时间、反应温度、双氧水加入量、催化剂加入量和初始溶液pH对间甲酚去除率的影响。实验结果表明：钛硅分子筛对双氧水氧化间甲酚具有显著的催化作用;在反应时间为90 min、反应温度为80 ℃、n（H₂O₂）∶n（间甲酚）为4、催化剂加入量为1.5 g/L、初始溶液pH为1.0~11.0的条件下,间甲酚去除率约为94%,间甲酚溶液的BOD₅/COD从氧化前的0.26提高到氧化后的0.38,可生化性显著提高。     

Utilization of blended fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash in geopolymer

In this paper, synthesis of geopolymer from fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash was studied in order to effectively utilize both ashes. FBC-fly ash and bottom ash were inter-ground to three different finenesses. The ashes were mixed with as-received PCC-fly ash in various proportions and used as source material for synthesis of geopolymer. Sodium silicate (Na₂SiO₃) and 10 M sodium hydroxide (NaOH) solutions at mass ratio of Na₂SiO₃/NaOH of 1.5 and curing temperature of 65 °C for 48 h were used for making geopolymer. X-ray diffraction (XRD), scanning electron microscopy (SEM), degree of reaction, and thermal gravimetric analysis (TGA) were performed on the geopolymer pastes. Compressive strength was also tested on geopolymer mortars. The results show that high strength geopolymer mortars of 35.0–44.0 MPa can be produced using mixture of ground FBC ash and as-received PCC-fly ash. Fine FBC ash is more reactive and results in higher degree of reaction and higher strength geopolymer as compared to the use of coarser FBC ash. Grinding increases reactivity of ash by means of increasing surface area and the amount of reactive phase of the ash. In addition, the packing effect due to fine particles also contributed to increase in strength of geopolymers.     

The potential of SO2 for reducing corrosion in WtE plants

Due to the high-temperature boiler corrosion induced by chloride-rich fly ash deposits, steam generation in today’s Waste-to-Energy (WtE) plants is typically designed only for 40 bar/400 °C as an economic compromise between acceptable corrosion rate and maximum power generation. The high-corrosive metal chlorides in the fly ash can react with SO₂ forming low-corrosive sulfates. The sulfation efficiency is enhanced by high SO₂ levels and sufficient residence time of the flue gas at high-temperatures (700–900 °C). The fly ash sulfation was tested in full scale in a Swedish WtE plant by applying the economic sulfur recirculation method. Probes of several alloys (16Mo3, Inconel 625, Sanicro 28) were exposed for 1000 h at controlled material temperatures in the superheater position, at normal and during sulfating operation respectively. Analyses of the fly ash showed that the molar Cl/S was decreased to values well below 1 and the corresponding corrosion rates of the individual material samples were less than half when sulfur recirculation was in operation. These positive findings demonstrate that the sulfur recirculation process has high potential for low-corrosive high-temperature steam generation (T ≈ 500 °C) and improved electricity production. Further steam superheating can be realized by staged superheating using small amounts of secondary fuel.     

Water extraction with CO2 bubbling as pretreatment of melting-furnace fly ash for metal recovery

In Japan, melting-furnace fly ash (MFA) generated from ash melting and gasification/melting plants is considered an “urban mine” due to its high metal content. This study aimed to develop a novel approach to pretreating MFA for metal recovery. Water extraction with CO₂ bubbling was investigated because MFA mainly consists of water-soluble salts containing elements such as Cl, Ca, Na, and K. Instead of acid addition, CO₂ bubbling was applied to maintain the optimal pH for minimizing the release of target metal elements and maximizing the removal of undesirable elements during water extraction. The results revealed that CO₂ bubbling effectively decreased the release of Pb, Zn, and Cd into the treatment water. This was mainly due to coprecipitation with CaCO₃, which was primarily formed by the reaction of Ca²⁺ from the MFA with CO₃ ²⁻ from the CO₂ gas. The bubbling process also helped accelerate the removal of Cl from MFA. Furthermore, the study showed that it is possible to lower the water-to-solid ratio to 5 with only a slight reduction in water extraction effect. Finally, approximately four times the concentration of target metals (rare metals and Cu, Pb, and Zn) was achieved by removing 90% of Cl, 70%–90% of Na and K, and 30%–40% of Ca through water extraction with CO₂ bubbling, resulting in a concentration of target metals that was nearly equal to that of ore.     

Sorbents for CO2 capture from high carbon fly ashes

Fly ashes with high-unburned-carbon content, referred to as fly ash carbons, are an increasing problem for the utility industry, since they cannot be marketed as a cement extender and, therefore, have to be disposed. Previous work has explored the potential development of amine-enriched fly ash carbons for CO(2) capture. However, their performance was lower than that of commercially available sorbents, probably because the samples investigated were not activated prior to impregnation and, therefore, had a very low surface area. Accordingly, the work described here focuses on the development of activated fly ash derived sorbents for CO(2) capture. The samples were steam activated at 850 degrees C, resulting in a significant increase of the surface area (1075m(2)/g). The activated samples were impregnated with different amine compounds, and the resultant samples were tested for CO(2) capture at different temperatures. The CO(2) adsorption of the parent and activated samples is typical of a physical adsorption process. The impregnation process results in a decrease of the surface areas, indicating a blocking of the porosity. The highest adsorption capacity at 30 and 70 degrees C for the amine impregnated activated carbons was probably due to a combination of physical adsorption inherent from the parent sample and chemical adsorption of the loaded amine groups. The CO(2) adsorption capacities for the activated amine impregnated samples are higher than those previously published for fly ash carbons without activation (68.6 vs. 45mg CO(2)/g sorbent).     

An LCA model for waste incineration enhanced with new technologies for metal recovery and application to the case of Switzerland

A process model of municipal solid waste incinerators (MSWIs) and new technologies for metal recovery from combustion residues was developed. The environmental impact is modeled as a function of waste composition as well as waste treatment and material recovery technologies. The model includes combustion with a grate incinerator, several flue gas treatment technologies, electricity and steam production from waste heat recovery, metal recovery from slag and fly ash, and landfilling of residues and can be tailored to specific plants and sites (software tools can be downloaded free of charge). Application of the model to Switzerland shows that the treatment of one tonne of municipal solid waste results on average in 425 kg CO₂-eq. generated in the incineration process, and 54 kg CO₂-eq. accrue in upstream processes such as waste transport and the production of operating materials. Downstream processes, i.e. residue disposal, generates 5 kg CO₂-eq. Savings from energy recovery are in the range of 67 to 752 kg CO₂-eq. depending on the assumptions regarding the substituted energy production, while the recovery of metals from slag and fly ash currently results in a net saving of approximately 35 kg CO₂-eq. A similar impact pattern is observed when assessing the MSWI model for aggregated environmental impacts (ReCiPe) and for non-renewable resource consumption (cumulative exergy demand), except that direct emissions have less and no relevance, respectively, on the total score. The study illustrates that MSWI plants can be an important element of industrial ecology as they provide waste disposal services and can help to close material and energetic cycles.     

粉煤灰-粉煤灰合成沸石对Cs~+的固化

以电厂废弃物粉煤灰为原料、采用碱熔-水热法制备了粉煤灰合成A型沸石(以下简称沸石),再以沸石对溶液中的Cs+进行分离富集,最后在碱激发剂的作用下以粉煤灰和吸附后的沸石制得地聚合物固化体。对固化体的性能进行了评价,并探讨了固化机理。实验结果表明:在吸附温度25℃、初始Cs+质量浓度100 mg/L、固液比10.0 g/L的条件下,沸石对的Cs+的吸附率达98%,比粉煤灰提高了2倍以上;沸石掺量为20%~30%(w)时,固化体的抗压强度符合GB 14569.1—2011要求,固化体中Cs+的42 d浸出率和累计浸出分数均远优于GB 14569.1—2011限值,表现出优异的抗浸出性能。     

Hydrodechlorination/detoxification of PCDDs,PCDFs, and co-PCBs in fly ash by using calcium polysulfide

Dioxins like polychlorinated dibenzo-p-dioxins (PCSDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are mainly emitted from waste incinerators (WIs) and have become an international research focus because of its serious concerns over the adverse health effects. The detoxification of PCCDs/Fs and PCBs is very difficult because of their stable chemical structure. A significant hydrodechlorination/detoxification of polychlorinated 1-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were achieved in fly ash by using an aqueous mixture of calcium hydroxide and sulfur. Two different fly ashes were studied: originating from municipal waste incinerator (FA1) and industrial waste incinerator (FA2). They were heated with the aqueous mixture at 150 °C for 30 or 60 min with agitation. Higher decomposition (87%) and detoxification (87.7%) of PCDD/Fs and PCBs were achieved at 150 °C with two runs; every run was for 30 min, compared to one run for 60 min. FA2 gave higher decomposition and detoxification as compared to FA1, which might be due to higher metal content that played a catalytic role to decompose and detoxify the PCDDs, PCDFs and PCBs. The decomposition and detoxification of PCDFs in fly ash was higher than PCDDs and was augmented with increasing number of chlorides on aromatic compounds. As the highly significant decomposition and detoxification of higher concentration of PCDD/Fs and PCBs were achieved in 1 hour without additive catalyst and at low temperature of 150 °C, therefore, the developed method is cost effective and most suitable to apply on commercial/industrial level. The detail results of hydrodechlorination/detoxification of PCDD, PCDFs at different conditions are described and its mechanism is discussed.     

粉煤灰的改性及对刚果红的吸附

分别采用沸水浸泡、酸浸、碱浸和加热的方法对粉煤灰进行改性处理,利用FTIR仪和XRD仪对改性粉煤灰的成分和官能团进行了分析,并利用改性粉煤灰对模拟刚果红废水进行脱色。实验结果表明：碱改性粉煤灰中含有大量官能团,以及NaPl型沸石类物质,能够明显提高粉煤灰对刚果红的吸附性能;与活性炭相比,碱改性粉煤灰具有更高的性价比;在初始刚果红质量浓度为20mg/L、碱改性粉煤灰加入量为50g/L的条件下,废水的脱色率可达87.52%;碱改性粉煤灰对刚果红的吸附过程遵循二级反应动力学,较好地符合Langmuir等温式和Freundlich等温式。     

Glass–ceramic from mixtures of bottom ash and fly ash

Along with the gradually increasing yield of the residues, appropriate management and treatment of the residues have become an urgent environmental protection problem. This work investigated the preparation of a glass–ceramic from a mixture of bottom ash and fly ash by petrurgic method. The nucleation and crystallization kinetics of the new glass–ceramic can be obtained by melting the mixture of 80% bottom ash and 20% fly ash at 950 °C, which was then cooled in the furnace for 1 h. Major minerals forming in the glass–ceramics mainly are gehlenite (Ca₂Al₂SiO₇) & akermanite (Ca₂MgSiO₇) and wollastonite (CaSiO₃). In addition, regarding chemical/mechanical properties, the chemical resistance showing durability, and the leaching concentration of heavy metals confirmed the possibility of engineering and construction applications of the most superior glass–ceramic product. Finally, petrurgic method of a mixture of bottom ash and fly ash at 950 °C represents a simple, inexpensive, and energy saving method compared with the conventional heat treatment.     

Heavy metals removal/stabilization from municipal solid waste incineration fly ash: a review and recent trends

Waste treatment using thermal technologies, such as incineration, leads to the production of pollutants and wastes, including fly ash (FA). Fly ash contains heavy metals (HMs) and other contaminants and can potentially pose high risks to the environment and negatively impact health and safety. Consequently, stabilizing fly ash prior to either use or landfilling is crucial. The toxicity of fly ash through heavy metal leaching can be assessed using leaching tests. The leaching rates of heavy metals primarily depend on the surrounding conditions as well as fly ash properties and metal speciation. Physical separation, leaching or extraction, thermal treatment and solidification/chemical stabilization are proposed as suitable approaches for fly ash treatment. Economic considerations, environmental concerns, energy consumption and processing times can define the efficiency and selection of the treatment approach. This review considers the latest findings and compares the advantages and shortcomings of different fly ash treatment methods with the aim of highlighting the recent advances in the field. The review concludes that the simultaneous implementation of various methods can lead to highly efficient heavy metals removal/stabilization while simultaneously taking economic and environmental considerations into account.

     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.