Hydrothermal synthesis of zeolites from coal fly ash

The fly ash, from the combustion of coal to produce energy and heat, is an industrial waste, in which large accumulations represent a serious environmental threat. To reduce the environmental burden and improve the economic benefits of energy production, the science and industry focus on the transformation of coal combustion byproducts into new functional materials. The fly ash was studied by modern analytical methods. As a result of the hydrothermal reaction, several types of zeolites were synthesised from the fly ash: analcime, faujasite (zeolite X) and gismondine (zeolite P). It was shown that the experimental conditions (temperature, reaction time and alkali concentration) have a significant influence on the type of zeolite and its content in the reaction products. The series of experiments resulted in building approximate crystallisation field of zeolites and other phases as the first stage of the formation of ceramic membrane and other materials.     

Preparation of zeolitic adsorbents from waste coal fly ash

Power plants burning coal generate a large amount of fly ash as waste matter. The objective of this study is to produce zeolitic adsorbents that possesses high adsorptive capacity for toxic cations. The sample was first pretreated with a High Intensity Magnetic Separator for the removal of iron and magnetic materials (mainly Fe₂O₃ and TiO₂). The zeolitic adsorbents were prepared under the various conditions of NaOH concentration (1–5 N), reaction time from 3 to 96 hours and at the various temperatures of 60, 80 and 100°C. The results of the experiment showed that the coal fly ash should be synthesized with 4 N NaOH for 48 hours at 100°C in order to have good adsorptive capacity. The zeolitic adsorbents showed higher cation exchange capacity values than the natural zeolite in removing NH ₄ ⁺ , Pb²⁺, Ca²⁺and Cd²⁺ions.     

Preparation of Na‐P1‐Type Zeolite and its Composite Material with Nanosized Magnetite

The Na‐P1‐type zeolite having a high cation‐exchange capacity (CEC) was obtained using the waste coal fly ash from thermal power stations and a 2M NaOH solution at 100°C. The Na‐P1‐type zeolite was formed with the reaction time of 6 h at 100°C, and its CEC value increased with an increase in the reaction time. The addition of a suitable amount of NaAlO₂ to the fly ash was also effective for improving the CEC value. A new composite material consisting of the Na‐P1‐type zeolite and magnetite was synthesized from the fly ash and iron chlorides because the magnetic collection was possible using this composite material after radioactive Cs⁺ ion adsorption. The existence of nanosized magnetites in the polycrystalline zeolite (several micrometers) was confirmed by TEM observations. The CEC and magnetic property of these composite materials were characterized.     

粉煤灰合成沸石的研究

燃煤电厂产生大量的副产物粉煤灰,但目前只有少量粉煤灰在水泥、混凝土行业得以利用.开发具有应用开发价值的高附加值产品是粉煤灰未来发展的一个方向.利用粉煤灰合成沸石的研究日益得到关注.综述了粉煤灰合成沸石的原理,传统的水热法、两步法和盐熔法等合成工艺,以及各种方法存在的问题、合成沸石的分析表征技术,并探讨了粉煤灰沸石在废水处理、催化等方面的应用开发前景.     

粉煤灰基沸石的制备及应用研究进展

粉煤灰是燃煤电厂产生的固体废弃物,其主要成分中包含大比例的SiO₂、Al₂O₃,是合成沸石的理想原料。粉煤灰合成沸石的方法随着研究的深入而逐渐成熟,从起初的一步水热法到现在的复合水热法,从以未经处理的粉煤灰为原料到现在使用预处理过的粉煤灰为原料,粉煤灰合成沸石的工艺一直在进步。从粉煤灰的预处理、合成沸石方法、产物应用领域三方面综述了研究进展,并对其整体发展趋势进行了展望。     

Microwave-assisted zeolite synthesis from coal fly ash in hydrothermal process

Coal fly ashes, which include much amount of silica and alumina, can be converted into zeolite by hydrothermal alkaline treatment. In the present work, the effect of microwave irradiation on the zeolite formation was investigated with emphasis on the change in yield of zeolite during the reaction. The fly ash was mixed with 2 M NaOH solution and heated by oil bath or microwave for 2 h. Zeolite Na-P1 formed after the conventional treatment using oil bath, but no zeolitic product was obtained by microwave heating. When microwave was applied in the course of hydrothermal treatment, zeolitization was promoted by the early-stage irradiation. This is due to the stimulated dissolution of SiO₂ and Al₂O₃ from coal fly ash. On the other hand, the microwave irradiation in the middle to later stage retarded the crystallization of zeolite. The microwave is effective to produce the zeolite from coal fly ash in a short period by control of irradiation schedule in the early stage.     

Alkaline hydrothermal zeolites synthesized from high SiO2 and Al2O3 co-disposal fly ash filtrates

A co-disposal reaction was used wherein fly ash (FA) was reacted with acid mine drainage (AMD), to collect filtrates for zeolite synthesis. Raw fly ash as well as fly ash leached with HCl were subjected to the same alkaline hydrothermal zeolite synthesis conditions, as for the co-disposal filtrates, in order to evaluate the zeolitic material obtained. The Si and Al contents of the fly ash (FA) filtrates were used as precursor species for the alkaline hydrothermal conversion of the fly ash filtrates into zeolites. These filtrates were then analysed by XRF spectrometry for quantitative determination of SiO₂ and Al₂O₃. The [SiO₂]/[Al₂O₃] ratio obtained in the filtrates range from 1.4 to 2.5. The [SiO₂]/[Al₂O₃] ratio was used to predict whether the fly ash filtrates could successfully be converted into faujasite zeolitic material by the adopted synthesis procedures. If the [SiO₂]/[Al₂O₃] ratio is higher than 1.5 in the co-disposal filtrates, it favours the formation of faujasite. The zeolite synthesis included an alkaline fusion of the co-disposal filtrates, followed by aging for 8 hours and hydrothermal conversion by crystallisation at 100 °C. Different variables were investigated during the synthesis of zeolite to ascertain their influence on the end product. These variables include adding different amounts of deionised water to the FA-related starting material, using different compositions of FA related starting material and different FA:NaOH ratios in fusing the starting material.     

Properties and potential applications of zeolitic materials produced from fly ash using simple method of synthesis

Very low energy-consuming procedure is proposed for synthesis of zeolitic materials from fly ash. Three different zeolite materials (X, P and S), rich in zeolite phases, Na-X (FAU), NaP1 (GIS) and sodalite (SOD) were produced from F-class fly ash, using NaOH and NaCl solutions under atmospheric pressure at temperature below 110 °C.Obtained zeolitic products were analysed for their composition and physicochemical properties then compared to the raw fly ash and commercial adsorbents. The zeolitization results in a significant increase of CEC (from 5.5 up to 239 meq 100 g^− 1), and the high ability to adsorb heavy metal ions (over 40 mg g^− 1) and retain complex and organic molecules (EGME), mostly evident for material X. Adsorptive purification of waste and working lubricating oils using zeolitic products allow to provide their commercial applications in petroleum industry. Leachability of toxic elements after standard post-reaction washing is environmentally safe.     

Application of zeolitised coal fly ashes to the depuration of liquid wastes

In this study, the application of some zeolitised fly ashes and synthetic zeolites to the decontamination of the leachate produced in a municipal solid waste (MSW) treatment plant and to the liquid waste from a pig farm was analyzed. Thus, the reduction of organic matter (BOD and COD), ammonium and total nitrogen, phosphorus and metals contents after a zeolite treatment was evaluated. Several synthetic zeolites were tested: some commercial zeolites and other synthetic zeolites and zeolitised ashes obtained after a coal fly ash alkaline hydrothermal process. Two forms of contact between the zeolitic material and the liquid waste were tested: in a stirred tank and in a column. In addition, other variables determined were the amount of zeolite and the residence time. The results showed that zeolites, especially zeolitised fly ash, clearly produced a strong reduction in the leachate nitrogen and phosphorus content.     

Hydrothermal synthesis of zeolitic material from circulating fluidized bed combustion fly ash for the highly efficient removal of lead from aqueous solution

The utilization of coal fly ash derived from circulating fluidized bed combustion (CFBFA) still faces great challenges because of its unique characteristics. In this study, a zeolitic material with Na-P1 zeolite as the main phase was successfully synthesized via a hydrothermal method by using CFBFA as the raw material. The effects of hydrothermal temperature, time, and added CTAB amount on the characterizations of synthesized materials were investigated by XRD, SEM, and XPS. The properties of the optimal zeolitic material and its adsorption performance for Pb²⁺ in aqueous solution were evaluated. The influences of pH, initial concentration, dosage, and temperature on Pb²⁺ adsorption were also examined. Results revealed the following optimal parameters for the synthesis of zeolitic material:NaOH concentration of 2 mol·L^-1, solid-to-liquid ratio of 1:10 g·ml^-1, hydrothermal temperature of 110℃, hydrothermal time of 9 h, and CTAB amount of 1 g (per 100 ml solution). The adsorption capacities of the zeolitic material reached 329.67, 424.69, and 542.22 mg·g^-1 when the pH values of aqueous solution were 5, 6, and 7, respectively. The Pb²⁺removal efficiency can reach more than 99% in aqueous solution with the initial concentrations of 100-300 mg·L^-1 under pH 6 and suitable adsorbent dosage. The adsorption and kinetics of Pb²⁺ on the zeolitic material can be described by Langmuir isotherm and pseudo-second-order kinetic models, respectively. The ion exchange between Pb²⁺ and Na⁺ and chemisorption are the main adsorption mechanism. All these findings imply that the synthesis of low-cost adsorbent for Pb²⁺ removal from weak acid and neutral aqueous solution provides a highly effective method to utilize CFBFA.     

Microscopic single particle characterization of zeolites synthesized in a soil polluted by copper or cadmium and treated with coal fly ash

In the perspective of the development of new soil remediation technologies, zeolites can be directly synthesized in soil from fused coal fly ash to reduce heavy metal mobility and availability. Such a process promotes the formation of metal hydroxide/oxide precipitates which can be also occluded inside the structure of the forming minerals. In this study, different types of zeolites (zeolite X, P, and A) were synthesized by treating soil samples, artificially contaminated by high concentrations of Cu or Cd ions, with fused coal fly ash at 30 and 60 °C. The formed zeolites were characterized for their amount, structure, chemical composition and size. To accomplish this survey, besides quantitative X-ray diffraction analyses (XRD), an automated single particle analysis (ASPA) method using electron probe X-ray microanalysis (EPXMA) was employed for the first time for direct zeolite characterization in soil samples. The obtained results provide new information for assessing the role of heavy metals in zeolite crystallization in coal fly ash-treated soils. Heavy metal contamination, while not significantly hindering the zeolite formation process, can influence crystal size and preferentially drive zeolite synthesis toward the formation of sodalite unit-based zeolite X and zeolite A, even at 60 °C. The presence and nature of metal precipitate occlusions inside the forming zeolite minerals might have also favored the preferential synthesis of certain zeolitic structures.     

粉煤灰合成沸石脱氮除磷的应用及展望

介绍粉煤灰合成沸石在氮磷废水处理中的应用。指出了粉煤灰合成沸石在处理氮磷废水方面具有处理效果好、占地少、便于管理控制等优点。粉煤灰来源广泛,价格低廉,将粉煤灰合成沸石处理氮磷废水可以以废治废,具有广阔的发展前景。     

粉煤灰沸石合成机理、方法及改性技术的研究

首先根据人工合成沸石的空间结构,分析了粉煤灰沸石离子交换性和吸附分离性特性;对粉煤灰合成沸石的合成机理--液相转变机理进行了分析;对水热合成法、碱处理法、盐热法、混碱气相合成法等粉煤灰合成沸石工艺进行了综述,并归纳总结了粉煤灰组成、液固比、碱的种类和浓度、反应温度与反应时间等因素对沸石合成的影响;最后,对粉煤灰合成沸石...     

A comparative study of two methods for the synthesis of fly ash-based sodium and potassium type zeolites

Fly ash (FA) from the Rugeley Power Station, West Midlands (England) was used in a study on synthesis at laboratory scale of zeolitic materials under various conditions by two different routes. Zeolitic materials were synthesized from FA by hydrothermal treatment in NaOH (Na-phillipsite, hydroxysodalite, hydroxycancrinite, tobermorite, analcime and herschelite) and KOH (hydroxysodalite, zeolite Barrer-KF, K-chabazite and zeolite Linde Type F) solutions. By fusion with NaOH followed by hydrothermal reaction, FA was converted into faujasite and hydroxysodalite. No zeolitic materials were obtained by this method using KOH as alkali activator. The process of synthesis was optimised by applying a wide range of experimental conditions with a wide range of reaction temperature, time, alkali hydroxide concentration and solid/solution ratio. The efficiency FA-based zeolites (FAZs) for heavy metal and ammonium uptake from synthetic solutions at laboratory scale have been investigated by the authors, revealing that these FAZs may reach appropriate cation exchange capacities for their application in industrial wastewater treatment.     

Effects of step change of heating source on synthesis of zeolite 4A from coal fly ash

Effects of step change of heating sources on the crystallization of zeolite 4A from coal fly ash by hydrothermal reaction were investigated with emphasis on the change in the crystallinity of the synthesized zeolite 4A. Most of the Si and Al components were effectively transformed into zeolite 4A by step change of the first conventional heating and then the second microwave heating of synthesis mixture dissolved from coal fly ash, and maximum crystallinity of zeolite 4A obtained was 91%. The first conventional heating also plays an important role in enhancing the nuclei formation that Si and Al in synthesis mixture reacted to form ring-like structures for combining sodalites, and further to small zeolite 4A seeds. The second microwave heating increases the crystallization rates from small zeolite 4A nuclei to more zeolite 4A crystals.The cation exchange capacity (CEC) of the zeolite 4A crystallized by step change of heating source from the conventional to the microwave was 5.5 meq/g compared to 5.7 meq/g for commercial zeolite 4A. Test results showed that removal efficiency of heavy metals by zeolite 4A synthesized from fly ash was more than 98% and similar to commercial zeolite 4A.     

粉煤灰基沸石处理氮磷废水的研究进展

近年来,粉煤灰因其价格低廉、产量高,且与沸石结构相似,常被用来作为合成沸石的原材料。在水处理方面,粉煤灰基沸石处理氮磷废水的研究颇受广大学者青睐。本文简介了粉煤灰的理化性质及利用现状,概述了粉煤灰基沸石因其独特的内部结构所具有的三个特性:离子交换性、吸附性、催化性。介绍了粉煤灰基沸石除氮、磷的机理,重点论述了粉煤灰基沸石对低、中、高不同浓度的氨氮废水、含磷废水、氮磷共存废水处理的进展情况。最后分析了该领域目前存在的问题及未来发展趋势。     

粉煤灰沸石及Pd改性沸石脱除煤气中单质汞的研究

以粉煤灰为原料,采用超临界水热法制备了一系列的粉煤灰沸石.首先,考察了不同种类粉煤灰制备的沸石的煤气脱汞性能,以及由同一种粉煤灰制备的不同晶型沸石的脱汞活性.其次,考察了活性评价温度和H2 S气体对粉煤灰沸石煤气脱汞性能的影响.结果表明,其中的两种粉煤灰制备的沸石有较好的脱汞活性,具有方钠石晶型的粉煤灰沸石(Z5s)的脱汞性能优于具有钙霞石晶型的粉煤灰沸石(Z5c),Z5s沸石的脱汞率在360 min内保持在90%以上.气氛中的H2 S气体有利于单质汞的脱除,而温度升高时脱汞率降低.粉煤灰沸石(Z5s)采用贵金属Pd改性后,其脱汞活性在中高温时高于Z5s沸石.     

粉煤灰基沸石用于飞行器尾焰红外抑制的分析与展望

颗粒介质的抗红外辐射方式是飞行器尾焰隐身的重要手段之一。为促进颗粒系材料抑制红外辐射的研究和发展,对尾焰隐身进行了系统分析。红外辐射抑制的内涵在于改变红外波段和削弱红外辐射的强度。通过综述粉煤灰基沸石的研究进展、颗粒材料气溶胶抑制红外辐射和喷射方式的研究进展,结合飞行器尾焰辐射组分分析,总结了目前存在的问题和日后的发展方向。粉煤灰作为火力发电厂产生的固体废弃物之一,具有产量高、成本低的特点。提出将粉煤灰在一定条件下合成沸石分子筛,并进一步制备粉煤灰基沸石负载改性二氧化钛材料,将其作为颗粒系应用材料,用于尾焰红外辐射的抑制,可以实现变废为宝,在降低制备成本的前提下保护了环境与人类健康,促进社会的可持续发展。对目前沸石各成分抑制红外辐射效果的研究进行了综述,利用其对高红外辐射气体的强吸附性以及改性二氧化钛的光催化性能进行可行性分析,设计了颗粒吸附和遮蔽喷射结构,充分展示了粉煤灰基沸石的优势,并对该材料在飞行器尾焰隐身方面的应用前景提出展望。     

Zeolites Synthesized from Class F Fly Ash and Sodium Aluminate Slurry

A Class F fly ash was combined with a sodium aluminate slurry (3:1 Na:Al) in an attempt to synthesize zeolites from a highly alkaline waste stream. The reaction was studied as a function of composition (3:2, 1:1, and 1:2 fly ash:slurry), time (1, 3, and 7 days), and temperature (80°, 130°, and 180°C). X-ray diffraction analyses of the products indicated that the fly ash and sodium aluminate had combined to form Zeolite A at 80°C, and NaP₁ (a gismondene-type) and an unnamed hydroxysodalite-type at 130° and 180°C. The fact that the pH of the reactants decreased from initial values in excess of 13 to near neutral (7–9) after reaction signifies that the bulk of the sodium had been incorporated into zeolitic phases. Because of the unique adsorptive and cation exchange capabilities of zeolites and the fact that some samples formed reasonably hard monoliths, zeolitic materials formed in this way might make excellent waste forms for "mixed wastes" which contain both radioactive and hazardous chemical species.     

Synthesis of zeolite Na-P1 from coal fly ash produced by gasification and its application as adsorbent for removal of Cr(VI) from water

The coal fly ash produced by gasification is estimated to be over 80 million ton per year in China by 2021. It has mainly been disposed as solid waste by landfill. There is lack of study focused on its utilization. In this paper, the coal fly ash produced by gasification was at first analyzed and then applied to synthesize zeolite as an adsorbent. The effects of synthesis conditions on the cation exchange capacity (CEC) of zeolite were investigated. The results from X-ray diffraction and scanning electron microscope indicated that the crystallinity of the synthesized zeolite is the most important factor to affect the CEC. When the synthesized zeolite with the highest CEC (275.5 meq/100 g) was used for the adsorption of Cr(VI) from aqueous solution, the maximum adsorption capacity for Cr(VI) was found to be 17.924 mg/g. The effects of pH, contact time and initial concentration on the adsorption of Cr(VI) were also investigated. The adsorption kinetics and isotherms can be well described by the pseudo-second-order model and Langmuir isotherm model, respectively.