Analcime geopolymers as sorbents in water treatment

Zeolite mineral, analcime [Na16(Al16Si32O96)·16H2O], is formed in mining industry as lithium carbonate is produced from spodumene (LiAlSi2O6) using sodium pressure leaching process (1). Zeolite structure possess aluminosilicate framework and pores occupied by water and exchangeable cations (2). Zeolites act as cation exchangers due to which they have been applied as sorbents in water treatment (2). Geopolymers (GP) consist of an anionic framework of corner-sharing SiO4 and AlO4, and the exchangeable cations are located in the voids in the same way as in zeolites (3). However, GP are x-ray amorphous unlike zeolites. Also, GP are excellent sorbent materials in water treatment for e.g. As3+, Cu2+, NH4+ Ni2+, Sb3+ (4-6). The ion-exchange capacity of analcime at room temperature is quite low (Querol et al. 2002) and therefore analcime was geopolymerized with a 1:1 mixture of 10 M sodium hydroxide (NaOH) and sodium silicate (SiO2:Na2O = 3.1-3.4) to improve the sorption properties of analcime. Then analcime GP were applied as sorbents in the removal of different anions and cations (e.g. ammonium, nitrate, potassium). Before sorption experiments, the GP were crushed and sieved to a particle size \u3c500 \u3eµm and washed with deionized water until pH was stable. Experiments were conducted in batch mode with synthetic wastewater. The effect of sorbent dosage, sorption time, temperature, and anion/cation solution concentration on the anion/cation removal efficiencies of analcime GP were studied. The results indicate that analcime GP could be used as sorbents in water treatment. The use of the analcime GP in water treatment could lead to cost savings in water treatment as a low-cost by-product based GP are used instead of the commercial ion exchange resins. Please click Additional Files below to see the full abstract

A comprehensive review of the reclamation of resources from spent lithium-ion batteries

Due to the increased application of lithium-ion batteries (LIBs), the number of spent LIBs has increased significantly in recent years, which has resulted in new waste management challenges for the recycling industry. The recycling of spent LIBs has gained enormous interest globally, as this can mitigate resource shortages and reduce the detrimental environmental impact of spent LIB waste. As the demand for LIBs continues to grow, it is important to recycle spent LIBs to establish a sustainable supply chain for the critical materials required for battery production. This comprehensive review addresses different strategies for resource recovery from LIBs and covers state-of-the-art processes for recycling LIBs. Additionally, the challenges and strategies for resource recovery from LIBs are highlighted. Furthermore, the advantages and disadvantages of different recycling processes are addressed

Utilisation of industrial by-products in water treatment:carbon-and silicate-based materials as adsorbents for metals and sulphate removal

Abstract Pollutant (such as metals and sulphate) contamination exists in the wastewaters of many industries, including mining operations, metal plating facilities, and tanneries. Adsorption is one of the most commonly used processes for the removal of pollutants from waters and wastewaters due to its high efficiency and simple operation. Activated carbon is the most frequently used adsorbent material, although its high cost inhibits its widespread use in wastewater treatment. Therefore, there is a need to develop other adsorbents from alternative inexpensive raw materials such as locally available industrial and mineral waste and by-products. The aim of this thesis was to study the possibility of using industrial waste materials such as carbon residue, metakaolin, blast-furnace slag and analcime as an inexpensive sorbent for iron, copper, nickel, arsenic, antimony and sulphate removal from aqueous solutions. To enhance their adsorption capacity, different chemical treatments (i.e. activation, modification, geopolymerisation) were performed. As a result, the level of removal of iron, copper and nickel by carbon residue and zinc chloride activated carbon residue was higher than that by the commercial activated carbon. Iron chloride modified carbon residue was the most effective sorbent material for sulphate removal when compared to the other studied chemically modified/activated carbon residues. Blast-furnace slag and metakaolin geopolymers as well as their raw materials, were examined for the simultaneous removal of nickel, arsenic and antimony from the spiked mine effluent. In the case of blast-furnace slag, geopolymerisation clearly increased the efficiency of nickel, arsenic and antimony removal to a beneficial level. The barium chloride modified blast-furnace-slag geopolymer was a very efficient sorbent material for sulphate removal and it could thus be a technically feasible sulphate sorbent for wastewater treatment (e.g. in the mining industry in applications in which very low sulphate levels are desired). Barium chloride modified acid washed analcime could also be a potential sorbent for sulphate removal.Tiivistelmä Teollisuuden jätevedet kuten kaivosvedet ja metalliteollisuuden prosessien jätevedet voivat sisältää monenlaisia haitallisia ja jopa myrkyllisiä aineita kuten metalleja ja sulfaattia. Adsorptiota käytetään yleisesti esimerkiksi metallien ja orgaanisten yhdisteiden poistossa vesiliuoksista, koska se on tehokas ja yksinkertainen menetelmä. Aktiivihiili on yleisimmin käytetty adsorbenttimateriaali vedenpuhdituksessa, mutta sen hinta joissain tapauksissa rajoittaa sen käyttöä. Tämän vuoksi on tarvetta kehittää vaihtoehtoisia adsorbenttimateriaaleja edullisista raaka-aineista. Viime vuosien aikana on raportoitu mm. teollisuus- ja mineraalijätteistä, joita voidaan hyödyntää vesien ja jätevesien puhdistuksessa. Tämän työn tavoitteena oli hyödyntää teollisuudesta muodostuvia jätemateriaaleja (hiilijäännös, metakaoliini, masuunikuona ja analsiimi) raudan, kuparin, nikkelin, arseenin, antimonin tai sulfaatin poistossa malli- ja jätevesistä. Materiaaleja käsiteltiin erilaisilla kemikaaleilla (aktivointi, modifiointi tai geopolymerointi), jotta niiden adsorptiotehokkuudet paranisivivat poistettavia aineita kohtaan. Tulokset osoittivat, että raudan, kuparin ja nikkelin poisto oli sekä käsittelemättömällä että sinkkikloridilla aktivoidulla hiilijäännöksellä korkeampi kuin kaupallisella aktiivihiilellä. Arseenin, nikkelin ja antimonin poistoa kaivosvedestä tutkittiin masuunikuona- ja metakaoliinigeopolymeereillä, joista masuunikuonageopolymeeri osoittautui tehokkaimmaksi metallien poistajaksi. Bariumkloridilla modifioitu masuunikuonageopolymeeri puolestaan poisti erittäin tehokkaasti sulfaattia kaivoksen jätevedestä. Rautakloridilla modifioitu hiilijäännös ja happopesty bariumkloridilla modifioitu analsiimi osoittatuivat myös lupaavaksi materiaaliksi sulfaatin poistossa

Adsorption of copper and zinc with alkali-activated blast furnace slag from mine water

Abstract Metal contamination is an alarming problem near mining areas all over the world. Released wastewaters and mining water loose different metals to environment affecting lakes, rivers and other water sources (Jain and Das, 2017). In this study, alkali-activated blast furnace slag was used as an adsorbent for mine effluent treatment. Alkali-activation was conducted by reacting ground granulated blast furnace slag and a mixture of sodium hydroxide and silicate. Water samples are obtained from the last pumping point of infiltration water. Metal content of this water is still above the environmental safety level and the water should be recirculated and repurified. The aim of this work is to find a method to purify the mine water at this testing point to reach the environmental safety level. Then water will be releasable back to the lake. Alkali-activated materials are widely tested and used in different kind of purification applications. These adsorbent materials are known since beginning of 1900 century but interest towards this kind of research has grown during the few last decades. There are a lot of possibilities for water research and purification processes with alkali-activated materials due to their strong and insoluble form and wide range of feasible materials available (Provis, 2014). Alkali-activated blast furnace slag was selected to be an adsorbent material for this work because it is cheap and easy to produce. It has also relatively good metal removing capacity. Same kinds of adsorbent materials have been tested for metals like nickel successfully (Luukkonen et al., 2016). This encouraged us to study more specific mining waters containing copper and zinc

Sulphate Removal from Water by Carbon Residue from Biomass Gasification: Effect of Chemical Modification Methods on Sulphate Removal Efficiency

Sulphate removal from mine water is a problem because traditional chemical precipitation does not remove all sulphates. In addition, it creates lime sediment as a secondary waste. Therefore, an inexpensive and environmental-friendly sulphate removal method is needed in addition to precipitation. In this study, carbon residues from a wood gasification process were repurposed as precursors to a suitable sorbent for SO42- ion removal. The raw material was modified using ZnCl2, BaCl2, CaCl2, FeCl3, or FeCl2. Carbon residues modified with FeCl3 were selected for further consideration because the removal efficiency toward sulphate was the highest. Batch sorption experiments were performed to evaluate the effects of the initial pH, initial SO42- ion concentration, and contact time on sulphate removal. The removal of SO42- ions using Fe-modified carbon residue was notably higher compared with unmodified carbon residue and commercially available activated carbon. The sorption data exhibited pseudo-second-order kinetics. The isotherm analysis indicated that the sorption data of Fe-modified carbon residues can be represented by the bi-Langmuir isotherm model

Column Adsorption Studies for the Removal of Ammonium Using Na-Zeolite-Based Geopolymers

The aim of this study was to examine the removal of ammonium ions from a synthetic model solution by using Na-zeolite-based geopolymers. Na-zeolite (=analcime) is a residue from mining industry. Three adsorbents were prepared from Na-zeolite using different production steps and metakaolin as a blending agent. These novel adsorbents were investigated in a fixed-bed column system where the effects of different flow rates with the initial ammonium concentration of 40 mg/L were studied. The Thomas, Bohart–Adams and Yoon–Nelson breakthrough curve models fitted well with the experimental data with a high R2 value. After adsorption experiments, adsorbents were regenerated using a mixture of 0.2 M NaCl and 0.1 M NaOH as a regeneration agent; after that, adsorbents were reutilised for ammonium ion adsorption for three adsorption–regeneration cycles. The results of the experiment indicate that all the prepared analcime-based geopolymers are suitable adsorbents for the removal of ammonium ions and that capacity remains nearly constant for two of them during two adsorption–regeneration cycles.peerReviewe

Removal of Ammonium Ions from Aqueous Solutions Using Alkali-Activated Analcime as Sorbent

Five alkali-activated analcime (ANA) sorbents (ANA-MK 1, ANA 2, ANA 3, ANA-MK 4, and ANA-MK 5) were developed for ammonium (NH4+) ion removal. Acid treatment and calcination were used as pre-treatments for analcime, and metakaolin (MK) was used as a blending agent in three sorbents. Sorption experiments were performed to evaluate the effects of sorbent dosage (1–20 g L−1), initial NH4+ ion concentration (5–1000 g L−1), and contact time (1 min–24 h). ANA-MK 1, ANA 2, and ANA-MK 4 were the most efficient sorbents for NH4+ ion removal, with a maximum experimental sorption uptake of 29.79, 26.00, and 22.24 mg g−1, respectively. ANA 3 and ANA-MK 5 demonstrated lower sorption capacities at 7.18 and 12.65 mg g−1, respectively. The results for the sorption of NH4+ ions onto the alkali-activated analcime surfaces were modeled using several isotherms. The Langmuir, Freundlich, Sips, and Bi-Langmuir isotherms were the best isotherm models to represent the studied systems. The results of the kinetic studies showed the maximum NH4+ ion removal percentage of the sorbents was ~80%, except for ANA-MK 5, which had a ~70% removal. Moreover, the pseudo-first-order, pseudo-second-order, and Elovich models were applied to the experimental data. The results showed that the sorption process for ANA-MK 1, ANA 2, ANA 3, and ANA-MK 4 followed the Elovich model, whereas the pseudo-second-order model provided the best correlation for ANA-MK 5

Removal of Ammonium Ions from Aqueous Solutions Using Alkali-Activated Analcime as Sorbent

Five alkali-activated analcime (ANA) sorbents (ANA-MK 1, ANA 2, ANA 3, ANA-MK 4, and ANA-MK 5) were developed for ammonium (NH4+) ion removal. Acid treatment and calcination were used as pre-treatments for analcime, and metakaolin (MK) was used as a blending agent in three sorbents. Sorption experiments were performed to evaluate the effects of sorbent dosage (1–20 g L−1), initial NH4+ ion concentration (5–1000 g L−1), and contact time (1 min–24 h). ANA-MK 1, ANA 2, and ANA-MK 4 were the most efficient sorbents for NH4+ ion removal, with a maximum experimental sorption uptake of 29.79, 26.00, and 22.24 mg g−1, respectively. ANA 3 and ANA-MK 5 demonstrated lower sorption capacities at 7.18 and 12.65 mg g−1, respectively. The results for the sorption of NH4+ ions onto the alkali-activated analcime surfaces were modeled using several isotherms. The Langmuir, Freundlich, Sips, and Bi-Langmuir isotherms were the best isotherm models to represent the studied systems. The results of the kinetic studies showed the maximum NH4+ ion removal percentage of the sorbents was ~80%, except for ANA-MK 5, which had a ~70% removal. Moreover, the pseudo-first-order, pseudo-second-order, and Elovich models were applied to the experimental data. The results showed that the sorption process for ANA-MK 1, ANA 2, ANA 3, and ANA-MK 4 followed the Elovich model, whereas the pseudo-second-order model provided the best correlation for ANA-MK 5.peerReviewe

Removal of Ammonium Ions from Aqueous Solutions Using Alkali-Activated Analcime as Sorbent

Five alkali-activated analcime (ANA) sorbents (ANA-MK 1, ANA 2, ANA 3, ANA-MK 4, and ANA-MK 5) were developed for ammonium (NH4+) ion removal. Acid treatment and calcination were used as pre-treatments for analcime, and metakaolin (MK) was used as a blending agent in three sorbents. Sorption experiments were performed to evaluate the effects of sorbent dosage (1–20 g L−1), initial NH4+ ion concentration (5–1000 g L−1), and contact time (1 min–24 h). ANA-MK 1, ANA 2, and ANA-MK 4 were the most efficient sorbents for NH4+ ion removal, with a maximum experimental sorption uptake of 29.79, 26.00, and 22.24 mg g−1, respectively. ANA 3 and ANA-MK 5 demonstrated lower sorption capacities at 7.18 and 12.65 mg g−1, respectively. The results for the sorption of NH4+ ions onto the alkali-activated analcime surfaces were modeled using several isotherms. The Langmuir, Freundlich, Sips, and Bi-Langmuir isotherms were the best isotherm models to represent the studied systems. The results of the kinetic studies showed the maximum NH4+ ion removal percentage of the sorbents was ~80%, except for ANA-MK 5, which had a ~70% removal. Moreover, the pseudo-first-order, pseudo-second-order, and Elovich models were applied to the experimental data. The results showed that the sorption process for ANA-MK 1, ANA 2, ANA 3, and ANA-MK 4 followed the Elovich model, whereas the pseudo-second-order model provided the best correlation for ANA-MK 5

Multiple heavy metal removal simultaneously by a biomass‐based porous carbon

Abstract Activated carbon from sawdust was produced with an environmentally friendly process involving single‐stage carbonization and activation with steam at 800°C. Production process is scalable because lignocellulosic biomass is ubiquitous worldwide as a waste or as a virgin material. Single‐stage production without any cooling steps between carbonization and activation is easier in larger scale production. Monometal adsorption and multimetal adsorption of cobalt, nickel, and zinc were investigated by using the produced carbon, with a commercial one as control. Effect of pH, initial metal concentration, adsorbent dosage, and adsorption time was evaluated in batch experiments. Multimetal experiments showed the order of the maximum adsorption capacities: zinc > nickel > cobalt. Experimental adsorption capacities were 17.2, 6.6, and 4.5 mg/g for zinc, nickel, and cobalt, respectively, in multisolute adsorption. In case of monometal adsorption, adsorption capacity was notably lower. Experimental data fitted into the single‐solute and multisolute Freundlich models. The best fit kinetic model varied among the metals. The Weber and Morris intraparticle diffusion model was used. Regeneration was performed with 0.1 M HNO₃, 0.1 M HCl, or 0.1 M H₂SO₄. The adsorption capacity remained at the same within three adsorption–desorption cycles