Synthesis, characterization of palygorskite supported zero-valent iron and its application for methylene blue adsorption

In this work, natural palygorskite impregnated with zero-valent iron (ZVI) was prepared and characterised. The combination of ZVI particles on surface of fibrous palygorskite can help to overcome the disadvantage of ultra-fine powders which may have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both effective surface area and catalyst performance. There is a significant increase of methylene blue (MB) decolourized efficiency on acid treated palygorskite with ZVI grafted, within 5 mins, the concentration of MB in the solution was decreased from 94 mg/L to around 20 mg/L and the equilibration was reached at about 30 to 60 mins with only around 10 mg/L MB remained in solution. Changes in the surface and structure of prepared materials were characterized using X-ray diffraction (XRD), infrared (IR) spectroscopy, surface analysing and scanning electron microscopy (SEM) with element analysis and mapping. Comparing with zero-valent iron and palygorskite, the presence of zero-valent iron reactive species on the palygorskite surface strongly increases the decolourization capacity for methylene blue, and it is significant for providing novel modified clay catalyst materials for the removal of organic contaminants from waste water.

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Catalytic cracking of tars derived from rice hull gasification over goethite and palygorskite

Palygorskite (P), goethite (G), and hydrothermally synthesized goethite (HG) were used as supports for Fe and Ni. The catalytic activity of these materials was investigated involving in P, G and HG (supported Fe and Ni) for catalytic decomposition of biomass tar derived from rice hull gasification. The materials were characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), and transmission electron microscopy (TEM) with an energy dispersive X-ray (EDS). The catalytic activity of P for removal of tar was significantly better than that of G and HG. However, the activity of G with 6 mass% Ni labeled as Ni6/G (tar conversion 94.6%), which was equal to Fe6Ni6/P (94.4%), was better than Ni6/P (64.4%) and Ni6/HG (46.7%). When the loading of Ni (mass%) was 6 mass% on G, tar conversion had the best value (94.6%) and yield of gaseous products reached 486.9, 167.8 and 22.2 mL/(g·tar) for H2, CO, CH4, respectively. The catalytic activity of goethite supported Ni was better in improving tar conversion and improving increased yield of H2, CO, CH4, which was attributed to the existence of Al/Fe substitution of goethite

Catalytic cracking of tar derived from rice hull gasification over palygorskite-supported Fe and Ni

The catalytic performance of Fe–Ni/PG (PG: palygorskite) catalysts pre-calcined and reduced at 500 ◦C for catalytic decomposition of tar derived through rice hull gasification was investigated. The materials were characterized by using X-ray diffraction, hydrogen temperature reduction, and transmission electron microscopy. The results showed that ferrites with spinel structure ((Fe, Ni)3O4) were formed during preparation of bimetallic systems during calcination and reduction of the precursors (Fe–Ni/PG catalysts) and NiO metal oxide particles were formed over Fe6–Ni9/PG catalyst. The obtained experimental data showed that Fe–Ni/PG catalysts had greater catalytic activity than natural PG. Tar removal using Fe6–Ni9/PG catalyst was as high as Fe10–Ni6/PG catalyst (99.5%). Fe6–Ni9/PG showed greater catalytic activity with greater H2 yield and showed stronger resistance to carbon deposition, attributed to the presence of NiO nanoparticles. Thus, the addition of nickel and iron oxides played an important role in catalytic cracking of rice hull biomass tar.

Effect of preparation method of palygorskite-supported Fe and Ni catalysts on catalytic cracking of biomass tar

In this study, the effect of catalyst preparation and additive precursors on the catalytic decomposition of biomass using palygorskite-supported Fe and Ni catalysts was investigated. The catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is concluded that the most active additive precursor was Fe(NO3)3·9H2O. As for the catalyst preparation method, co-precipitation had superiority over incipient wetness impregnation at low Fe loadings.

Characterization and catalytic performance of Fe3Ni8/palygorskite for catalytic cracking of benzene

Catalytic decomposition is a very attractive way to convert tar components into H2, CO and other useful chemicals. The performance of Fe3Ni8/PG (palygorskite, PG) reduced in hydrogen at different temperatures for the catalytic decomposition of benzene has been assessed. Benzene was used as the model biomass tar. The effects of calcination atmosphere, temperatures and benzene concentration on catalytic cracking of benzene were measured. The results of XRD (X-Ray Diffraction), TEM (Transmission Electron Microscope), TPR (Temperature Program Reduction), TPSR (Temperature Program Surface Reduction), TC (Total Carbon), the reactivity component and reaction mechanism over Fe3Ni8/PG for catalytic cracking of benzene are discussed. The results showed particles of awaruite (Fe, Ni) about 2–30 nm were found on the surface of palygorskite by TEM when the calcination temperature was 600 °C. Particles with size smaller than 30 nm were obtained on all prepared Fe3Ni8/PG catalysts as shown by XRD. The nanoparticles proved to be the reactive component for catalytic cracking of benzene and the increase of active particle size caused the decrease in the reactivity of Fe3Ni8/PG. Fe3Ni8/PG annealed in hydrogen at 600 °C was proved to have the best reactivity in experiments (45% hydrogen yield). High concentration benzene (448 g/m3) accelerated the formation of carbon deposition. However, iron oxide decreases carbon deposition and increases the stability of catalyst for catalytic cracking of benzene. The application of Fe3Ni8/PG catalysts was proved a very effective catalyst for the catalytic cracking of benzene.

The difference of thermal stability between Fe-substituted palygorskite and Al-rich palygorskite

Sedimentary palygorskite (SP) and hydrothermal palygorskite (HP) were characterized by XRF, TG/DSC, andXRD. The total iron and dissociative iron in palygorskite were detected using spectrophotometry. The results showed that about 3.57 wt% of Fe2O3 was detected in SP in contrast with 0.4 wt% in HP. SP was a Fe-substituted palygorskite, and HP was an Al-rich palygorskite. The occurrence of Fe substitution in SP resulted in two mass loss steps of coordinated water and resulted in a larger d spacing. The SP showed greater thermal stability than the HP. It was proposed the change of (200) diffraction peak and (240) diffraction peak reflect changes of tetrahedral and octahedral structures in palygorskite.

Effect of rehydration on structure and surface properties of thermally treated palygorskite

Palygorskite has a fibrous like morphology with a distinctive layered appearance. The simplified formula of palygorskite (Mg5Si8O20(OH)2(OH2)4 nH2O) indicates that two different types of water are present. The dehydration and rehydration of palygorskite have been studied using thermogravimetry and H2O-tem- perature programmed desorption. X-ray diffractograms, NH3 adsorption profiles, and NH3 desorption profiles were obtained for thermally treated palygorskite as a function of temperature. The results proved water molecules were mainly derived from Si–OH units. In addition, five kinds of acid sites were found for palygorskite. The number of acid sites of external surfaces was larger than that of the internal sur- faces. Bonding on the internal surface acid sites was stronger than the bonding of the external surfaces. Rehydration restored the folded structure of palygorskite when thermal treatment temperature was lower than 300 oC.

CO2 reforming of toluene as model compound of biomass tar on Ni/Palygorskite

Catalytic CO2 reforming of biomass tar on palygorskite-supported nickel catalysts using toluene as a model compound of biomass tar was investigated. The experiments were performed in a bench scale installation a fixed bed reactor. All experiments were carried out at 650, 750, 800 °C and atmospheric pressure. The effect of Ni loading, reaction temperature and concentration of CO2 on H2 yield and carbon deposit was investigated. Ni/Palygorskite (Ni/PG) catalysts with Ni/PG ratios of 0%, 2%, 5% and 8% were tested, the last two show the best performance. H2 yield and carbon deposit diminished with the increase of reaction temperature, Ni loading, and CO2 concentration.

Effect of palygorskite clay on pyrolysis of rape straw : an in situ catalysis study

Biomass tar restricts the wide application and development of biomass gasification technology. In the present paper, palygorskite, a natural magnesium-containing clay mineral, was investigated for catalytic pyrolysis of rape straw in situ and compared with the dolomite researched widely. The two types of natural minerals were characterized with XRD and BET. The results showed that combustible gas derived from the pyrolysis increased with an increase in gasification temperature. The Hconversion and Cconversion increased to 44.7% and 31% for the addition of palygorskite and increased to 41.3% and 31.3% for the addition of dolomite at the gasification temperature of 800 °C, compared with 15.1% and 5.6% without addition of the two types of material. It indicated that more biomass was converted into combustible gases implying the decrease in biomass tar under the function of palygorskite or dolomite and palygorskite had a slightly better efficiency than that of dolomite in the experimental conditions.

Bisphenol A degradation enhanced by air bubbles via advanced oxidation using in situ generated ferrous ions from nano zero-valent iron/palygorskite composite materials

Novel nano zero-valent iron/palygorskite composite materials prepared by evaporative and centrifuge methods are tested for the degradation of bisphenol A in an aqueous medium. A systematic study is presented which showed that nano zero-valent iron material has little effect on bisphenol A degradation. When hydrogen peroxide was added to initiate the reaction, some percentage of bisphenol A removal (∼20%) was achieved; however, with the aid of air bubbles, the percentage removal can be significantly increased to ∼99%. Compared with pristine nano zero-valent iron and commercial iron powder, nano zero-valent iron/palygorskite composite materials have much higher reactivity towards bisphenol A and these materials are superior as they have little impact on the solution pH. However, for pristine nano zero-valent iron, it is difficult to maintain the reaction system at a favourable low pH which is a key factor in maintaining high bisphenol A removal. All materials were characterized by X-ray diffraction, scanning electron microscopy, elemental analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. The optimum conditions were obtained based on a series of batch experiments. This study has extended the application of nano zero-valent iron/palygorskite composites as effective materials for the removal of phenolic compounds from the environment.

Adsorption of the herbicide 2,4-D on organo-palygorskite

Among the clay minerals, montmorillonite is the most extensively studied material using as adsorbents, but palygorskite and its organically modified products have been least explored for their potential use in contaminated water remediation. In this study, an Australian palygorskite was modified with cationic surfactants octadecyl trimethylammonium bromide and dioctadecyl dimethylammonium bromide at different doses. A full structural characterization of prepared organo-palygorskite by X-ray diffraction, infrared spectroscopy, surface analysis and thermogravimetric analysis was performed. The morphological changes of palygorskite before and after modification were recorded using scanning electron microscopy, which showed the surfactant molecules can attach on the surface of rod-like crystals and thus can weaken the interactions between palygorskite single crystals. Real surfactants loadings on organo-palygorskites were also calculated based on thermogravimetric analysis. 1 CEC, 2 CEC octadecyl trimethylammonium bromide modified palygorskites, 1 CEC and 2 CEC dioctadecyl dimethylammonium bromide modified palygorskites absorbed as much as 12 mg/g, 42 mg/g, 9 mg/g and 25 mg/g of 2,4- dichlorophenoxyacetic acid respectively. This study has shown a potential on organo-palygorskites for organic herbicide adsorption especially anionic ones from waste water. In addition, equilibration time effects and the Langmuir and Freundlich models fitting were also investigated in details.

Development and application of Palygorskite porous ceramsite in a biological aerated filter (BAF)

Novel filter Palygorskite porous ceramsite (PC) was prepared using Palygorskite clay, poreforming material sawdust, and sodium silicate with a mass ratio of 10:2:1 after sintering at 700°C for 180 min. PC was characterized with X-ray diffraction, X-ray fluorescence, scanning electron microscopy, elemental, and porosimetry. PC had a total porosity of 67% and specific surface area of 61 m2/g. In order to assess the usefulness of PC as a medium for biological aerated filters (BAF), PC and (commercially available ceramsite) CAC were used to treat wastewater city in two laboratory-scale upflow BAFs. The results showed that the reactor containing PC was more efficient than the reactor containing CAC in terms of total organic carbon (TOC), ammonia nitrogen (NH3-N), and the removal of total nitrogen (TN) and phosphorus (P). This system was found to be more efficient at water temperatures ranging from 20 to 26°C, an air–water (A/W) ratio of 3:1, dissolved oxygen concentration >4.00 mg/L, and hydraulic retention time (HRT) ranging from 0.5 to 7 h. The interconnected porous structure produced for PC was suitable for microbial growth, and primarily protozoan and metazoan organisms were found in the biofilm. Microorganism growth also showed that, under the same submerged culture conditions, the biological mass in PC was significantly higher than in CAC (34.1 and 2.2 mg TN/g, respectively). In this way, PC media can be considered suitable for the use as a medium in novel biological aerated filters for the simultaneous removal of nitrogen and phosphorus.