Use of zeolite-rich rocks and waste materials for the production of structural lightweight concretes

This paper aims at testing the use of mixtures constituted by natural zeolitized products and SiC-bearing industrial wastes (sludge deriving from polishing of porcelain stoneware tiles, hereafter DPM) for the production of lightweight expanded aggregates as constituents of structural and/or thermo-insulating lightweight concretes. Two commercial products have been used as zeolite natural source: Cab70 (Yellow facies of Campanian Ignimbrite) and IZclino (Turkish clinoptilolite-rich epiclastite). Different amounts of a calcareous material (Pozzano limestones — hereafter CP) from the Sorrento peninsula (Naples — Italy) were also added to a Cab70–DPM mixture. All raw materials were characterized by means of mineralogical (XRPD) and chemical (XRF) analyses. All the products and mixtures were tested from a technological point of view by means of fusibility and firing tests in order to evaluate the expanding properties. It was evidenced that the expansion of the mixture was deeply depending on the occurrence of SiC in the industrial waste. The addition of CP (10 wt.%) to the mixtures accounts for an even increased expansion, though this is accompanied by a worsening of the mechanical features of the material.These results along with literature data allowed to select 3 mixtures (70% Cab70–30% DPM, 70% IZclino–30% DPM, 60% Cab70–30% DPM–10% CP) and each of them was used for the preparation of 5 l of lightweight aggregates afterward employed for the manufacture of lightweight concretes. It was remarked that natural zeolitized materials mixed with DPM (30 wt.%) can provide lightweight aggregates with densities ranging between 0.8 and 1.0 g/cm³ suitable for the preparation of structural lightweight concretes. The addition to the mixture of CP (10 wt.%) produces less dense aggregates (0.6–0.7 g/cm³) potentially useful for the manufacture of thermo insulating lightweight concretes.     

Adsorption of chromate by surfactant-modified zeolites and MCM-41 molecular sieve

Synthetic and natural zeolites, modified by the quaternary amines, i.e. hexadecyltrimethylammonium (HDTMA) bromide and n-cetylpyridinium bromide (CPB) as well as MCM-41 molecular sieve were employed for removal of chromate from aqueous solution. Obtained data from chromate adsorption experiments over the mentioned materials were compared. It was shown that adsorption data for modified zeolite using the amine was consistent with Langmuir isotherm equation. The maximum chromate adsorption over as synthesized MCM-41 was much greater than that of the natural clinoptilolite and ZSM-5 zeolites.     

Effect of clinoptilolite addition and solids retention time on the extracellular polymeric substances composition and soluble chemical oxygen demands in activated sludge

This study was carried out to compare EPS (Extracellular Polymeric Substances) composition between conventional activated sludge (AS) and activated sludge dosed with clinoptilolite (CAS). Additionally, those were compared with organic removal efficiency in the effluent in conjunction with EPS concentrations. The experiments were conducted at SRT (Solids Retention Time) ranging from 5 to 100 d. For the CAS, proteins were more readily observed for SRT 20 and 100 d compared to that of the AS. Polysaccharide concentration in the sludge was greatly increased for the CAS, but it was significantly diminished when the SRT was extended. The level of EPS concentration observed from the effluent had the same pattern of variation for the two different types of systems. Regardless of type of reactor, the ratio of proteins for sludge versus effluent was independent of SRT, but the ratio of polysaccharides diminished as SRT increased. In the long run, the degree of protein synthesis directly ascribed to concurrent enhancement of SCOD removal efficiency was slightly more in the CAS. It was decided that clinoptilolite added system could be more reliably retrofitted to a conventional activated sludge process.     

A study on natural clinoptilolite for CO2/N2 gas separation

Based on its low cost and low water adsorption capacity, compared to synthetic zeolites (A-type, X-type and Y-type), natural, untreated clinoptilolite was examined as a potential adsorbent for a separation process targeting on removal of CO₂ from flue gas. Taking into consideration typical flue gas composition and temperature, adsorptive properties of binary CO₂/N₂ mixtures were tested in the temperature range of 268 to 403 K and compared with literature data. The results showed that CO₂ concentration, total pressure, and temperature strongly affect selectivity and working capacity, restricting the conditions under which the material could be used as an efficient adsorbent.     

吸附法去除溶液中Mg~(2+)、Pb~(2+)的试验研究

以去除纯碱副产物氯化钙中的Mg2+和Pb2+,制取高纯氯化钙为目的,采用吸附的方法,研究了不同吸附剂对Mg2+、Pb2+的分离效果,以及吸附时间、温度、pH值等因素对改性斜发沸石吸附效果的影响。试验结果表明:改性斜发沸石对氯化钙中Mg2+、Pb2+有较好的吸附去除效果,吸附时间100min、温度30℃、100ml质量分数为0.5%的氯化钙溶液加吸附剂1.5g、pH10为最优吸附条件。     

New synthesis technique of supported ZSM-5 using organo-alumino-silicic gels

This contribution deals with the synthesis of a silicon-rich ZSM-5 obtained from an amorphous organo-alumino-silicic gel. The gel was formed by reacting a mechanical mixture of RHA (rice hull ash), silica’s source, and of natural clinoptilolite, source of alumina, with glycerol during 2 h at 200 °C. After a maturation period of one day at 60 °C, the reaction product was hydrolyzed by a tetra-propyl-ammonium (TPA) solution and then aged for two days at 135 °C in a stainless steel autoclave. After washing and drying, the X-ray pattern showed a well crystallized ZSM-5. The textural analysis of the slowly calcined solid at 500 °C for 4 h, and the SEM micrographies evidence that the zeolite was supported on mesoporous silica. The proportion of both components depends on the tunable hydrolysis conditions.     

Optimized experimental design for natural clinoptilolite zeolite ball milling to produce nano powders

Nano powder of natural clinoptilolite zeolite was mechanically prepared by using a planetary ball mill. Statistical experimental design was applied to optimize wet and dry milling of clinoptilolite zeolite. To determine appropriate milling conditions with respect to the final product crystallinity, particle size and distribution, different milling parameters such as dry and wet milling durations, rotational speed, balls to powder ratio and water to powder ratio (for the wet milling) were investigated. Laser beam scattering technique, scanning electron microscopy and X-ray diffraction analyses were carried out to characterize samples. Results showed that larger than 1 mm particle size of clinoptilolite powder may mechanically be reduced into the size range of less than 100 nm to 30 μm by means of planetary ball milling.     

Preparation,characterization and anticorrosive properties of a novel polyaniline/clinoptilolite nanocomposite

Nanocomposite of polyaniline (PANI) with natural clinoptilolite (Clino) was prepared. Formation of nanocomposite and incorporation of polyaniline in the clinoptilolite channels was confirmed and characterized using FTIR spectroscopy studies, X-ray diffraction (XRD) pattern, scanning electron microscopy (SEM) and cyclic voltammetry techniques. The anticorrosive properties of a 20 μm thickness coating of PANI/Clino nanocomposite with various weight ratios (1, 3 and 5%, w/w) of clinoptilolite content on iron coupons was evaluated and compared with pure polyaniline coating. According to the results in acidic environments PANI/Clino nanocomposite has enhanced corrosion protection effect in comparison to pure polyaniline coating. Comparative experiments revealed that PANI/Clino nanocomposite with 3% (w/w) clinoptilolite content has the best protective properties. Further experiments showed that the PANI/Clino nanocomposite has considerably different corrosion protection efficiencies in various corrosive environments.     

Regeneration von mit Ammoniak beladenem Klinoptilolith durch ein nicht‐thermisches Plasmaverfahren

Adsorbents are widely‐used in the area of cleaning as well as enrichment of gas components. For the regeneration of clinoptilolite loaded with ammonia, a packed‐bed reactor was developed on the basis of a dielectric barrier discharge. It was proved that adsorbed NH₃ is released at relatively low temperature and low energy consumption. For the further optimization of the method the influence of the power and the pulse break ratio of sustaining voltage were tested. It was shown that with the chosen plasma method the absorber material was loaded repeatedly and subsequently regenerated.     

Zeolites in biomedical application: Zn-exchanged clinoptilolite-rich rock as active carrier for antibiotics in anti-acne topical therapy

A clinoptilolite-rich rock was evaluated as inorganic Zn²⁺ releasing carrier for antibiotic erythromycin. The perspective is its use in the topical treatment of acne, a diffused skin pathology, given the efficacy of zinc-erythromycin combination against resistant Propionibacterium strains. The tested rock is an ash-rich epiclastite collected in Northern–Central part of Sardinia island (Italy). ICP chemical analyses of the bulk rock evidenced a composition compatible with topical applications. A 66 wt.% of clinoptilolite content was determined by means of XRD analysis (reference intensity ratio [RIR] technique). EDS chemical analyses of zeolite crystals were performed on polished thin section. The CEC of the rock is 1.45±0.08 meq/g. Using a specific exchange method, the material was previously Na-conditioned then Zn-conditioned. A substantially complete Zn-form was obtained, as demonstrated by AAS analyses. A back-exchange reaction toward Na-form was performed in the same conditions (65 °C in 1 M NaCl solution): zinc release was fast and almost complete (94%). Zn-conditioned powder was then micronized to achieve a volume/surface ratio suitable for a topical therapy. After micronization, the specific surface area, determined by BET gas adsorption, was 30.2 m²/g, and 92% of the powdered rock was lower than 30 μm in size (measured by a Coulter Counter apparatus); the so-called “volume-surface diameter” was 6.48 μm, compatible with the intended topical application. Zn²⁺ release was measured on micronized rock at 37 °C both in physiologic solution as in 0.05 M KH₂PO₄/Na₂HPO₄ buffer. Also in these conditions, a prompt and significant zinc release was recorded: after 30 min, 68% and 60%, respectively. Erythromycin was charged onto the micronized material using a solvent evaporation method. HPLC determinations showed that 85% of the drug contacted with the carrier was loaded. The simultaneous release of zinc and erythromycin were evaluated in phosphate buffer. Eighty-two percent of the loaded antibiotic was released after 30 min. Zinc exchange is substantially unaffected by the contemporary drug release. The request to file an international patent for this pharmaceutical application has been accepted by the European International Preliminary Examination Office.